1、Designation: D874 13a (Reapproved 2018) British Standard 4716Standard Test Method forSulfated Ash from Lubricating Oils and Additives1This standard is issued under the fixed designation D874; the number immediately following the designation indicates the year oforiginal adoption or, in the case of r
2、evision, 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 of the U.S. Department of Defense.1. Scope1.1 This test m
3、ethod covers the determination of the sul-fated ash from unused lubricating oils containing additives andfrom additive concentrates used in compounding. These addi-tives usually contain one or more of the following metals:barium, calcium, magnesium, zinc, potassium, sodium, and tin.The elements sulf
4、ur, phosphorus, and chlorine can also bepresent in combined form.1.2 Application of this test method to sulfated ash levelsbelow 0.02 % by mass is restricted to oils containing ashlessadditives. The lower limit of the test method is 0.005 % bymass sulfated ash.NOTE 1This test method is not intended
5、for the analysis of usedengine oils or oils containing lead. Neither is it recommended for theanalysis of nonadditive lubricating oils, for which Test Method D482 canbe used.NOTE 2There is evidence that magnesium does not react the same asother alkali metals in this test. If magnesium additives are
6、present, the datais interpreted with caution.NOTE 3There is evidence that samples containing molybdenum cangive low results because molybdenum compounds are not fully recoveredat the temperature of ashing.1.3 Fatty acid methyl ester (FAME) conforming to EN14213 and EN 14214, when tested using this t
7、est method, wereshown to meet its precision.1.4 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.5 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of
8、 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.1.6 This international standard was developed in accor-dance with internationally recognized principles on standard-ization establi
9、shed in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D482 Test Method for Ash from Petroleum ProductsD1193 Specificati
10、on for Reagent WaterD4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System Performan
11、ce2.2 CEN Standards:3EN 14213 Heating FuelsFatty Acid Methyl Esters(FAME)Requirements and Test MethodsEN 14214 Automotive FuelsFatty Acid Methyl Esters(FAME) for Diesel EnginesRequirements and TestMethods3. Terminology3.1 Definitions:3.1.1 sulfated ash, nthe residue remaining after thesample has bee
12、n carbonized, and the residue subsequentlytreated with sulfuric acid and heated to constant weight.4. Summary of Test Method4.1 The sample is ignited and burned until only ash andcarbon remain. After cooling, the residue is treated withsulfuric acid and heated at 775 C until oxidation of carbon is1T
13、his test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.03 on Elemental Analysis.Current edition approved April 1, 2018. Published June 2018. Originallyapproved in 1946. Last previous editi
14、on approved in 2013 as D874 13a. DOI:10.1520/D0874-13AR18.In the IP, this test method is under the jurisdiction of the StandardizationCommittee. This test method has been approved by the sponsoring committees andaccepted by the cooperating societies in accordance with established procedures.2For ref
15、erenced 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 ASTM website.3Available from European Committee for Standardization (CEN), AvenueM
16、arnix 17, B-1000, Brussels, Belgium, http:/www.cen.eu.Copyright 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 standardization established in
17、the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1complete. The ash is then cooled, re-treated with sulfuric acid,and heated at 775 C to constant weight.5. Significa
18、nce and Use5.1 The sulfated ash can be used to indicate the concentra-tion of known metal-containing additives in new oils. Whenphosphorus is absent, barium, calcium, magnesium, sodiumand potassium are converted to their sulfates and tin (stannic)and zinc to their oxides (Note 4). Sulfur and chlorin
19、e do notinterfere, but when phosphorus is present with metals, itremains partially or wholly in the sulfated ash as metalphosphates.NOTE 4Since zinc sulfate slowly decomposes to its oxide at theignition temperature specified in the test method, samples containing zinccan give variable results unless
20、 the zinc sulfate is completely converted tothe oxide.5.2 Because of above inter-element interferences, experi-mentally obtained sulfated ash values may differ from sulfatedash values calculated from elemental analysis. The formationof such non-sulfated species is dependent on the temperature ofashi
21、ng, time ashed, and the composition of metal compoundspresent in oils. Hence, sulfated ash requirement generallyshould not be used in product specifications without a clearunderstanding between a buyer and a seller of the unreliabilityof an ash value as an indicator of the total metallic compoundcon
22、tent.46. Apparatus6.1 Evaporating Dish or Crucible; 50 mL to 100 mL forsamples containing more than 0.02 % by mass sulfated ash, or120 mL to 150 mL for samples containing less than 0.02 % bymass sulfated ash, and made of porcelain, fused silica, orplatinum. (WarningDo not use platinum when the sampl
23、e islikely to contain elements such as phosphorus, which attackplatinum under the conditions of the test.)NOTE 5For best results on samples containing less than 0.1 % bymass sulfated ash, platinum dishes are used. The precision values shownin Section 13 for this type of sample were so obtained.6.2 E
24、lectric Muffle FurnaceThe furnace shall be capableof maintaining a temperature of 775 C 6 25 C and preferablyhave apertures at the front and rear to allow a slow natural draftof air to pass through the furnace.6.3 Balance, capable of weighing to 0.1 mg.7. Reagents7.1 Purity of ReagentsReagent grade
25、chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available, or to other recognizedstandards for reagent chemical
26、s.5Other grades may be used,provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.7.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water defined byTypes
27、 II or III of Specification D1193.7.3 Low-Ash Mineral OilWhite oil having a sulfated ashlower than the limit capable of being determined by this testmethod.NOTE 6Determine the sulfated ash of this oil by the procedure givenin 9.1 9.11 below using 100 g of white oil weighed to the nearest 0.5 gin a 1
28、20 mL to 150 mL platinum dish. Deduct the sulfuric acid blank asdescribed in 9.11.7.4 Sulfuric Acid (relative density 1.84)Concentrated sul-furic acid (H2SO4). (WarningPoison. Corrosive. Strongoxidizer.)7.5 Sulfuric Acid (1 + 1)Prepare by slowly adding 1volume of concentrated sulfuric acid (relative
29、 density 1.84) to1 volume of water with vigorous stirring. (WarningMixingthis acid into water generates considerable heat. Whennecessary, cool the solution before adding more acid. Do notallow the solution to boil.)7.6 Propan-2-ol, (WarningFlammable, can be explosivewhen evaporated to or near drynes
30、s.) 99 % minimum purity.7.7 Toluene, (WarningFlammable, toxic.) 99 % mini-mum purity.7.8 Quality Control (QC) Samples, preferably are portionsof one or more liquid petroleum materials that are stable andrepresentative of the samples of interest. These QC samplescan be used to check the validity of t
31、he testing process asdescribed in Section 12.8. Sampling8.1 Obtain samples in accordance with the instructions inPractice D4057 or D4177. The sample shall be thoroughlymixed before removal of the laboratory test portion.9. Procedure9.1 Select the size of the evaporating dish or crucibleaccording to
32、the quantity of sample necessary (see 9.3).9.2 Heat the evaporating dish or crucible that is used for thetest at 775 C 6 25 C for a minimum of 10 min. Cool to roomtemperature in a suitable container and weigh to the nearest0.1 mg.NOTE 7The container in which the dish is cooled does not contain adesi
33、ccating agent.9.3 Weigh into the dish a quantity of sample given asfollows:4Further discussion of these interferences can be found in Nadkarni, R. A.,Ledesma, R. R., and Via, G. H., “Sulfated Ash TM: Limitations of Reliability andReproducibility,” SAE Technical Paper No. 952548, available from SAE,
34、400Commonwealth Drive, Warrendale, PA 15096-0001, U.S.A.5Reagent Chemicals, American Chemical Society Specifications , AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Lt
35、d., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D874 13a (2018)2W 5 10/a (1)where:W = mass of test specimen, g, anda = expected sulfated ash, mass %.However, do not take a quantity in excess of 80 g. In the c
36、aseof lubricating oil additives yielding a sulfated ash of 2 % bymass or more, dilute the weighed sample in the dish withapproximately 10 times its weight of low-ash mineral oil. If theamount of sulfated ash found differs from the expected amountby more than a factor of two, repeat the analysis with
37、 adifferent weight of sample calculated from the first analysisunless the calculated sample size 80 g.9.4 Heat the dish or crucible and sample carefully until thecontents can be ignited with a flame. Maintain at such atemperature that the sample continues to burn at a uniform andmoderate rate. When
38、burning ceases, continue to heat gentlyuntil no further smoke or fumes are evolved.9.4.1 If the sample contains sufficient moisture to causefoaming and loss of material from the dish, discard the sampleand to an additional sample add 1 mL to 2 mL of 99 %propan-2-ol (WarningFlammable) before heating.
39、 If this isnot satisfactory, add 10 mL of a mixture of equal volumes oftoluene (WarningFlammable, Vapor harmful.) and propan-2-ol and mix thoroughly. Place several strips of ashless filterpaper in the mixture and heat; when the paper begins to burn,the greater part of the water will have been remove
40、d.9.5 Allow the dish to cool to room temperature, thencompletely moisten the residue by the dropwise addition ofsulfuric acid (relative density 1.84). Carefully heat the dish ata low temperature on a hot plate or over a gas burner, avoidingspattering, and continue heating until fumes are no longerev
41、olved.9.6 Place the dish in the furnace at 775 C 6 25 C for30 min 6 5 min until oxidation of the carbon is complete oralmost complete.9.7 Allow the dish to cool to room temperature.Add 3 dropsof water and 10 drops of sulfuric acid (1 + 1). Move the dish soas to moisten the entire residue. Again heat
42、 the dish inaccordance with 9.5.9.8 Again place the dish in the furnace at 775 C 6 25 Cand maintain at that temperature for 30 min 6 5 min (see Note8). Cool the dish to room temperature in a suitable container(see Note 7). Zinc dialkyl or alkaryl dithiophosphates andblends containing these additives
43、 can give a residue that ispartially black at this stage. In this case, repeat 9.7 and 9.8 untila white residue is obtained.NOTE 8A study conducted by two separate laboratories investigatingwhether heating sulfated ash residues for extended periods of time (forexample, overnight) in a furnace at 775
44、 C 6 25 C as opposed to 30 minas required in 9.8 revealed that a significant difference in sulfated ashresults can exist. The study indicated that lower sulfated ash results wereobtained on the samples left in the furnace overnight versus those thatwere heated in 30 min cycles. A thermogravimetric a
45、nalysis also con-firmed that the samples evaluated continued to lose weight at 775 C as afunction of time. As such, it is essential that the 30 min heating timerequirement be adhered to in performing the test method. Detailsconcerning the study can be found in ASTM Research Report RR:D02-1597.69.9 W
46、eigh the dish and residue to the nearest 0.1 mg.9.10 Repeat 9.8 and 9.9 until two successive weighingsdiffer by no more than 1.0 mg.NOTE 9Normally one repeat will suffice, unless a high proportion ofzinc is present, when three or four heating periods can be required.9.11 For samples expected to cont
47、ain 0.02 % mass or less ofsulfated ash, determine a sulfuric acid blank by adding 1 mL ofthe concentrated sulfuric acid to a tared platinum dish orcrucible, heating until fumes are no longer evolved and thenheating in the furnace at 775 C 6 25 C for 30 min 6 5 min.Cool the dish or crucible to room t
48、emperature in a suitablecontainer (see Note 7) and weigh to the nearest 0.1 mg. If anyash is found in the sulfuric acid, make an adjustment to theweight of sulfated ash obtained by subtracting the weight ofash contributed by the sulfuric acid, determined from the totalvolume of sulfuric acid used an
49、d the weight of ash found forthe 1 mL blank, from the total grams of sulfated ash for thesample. Use this corrected weight, w, in calculating the percentsulfated ash.10. Calculation10.1 Calculate the sulfated ash as a percentage of theoriginal sample as follows:Sulfated ash, mass% 5 w/W! 3100 (2)where:w = grams of sulfated ash, andW = grams of sample used.11. Report11.1 Report the result to the nearest 0.001 % by mass forsamples below 0.02 % by mass and to the nearest 0.01 % bymass for higher levels as the sulfated ash, Test Method D874.
