1、Designation: D5185 18Standard Test Method forMultielement Determination of Used and Unused LubricatingOils and Base Oils by Inductively Coupled Plasma AtomicEmission Spectrometry (ICP-AES)1This standard is issued under the fixed designation D5185; the number immediately following the designation ind
2、icates the year oforiginal adoption or, in the 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.This standard has been approved for use by agencies o
3、f the U.S. Department of Defense.INTRODUCTIONCosts associated with maintenance due to engine and machine wear can be significant. Therefore,diagnostic methods for determining the condition of engines and other machinery can be important.This test method is intended to quantify, for the purpose of eq
4、uipment monitoring, the concentrationof metals in used lubricating oils. Although the precision statement was determined by analyzing avariety of used oils this test method can, in principle, be used for the analysis of unused oils to providemore complete elemental composition data than Test Methods
5、 D4628, D4927,orD4951.1. Scope*1.1 This test method covers the determination of additiveelements, wear metals, and contaminants in used and unusedlubricating oils and base oils by inductively coupled plasmaatomic emission spectrometry (ICP-AES). The specific ele-ments are listed in Table 1.1.2 This
6、test method covers the determination of selectedelements, listed in Table 1, in re-refined and virgin base oils.1.3 For analysis of any element using wavelengths below190 nm, a vacuum or inert-gas optical path is required. Thedetermination of sodium and potassium is not possible on someinstruments h
7、aving a limited spectral range.1.4 This test method uses oil-soluble metals for calibrationand does not purport to quantitatively determine insolubleparticulates. Analytical results are particle size dependent, andlow results are obtained for particles larger than a fewmicrometers.21.5 Elements pres
8、ent at concentrations above the upper limitof the calibration curves can be determined with additional,appropriate dilutions and with no degradation of precision.1.6 For elements other than calcium, sulfur, and zinc, thelow limits listed in Table 2 and Table 3 were estimated to be tentimes the repea
9、tability standard deviation. For calcium, sulfur,and zinc, the low limits represent the lowest concentrationstested in the interlaboratory study.1.7 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.8 This standard does not purp
10、ort to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.Specific warning statements ar
11、e given in 6.1, 8.2, and 8.4.1.9 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Orga
12、nization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:3C1109 Practice for Analysis of Aqueous Leachates fromNuclear Waste Materials Using Inductively Coupled1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, a
13、nd Lubricants and is the direct responsibility ofSubcommittee D02.03 on Elemental Analysis.Current edition approved April 1, 2018. Published April 2018. Originallyapproved in 1991. Last previous edition approved in 2013 as D5185 131. DOI:10.1520/D5185-18.2Eisentraut, K. J., Newman, R. W., Saba, C. S
14、., Kauffman, R. E., and Rhine, W.E., Analytical Chemistry, Vol 56, 1984.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe AS
15、TM website.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardi
16、zation established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1Plasma-Atomic Emission SpectroscopyD1552 Test Method for Sulfur in Petroleum Products byHigh
17、Temperature Combustion and Infrared (IR) Detec-tion or Thermal Conductivity Detection (TCD)D4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD4307 Practice for Preparation of Liquid Blends for Use asAnalytical
18、 StandardsD4628 Test Method for Analysis of Barium, Calcium,Magnesium, and Zinc in Unused Lubricating Oils byAtomic Absorption SpectrometryD4927 Test Methods for Elemental Analysis of Lubricantand Additive ComponentsBarium, Calcium,Phosphorus, Sulfur, and Zinc by Wavelength-DispersiveX-Ray Fluoresce
19、nce SpectroscopyD4951 Test Method for Determination of Additive Elementsin Lubricating Oils by Inductively Coupled PlasmaAtomic Emission SpectrometryD7260 Practice for Optimization, Calibration, and Valida-tion of Inductively Coupled Plasma-Atomic EmissionSpectrometry (ICP-AES) for Elemental Analysi
20、s of Petro-leum Products and LubricantsE135 Terminology Relating to Analytical Chemistry forMetals, Ores, and Related Materials3. Terminology3.1 Definitions:3.1.1 emission spectroscopyrefer to Terminology E135.3.2 Definitions of Terms Specific to This Standard:3.2.1 additive element, na constituent
21、of a chemical com-pound that improves the performance of a lubricating oil.3.2.2 analyte, nan element whose concentration is beingdetermined.3.2.3 Babington-type nebulizer, na device that generatesan aerosol by flowing a liquid over a surface that contains anorifice from which gas flows at a high ve
22、locity.3.2.4 calibration, nthe process by which the relationshipbetween signal intensity and elemental concentration is deter-mined for a specific element analysis.3.2.5 calibration curve, nthe plot of signal intensity ver-sus elemental concentration using data obtained by makingmeasurements with st
23、andards.3.2.6 contaminant, na foreign substance, generallyundesirable, introduced into a lubricating oil.3.2.7 detection limit, nthe concentration of an analyte thatresults in a signal intensity that is some multiple (typically two)TABLE 1 Elements Determined and Suggested WavelengthsAElement Wavele
24、ngth, nmAluminum 308.22, 396.15, 309.27Barium 233.53, 455.40, 493.41Boron 249.77Calcium 315.89, 317.93, 364.44, 422.67Chromium 205.55, 267.72Copper 324.75Iron 259.94, 238.20Lead 220.35Magnesium 279.08, 279.55, 285.21Manganese 257.61, 293.31, 293.93Molybdenum 202.03, 281.62Nickel 231.60, 227.02, 221.
25、65Phosphorus 177.51, 178.29, 213.62, 214.91, 253.40Potassium 766.49Sodium 589.59Silicon 288.16, 251.61Silver 328.07Sulfur 180.73, 182.04, 182.62Tin 189.99, 242.95Titanium 337.28, 350.50, 334.94Vanadium 292.40, 309.31, 310.23, 311.07Zinc 202.55, 206.20, 213.86, 334.58, 481.05AThese wavelengths are on
26、ly suggested and do not represent all possiblechoices.TABLE 2 RepeatabilityElement Range, mg/kg Repeatability, g/gAAluminum 640 0.71 X0.41Barium 0.54 0.24 X0.66Boron 430 0.26 XCalcium 409000 0.0020 X1.4Chromium 140 0.17 X0.75Copper 2160 0.12 X0.91Iron 2140 0.13 X0.80Lead 10160 1.6 X0.32Magnesium 517
27、00 0.16 X0.86Manganese 5700 0.010 X1.3Molybdenum 5200 0.29 X0.70Nickel 540 0.52 X0.49Phosphorus 101000 1.3 X0.58Potassium 401200 3.8 X0.33Silicon 850 1.3 X0.26Silver 0.550 0.15 X0.83Sodium 770 0.49 X0.66Sulfur 9006000 0.49 X0.81Tin 1040 2.4 X0.17Titanium 540 0.54 X0.37Vanadium 150 0.061 XZinc 601600
28、 0.15 X0.88Awhere: X = mean concentration, g/g.TABLE 3 ReproducibilityElement Range, mg/kg Reproducibility, g/gAAluminum 640 3.8 X0.26Barium 0.54 0.59 X0.92Boron 430 13 X0.01Calcium 409000 0.015 X1.3Chromium 140 0.81 X0.61Copper 2160 0.24 XIron 2140 0.52 X0.80Lead 10160 3.0 X0.36Magnesium 51700 0.72
29、 X0.77Manganese 5700 0.13 X1.2Molybdenum 5200 0.64 X0.71Nickel 540 1.5 X0.50Phosphorus 101000 4.3 X0.50Potassium 401200 6.6 X0.29Silicon 850 2.9 X0.39Silver 0.550 0.35 XSodium 770 1.1 X0.71Sulfur 9006000 1.2 X0.75Tin 1040 2.1 X0.62Titanium 540 2.5 X0.47Vanadium 150 0.28 X1.1Zinc 601600 0.083 X1.1Awh
30、ere: X = mean concentration, g/g.D5185 182times the standard deviation of the background intensity at themeasurement wavelength.3.2.8 inductively-coupled plasma (ICP), na high-temperature discharge generated by flowing an ionizable gasthrough a magnetic field induced by a load coil that surroundsthe
31、 tubes carrying the gas.3.2.9 linear response range, nthe elemental concentrationrange over which the calibration curve is a straight line, withinthe precision of the test method.3.2.10 profiling, na technique that determines the wave-length for which the signal intensity measured for a particularan
32、alyte is a maximum.3.2.11 radio frequency (RF), nthe range of frequenciesbetween the audio and infrared ranges (3 kHz to 300 GHz).3.2.12 wear metal, nan element introduced into the oil bywear of oil-wetted parts.4. Summary of Test Method4.1 Aweighed portion of a thoroughly homogenized used orunused
33、lubricating oil, or base oil, is diluted tenfold by weightwith mixed xylenes or other suitable solvent. Standards areprepared in the same manner. A mandatory internal standard isadded to the solutions to compensate for variations in testspecimen introduction efficiency. The solutions are introducedt
34、o the ICP instrument by free aspiration or an optionalperistaltic pump. By comparing emission intensities of ele-ments in the test specimen with emission intensities measuredwith the standards, the concentrations of elements in the testspecimen are calculable.4.2 Standard operating parameters and ot
35、her considerationsto be considered in using ICP-AES technique are given inPractice D72605. Significance and Use5.1 This test method covers the rapid determination of 22elements in used and unused lubricating oils and base oils, andit provides rapid screening of used oils for indications of wear.Test
36、 times approximate a few minutes per test specimen, anddetectability for most elements is in the low mg/kg range. Inaddition, this test method covers a wide variety of metals invirgin and re-refined base oils. Twenty-two elements can bedetermined rapidly, with test times approximating severalminutes
37、 per test specimen.5.2 When the predominant source of additive elements inused lubricating oils is the additive package, significant differ-ences between the concentrations of the additive elements andtheir respective specifications can indicate that the incorrect oilis being used. The concentration
38、s of wear metals can beindicative of abnormal wear if there are baseline concentrationdata for comparison. A marked increase in boron, sodium, orpotassium levels can be indicative of contamination as a resultof coolant leakage in the equipment. This test method can beused to monitor equipment condit
39、ion and define when correc-tive actions are needed.5.2.1 The significance of metal analysis in used lubricatingoils is tabulated in Table 4.5.3 The concentrations of metals in re-refined base oils canbe indicative of the efficiency of the re-refining process. Thistest method can be used to determine
40、 if the base oil meetsspecifications with respect to metal content.6. Interferences6.1 SpectralCheck all spectral interferences expectedfrom the elements listed in Table 1. Follow the manufacturersoperating guide to develop and apply correction factors tocompensate for the interferences. To apply in
41、terferencecorrections, all concentrations must be within the previouslyestablished linear response range of each element listed inTable 1.(WarningCorrect profiling is important to revealspectral interferences from high concentrations of additiveelements on the spectral lines used for determining wea
42、rmetals.)6.1.1 Spectral interferences can usually be avoided byjudicious choice of analytical wavelengths. When spectralinterferences cannot be avoided, the necessary correctionsTABLE 4 Wear Metals (Elements) in Used Lubricating OilsElements Wear IndicationAluminum Piston and bearings wear, push rod
43、s, air cooler, pump hosings, oil pumps, gear castings, box castingsAntimony Crankshaft and camshaft bearingsBoron Coolant leakage in systemCadmium BearingsChromium Ring wear, cooling system leakage, chromium-plated parts in aircraft engines, cylinder liners, seal ringsCopper Wear in bushings, inject
44、or shields, coolant core tubes, thrust washers, valve guides, connecting rods, piston rings, bearings, sleeves,bearing cagesIron Wear from engine block, cylinder, gears, cylinder liners, valve guides, wrist pins, rings, camshaft, oil pump, crankshaft, ball and rollerbearings, rustLead Bearings, fuel
45、 blowby, thrust bearings, bearing cages, bearing retainersMagnesium Cylinder liner, gear box housings in aircraft enginesMolybdenum Wear in bearing alloys and in oil coolers; various molybdenum-alloyed components in aircraft engines, piston ringsNickel Bearings, valves, gear platingsSilicon Dirt int
46、rusion from improper air cleaner, seal materialsSilver Wrist pin bearings in railroad and auto engines, silver plotted spline lubricating pumpSodium Antifreeze leakageTin Bearings and coatings of connecting rods and iron pistonsTitanium Various titanium-alloyed components in aircraft enginesTungsten
47、 BearingsZinc Neoprene seals, galvanized pipingEditorially corrected.D5185 183should be made using the computer software supplied by theinstrument manufacturer or the empirical method describedbelow. Details of the empirical method are given in TestMethod C1109 and by Boumans.4This empirical correct
48、ionmethod cannot be used with scanning spectrometer systemswhen both the analytical and interfering lines cannot be locatedprecisely and reproducibly. With any instrument, the analystmust always be alert to the possible presence of unexpectedelements producing interfering spectral lines.6.1.2 The em
49、pirical method of spectral interference correc-tion uses interference correction factors. These factors aredetermined by analyzing the single-element, high-purity solu-tions under conditions matching as closely as possible thoseused for test specimen analysis. Unless plasma conditions canbe accurately reproduced from day to day, or for longerperiods, interference correction factors found to affect theresults significantly must be redetermined each time specimensare analyzed.6.1.3 Interference correction factors, K
