1、Designation: D5184 12 (Reapproved 2017)Standard Test Methods forDetermination of Aluminum and Silicon in Fuel Oils byAshing, Fusion, Inductively Coupled Plasma AtomicEmission Spectrometry, and Atomic AbsorptionSpectrometry1This standard is issued under the fixed designation D5184; the number immedia
2、tely following the designation indicates 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.1. Scope1.1 These t
3、est methods cover the determination of alumi-num and silicon in fuel oils at concentrations between 5 mg kgand 150 mg kg for aluminum and 10 mg kg and 250 mg kg forsilicon.1.2 Test Method AInductively coupled plasma atomicemission spectrometry is used in this test method to quantita-tively determine
4、 aluminum and silicon.1.3 Test Method BFlame atomic absorption spectrometryis used in this test method to quantitatively determine alumi-num and silicon.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
5、not purport 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 and health practices and determine the applica-bility of regulatory limitations prior to use. Specific warningstatements are given
6、in Sections 7.6, 10.1, and 11.5.1.6 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 O
7、rganization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent WaterD4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD6299 Practice for Apply
8、ing Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System PerformanceD6792 Practice for Quality Management Systems in Petro-leum Products, Liquid Fuels, and Lubricants TestingLaboratoriesD7260 Practice for Optimization, Calibration, and Valida-tion of
9、Inductively Coupled Plasma-Atomic EmissionSpectrometry (ICP-AES) for Elemental Analysis of Petro-leum Products and LubricantsD7740 Practice for Optimization, Calibration, and Valida-tion of Atomic Absorption Spectrometry for Metal Analy-sis of Petroleum Products and LubricantsE135 Terminology Relati
10、ng to Analytical Chemistry forMetals, Ores, and Related Materials3. Terminology3.1 Definitions:3.1.1 emission spectroscopy, nRefer to TerminologyE135.3.2 Definitions of Terms Specific to This Standard:3.2.1 calibration, nthe process by which the relationshipbetween signal intensity and elemental con
11、centration is deter-mined for a specific element analysis.3.2.2 check standard, nin calibration, an artifact measuredperiodically, the results of which typically are plotted on acontrol chart to evaluate the measurement process.4. Summary of Test Methods4.1 A weighed quantity of homogenized sample i
12、s heated ina clean platinum dish, the combustible material is removed byburning and the carbon finally removed by heating in a mufflefurnace at a temperature of 550 C 6 25 C. The residue isfused with a lithium tetraborate/lithium fluoride flux. The fused1These test methods are under the jurisdiction
13、 of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and are the direct responsibilityof Subcommittee D02.03 on Elemental Analysis.Current edition approved May 1, 2017. Published June 2017. Originallyapproved in 1991. Last previous edition approved in 2012 as D5184 12. DOI:10.15
14、20/D5184-12R17.2For 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 ASTM website.Copyright ASTM International, 100 Barr Harbor
15、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 the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations
16、 issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1mixture is digested in a solution of tartaric acid and hydrochlo-ric acid and diluted to volume with water. The resultingsolution is aspirated into an inductively-coupled plasma andthe emission intensities of alumin
17、um and silicon lines aremeasured. Standard calibration solutions are also aspirated andaluminum and silicon intensities are measured for comparison.Alternatively, the resulting solution is aspirated into the flameof an atomic absorption spectrometer and the absorptions of theresonance radiation of a
18、luminum and silicon are measured.Standard calibration solutions are also aspirated and aluminumand silicon absorption intensities are measured for comparison.4.2 Information on proper protocols for conducting atomicabsorption spectrometry can be found in Practice D7740.4.3 Information on Proper prot
19、ocols for conducting induc-tively coupled plasma-atomic absorption spectrometry can befound in Practice D7260.5. Significance and Use5.1 Catalyst fines in fuel oils can cause abnormal enginewear. These test methods provide a means of determiningsilicon and aluminum, the major constituents of the cat
20、alysts.6. Apparatus6.1 Balance, capable of weighing to 0.1 g, capacity of150 g.6.2 Choice of Instrument:6.2.1 Inductively-Coupled Plasma Atomic EmissionSpectrometerEither a sequential or simultaneous spectrom-eter is suitable, if equipped with an ICP torch and RF generatorto form and sustain the pla
21、sma.6.2.2 Atomic Absorption SpectrometerA suitable instru-ment will consist of modulated hollow cathode lamps or othersources of resonance radiation of aluminum and silicon, anitrous oxide/acetylene burner, and a spectrometer with asuitable detection and read-out system.6.3 Homogenizer, non-aerating
22、, high-speed shear mixer tohomogenize the sample.NOTE 1Ultrasonic bath and ultrasonic probe type homogenizers werenot evaluated in the development of these test methods.6.4 Electric Muffle Furnace, capable of being maintained attemperatures of 550 C 6 25 C and 925 C 6 25 C. Thefurnace preferably hav
23、ing suitable apertures at front and rear toallow a slow, natural draft of air to pass through.6.5 Electric Hot Plate, with or without magnetic stirringcapability.6.6 Electric Oven, maintained at a temperature of 50 C to60 C.6.7 Graduated Cylinders, 10 mL, 25 mL, 50 mL, and100 mL.6.8 Pipettes, 1 mL,
24、2 mL, 5 mL, 10 mL, 20 mL, and 25 mL.6.9 Platinum Dish, 100 mL capacity, cleaned with fusedpotassium hydrogen sulfate.6.10 Volumetric Flasks, 100 mL and 1000 mL.6.11 All glassware must be carefully cleaned with 1 + 1hydrochloric acid and rinsed thoroughly with water to mini-mize contamination. The us
25、e of chromic acid cleaning solutionis not recommended.6.12 Zirconium crucible with close fitting zirconium lid,30 mL to 50 mL capacity.7. Reagents7.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to the specif
26、ications of the Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications are available.3Other 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 P
27、urity of WaterUnless otherwise indicated, referenceto water shall be understood to mean reagent water conformingto Type II of Specification D1193.7.3 FluxMixture of 90 % lithium tetraborate and 10 %lithium fluoride.NOTE 2Lithium fluoride is necessary to prevent heavy metal corro-sion of the platinum
28、 dish and to lower the fusion temperature.7.4 Hydrochloric acid (36 % (m/m)concentrated hydro-chloric acid.7.5 Potassium Hydrogen Sulfate, fused solid.7.6 2-Propanol (Isopropyl Alcohol) (WarningFlammable; can be explosive when evaporated to or neardryness.)7.7 Aqueous Standard Solutions.7.7.1 Alumin
29、um Standard SolutionsObtain a ready made,aqueous standard or prepare a standard from aluminum wire.7.7.1.1 Aluminum Solution (1000 mg L)Aqueous, readymade commercial standard.7.7.1.2 Aluminum Solution (1000 mg L)Cut an arbitrarylength of 99.99 % minimum purity aluminum wire (2 mmdiameter aluminum wi
30、re has been found satisfactory). Measurethe length to the nearest 0.1 cm and weigh the aluminum wireto the nearest 0.001 g. Determine the mass/cm for the alumi-num wire and cut a length of aluminum wire that is calculatedto be slightly greater than 1.000 g. Trim off the excess wireuntil the mass is
31、1.000 g 6 0.005 g. Dissolve the aluminumwire in 50 mL of concentrated hydrochloric acid. Heat gently.Cool and transfer the solution to 1000 mL volumetric flask.Dilute to the mark with water.7.7.2 Silicon Standard SolutionsObtain a ready made,aqueous standard or prepare a standard from silicon dioxid
32、e.7.7.2.1 Silicon Solution (1000 mg L)Aqueous, readymade commercial standard.3Reagent 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 Laborat
33、oryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D5184 12 (2017)27.7.2.2 Silicon Solution (1000 mg L)Using a zirconiumcrucible with a close fitting lid, fuse 2.140 g 6 0.0107 g ofsilicon di
34、oxide (99.99 % purity) with 8 g of sodium hydroxideuntil a clear melt is obtained. Cool and dissolve the melt in100 mLof a solution of 1 part hydrochloric acid by volume and2 parts water by volume. Transfer this solution to a 1000 mLvolumetric flask and dilute to the mark with water.Immediately, tra
35、nsfer the contents of the flask to a plasticbottle.7.8 Tartaric Acid/Hydrochloric Acid SolutionDissolve 5 gof tartaric acid in about 500 mL of water acidified with 40 mLof concentrated hydrochloric acid and dilute to 1000 mL withwater.7.9 Toluene/2-Propanol Solution (1 + 1)Mix one vol-ume of toluene
36、 with one volume of 2-propanol.7.10 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 the testing process asdescribed in Section 18.8. Quali
37、ty Control (QC) Sample Preparation8.1 Preparation of QC Samples shall follow the sameprotocol as defined for the test specimen (Sections 9, 10, and11).9. Sampling9.1 The objective of sampling is to obtain a sample fortesting purposes that is representative of the entire quantity.Thus, take samples i
38、n accordance with the instructions inPractice D4057 or D4177 . Typically, a gallon size containerfilled to approximately three-fourths of capacity is satisfactory.10. Sample Handling10.1 HomogenizationIt is extremely important to homog-enize the fuel oil in the sample container in order to obtain ar
39、epresentative specimen. (WarningFailure to use this ho-mogenization procedure can invalidate the results becausenon-representative aliquots could be obtained and this couldlead to erroneous results.)10.2 Place the sample container in an oven at a temperatureof 50 C to 60 C. Keep the container in the
40、 oven until thesample comes to temperature. Insert the shaft of a high speedhomogenizer into the sample container so that the head of theshaft is immersed to approximately 5 mm from the bottom ofthe sample vessel. Mix the sample for about 5 min.11. Specimen Preparation11.1 Weigh a clean platinum dis
41、h to the nearest 0.1 g.Immediately transfer up to 50 g (but not less than 20 g) of thewell-mixed sample, preferably containing about 1.3 mgaluminum, to the platinum dish and re-weigh the dish andcontents to the nearest 0.1 g to obtain the weight of thespecimen.NOTE 3The specimen mass proposed, based
42、 on the aluminum contentwill suffice for silicon as both elements are usually found in fuel oils atsimilar concentrations.11.2 Warm the dish and contents gently with a bunsen flameuntil the sample can be ignited. Maintain the contents of thebasin at a temperature such that most of the combustiblemat
43、erial is removed and only carbon and ash remain.NOTE 4If the specimen contains considerable amounts of moisture,foaming and frothing can cause loss of material. If this is the case, discardthe specimen and to a fresh portion add 1 mLto 2 mLof 2-propanol beforeheating. If this is not satisfactory, ad
44、d 10 mL of a mixture of equal partsof toluene and 2-propanol and mix thoroughly. Place several strips ofashless filter paper in the mixture and warm gently. When the paper beginsto burn, the greater part of the water will have been removed.11.3 Place the dish and contents in a muffle furnace main-ta
45、ined at a temperature of 550 C 6 25 C. Maintain the mufflefurnace at this temperature until all the carbon is removed andonly ash remains. This may require more than 10 h in themuffle furnace and may conveniently be done overnight.11.4 Cool the dish to room temperature, add 0.4 g of fluxand mix with
46、 the ash. Place the dish in a muffle furnacemaintained at a temperature of 925 C 6 25 C for 5 min.Remove the dish and ensure contact of the flux with the ash.Replace the dish in the muffle furnace and maintain at atemperature of 925 C 6 25 C for 10 min.11.5 Remove the dish, cool the fusion melt to r
47、oom tem-perature and add 50 mL of the tartaric acid/hydrochloric acidsolution. Place the dish and contents on the hot plate main-tained at a temperature of approximately 80 C. Heat until themelt is dissolved. (WarningVaporization of a significantamount of the liquid can lead to precipitation of an i
48、nsolubleform of silica leading to erroneous results.)NOTE 5Prolonged heating can be necessary to dissolve the meltcompletely and obtain a solution. Agitation or the use of magnetic stirringcan be employed to speed dissolution of the melt.11.6 Allow the solution to cool and then transfer it to a100 m
49、L flask with water, washing the dish several times toensure transfer is complete. Make up to the mark with water.Then, transfer the solution to a plastic bottle.NOTE 6Transferring the test solution to a plastic bottle is desirablebecause the dilute acid solution contains fluoboric acid from dissolution ofthe flux. Storage tests have shown that there is no significant attack ofglassware in the short term (up to one week), and that the solution does notcontain fluoride ion above the 5 mg L concentration.12. Preparation of Calibra
