ASTM D3524-14(2020)

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: D3524 − 14 (Reapproved 2020)
Standard Test Method for
Diesel Fuel Diluent in Used Diesel Engine Oils by Gas
Chromatography
This standard is issued under the fixed designation D3524; 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 mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
1.1 This test method covers the use of gas chromatography
to determine the amount of diesel fuel in used engine lubricat-
2. Referenced Documents
ing oil. This test is limited to SAE 30 oil. The diesel fuel
2.1 ASTM Standards:
diluent is analyzed at concentrations up to 12 % by mass.
NOTE 1—This test method may be applicable to higher viscosity grade
D4626 Practice for Calculation of Gas Chromatographic
oils. However, such oils were not included in the program used to develop
Response Factors
the precision statement.
E260 Practice for Packed Column Gas Chromatography
1.2 This test method is limited to gas chromatographs
E355 Practice for Gas ChromatographyTerms and Relation-
equipped with flame ionization detectors and temperature
ships
programmable ovens.
E594 Practice for Testing Flame Ionization Detectors Used
NOTE 2—The use of other detectors and instrumentation has been
in Gas or Supercritical Fluid Chromatography
reported. However, the precision statement applies only when the instru-
E1510 Practice for Installing Fused Silica Open Tubular
mentation specified is employed.
Capillary Columns in Gas Chromatographs
1.3 There is some overlap of the boiling ranges of diesel
fuel and SAE 30 engine oils. Moreover, the boiling range of
3. Terminology
SAE 30 oils from various sources can vary appreciably. As a
3.1 Definitions:
result, the calibration can be altered by as much as 2 %, in
3.1.1 For definition of gas chromatography terms, refer to
terms of fuel dilution. When testing unknown or mixed brands
Practice E355.
ofusedengineoil,itshouldberealizedthattheprecisionofthe
3.2 Definitions of Terms Specific to This Standard:
method may be poorer than the precision obtained when
3.2.1 fuel dilution, n—the amount, expressed as a
calibrating with a new oil representative of the used oil being
percentage, of diesel fuel found in engine lubricating oil.
tested.
3.2.1.1 Discussion—Fuel dilution may be the result of
1.4 The values stated in SI units are to be regarded as the
engine wear or improper performance.
standard. The values stated in inch-pound units are for infor-
3.2.2 fuel diluent, n—in used oil analysis, is the unburned
mation only.
fuel components that enter the engine crankcase causing
1.5 This standard does not purport to address all of the
dilution of the oil.
safety concerns, if any, associated with its use. It is the
3.2.2.1 Discussion—In this method, the fuel diluent compo-
responsibility of the user of this standard to establish appro-
nents being determined are from diesel fuel.
priate safety, health, and environmental practices and deter-
3.3 Abbreviations:
mine the applicability of regulatory requirements prior to use.
3.3.1 Acommonabbreviationofhydrocarboncompoundsis
1.6 This international standard was developed in accor-
to designate the number of carbon atoms in the compound. A
dance with internationally recognized principles on standard-
prefix is used to indicate the carbon chain form, while a
ization established in the Decision on Principles for the
subscripted suffix denotes the number of carbon atoms.
Development of International Standards, Guides and Recom-
For example: normal decane n–C
iso-tetradecane i–C
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricantsand is the direct responsibility of
Subcommittee D02.B0 on Automotive Lubricants. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Nov. 1, 2020. Published November 2020. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1976. Last previous edition approved in 2014 as D3524 – 14. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D3524-14R20. the ASTM website.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3524 − 14 (2020)
4. Summary of Test Method temperature required. Connection of the column to the sample
inlet system must be such that no temperature zones below the
4.1 Gas chromatographic techniques are used for analyzing
column temperature (cold spots) exist.
the samples, by adding a known percentage of n-decane as an
internal standard, in order to determine the mass percent of 6.2 Data Acquisition System:
diesel fuel in the lubricating oil. A calibration curve is 6.2.1 Integrator—Means must be provided for determining
previously constructed which plots the diesel fuel to n-decane the accumulated area under the chromatogram. This can be
response ratio versus the mass percent of diesel fuel in done by means of an electronic integrator or computer based
lubricating oil mixtures containing a constant amount of chromatography data system. The integrator/computer system
internal standard. The mass percent of diesel fuel in the must have chromatographic software for measuring the reten-
samples is determined by interpolation from the calibration tion times and areas of eluting peaks (peak detection mode).
curve. The electronic range of the integrator/computer (for example,
1 V, 10 V) must be within the linear range of the detector/
5. Significance and Use
electrometer system used. It is desirable that the system be
capable of subtracting each area slice of a blank run from the
5.1 Some fuel dilution of the engine oil may take place
corresponding area slice of a sample run.
duringnormaloperation.However,excessivefueldilutionisof
concern in terms of possible performance problems. This
NOTE 4—Best precision and automatic operation can be achieved with
method provides a means to determine the magnitude of the an electronic integration system using a computer for data acquisition and
control of the gas chromatograph.
fuel dilution, providing the user with the ability to predict
NOTE 5—Some gas chromatographs have an algorithm built into their
performance and to take appropriate action.
operating software that allows a mathematical model of the baseline
profile to be stored in memory. This profile is automatically subtracted
6. Apparatus
from the detector signal on subsequent sample analyses to compensate for
any baseline offset. Some integration systems also store and automatically
6.1 Gas Chromatograph—Any gas chromatograph can be
subtract a blank analysis from subsequent analytical determinations.
used that has the following performance characteristics:
6.3 Column—Any column and conditions may be used,
6.1.1 Detector—A flame ionization detector is used. The
provided that under the conditions of the test, the separations
detector must have sufficient sensitivity to detect 1.0 % decane
occur in order of increasing boiling points. Moreover, the
with a peak height of at least 10 % of full scale on the data
column must meet the performance requirements described in
acquisition device under the conditions prescribed in this
8.2.1.Thecolumnresolution,R,shallbeatleast3andnotmore
method. Follow the directions given in Practice E594. When
than 8. Since a stable baseline is an essential requirement of
operating at this sensitivity level, detector stability must be
this method, compensation is required for column bleed,
such that a baseline drift of not more than 1 % full scale per
septum bleed, detector temperature control, constancy of
hour is obtained. The detector must be capable of operating
carrier gas flow and instrument drift.
continuously at a temperature equivalent to the maximum
column temperature employed. Connection of the column to
6.4 Flow Controllers—The gas chromatograph must be
the detector must be such that no temperature zones exist
equipped with mass flow controllers capable of maintaining
below the column temperature (cold spots). Although thermal
carrier gas flow constant to 61 % over the full operating
conductivity detectors have been used for this test, their use is
temperature range of the column. The inlet pressure of the
not recommended.
carrier gas supplied to the gas chromatograph must be suffi-
ciently high to compensate for the increase in column back-
NOTE 3—It is not desirable to operate a thermal conductivity detector at
pressure as the column temperature is raised.An inlet pressure
a temperature 5 °C to 10 °C higher than the maximum column tempera-
ture employed. Operation at higher temperature generally contributes to of 550 kPa (80 psig) has been found to be satisfactory with the
higher noise levels and greater drift, and can also shorten the useful life of
columns described in Table 1.
the detector.
6.5 Sample Introduction Devices:
6.1.2 Column Temperature Programmer—The chromato-
6.5.1 Micro Syringe—A micro syringe, usually 10 µL, is
graph must be capable of linear programmed temperature
used for sample introduction.
operation over a range sufficient to establish a retention time of
6.5.2 Automatic sampling devices that reproducibly inject
at least 1 min for the initial peak(s) and to elute the entire
the same volume are highly recommended. The sample intro-
sample before reaching the upper end of the temperature
duction devices should operate in a synchronous manner with
program. The programming rate must be sufficiently reproduc-
the gas chromatograph.
ible to obtain retention time repeatability of 0.1 min (6 s) for
6.6 Vial, 15 mL, screw cap.
each component in the calibration mixture described in 7.8.
6.1.3 Sample Inlet System—The sample inlet system must
7. Reagents and Materials
be capable of operating continuously at a temperature equiva-
lenttothemaximumcolumntemperatureemployed,orprovide 7.1 Purity of Reagents—Reagent grade chemicals shall be
an on-column inlet with some means of programming the inlet, used in all tests. Unless otherwise indicated, it is intended that
including the point of sample introduction, up to the maximum all reagents conform to the specifications of the Committee on
D3524 − 14 (2020)
TABLE 1 Typical Operating Conditions
Packed Columns Open Tubular Capillary Columns
Column length, m (ft) 0.610 (2) 5 – 10
Column outside diameter, mm (in.) 3.2 (1/8) —
Column inside diameter, mm (in.) 2.36 (0.093) 0.53
Liquid phase methylsilicone gum or liquid cross-linked bonded polydimethylsiloxane
Percent liquid phase 10 —
Support material crushed fire brick or diatomaceous earth —
Treatment acid washed, silanized —
Support mesh size 80/100 —
Stationary phase thickness, microns — 0.88 – 2.65
Column temperature, initial, °C 70 70
Column temperature, final, °C 325 325
Programming rate, °C/min 16 16
Carrier gas helium or nitrogen helium or nitrogen
Carrier gas flow rate, mL/min 30 30
Detector Flame Ionization Detector Flame Ionization Detector
Detector temperature, °C 350 350
Injection port temperature, °C 300 300
Sample size, µL 1 0.1 – 0.2 (from 1/10 dilution in CS )
Analytical Reagents of the American Chemical Society where 7.8 Calibration Mixtures—Aminimum of three mixtures of
such specifications are available. Other grades may be used, diesel fuel and lubricating oil (Warning—Combustible liquid)
provided it is first ascertained that the reagent is of sufficiently of a similar type to that being analyzed are prepared to cover
high purity to permit its use without lessening the accuracy of the range up to 12 % by mass diesel fuel. If open tubular
the determination. columns are used, this calibration mixture shall be diluted 1/10
with carbon disulfide (CS ).
7.2 Liquid Phase for Columns—Methylsilicone gums and
mass of fuel
liquids provide the proper chromatographic hydrocarbon elu-
Diesel fuel, mass % 5 3100 (1)
tion characteristics for this test method. mass of fuel and oil
~ !
7.9 n-Decane, 99 % minimum purity. (Warning—
7.3 Solid Support—Usually crushed fire brick or diatoma-
Combustible liquid; vapor harmful.)
ceous earth is used for the packed columns. Sieve size and
supportloadingshouldbesuchaswillgiveoptimumresolution
7.10 n-Hexadecane, 95 % minimum purity. (Warning—
and analysis time. In general, particle size ranging from 60 to
Combustible liquid; vapor harmful.)
100 sieve mesh, and support loadings of 3 % to 10 %, have
7.11 n-Octadecane, 95 % minimum purity (Warning—
been found most satisfactory.
Combustible liquid; vapor harmful.)
7.4 Carrier Gas—Helium or nitrogen (Warning—Helium
7.12 To test column resolution, prepare a mixture of 1 % by
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