1、Designation: D6417 09D6417 15Standard Test Method forEstimation of Engine Oil Volatility by Capillary GasChromatography1This standard is issued under the fixed designation D6417; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the
2、year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope*Scope1.1 This test method covers an estimation of the amount of engine oil volatilized at 371C (700F).371 C (700
3、F).1.1.1 This test method can also be used to estimate the amount of oil volatilized at any temperature between 126126 C and371C,371 C, if so desired.1.2 This test method is limited to samples having an initial boiling point (IBP) greater than 126C (259F)126 C (259 F) orthe first calibration point a
4、nd to samples containing lubricant base oils with end points less than 615C (1139F)615 C (1139 F)or the last n-paraffins in the calibration mixture. By using some instruments and columns, it is possible to extend the useful rangeof the test method.1.3 This test method uses the principles of simulate
5、d distillation methodology.1.4 This test method may be applied to both lubricant oil base stocks and finished lubricants containing additive packages.Theseadditive packages generally contain high molecular weight, nonvolatile components that do not elute from the chromatographiccolumn under the test
6、 conditions. The calculation procedure used in this test method assumes that all of the sample elutes fromthe column and is detected with uniform response. This assumption is not true for samples with nonvolatile additives, andapplication of this test method under such conditions will yield results
7、higher than expected. For this reason, results by this testmethod are reported as area percent of oil.1.5 The values stated in SI units are to be regarded as standard. The values stated in inch-pound units are provided forinformation only.1.6 This standard does not purport to address all of the safe
8、ty concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D2887 Test Method for Boiling Range
9、 Distribution of Petroleum Fractions by Gas ChromatographyD4626 Practice for Calculation of Gas Chromatographic Response FactorsD5800 Test Method for Evaporation Loss of Lubricating Oils by the Noack MethodD6352 Test Method for Boiling Range Distribution of Petroleum Distillates in Boiling Range fro
10、m 174 C to 700 C by GasChromatographyE355 Practice for Gas Chromatography Terms and RelationshipsE594 Practice for Testing Flame Ionization Detectors Used in Gas or Supercritical Fluid ChromatographyE1510 Practice for Installing Fused Silica Open Tubular Capillary Columns in Gas Chromatographs2.2 Co
11、ordinating European Council Standard:CEC L-4093 Evaporation Loss of Lubricating Oils (NOACK Evaporative Tester)31 This test method is under the jurisdiction ofASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of SubcommitteeD02.04.0H on Chromatog
12、raphic Distribution Methods.Current edition approved June 1, 2009June 1, 2015. Published June 2009July 2015. Originally approved in 1999. Last previous edition approved in 20032009 asD6417D6417 09.03. DOI: 10.1520/D6417-09.10.1520/D6417-15.2 For referencedASTM standards, visit theASTM website, www.a
13、stm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.3 Available from Coordinating European Council (CEC), C/o Interlynk Administrative Services, Ltd., P.O. Box 6475, Earl Sh
14、ilton, Leicester, LE9 9ZB, U.K.,http:/www.cectests.org.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes a
15、ccurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Har
16、bor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13. Terminology3.1 DefinitionsThis test method makes reference to many common gas chromatographic procedures, terms, and relationships.Detailed definitions of these can be found in Practices E355, E594, and E1510.3.2 Definitions
17、of Terms Specific to This Standard:3.2.1 area slicethe area resulting from the integration of the chromatographic detector signal within a specified retention timeinterval. In area slice mode (see 6.5.2), peak detection parameters are bypassed and the detector signal integral is recorded as areaslic
18、es of consecutive, fixed duration time intervals.3.2.2 corrected area slicean area slice corrected for baseline offset by subtraction of the exactly corresponding area slice ina previously recorded blank (nonsample) analysis.3.2.3 cumulative corrected areathe accumulated sum of corrected area slices
19、 from the beginning of the analysis through agiven retention time (RT), ignoring any nonsample area (for example, solvent).3.2.4 slice ratethe time interval used to integrate the continuous (analog) chromatographic detector response during ananalysis. The slice rate is expressed in hertz (for exampl
20、e, integrations or slices per second).3.2.5 slice timethe cumulative slice rate (analysis time) associated with each area slice throughout the chromatographicanalysis. The slice time is the time at the end of each contiguous area slice.3.2.6 total sample areathe cumulative corrected area from the in
21、itial point to the final area point.3.3 AbbreviationsA common way to abbreviate hydrocarbon compounds is to designate the number of carbon atoms in thecompound. A prefix is used to indicate the carbon chain form while a subscript suffix denotes the number of carbon atoms (forexample, normal decane n
22、-C10; iso-tetradecane = i-C14).4. Summary of Test Method4.1 Anonpolar open tubular (capillary) gas chromatographic column is used to elute the hydrocarbon components of the samplein order of increasing boiling point.4.2 A sample aliquot is diluted with a viscosity reducing solvent and introduced int
23、o the chromatographic system. At least onelaboratory analyzed samples using neat injection without solvent dilution. The precision of the method was calculated on dilutedsamples. If a laboratory chooses to use neat injection, it should first confirm that it is obtaining similar results. Sample vapor
24、izationis provided by separate heating of the point of injection or in conjunction with column oven heating.4.3 The column oven temperature is raised at a reproducible linear rate to effect separation of the hydrocarbon components inorder of increasing boiling point. The elution of sample components
25、 is quantitatively determined by a flame ionization detector(FID). The detector signal integral is recorded as area slices for consecutive RT intervals during the analysis.4.4 RTs of known hydrocarbons spanning the scope of the test method (C8-C60) are determined and correlated to their boilingpoint
26、 temperatures. The RT at 371C (700F)371 C (700 F) is calculated using linear regression, utilizing the calibrationdeveloped from the n-paraffins.The cumulative corrected area of the sample determined to the 371C371 C RTis used to calculatethe percentage of oil volatilized at 371C.371 C.5. Significan
27、ce and Use5.1 The determination of engine oil volatility at 371C (700F)371 C (700 F) is a requirement in some lubricant specifications.5.2 This test method is intended as an alternative to Test Methods D5800 and the Noack method for the determination of engineoil volatility (CEC L-4093). The data ob
28、tained from this test method are not directly equivalent to Test Method D5800. Thecalculated results of the oil volatility estimation by this test method can be biased by the presence of additives (polymericmaterials), which may not completely elute from the gas chromatographic column, or by heavier
29、 base oils not completely elutingfrom the column. The results of this test method may also not correlate with other oil volatility methods for nonhydrocarbonsynthetic oils.5.3 This test method can be used on lubricant products not within the scope of other test methods using simulated distillationme
30、thodologies, such as Test Method D2887D6352.6. Apparatus6.1 ChromatographThe gas chromatographic system used must have the following performance characteristics:6.1.1 Column Oven, capable of sustained and linear programmed temperature operation from near ambient (for example,3535 C to 50C)50 C) up t
31、o 400C.400 C.6.1.2 Column Temperature ProgrammerThe chromatograph must be capable of linear programmed temperature operation upto 400C400 C at selectable linear rates up to 20C/min.20 Cmin. The programming rate must be sufficiently reproducible toobtain the RT repeatability of 0.1 min (6 s) 0.1 min
32、(6 s) for each component in the calibration mixture described in 7.6.6.1.3 DetectorThis test method requires a FID. The detector must meet or exceed the following specifications as detailed inPractice E594.D6417 1526.1.3.1 Operating Temperature, up to 400C.400 C.6.1.3.2 Sensitivity, 0.005 coulombs/g
33、 carbon, 0.005 Ccarbon.g.6.1.3.3 Minimum Detectability, carbon, 1 1011 g carbon / s.g/s.6.1.3.4 Linear Range, 106.6.1.3.5 Connection of the column to the detector must be such that no temperature below the column temperature exists. Referto Practice E1510 for proper installation and conditioning of
34、the capillary column.6.1.4 Sample Inlet SystemAny sample inlet system capable of meeting the performance specification in 7.6 may be used.Programmed temperature vaporization (PTV) and programmable cool on-column injection systems have been used successfully.6.2 MicrosyringeA microsyringe with a 23 g
35、age, 23 gauge, or smaller, stainless steel needle is used for on-column sampleintroduction. Syringes of 0.1 L to 10 L 0.1 L to 10 L capacity have been used.6.2.1 Automatic syringe injection is recommended to achieve best precision.6.3 ColumnThis test method is limited to the use of nonpolar wall coa
36、ted open tubular (WCOT) columns of high thermalstability. Glass, fused silica, and stainless steel columns with a 0.53-mm0.53 mm diameter have been successfully used.Cross-linked or bonded methyl silicone liquid phases with film thickness from 0.100.10 m to 1.0 m 1.0 m have been used. Thecolumn leng
37、th and liquid phase film thickness must allow the elution of at least C60 n-paraffin (boiling point = 615C).615 C).The column and conditions must provide separation of typical petroleum hydrocarbons in order of increasing boiling point andmeet the column resolution requirements of 8.2.1.6.4 Carrier
38、Gas Flow/Pressure ControlThe optimum carrier gas flow for the column and chromatographic system should beused. It is recommended that the system be equipped with a constant pressure/constant flow device capable of maintaining thecarrier gas at a constant flow rate throughout the temperature program.
39、6.5 Data Acquisition System:6.5.1 RecorderA 00 mV to 1 mV 1 mV range recording potentiometer, or equivalent, with a full-scale response time of 2 s,2 s, or less, may be used to provide a graphical display.6.5.2 IntegratorMeans must be provided for determining the accumulated area under the chromatog
40、ram. This can be done bymeans of an electronic integrator or computer based chromatography data system. The integrator/computer system must havenormal chromatographic software for measuring the retention time and areas of eluting peaks (peak detection mode). In addition,the system must be capable of
41、 converting the continuously integrated detector signal into area slices of fixed duration (area slicemode). These contiguous area slices, collected for the entire analysis, are stored for later processing. The electronic range of theintegrator/computer (for example, 1 V, 10 V) 1 V, 10 V) must be wi
42、thin the linear range of the detector/electrometer system used.NOTE 1Some gas chromatographs have an algorithm built into their operating software that allows a mathematical model of the baseline profile tobe stored in memory. This profile is automatically subtracted from the detector signal on subs
43、equent sample runs to compensate for the column bleed.Some integration systems also store and automatically subtract a blank analysis from subsequent analytical determinations.7. Reagents and Materials7.1 Carrier GasHelium, nitrogen, or hydrogen of high purity. (WarningHelium and nitrogen are compre
44、ssed gases underhigh pressure. Hydrogen is an extremely flammable gas under high pressure.) Additional purification is recommended by the useof molecular sieves or other suitable agents to remove water, oxygen, and hydrocarbons. Available pressure must be sufficient toensure a constant carrier gas f
45、low rate.7.2 HydrogenHydrogen of high purity (for example, hydrocarbon free) is used as fuel for the FID. (WarningHydrogen isan extremely flammable gas under high pressure.)7.3 AirHigh purity (for example, hydrocarbon free) compressed air is used as the oxidant for the FID. (WarningCompressed air is
46、 a gas under high pressure and supports combustion.)7.4 Carbon Disulfide (CS2) (99+ % pure), may be used as a viscosity reducing solvent. It is miscible with asphaltichydrocarbons and provides relatively little response with the FID. The quality (hydrocarbon content) should be determined by thistest
47、 method prior to use as a sample diluent. (WarningCarbon disulfide is extremely flammable and toxic.)7.5 Cyclohexane(99+ % pure), may be used as a viscosity reducing solvent. It is miscible with asphaltic hydrocarbons;however, it responds well to the FID. The quality (hydrocarbon content) should be
48、determined by this test method prior to use asa sample diluent. ( WarningCyclohexane is flammable.)7.6 Calibration MixtureA qualitative mixture of n-paraffins (nominally C8 to C60) dissolved in a suitable solvent. The finalconcentration should be approximately 1 part of n-paraffin mixture to 100 par
49、ts of solvent. It is recommended that at least onecompound in the mixture have a boiling point lower than the IBP of the sample being analyzed, as defined in the scope of this testmethod (see 1.1). It is recommended that the calibration mixture contain at least eleven known n-paraffins (for example, C8, C9,C10, C12, C16, C20, C30, C40, C50, C52 and C60). Boiling points of n-paraffins are listed in Table 1.NOTE 2A suitable calibration mixture can be obtained by dissolving a synthetic wax in a vol
