ASTM D6417-15(2019)

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: D6417 − 15 (Reapproved 2019)
Standard Test Method for
Estimation of Engine Oil Volatility by Capillary Gas
Chromatography
This standard is issued under the fixed designation D6417; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 1.7 This international standard was developed in accor-
dance with internationally recognized principles on standard-
1.1 This test method covers an estimation of the amount of
ization established in the Decision on Principles for the
engine oil volatilized at 371°C (700°F).
Development of International Standards, Guides and Recom-
1.1.1 This test method can also be used to estimate the
mendations issued by the World Trade Organization Technical
amount of oil volatilized at any temperature between 126°C
Barriers to Trade (TBT) Committee.
and 371°C, if so desired.
1.2 This test method is limited to samples having an initial
2. Referenced Documents
boiling point (IBP) greater than 126°C (259°F) or the first
2.1 ASTM Standards:
calibration point and to samples containing lubricant base oils
D2887Test Method for Boiling Range Distribution of Pe-
with end points less than 615°C (1139°F) or the last
troleum Fractions by Gas Chromatography
n-paraffins in the calibration mixture. By using some instru-
D4626Practice for Calculation of Gas Chromatographic
ments and columns, it is possible to extend the useful range of
Response Factors
the test method.
D5800Test Method for Evaporation Loss of Lubricating
1.3 This test method uses the principles of simulated distil-
Oils by the Noack Method
lation methodology.
D6352Test Method for Boiling Range Distribution of Pe-
troleum Distillates in Boiling Range from 174°C to
1.4 This test method may be applied to both lubricant oil
700°C by Gas Chromatography
base stocks and finished lubricants containing additive pack-
E355PracticeforGasChromatographyTermsandRelation-
ages. These additive packages generally contain high molecu-
ships
lar weight, nonvolatile components that do not elute from the
E594Practice for Testing Flame Ionization Detectors Used
chromatographic column under the test conditions. The calcu-
in Gas or Supercritical Fluid Chromatography
lationprocedureusedinthistestmethodassumesthatallofthe
E1510Practice for Installing Fused Silica Open Tubular
sample elutes from the column and is detected with uniform
Capillary Columns in Gas Chromatographs
response. This assumption is not true for samples with non-
volatile additives, and application of this test method under
2.2 Coordinating European Council Standard:
suchconditionswillyieldresultshigherthanexpected.Forthis
CEC L-40–93Evaporation Loss of Lubricating Oils (NO-
reason, results by this test method are reported as area percent
ACK Evaporative Tester)
of oil.
3. Terminology
1.5 The values stated in SI units are to be regarded as
standard. The values stated in inch-pound units are provided
3.1 Definitions—This test method makes reference to many
for information only.
common gas chromatographic procedures, terms, and relation-
ships. Detailed definitions of these can be found in Practices
1.6 This standard does not purport to address all of the
E355, E594, and E1510.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
3.2 Definitions of Terms Specific to This Standard:
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
This test method is under the jurisdiction of ASTM Committee D02 on contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of Standards volume information, refer to the standard’s Document Summary page on
Subcommittee D02.04.0H on Chromatographic Distribution Methods. the ASTM website.
Current edition approved Dec. 1, 2019. Published December 2019. Originally Available from Coordinating European Council (CEC), C/o Interlynk Admin-
approved in 1999. Last previous edition approved in 2015 as D6417–15. DOI: istrative Services, Ltd., P.O. Box 6475, Earl Shilton, Leicester, LE9 9ZB, U.K.,
10.1520/D6417-15R19. http://www.cectests.org.
*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
D6417 − 15 (2019)
3.2.1 area slice—the area resulting from the integration of 5. Significance and Use
the chromatographic detector signal within a specified reten-
5.1 The determination of engine oil volatility at 371°C
tiontimeinterval.Inareaslicemode(see6.5.2),peakdetection
(700°F) is a requirement in some lubricant specifications.
parameters are bypassed and the detector signal integral is
5.2 This test method is intended as an alternative to Test
recorded as area slices of consecutive, fixed duration time
Methods D5800 and the Noack method for the determination
intervals.
ofengineoilvolatility(CECL-40–93).Thedataobtainedfrom
3.2.2 corrected area slice—an area slice corrected for base-
this test method are not directly equivalent to Test Method
line offset by subtraction of the exactly corresponding area
D5800.Thecalculatedresultsoftheoilvolatilityestimationby
slice in a previously recorded blank (nonsample) analysis.
this test method can be biased by the presence of additives
3.2.3 cumulative corrected area—the accumulated sum of
(polymeric materials), which may not completely elute from
correctedareaslicesfromthebeginningoftheanalysisthrough
the gas chromatographic column, or by heavier base oils not
a given retention time (RT), ignoring any nonsample area (for
completely eluting from the column. The results of this test
example, solvent).
methodmayalsonotcorrelatewithotheroilvolatilitymethods
for nonhydrocarbon synthetic oils.
3.2.4 slice rate—the time interval used to integrate the
continuous (analog) chromatographic detector response during
5.3 This test method can be used on lubricant products not
an analysis. The slice rate is expressed in hertz (for example,
within the scope of other test methods using simulated distil-
integrations or slices per second).
lation methodologies, such as Test Method D6352.
3.2.5 slice time—the cumulative slice rate (analysis time)
6. Apparatus
associatedwitheachareaslicethroughoutthechromatographic
analysis. The slice time is the time at the end of each
6.1 Chromatograph—Thegaschromatographicsystemused
contiguous area slice.
must have the following performance characteristics:
6.1.1 Column Oven, capable of sustained and linear pro-
3.2.6 total sample area—thecumulativecorrectedareafrom
grammed temperature operation from near ambient (for
the initial point to the final area point.
example, 35°C to 50°C) up to 400°C.
3.3 Abbreviations—Acommon way to abbreviate hydrocar-
6.1.2 Column Temperature Programmer—The chromato-
bon compounds is to designate the number of carbon atoms in
graph must be capable of linear programmed temperature
the compound. A prefix is used to indicate the carbon chain
operation up to 400°C at selectable linear rates up to
form while a subscript suffix denotes the number of carbon
20°C⁄min. The programming rate must be sufficiently repro-
atoms (for example, normal decane n-C ; iso-tetradecane =
ducible to obtain the RT repeatability of 0.1min (6s) for each
i-C ).
component in the calibration mixture described in 7.6.
6.1.3 Detector—This test method requires a FID. The de-
4. Summary of Test Method
tector must meet or exceed the following specifications as
4.1 A nonpolar open tubular (capillary) gas chromato-
detailed in Practice E594.
graphiccolumnisusedtoelutethehydrocarboncomponentsof
6.1.3.1 Operating Temperature, up to 400°C.
the sample in order of increasing boiling point.
6.1.3.2 Sensitivity, carbon, >0.005C⁄g.
−11
4.2 A sample aliquot is diluted with a viscosity reducing 6.1.3.3 Minimum Detectability, carbon,1×10 g/s.
solvent and introduced into the chromatographic system. At 6.1.3.4 Linear Range, 10 .
least one laboratory analyzed samples using neat injection 6.1.3.5 Connection of the column to the detector must be
without solvent dilution. The precision of the method was such that no temperature below the column temperature exists.
calculated on diluted samples. If a laboratory chooses to use Refer to Practice E1510 for proper installation and condition-
neat injection, it should first confirm that it is obtaining similar ing of the capillary column.
results.Samplevaporizationisprovidedbyseparateheatingof 6.1.4 Sample Inlet System—Any sample inlet system ca-
the point of injection or in conjunction with column oven pable of meeting the performance specification in 7.6 may be
heating. used. Programmed temperature vaporization (PTV) and pro-
grammable cool on-column injection systems have been used
4.3 Thecolumnoventemperatureisraisedatareproducible
successfully.
linear rate to effect separation of the hydrocarbon components
in order of increasing boiling point. The elution of sample 6.2 Microsyringe—A microsyringe with a 23gauge, or
components is quantitatively determined by a flame ionization smaller, stainless steel needle is used for on-column sample
detector (FID). The detector signal integral is recorded as area introduction. Syringes of 0.1µL to 10µL capacity have been
slices for consecutive RT intervals during the analysis. used.
6.2.1 Automatic syringe injection is recommended to
4.4 RTs of known hydrocarbons spanning the scope of the
achieve best precision.
test method (C -C ) are determined and correlated to their
8 60
boiling point temperatures. The RT at 371°C (700°F) is 6.3 Column—This test method is limited to the use of
calculated using linear regression, utilizing the calibration nonpolar wall coated open tubular (WCOT) columns of high
developed from the n-paraffins. The cumulative corrected area thermal stability. Glass, fused silica, and stainless steel col-
of the sample determined to the 371°C RTis used to calculate umns with a 0.53mm diameter have been successfully used.
the percentage of oil volatilized at 371°C. Cross-linkedorbondedmethylsiliconeliquidphaseswithfilm
D6417 − 15 (2019)
thicknessfrom0.10µmto1.0µmhavebeenused.Thecolumn 7.5 Cyclohexane—(99+%pure),maybeusedasaviscosity
lengthandliquidphasefilmthicknessmustallowtheelutionof reducing solvent. It is miscible with asphaltic hydrocarbons;
at least C60 n-paraffin (boiling point = 615°C). The column however,itrespondswelltotheFID.Thequality(hydrocarbon
and conditions must provide separation of typical petroleum content) should be determined by this test method prior to use
hydrocarbons in order of increasing boiling point and meet the as a sample diluent. (Warning—Cyclohexane is flammable.)
column resolution requirements of 8.2.1.
7.6 Calibration Mixture—A qualitative mixture of
6.4 Carrier Gas Flow/Pressure Control—The optimum car- n-paraffins (nominally C to C ) dissolved in a suitable
8 60
rier gas flow for the column and chromatographic system solvent.Thefinalconcentrationshouldbeapproximately1part
shouldbeused.Itisrecommendedthatthesystembeequipped ofn-paraffinmixtureto100partsofsolvent.Itisrecommended
with a constant pressure/constant flow device capable of that at least one compound in the mixture have a boiling point
maintaining the carrier gas at a constant flow rate throughout lower than the IBPof the sample being analyzed, as defined in
the temperature program. the scope of this test method (see 1.1). It is recommended that
the calibration mixture contain at least eleven known
6.5 Data Acquisition System:
n-paraffins (for example, C,C,C ,C ,C ,C ,C ,C ,
8 9 10 12 16 20 30 40
6.5.1 Recorder—A 0 mV to 1 mV range recording
C ,C and C ). Boiling points of n-paraffins are listed in
50 52 60
potentiometer, or equivalent, with a full-scale response time of
Table 1.
2s, or less, may be used to provide a graphical display.
6.5.2 Integrator—Means must be provided for determining NOTE 2—A suitable calibration mixture can be obtained by dissolving
a synthetic wax in a volatile solvent (for example, carbon disulfide or
the accumulated area under the chromatogram. This can be
cyclohexane). Solutions of 1 part synthetic wax to 200 parts solvent can
done by means of an electronic integrator or computer based
beprepared.Lowerboilingpointparaffinswillhavetobeaddedtoensure
chromatography data system. The integrator/computer system
conformance with 7.5. The synthetic wax can be obtained from the
musthavenormalchromatographicsoftwareformeasuringthe
Petrolite Company as well as from chromatography suppliers under the
retention time and areas of eluting peaks (peak detection nameofPolywax500orPolywax655.Thismixtureisusedformeasuring
the resolution (see 8.2.1).
mode). In addition, the system must be capable of converting
the continuously integrated detector signal into area slices of
7.7 Response Linearity Mixture—Prepare a quantitatively
fixed duration (area slice mode). These contiguous area slices,
weighed mixture of about ten individual paraffins (>99%
collectedfortheentireanalysis,arestoredforlaterprocessing.
purity), covering the boiling range of the test method. The
The electronic range of the integrator/computer (for example,
highest boiling point component should be at least n-C . The
1V, 10V) must be within the linear range of the detector/
mixture must contain n-C . Use a suitable solvent to provide
electrometer system used.
a solution of each component at approximately 0.5% to 2.0%
by mass.
NOTE 1—Some gas chromatographs have an algorithm built into their
operating software that allows a mathematical model of the baseline
profile to be stored in memory. This profile is automatically subtracted 8. Preparation of Apparatus
from the detector signal on subsequent sample runs to compensate for the
8.1 Gas Chromatograph Setup:
column bleed. Some integration systems also store and automatically
8.1.1 Place the gas chromatograph and ancillary equipment
subtract a blank analysis from subsequent analytical determinations.
into operation in accordance with the manufacturer’s instruc-
7. Reagents and Materials tions. Recommended operating conditions are shown in Table
2.
7.1 Carrier Gas—Helium, nitrogen, or hydrogen of high
8.1.2 When attaching the column to the detector inlet,
purity. (Warning—Helium and nitrogen are compressed gases
ensure that the end of the column terminates as close as
under high pressure. Hydrogen is an extremely flammable gas
possible to the FID jet. Follow the instructions in Practice
under high pressure.) Additional purification is recommended
E1510.
by the use of molecular sieves or other suitable agents to
8.1.3 The FID should be periodically inspected and, if
remove water, oxygen, and hydrocarbons. Available pressure
necessary, remove any foreign deposits formed in the detector
must be sufficient to ensure a constant carrier gas flow rate.
from combustion of silicone liquid phase or other materials.
7.2 Hydrogen—Hydrogen of high purity (for example, hy-
Such deposits will change the response characteristics of the
drocarbon free) is used as fuel for the FID. (Warning—
detector.
Hydrogenisanextremelyflammablegasunderhighpressure.)
8.1.4 The inlet liner and initial portion of the column must
7.3 Air—High purity (for example, hydrocarbon free) com- be periodically inspected and replaced, if necessary, to remove
extraneous deposits or sample residue.
pressed air is used as the oxidant for the FID. (Warning—
Compressed air is a gas under high pressure and supports 8.1.5 Column Conditioning—A new column will require
combustion.) conditioning at the upper test method operating temperature to
reduce or eliminate significant liquid phase bleed, resulting in
7.4 Carbon Disulfide (CS ) (99+% pure), may be used as a
a stable chromatographic baseline. Follow the guidelines
viscosity reducing solvent. It is miscible with asphaltic hydro-
outlined in Practice E1510.
carbons and provides relatively little response with the FID.
The quality (hydrocarbon content) should be determined by 8.2 System Performance Specification:
this test method prior to use as a sample diluent. (Warning— 8.2.1 Column Resolution—The column resolution, influ-
Carbon disulfide is extremely flammable and toxic.) enced by both the column’s physical parameters and operating
D6417 − 15 (2019)
A,B
TABLE 1 Boiling Points of n-Paraffins TABLE 2 Recommended Operating Conditions
Carbon Boiling Boiling Carbon Boiling Boiling
Injector Cool on-column or equivalent
Number Point °C Point °F Number Point °C Point °F
Injection temperature oven-track mode
2 −89 −127 52 584 1083
3 −42 −44 53 588 1090
Auto sampler required for best precision
4 0 31 54 592 1098
5 36 97 55 596 1105
Data collection data is collected as independent area slices
6 69 156 56 600 1112
(average slice data collection rate is 3/s)
7 98 209 57 604 1119
8 126 258 58 608 1126
Column Capillary, 5 m × 0.53 mm id
9 151 303 59 612 1134
film thickness; 0.1 µm to 1.0 µm (polymethylsiloxane)
10 174 345 60 615 1139
11 196 385 61 619 1146
Flow conditions UHP helium at 12 mL ⁄min (constant flow) or optimized
12 216 421 62 622 1152
for the column (make-up gas helium at 18 mL ⁄min)
13 235 456 63 625 1157
14 254 488 64 629 1164
Detector Flame Ionization;
15 271 519 65 632 1170
Temperature: 390 °C
16 287 548 66 635 1175
17 302 576 67 638 1180
Oven program initial oven temperature 50 °C,
18 316 601 68 641 1186
initial hold 0 min,
19 330 625 69 644 1191
program rate 10 °C ⁄min,
20 344 651 70 647 1197
final oven temperature 380 °C,
21 356 675 71 650 1202
final hold 12 min,
22 369 696 72 653 1207
equilibration time 2 min
23 380 716 73 655 1211
24 391 736 74 658 1216
Sample size 0.1 µL to 0.5 µL
25 402 755 75 661 1222
26 412 774 76 664 1227
Sample dilution 2 % by mass in carbon disulfide
27 422 791 77 667 1233
28 431 808 78 670 1238
Calibration dilution 1 % by mass in carbon disulfide
29 440 824 79 673 1243
30 449 840 80 675 1247
31 458 856 81 678 1252
32 466 870 82 681 1258
33 474 885 83 683 1261
34 481 898 84 686 1267
ing this test method. Resolution is determined using Eq 1 and
35 489 912 85 688 1270
the C and C paraffins from a calibration mixture analysis
36 496 925 86 691 1276 50 52
37 503 937 87 693 1279 (see 7.6 and Note 2). Resolution ( R) should be at least one,
38 509 948 88 695 1283
using the identical conditions employed for sample analyses.
39 516 961 89 697 1287
40 522 972 90 700 1292
R 52 ~t 2 t !/~1.699 ~w 1w !! (1)
2 1 2 1
41 528 982 91 702 1296
42 534 993 92 704 1299
where:
43 540 1004 93 706 1303
R = resolution,
44 545 1013 94 708 1306
45 550 1022 95 710 1310 t = time (s) for the n-C peak maximum,
1 50
46 556 1033 96 712 1314
t = time (s) for the n-C peak maximum,
2 52
47 561 1042 97 714 1317
w = peak width (s), at half height, of the n-C peak, and
1 50
48 566 1051 98 716 1321
w = peak width (s), at half height, of the n-C peak.
49 570 1058 99 718 1324 2 52
50 575 1067 100 720 1328
8.2.2 Detector Response Calibration—This test method as-
51 579 1074
sumes that the FID response to petroleum hydrocarbons is
A
API Project 44, October 31, 1972 is believed to have provided the original normal
proportional to the mass of individual components. This must
paraffin boiling point data that are listed in Table 1. However, over the years some
of the data contained in both API Project 44 (Thermodynamics Research Center beverifiedwhenthesystemisputinserviceandwheneverany
Hydrocarbon Project) and D6417 have changed and they are no longer equivalent.
changes are made to the system or operational parameters.
Table 1 represents the current normal paraffin boiling point values accepted by
Analyze the response linearity mixture (see 7.7), using the
Subcommittee D02.04 and found in all test methods under the jurisdiction of
Section D02.04.0H.
identical procedure to be used for the analysis of samples (see
B
D6417 has traditionally used n-paraffin boiling points rounded to the nearest
Section 9). Calculate the relative response factor for each
whole degree for calibration. The boiling points listed in Table 1 are correct to the
n-paraffin (relative to n-tetracontane) as per Practice D4626
nearest whole number in both degrees Celsius and degrees Fahrenheit. However,
if a conversion is made from one unit to the other and then rounded to a whole
and Eq 2:
number, the results will not agree with the table values for a few carbon numbers.
For example, the boiling point of n-heptane is 98.425 °C, which is correctly F 5 M /A / M /A (2)
~ ! ~ !
n n n 40 40
rounded to 98 °C in the table. However, converting 98.425 °C gives 209.165 °F,
which rounds to 209 °F, while converting 98 °C gives 208.4 °F, which rounds to where:
208 °F. Carbon numbers 2, 4, 7, 8, 9, 13, 14, 15, 16, 25, 27, and 32 are affected
F = relative response factor,
n
by rounding.
M = mass of the n-paraff
...