1、Designation: D 6417 09An American National StandardStandard Test Method forEstimation of Engine Oil Volatility by Capillary GasChromatography1This standard is issued under the fixed designation D 6417; the number immediately following the designation indicates the year oforiginal adoption or, in the
2、 case of revision, the 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*1.1 This test method covers an estimation of the amount ofengine oil volatilized at 371C (
3、700F).1.1.1 This test method can also be used to estimate theamount of oil volatilized at any temperature between 126 and371C, if so desired.1.2 This test method is limited to samples having an initialboiling point (IBP) greater than 126C (259F) or the firstcalibration point and to samples containin
4、g lubricant base oilswith end points less than 615C (1139F) or the last n-paraffinsin the calibration mixture. By using some instruments andcolumns, it is possible to extend the useful range of the testmethod.1.3 This test method uses the principles of simulated distil-lation methodology.1.4 This te
5、st method may be applied to both lubricant oilbase stocks and finished lubricants containing additive pack-ages. These additive packages generally contain high molecu-lar weight, nonvolatile components that do not elute from thechromatographic column under the test conditions. The calcu-lation proce
6、dure used in this test method assumes that all of thesample elutes from the column and is detected with uniformresponse. This assumption is not true for samples with non-volatile additives, and application of this test method undersuch conditions will yield results higher than expected. For thisreas
7、on, results by this test method are reported as area percentof oil.1.5 The values stated in SI units are to be regarded asstandard. The values stated in inch-pound units are providedfor information only.1.6 This standard does not purport to address all of thesafety concerns, if any, associated with
8、its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 2887 Test Method for Boiling Range Distribution ofPetroleum Fractio
9、ns by Gas ChromatographyD 4626 Practice for Calculation of Gas ChromatographicResponse FactorsD 5800 Test Method for Evaporation Loss of LubricatingOils by the Noack MethodE 355 Practice for Gas Chromatography Terms and Rela-tionshipsE 594 Practice for Testing Flame Ionization Detectors Usedin Gas o
10、r Supercritical Fluid ChromatographyE 1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Gas Chromatographs2.2 Coordinating European Council Standard:CEC L-4093 Evaporation Loss of Lubricating Oils(NOACK Evaporative Tester)33. Terminology3.1 DefinitionsThis test method makes
11、reference to manycommon gas chromatographic procedures, terms, and relation-ships. Detailed definitions of these can be found in PracticesE 355, E 594, and E 1510.3.2 Definitions of Terms Specific to This Standard:3.2.1 area slicethe area resulting from the integration ofthe chromatographic detector
12、 signal within a specified reten-tion time interval. In area slice mode (see 6.5.2), peak detectionparameters are bypassed and the detector signal integral isrecorded as area slices of consecutive, fixed duration timeintervals.3.2.2 corrected area slicean area slice corrected for base-line offset by
13、 subtraction of the exactly corresponding areaslice in a previously recorded blank (nonsample) analysis.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0H on Chromatographic Distribution Meth
14、ods.Current edition approved June 1, 2009. Published June 2009. Originallyapproved in 1999. Last previous edition approved in 2003 as D 641703.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards vo
15、lume information, refer to the standards Document Summary page onthe ASTM website.3Available from Coordinating European Council (CEC), C/o Interlynk Admin-istrative Services, Ltd., P.O. Box 6475, Earl Shilton, Leicester, LE9 9ZB, U.K.,http:/www.cectests.org.1*A Summary of Changes section appears at
16、the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.3.2.3 cumulative corrected areathe accumulated sum ofcorrected area slices from the beginning of the analysis througha given retention time (RT), ignoring any no
17、nsample area (forexample, solvent).3.2.4 slice ratethe time interval used to integrate thecontinuous (analog) chromatographic detector response duringan analysis. The slice rate is expressed in hertz (for example,integrations or slices per second).3.2.5 slice timethe cumulative slice rate (analysis
18、time)associated with each area slice throughout the chromatographicanalysis. The slice time is the time at the end of eachcontiguous area slice.3.2.6 total sample areathe cumulative corrected areafrom the initial point to the final area point.3.3 AbbreviationsAcommon way to abbreviate hydrocar-bon c
19、ompounds is to designate the number of carbon atoms inthe compound. A prefix is used to indicate the carbon chainform while a subscript suffix denotes the number of carbonatoms (for example, normal decane n-C10; iso-tetradecane =i-C14).4. Summary of Test Method4.1 A nonpolar open tubular (capillary)
20、 gas chromato-graphic column is used to elute the hydrocarbon components ofthe sample in order of increasing boiling point.4.2 A sample aliquot is diluted with a viscosity reducingsolvent and introduced into the chromatographic system. Atleast one laboratory analyzed samples using neat injectionwith
21、out solvent dilution. The precision of the method wascalculated on diluted samples. If a laboratory chooses to useneat injection, it should first confirm that it is obtaining similarresults. Sample vaporization is provided by separate heating ofthe point of injection or in conjunction with column ov
22、enheating.4.3 The column oven temperature is raised at a reproduciblelinear rate to effect separation of the hydrocarbon componentsin order of increasing boiling point. The elution of samplecomponents is quantitatively determined by a flame ionizationdetector (FID). The detector signal integral is r
23、ecorded as areaslices for consecutive RT intervals during the analysis.4.4 RTs of known hydrocarbons spanning the scope of thetest method (C8-C60) are determined and correlated to theirboiling point temperatures. The RT at 371C (700F) iscalculated using linear regression, utilizing the calibrationde
24、veloped from the n-paraffins. The cumulative corrected areaof the sample determined to the 371C RT is used to calculatethe percentage of oil volatilized at 371C.5. Significance and Use5.1 The determination of engine oil volatility at 371C(700F) is a requirement in some lubricant specifications.5.2 T
25、his test method is intended as an alternative to TestMethods D 5800 and the Noack method for the determinationof engine oil volatility (CEC L-4093). The data obtained fromthis test method are not directly equivalent to Test MethodD 5800. The calculated results of the oil volatility estimationby this
26、 test method can be biased by the presence of additives(polymeric materials), which may not completely elute fromthe gas chromatographic column, or by heavier base oils notcompletely eluting from the column. The results of this testmethod may also not correlate with other oil volatility methodsfor n
27、onhydrocarbon synthetic oils.5.3 This test method can be used on lubricant products notwithin the scope of other test methods using simulated distil-lation methodologies, such as Test Method D 2887.6. Apparatus6.1 ChromatographThe gas chromatographic systemused must have the following performance ch
28、aracteristics:6.1.1 Column Oven, capable of sustained and linear pro-grammed temperature operation from near ambient (for ex-ample, 35 to 50C) up to 400C.6.1.2 Column Temperature ProgrammerThe chromato-graph must be capable of linear programmed temperatureoperation up to 400C at selectable linear ra
29、tes up to 20C/min.The programming rate must be sufficiently reproducible toobtain the RT repeatability of 0.1 min (6 s) for each componentin the calibration mixture described in 7.6.6.1.3 DetectorThis test method requires a FID. The de-tector must meet or exceed the following specifications asdetail
30、ed in Practice E 594.6.1.3.1 Operating Temperature, up to 400C.6.1.3.2 Sensitivity, 0.005 coulombs/g carbon.6.1.3.3 Minimum Detectability,13 1011g carbon / s.6.1.3.4 Linear Range,106.6.1.3.5 Connection of the column to the detector must besuch that no temperature below the column temperature exists.
31、Refer to Practice E 1510 for proper installation and condition-ing of the capillary column.6.1.4 Sample Inlet SystemAny sample inlet system ca-pable of meeting the performance specification in 7.6 may beused. Programmed temperature vaporization (PTV) and pro-grammable cool on-column injection system
32、s have been usedsuccessfully.6.2 MicrosyringeA microsyringe with a 23 gage, orsmaller, stainless steel needle is used for on-column sampleintroduction. Syringes of 0.1 L to 10 L capacity have beenused.6.2.1 Automatic syringe injection is recommended toachieve best precision.6.3 ColumnThis test metho
33、d is limited to the use ofnonpolar wall coated open tubular (WCOT) columns of highthermal stability. Glass, fused silica, and stainless steel col-umns with a 0.53-mm diameter have been successfully used.Cross-linked or bonded methyl silicone liquid phases with filmthickness from 0.10 to 1.0 m have b
34、een used. The columnlength and liquid phase film thickness must allow the elution ofat least C60 n-paraffin (boiling point = 615C). The columnand conditions must provide separation of typical petroleumhydrocarbons in order of increasing boiling point and meet thecolumn resolution requirements of 8.2
35、.1.6.4 Carrier Gas Flow/Pressure ControlThe optimum car-rier gas flow for the column and chromatographic systemshould be used. It is recommended that the system be equippedwith a constant pressure/constant flow device capable ofmaintaining the carrier gas at a constant flow rate throughoutthe temper
36、ature program.6.5 Data Acquisition System:D64170926.5.1 RecorderA 0 to 1 mV range recording potentiom-eter, or equivalent, with a full-scale response time of 2 s, orless, may be used to provide a graphical display.6.5.2 IntegratorMeans must be provided for determiningthe accumulated area under the c
37、hromatogram. This can bedone by means of an electronic integrator or computer basedchromatography data system. The integrator/computer systemmust have normal chromatographic software for measuring theretention time and areas of eluting peaks (peak detectionmode). In addition, the system must be capa
38、ble of convertingthe continuously integrated detector signal into area slices offixed duration (area slice mode). These contiguous area slices,collected for the entire analysis, are stored for later processing.The electronic range of the integrator/computer (for example, 1V, 10 V) must be within the
39、 linear range of the detector/electrometer system used.NOTE 1Some gas chromatographs have an algorithm built into theiroperating software that allows a mathematical model of the baselineprofile to be stored in memory. This profile is automatically subtractedfrom the detector signal on subsequent sam
40、ple runs to compensate for thecolumn bleed. Some integration systems also store and automaticallysubtract a blank analysis from subsequent analytical determinations.7. Reagents and Materials7.1 Carrier GasHelium, nitrogen, or hydrogen of highpurity. (WarningHelium and nitrogen are compressed gasesun
41、der high pressure. Hydrogen is an extremely flammable gasunder high pressure.) Additional purification is recommendedby the use of molecular sieves or other suitable agents toremove water, oxygen, and hydrocarbons. Available pressuremust be sufficient to ensure a constant carrier gas flow rate.7.2 H
42、ydrogenHydrogen of high purity (for example, hy-drocarbon free) is used as fuel for the FID. (WarningHydrogen is an extremely flammable gas under high pressure.)7.3 AirHigh purity (for example, hydrocarbon free) com-pressed air is used as the oxidant for the FID. (WarningCompressed air is a gas unde
43、r high pressure and supportscombustion.)7.4 Carbon Disulfide (CS2) (99+ % pure), may be used as aviscosity reducing solvent. It is miscible with asphaltic hydro-carbons and provides relatively little response with the FID.The quality (hydrocarbon content) should be determined bythis test method prio
44、r to use as a sample diluent. (WarningCarbon disulfide is extremely flammable and toxic.)7.5 Cyclohexane(99+ % pure), may be used as a viscosityreducing solvent. It is miscible with asphaltic hydrocarbons;however, it responds well to the FID. The quality (hydrocarboncontent) should be determined by
45、this test method prior to useas a sample diluent. (WarningCyclohexane is flammable.)7.6 Calibration MixtureA qualitative mixture ofn-paraffins (nominally C8to C60) dissolved in a suitablesolvent. The final concentration should be approximately 1 partof n-paraffin mixture to 100 parts of solvent. It
46、is recommendedthat at least one compound in the mixture have a boiling pointlower than the IBP of the sample being analyzed, as defined inthe scope of this test method (see 1.1). It is recommended thatthe calibration mixture contain at least eleven knownn-paraffins (for example, C8,C9,C10,C12,C16,C2
47、0,C30,C40,C50,C52and C60). Boiling points of n-paraffins are listed inTable 1.NOTE 2A suitable calibration mixture can be obtained by dissolvingTABLE 1 Boiling Points of n-ParaffinsA,BCarbonNumberBoilingPoint CBoilingPoint FCarbonNumberBoilingPoint CBoilingPoint F2 89 127 52 584 10833 42 44 53 588 1
48、0904 0 31 54 592 10985 36 97 55 596 11056 69 156 56 600 11127 98 209 57 604 11198 126 258 58 608 11269 151 303 59 612 113410 174 345 60 615 113911 196 385 61 619 114612 216 421 62 622 115213 235 456 63 625 115714 254 488 64 629 116415 271 519 65 632 117016 287 548 66 635 117517 302 576 67 638 118018
49、 316 601 68 641 118619 330 625 69 644 119120 344 651 70 647 119721 356 675 71 650 120222 369 696 72 653 120723 380 716 73 655 121124 391 736 74 658 121625 402 755 75 661 122226 412 774 76 664 122727 422 791 77 667 123328 431 808 78 670 123829 440 824 79 673 124330 449 840 80 675 124731 458 856 81 678 125232 466 870 82 681 125833 474 885 83 683 126134 481 898 84 686 126735 489 912 85 688 127036 496 925 86 691 127637 503 937 87 693 127938 509 948 88 695 128339 516 961 89 697 128740 522 972 90 700 129241 528 982 91 702 129642
