ASTM D5184-22

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it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
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Designation: D5184 − 12 (Reapproved 2017) D5184 − 22
Standard Test Methods for
Determination of Aluminum and Silicon in Fuel Oils by
Ashing, Fusion, Inductively Coupled Plasma Atomic
Emission Spectrometry, and Atomic Absorption
Spectrometry
This standard is issued under the fixed designation D5184; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope Scope*
1.1 These test methods cover the determination of aluminum and silicon in fuel oils at concentrations between 5 mg ⁄kg and
150 mg ⁄kg for aluminum and 10 mg ⁄kg and 250 mg ⁄kg for silicon.
1.2 Test Method A—Inductively coupled plasma atomic emission spectrometry is used in this test method to quantitatively
determine aluminum and silicon.
1.3 Test Method B—Flame atomic absorption spectrometry is used in this test method to quantitatively determine aluminum and
silicon.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. Specific warning statements are given in Sections 7.6, 10.1, and 11.5.
1.6 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
D1193 Specification for Reagent Water
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4175 Terminology Relating to Petroleum Products, Liquid Fuels, and Lubricants
D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-
ment System Performance
These test methods are under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and are the direct responsibility of
Subcommittee D02.03 on Elemental Analysis.
Current edition approved May 1, 2017Oct. 1, 2022. Published June 2017October 2022. Originally approved in 1991. Last previous edition approved in 20122017 as
D5184 – 12.D5184 – 12 (2017). DOI: 10.1520/D5184-12R17.10.1520/D5184-22.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5184 − 22
D6792 Practice for Quality Management Systems in Petroleum Products, Liquid Fuels, and Lubricants Testing Laboratories
D7260 Practice for Optimization, Calibration, and Validation of Inductively Coupled Plasma-Atomic Emission Spectrometry
(ICP-AES) for Elemental Analysis of Petroleum Products and Lubricants
D7740 Practice for Optimization, Calibration, and Validation of Atomic Absorption Spectrometry for Metal Analysis of
Petroleum Products and Lubricants
E135 Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
3. Terminology
3.1 Definitions:
3.1.1 emission spectroscopy, n—Refer to Terminology E135.
3.1.1 For definitions of terms used in this test method, refer to Terminology D4175.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 calibration, n—the process by which the relationship between signal intensity and elemental concentration is determined for
a specific element analysis.
3.2.2 check standard, n—in calibration, an artifact measured periodically, the results of which typically are plotted on a control
chart to evaluate the measurement process.
4. Summary of Test Methods
4.1 A weighed quantity of homogenized sample is heated in a clean platinum dish, the combustible material is removed by burning
and the carbon finally removed by heating in a muffle furnace at a temperature of 550 °C 6 25 °C. The residue is fused with a
lithium tetraborate/lithium fluoride flux. The fused mixture is digested in a solution of tartaric acid and hydrochloric acid and
diluted to volume with water. The resulting solution is aspirated into an inductively-coupled plasma and the emission intensities
of aluminum and silicon lines are measured. Standard calibration solutions are also aspirated and aluminum and silicon intensities
are measured for comparison. Alternatively, the resulting solution is aspirated into the flame of an atomic absorption spectrometer
and the absorptions of the resonance radiation of aluminum and silicon are measured. Standard calibration solutions are also
aspirated and aluminum and silicon absorption intensities are measured for comparison.
4.2 Information on proper protocols for conducting atomic absorption spectrometry can be found in Practice D7740.
4.3 Information on Proper protocols for conducting inductively coupled plasma-atomic absorption spectrometry can be found in
Practice D7260.
5. Significance and Use
5.1 Catalyst fines in fuel oils can cause abnormal engine wear. These test methods provide a means of determining silicon and
aluminum, the major constituents of the catalysts.
6. Apparatus
6.1 Balance, capable of weighing to 0.1 g, capacity of 150 g.
6.2 Choice of Instrument:
6.2.1 Inductively-Coupled Plasma Atomic Emission Spectrometer—Either a sequential or simultaneous spectrometer is suitable,
if equipped with an ICP torch and RF generator to form and sustain the plasma.
6.2.2 Atomic Absorption Spectrometer—A suitable instrument will consist of modulated hollow cathode lamps or other sources
of resonance radiation of aluminum and silicon, a nitrous oxide/acetylene burner, and a spectrometer with a suitable detection and
read-out system.
6.3 Homogenizer, non-aerating, high-speed shear mixer to homogenize the sample.
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NOTE 1—Ultrasonic bath and ultrasonic probe type homogenizers were not evaluated in the development of these test methods.
6.4 Electric Muffle Furnace, capable of being maintained at temperatures of 550 °C 6 25 °C and 925 °C 6 25 °C. The furnace
preferably having suitable apertures at front and rear to allow a slow, natural draft of air to pass through.
6.5 Electric Hot Plate, with or without magnetic stirring capability.
6.6 Electric Oven, maintained at a temperature of 50 °C to 60 °C.
6.7 Graduated Cylinders, 10 mL, 25 mL, 50 mL, and 100 mL.
6.8 Pipettes, 1 mL, 2 mL, 5 mL, 10 mL, 20 mL, and 25 mL.
6.9 Platinum Dish, 100 mL capacity, cleaned with fused potassium hydrogen sulfate.
6.10 Volumetric Flasks, 100 mL and 1000 mL.
6.11 All glassware must be carefully cleaned with 1 + 1 hydrochloric acid and rinsed thoroughly with water to minimize
contamination. The use of chromic acid cleaning solution is not recommended.
6.12 Zirconium crucible with close fitting zirconium lid, 30 mL to 50 mL capacity.
7. Reagents
7.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society where such
specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
7.2 Purity of Water—Unless otherwise indicated, reference to water shall be understood to mean reagent water conforming to Type
II of Specification D1193.
7.3 Flux—Mixture of 90 % lithium tetraborate and 10 % lithium fluoride.
NOTE 2—Lithium fluoride is necessary to prevent heavy metal corrosion of the platinum dish and to lower the fusion temperature.
7.4 Hydrochloric acid (36 % (m/m))—concentrated hydrochloric acid.
7.5 Potassium Hydrogen Sulfate, fused solid.
7.6 2-Propanol (Isopropyl Alcohol) (Warning—Flammable; can be explosive when evaporated to or near dryness.)
7.7 Aqueous Standard Solutions.
7.7.1 Aluminum Standard Solutions—Obtain a ready made, aqueous standard or prepare a standard from aluminum wire.
7.7.1.1 Aluminum Solution (1000 mg ⁄L)—Aqueous, ready made commercial standard.
Reagent Chemicals, American Chemical Society Specifications,ACS Reagent Chemicals, Specifications and Procedures for Reagents and Standard-Grade Reference
Materials, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, see Analar Standards for
Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC),
Rockville, MD.
D5184 − 22
7.7.1.2 Aluminum Solution (1000 mg ⁄L)—Cut an arbitrary length of 99.99 % minimum purity aluminum wire (2 mm diameter
aluminum wire has been found satisfactory). Measure the length to the nearest 0.1 cm and weigh the aluminum wire to the nearest
0.001 g. Determine the mass/cm for the aluminum wire and cut a length of aluminum wire that is calculated to be slightly greater
than 1.000 g. Trim off the excess wire until the mass is 1.000 g 6 0.005 g. Dissolve the aluminum wire 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 Solutions—Obtain a ready made, aqueous standard or prepare a standard from silicon dioxide.
7.7.2.1 Silicon Solution (1000 mg ⁄L)—Aqueous, ready made commercial standard.
7.7.2.2 Silicon Solution (1000 mg ⁄L)—Using a zirconium crucible with a close fitting lid, fuse 2.140 g 6 0.0107 g of silicon
dioxide (99.99 % purity) with 8 g of sodium hydroxide until a clear melt is obtained. Cool and dissolve the melt in 100 mL of a
solution of 1 part hydrochloric acid by volume and 2 parts water by volume. Transfer this solution to a 1000 mL volumetric flask
and dilute to the mark with water. Immediately, transfer the contents of the flask to a plastic bottle.
7.8 Tartaric Acid/Hydrochloric Acid Solution—Dissolve 5 g of tartaric acid in about 500 mL of water acidified with 40 mL of
concentrated hydrochloric acid and dilute to 1000 mL with water.
7.9 Toluene/2-Propanol Solution (1 + 1)—Mix one volume of toluene with one volume of 2-propanol.
7.10 Quality Control (QC) Samples, preferably are portions of one or more liquid petroleum materials that are stable and
representative of the samples of interest. These QC samples can be used to check the validity of the testing process as described
in Section 18.
8. Quality Control (QC) Sample Preparation
8.1 Preparation of QC Samples shall follow the same protocol as defined for the test specimen (Sections 9, 10, and 11).
9. Sampling
9.1 The objective of sampling is to obtain a sample for testing purposes that is representative of the entire quantity. Thus, take
samples in accordance with the instructions in Practice D4057 or D4177 . Typically, a gallon size container filled to approximately
three-fourths of capacity is satisfactory.
10. Sample Handling
10.1 Homogenization—It is extremely important to homogenize the fuel oil in the sample container in order to obtain a
representative specimen. (Warning—Failure to use this homogenization procedure can invalidate the results because non-
representative aliquots could be obtained and this could lead to erroneous results.)
10.2 Place the sample container in an oven at a temperature of 50 °C to 60 °C. Keep the container in the oven until the sample
comes to temperature. Insert the shaft of a high speed homogenizer into the sample container so that the head of the shaft is
immersed to approximately 5 mm from the bottom of the sample vessel. Mix the sample for about 5 min.
11. Specimen Preparation
11.1 Weigh a clean platinum dish to the nearest 0.1 g. Immediately transfer up to 50 g (but not less than 20 g) of the well-mixed
sample, preferably containing about 1.3 mg aluminum, to the platinum dish and re-weigh the dish and contents to the nearest 0.1 g
to obtain the weight of the specimen.
NOTE 3—The specimen mass proposed, based on the aluminum content will suffice for silicon as both elements are usually found in fuel oils at similar
concentrations.
11.2 Warm the dish and contents gently with a bunsen flame until the sample can be ignited. Maintain the contents of the basin
at a temperature such that most of the combustible material is removed and only carbon and ash remain.
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NOTE 4—If the specimen contains considerable amounts of moisture, foaming and frothing can cause loss of material. If this is the case, discard the
specimen and to a fresh portion add 1 mL to 2 mL of 2-propanol before heating. If this is not satisfactory, add 10 mL of a mixture of equal parts of toluene
and 2-propanol and mix thoroughly. Place several strips of ashless filter paper in the mixture and warm gently. When the paper begins to burn, the greater
part of the water will have been removed.
11.3 Place the dish and contents in a muffle furnace maintained at a temperature of 550 °C 6 25 °C. Maintain the muffle furnace
at this temperature until all the carbon is removed and only ash remains. This may require more than 10 h in the muffle furnace
and may conveniently be done overnight.
11.4 Cool the dish to room temperature, add 0.4 g of flux and mix with the ash. Place the dish in a muffle furnace maintained 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 a temperature of 925 °C 6 25 °C for 10 min.
11.5 Remove the dish, cool the fusion melt to room temperature and add 50 mL of the tartaric acid/hydrochloric acid solution.
Place the dish and contents on the hot plate maintained at a temperature of approximately 80 °C. Heat until the melt is dissolved.
(Warning—Vaporization of a significant amount of the liquid can lead to precipitation of an insoluble form of silica leading to
erroneous results.)
NOTE 5—Prolonged heating can be necessary to dissolve the melt completely and obtain a solution. Agitation or the use of magnetic stirring can be
employed to speed dissolution of the melt.
11.6 Allow the solution to cool and then transfer it to a 100 mL flask with water, washing the dish several times to ensure transfer
is complete. Make up to the mark with water. Then, transfer the solution to a plastic bottle.
NOTE 6—Transferring the test solution to a plastic bottle is desirable because the dilute acid solution contains fluoboric acid from dissolution of the flux.
Storage tests have shown that there is no significant attack of glassware in the short term (up to one week), and that the solution does not contain fluoride
ion above the 5 mg ⁄L concentration.
12. Preparation of Calibration Solutions
12.1 Blank Solution—Prepare a blank solution containing only 0.4 g flux and 50 mL of the tartaric acid/hydrochloric acid solution
diluted to 100 mL. Transfer it to a plastic bottle
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