ASTM D6443-99
(Test Method)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)
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)
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) (see also 40 CFR 136 Appendix B) or limit of quantification (LOQ), 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 instrinsic 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 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 and health practices and determine the applicability of regulatory limitations prior to use.
General Information
Relations
Buy Standard
Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
AnAmerican National Standard
Designation:D6443–99
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 D 6443; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use.
1.1 This test method covers the determination of calcium,
chlorine, copper, magnesium, phosphorus, sulfur, and zinc in
2. Referenced Documents
unused lubricating oils, additives, and additive packages by
2.1 ASTM Standards:
wavelength dispersive X-ray fluorescence spectrometry. Ma-
D 1552 Test Method for Sulfur in Petroleum Products
trix effects are handled with mathematical corrections.
(High-Temperature Method)
1.2 For each element, the upper limit of the concentration
D 4057 Practice for Manual Sampling of Petroleum and
range covered by this test method is defined by the highest
Petroleum Products
concentration listed in Table 1. Samples containing higher
D 4177 Practice for Automatic Sampling of Petroleum and
concentrations can be analyzed following dilution.
Petroleum Products
1.3 For each element, the lower limit of the concentration
D 4307 PracticeforPreparationofLiquidBlendsforUseas
range covered by this test method can be estimated by the limit
2 Analytical Standards
of detection (LOD) (see also 40 CFR 136 Appendix B) or
D 4628 Test Method for Analysis of Barium, Calcium,
limit of quantification (LOQ), both of which can be estimated
Magnesium, and Zinc in Unused Lubricating Oils by
from S , the repeatability standard deviation. LOD and LOQ
r
Atomic Absorption Spectrometry
values, determined from results obtained in the interlaboratory
D 4927 Test Methods for Elemental Analysis of Lubricant
study on precision, are listed in Table 2.
and Additive Components—Barium, Calcium, Phospho-
1.3.1 LOD and LOQ are not intrinsic constants of this test
rus, Sulfur, and Zinc by Wavelength-Dispersive X-Ray
method. LOD and LOQ depend upon the precision attainable
Fluorescence Spectroscopy
by a laboratory when using this test method.
D 4951 Test Method for Determination of Additive Ele-
1.4 This test method uses regression software to determine
ments in Lubricating Oils by Inductively Coupled Plasma
calibration parameters, which can include influence coeffi-
Atomic Emission Spectrometry
cients (that is, interelement effect coefficients) (Guide E 1361),
D 5185 Test Method for Determination of Additive Ele-
herein referenced as alphas. Alphas can also be determined
ments, Wear Metals, and Contaminants in Used Lubricat-
from theory using relevant software.
ing Oils and Determination of Selected Elements in Base
1.5 Setup of this test method is intended for persons trained
Oils by Inductively Coupled Plasma Atomic Emission
inthepracticeofX-rayspectrometry.Followingsetup,thistest
Spectrometry (ICP-AES)
method can be used routinely.
E 29 Practice for Using Significant Digits in Test Data to
1.6 The values stated in either SI units or angstrom units are
Determine Conformance with Specifications
to be regarded separately as standard.
E 1361 Guide for Correction of Interelement Effects in
1.7 This standard does not purport to address all of the
X-Ray Spectrometric Analysis
safety concerns, if any, associated with its use. It is the
2.2 Government Standard:
responsibility of the user of this standard to establish appro-
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
This test method is under the jurisdiction of ASTM Committee D-2 on contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee Standards volume information, refer to the standard’s Document Summary page on
D02.03 on Elemental Analysis. the ASTM website.
Current edition approved July 10, 1999. Published September 1999. Available from Superintendent of Documents, U.S. Government Printing
Analytical Chemistry, Vol 55, pp. 2210-2218. Office, Washington, DC 20402.
Copyright ©ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA19428-2959, United States.
D6443–99
TABLE 1 Calibration Standard Compositions, Concentrations in
4.3 This test method is not intended for use on samples that
Mass%
contain some component that significantly interferes with the
Std. No. Ca Cl Cu Mg P S Zn
analysis of the elements specified in the scope.
1 0.02 0.02 0.01 0.20 0.25 1.00 0.02
4.4 This test method can complement other test methods for
2 0.02 0.02 0.05 0.20 0.02 0.02 0.25
lube oils and additives, including Test Methods D 4628,
3 0.02 0.20 0.01 0.05 0.25 0.02 0.25
D 4927, D 4951, and D 5185.
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
6 0.40 0.02 0.05 0.05 0.25 0.02 0.02
5. Interferences
7 0.40 0.20 0.01 0.20 0.02 0.02 0.02
5.1 The additive elements can affect the magnitudes of the
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
measured intensities for each analyte. In general, the
10 0 0 0 000 0
X-radiation emitted by each analyte can be absorbed by the
other elements.Also, the X-radiation emitted by an analyte can
be enhanced by some other component. The magnitudes of the
TABLE 2 Estimated LOD and LOQ, Units are Mass%
absorption and enhancement effects can be significant. How-
Ca Cl Cu Mg P Zn
ever,implementationofaccuratelydeterminedalphasintheset
LOD 0.0002 0.0004 0.0002 0.0039 0.0006 0.0002
LOQ 0.0008 0.0015 0.0007 0.0130 0.0020 0.0007
of calibration parameters can satisfactorily correct for absorp-
tion and enhancement effects, thereby making this test method
quantitative.
5.2 Molybdenum lines can spectrally overlap lines of mag-
40 CFR 136 Appendix B Definition and Procedure for the
nesium, phosphorus, sulfur, and chlorine. Lead lines can
Determination of the Method Detection Limit—Revision
spectrally overlap sulfur. Thus, this test method cannot be
1.11 (pp. 265-267)
applied if molybdenum or lead are present at significant
concentrations and if accurate overlap corrections cannot be
3. Summary of Test Method
made.
5.3 When a large d-spacing diffraction structure containing
3.1 The X-ray fluorescence spectrometer is initially cali-
silicon is used as the analyzing crystal, corrections for the
brated by the following procedure. For each element, the slope
fluorescence of silicon may be needed. Calcium X rays from
and intercept of the calibration curve are determined by
sample specimens cause silicon to fluoresce. This silicon
regressing concentration data and intensities measured on a set
radiation contributes to fluctuations in the background for
of physical standards. Empirical alphas can also be determined
magnesium measurements. If the effect is significant, this
by regression when the appropriate set of physical standards is
interference may be treated as a line overlap due to calcium.
used for calibration.Theoretical alphas, calculated with special
software, can also be used. In addition, a combination of
6. Apparatus
theoretical and empirical alphas can be used.
6.1 X-ray Spectrometer, equipped for detection of soft
3.2 AsampleisplacedintheX-raybeam,andtheintensities
X-ray radiation in the range from 1 to 10 angstroms. For
of the appropriate fluorescence lines are measured. A similar
optimum sensitivity, the spectrometer is equipped with the
measurement is made at a wavelength offset from each
following:
fluorescence line in order to obtain a background correction.
6.1.1 X-ray Tube Source, with chromium, rhodium, or
Enhancement or absorption of the X-ray fluorescence of an
scandium target. Scandium can be advantageous for sensitivity
analyte by an interfering element in the sample can occur, and
enhancement of the low atomic number analytes. Other targets
these effects can be handled in the data reduction by imple-
may also be employed. Avoid spectral interferences from tube
mentation of alphas. Concentrations of the analytes are deter-
lines on the analyte lines.
mined by comparison of net signals against calibration curves,
6.1.2 Helium, purgeable optical path.
which include influence coefficients (that is, alphas) calculated
6.1.3 Interchangeable Analyzer Crystals, germanium,
from theory, empirical data, or a combination of theory and
lithiumfluoride(LiF ),graphite,pentaerythritol(PE),ora50
empirical data. 200
angstrom diffraction structure, or a combination thereof. Other
suitable crystals can be used.
4. Significance and Use
6.1.4 Pulse-Height Analyzer.
4.1 Lubricatingoilscanbeformulatedwithadditives,which
6.1.5 Detector, gas flow proportional, or tandem gas flow
can act as detergents, anti-oxidants, anti-wear agents, and so
proportional and scintillation counter.
forth. Some additives can contain one or more of calcium,
NOTE 1—A gas sealed proportional counter was used in the interlabo-
copper, magnesium, phosphorus, sulfur, and zinc. This test
ratory study on precision and was found to be satisfactory.
method can be used to determine if the oils, additives, and
additive packages meet specification with respect to content of
6.2 Mixing Device Such As a Shaker, Ultrasonic Bath, or
these elements. Vortex Mixer, capable of handling from 30-mL to 1-L bottles.
4.2 This test method can also be used to determine if 6.3 X-ray Disposable Plastic Cells, with suitable film win-
lubricating oils, additives, and additive packages meet specifi- dow. Suitable films can include polyester, polypropylene, or
cation with respect to chlorine concentration. In this context, polyimide. A film thickness of 4 µm is preferred. Avoid using
specification can refer to contamination. film that contains any of the analytes.
D6443–99
TABLE 3 Suggested Channel Settings
Detector, Peak, Bkgd
Flow, Angles,
Scintillation, Degrees 2
Analyte kV, mA Crystal Collimator Both theta
Ca 40, 70 LiF(200) Coarse, 0.70mm Flow 113.16, 116.16
Cl 40, 70 Ge Coarse, 0.70mm Flow 92.80, 94.80
Cu 45, 60 LiF(200) Fine, Inter., 0.30 mm Both 45.03, 47.03
Synthetic multilayer,
Mg 40, 70 50 angstroms Coarse, 0.70mm Flow 23.05, 25.80
P 40, 70 Ge Coarse, 0.70mm Flow 141.00, 137.00
S 40, 70 Ge Coarse, 0.70mm Flow 110.75, 116.75
Zn 45, 60 LiF(200) Fine, Inter., 0.30 mm Both 41.76, 47.03
TABLE 4 Repeatability and Reproducibility for Oils, Units are
trations. Test Method D 1552, or other appropriate methods,
Mass%
can be used to determine sulfur content.
7.5.1.2 Secondary standards, such as those prepared from
NOTE 1—X = concentration in mass %.
petroleum additives, for example, can also be used if their use
Analyte Concns Repeatability Reproducibility
does not affect the analytical results by more than the repeat-
0.5 0.5
Ca .001 - .200 .006914 (X+.0007) .04762 (X+.0007)
Cl .001 - .030 .0356 (X+.0086) .05612 (X+.0340) ability of this test method.
0.4 0.4
Cu .001 - .030 .002267 (X+.0013) .01068 (X+.0013)
7.5.2 Di-n-butyl Sulfide, a high-purity standard with a cer-
0.333 0.333
Mg .003 - .200 .01611 (X+.0008) .05208 (X+.0008)
0.7 0.7
tified analysis for total sulfur content.
P .001 - .200 .02114 X .09112 X
0.9 0.9
S .030 - .800 .02371 X .1623 X
0.7 0.7
NOTE 3—Di-n-butyl sulfide is flammable and toxic.
Zn .001 - .200 .01225 X .06736 X
7.5.3 Oil-soluble Chlorine-containing Compound, a high
purity standard with a certified analysis for total chlorine
content.
7. Reagents and Materials
7.5.4 Stabilizers, Stabilizers can be used to ensure unifor-
7.1 Purity of Reagents—Reagent grade chemicals shall be
mity of the calibration standard blends. Use stabilizers that do
used in all tests. Unless otherwise indicated, it is intended that
not contain a detectable amount of any analyte.
all reagents conform to the specifications of the Committee on
Analytical Reagents of theAmerican Chemical Society, where
5 8. Sampling and Sample Handling
such specifications are available. Other grades can be used,
provided it is first ascertained that the reagent is of sufficiently 8.1 Take samples in accordance with the instructions in
high purity to permit its use without lessening the accuracy of
Practice D 4057 or D 4177, when applicable.
the determination.
8.2 Mixwellsamplesandcalibrationstandardblendsbefore
7.2 Helium, preferably ultrahigh purity (at least 99.95 %),
introduction into the X-ray instrument.
for optical path of spectrometer.
7.3 P-10 Ionization Gas,90volume%argonand10volume
9. Preparation of Calibration Standards
% methane for the flow proportional counter.
9.1 Prepare calibration standard blends by accurate dilution
NOTE 2—P-10 gas was used in the interlaboratory study on precision.
of the oil-soluble standard solutions with the dilution solvent.
Other satisfactory gases or gas mixtures can be applicable.
Theseblends(PracticeD4307),withaccuratelyknownanalyte
concentrations, shall approximate the nominal values listed in
7.4 Dilution Solvent, a hydrocarbon solvent, which does not
contain a detectable amount of any analyte. U.S.P. white Table 1.
(mineral) oil has been found to be satisfactory. 9.1.1 When empirical alphas are determined by regression,
7.5 Calibration Standard Materials: prepare and measure all standard blends listed in Table 1.
7.5.1 Concentrated Solutions of Oil-soluble Compounds,
9.1.2 When theoretical alphas are used, a subset of the
each containing one of the following: calcium, copper, mag-
standard blends (for example, standards 2, 6, 8, and 10) can be
nesium, phosphorus, or zinc.
satisfactory.
7.5.1.1 Some commercially available oil-soluble standard
9.2 Drift Correction Monitors (Optional)—The use of drift
materials are prepared from sulfonates and therefore contain
correction monitors for determination and correction of instru-
sulfur. To use these materials for preparation of the calibration
mentdriftcanbeadvantageous.Monitorsarestable,soliddisks
standard blends, it is necessary to know their sulfur concen-
or pellets containing all elements covered by this test method.
Two disks are preferred to correct for both sensitivity and base
line drifts. The high-concentration drift monitor provides
high-count rates, so that for each analyte, counting error is less
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, D.C. For suggestions on the testing of reagents not
than 0.25 % relative. The low-concentration drift monitor
listed by the American Chemical Society, see Anal
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.