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.

Designation: D7303 − 17

Standard Test Method for

Determination of Metals in Lubricating Greases by
Inductively Coupled Plasma Atomic Emission Spectrometry1
This standard is issued under the fixed designation D7303; 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* 1.2 Elements present at concentrations above the upper limit

1.1 This test method covers the determination of a number of the calibration curves can be determined with additional
of metals such as aluminum, antimony, barium, calcium, iron, appropriate dilutions of dissolved samples and with no degra-
lithium, magnesium, molybdenum, phosphorus, silicon, dation of precision.
sodium, sulfur, and zinc in unused lubricating greases by 1.3 The development of the technique behind this test
inductively coupled plasma atomic emission spectrometry method is documented by Fox.3
(ICP-AES) technique. 1.4 The values stated in SI units are to be regarded as the
1.1.1 The range of applicability for this test method, based standard. The values given in parentheses are for information
on the interlaboratory study conducted in 2005,2 is aluminum only.
(10 to 600), antimony (10 to 2300), barium (50 to 800),
calcium (20 to 50 000), iron (10 to 360), lithium (300 to 3200), 1.5 This standard does not purport to address all of the
magnesium (30 to 10 000), molybdenum (50 to 22 000), safety concerns, if any, associated with its use. It is the
phosphorus (50 to 2000), silicon (10 to 15 000), sodium (30 to responsibility of the user of this standard to establish appro-
1500), sulfur (1600 to 28 000), and zinc (300 to 2200), all in priate safety and health practices and determine the applica-
mg/kg. Lower levels of elements may be determined by using bility of regulatory limitations prior to use. Specific warning
larger sample weights, and higher levels of elements may be statements are given in Sections 8 and 10.
determined by using smaller amounts of sample or by using a 1.6 This international standard was developed in accor-
larger dilution factor after sample dissolution. However, the dance with internationally recognized principles on standard-
test precision in such cases has not been determined, and may ization established in the Decision on Principles for the
be different than the ones given in Table 1. Development of International Standards, Guides and Recom-
1.1.2 It may also be possible to determine additional metals mendations issued by the World Trade Organization Technical
such as bismuth, boron, cadmium, chromium, copper, lead, Barriers to Trade (TBT) Committee.
manganese, potassium, titanium, etc. by this technique.
However, not enough data is available to specify the precision 2. Referenced Documents
for these latter determinations. These metals may originate into 2.1 ASTM Standards:4
greases through contamination or as additive elements. D1193 Specification for Reagent Water
1.1.3 During sample preparation, the grease samples are D3340 Test Method for Lithium and Sodium in Lubricating
decomposed with a variety of acid mixture(s). It is beyond the Greases by Flame Photometer (Withdrawn 2013)5
scope of this test method to specify appropriate acid mixtures D4057 Practice for Manual Sampling of Petroleum and
for all possible combination of metals present in the sample. Petroleum Products
But if the ash dissolution results in any visible insoluble D4951 Test Method for Determination of Additive Elements
material, the test method may not be applicable for the type of in Lubricating Oils by Inductively Coupled Plasma
grease being analyzed, assuming the insoluble material con- Atomic Emission Spectrometry
tains some of the analytes of interest.

1 3
This test method is under the jurisdiction of ASTM Committee D02 on Fox, B. S., “Elemental Analysis of Lubricating Grease by Inductively Coupled
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of Plasm Atomic Emission Spectrometry (ICP-AES),” J. ASTM International, Vol 2,
Subcommittee D02.03 on Elemental Analysis. No. 8, 2005, pp. 12966.
4
Current edition approved June 1, 2017. Published June 2017. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 2006. Last previous edition approved in 2012 as D7303 – 12. DOI: contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
10.1520/D7303-17. Standards volume information, refer to the standard’s Document Summary page on
2
Supporting data have been filed at ASTM International Headquarters and may the ASTM website.
5
be obtained by requesting Research Report RR:D02-1608. Contact ASTM Customer The last approved version of this historical standard is referenced on
Service at [email protected]. www.astm.org.

*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

1
 D7303 − 17
TABLE 1 Precision of Grease Analysis mining their concentrations can be an important aspect of
NOTE 1—X is the mean concentration in mg/kg. grease manufacture. The metal content can also indicate the
Range,
amount of thickeners in the grease. Additionally, a reliable
Element Repeatability Reproducibility analysis technique can also assist in the process of trouble
mg/kg
Aluminum 10–600 0.2163 X0.9 6.8156 X0.9 shooting problems with new and used grease in the field.
Antimony 10–2300 0.3051 X0.8191 4.6809 X0.8191
Barium 50–800 0.3165 X0.7528 2.9503 X0.7528 5.2 Although widely used in other sectors of the oil industry
Calcium 20–50 000 2.2853 X0.7067 3.0571 X0.7067 for metal analysis, ICP-AES based Test Methods D4951 or
Iron 10–360 0.8808 X0.7475 2.5737 X0.7475 D5185 cannot be used for analyzing greases because of their
Lithium 300–3200 0.0720 X1.0352 0.1476 X1.0352
Magnesium 30–10 000 0.6620 X0.6813 2.6155 X0.6813 insolubility in organic solvents used in these test methods.
Molybdenum 50–22 000 0.1731 X0.9474 0.4717 X0.9474 Hence, grease samples need to be brought into aqueous
Phosphorus 50–2000 1.2465 X0.6740 4.0758 X0.6740 solution by acid decomposition before ICP-AES measure-
Silicon 10–15 000 1.3859 X0.9935 4.8099 X0.9935
Sodium 30–1500 6.5760 X0.5 11.571 X0.5 ments.
Sulfur 1600–28 000 1.0507 X0.8588 1.5743 X0.8588
Zinc 300–2200 0.1904 X0.8607 0.5912 X0.8607
5.3 Test Method D3340 has been used to determine lithium
and sodium content of lubricating greases using flame photom-
etry. This technique is no longer widely used. This new test
method provides a test method for multi-element analysis of
D5185 Test Method for Multielement Determination of
grease samples. This is the first D02 standard available for
Used and Unused Lubricating Oils and Base Oils by
simultaneous multi-element analysis of lubricating greases.
Inductively Coupled Plasma Atomic Emission Spectrom-
etry (ICP-AES) 6. Interferences
D6299 Practice for Applying Statistical Quality Assurance
and Control Charting Techniques to Evaluate Analytical 6.1 Spectral—Spectral interferences can usually be avoided
Measurement System Performance by judicious choice of analytical wavelengths. There are no
D6792 Practice for Quality Management Systems in Petro- known spectral interferences between elements covered by this
leum Products, Liquid Fuels, and Lubricants Testing test method when using the spectral lines listed in Table 2.
Laboratories However, if spectral interferences exist because of other
D7260 Practice for Optimization, Calibration, and Valida- interfering elements or selection of other spectral lines, correct
tion of Inductively Coupled Plasma-Atomic Emission for the interferences using the technique described in Test
Spectrometry (ICP-AES) for Elemental Analysis of Petro- Method D5185.
leum Products and Lubricants 6.1.1 Follow the instrument manufacturer’s operating guide
to develop and apply correction factors to compensate for the
3. Terminology interferences.
3.1 Definitions—Refer to terminology identified in Test 6.2 Chemical—If the grease sample contains refractory
Method D5185 for spectroscopy terms used in this standard. additives such as silicon or molybdenum, it is possible that
some of these elements may remain undissolved in the residue,
4. Summary of Test Method and may result in lower recoveries.
4.1 A weighed portion of the grease sample is weighed and 6.2.1 If HF is used for dissolution of grease residues,
subjected to alternate means of sample dissolution which may elements such as silicon may be lost as SiF6. Residual HF can
include sulfated ashing in a muffle furnace or by closed vessel also attack the ICP sample introduction system. HF can be
microwave digestion in acid. Ultimately these diluted acid passivated by adding dilute boric acid to the acid solution.
solutions are analyzed using ICP-AES. Aqueous calibration
standards are used. The solutions are introduced to the ICP
instrument by free aspiration or an optional peristaltic pump. TABLE 2 Suggested WavelengthsA,B for Elements Determined in
Grease Samples
By comparing emission intensities of elements in the test Element Wavelength, nm
specimen with those measured with the calibration standards, Aluminum 167.038, 308.22, 396.15, 309.27
the concentrations of elements in the test specimen can be Antimony 206.83, 217.58, 231.15
calculated. Barium 223.53, 233.527, 455.40, 493.41
Calcium 315.88, 317.93, 364.4, 396.85, 422.67
4.2 Additional information on using inductively coupled Iron 238.20, 259.94
plasma-atomic emission spectrometry can be found in Practice Lithium 670.78, 610.36, 460.29
Magnesium 279.08, 279.55, 280.278, 285.21
D7260. Molybdenum 135.387, 202.03, 281.62
Phosphorus 177.51, 178.29, 213.62, 214.91, 253.40
5. Significance and Use Silicon 288.16, 251.618
Sodium 589.595
5.1 Lubricating greases are used in almost all bearings used Sulfur 182.04, 180.73, 182.63
in any machinery. Lubricating grease is composed of ~90 % Zinc 202.55, 206.20, 213.86, 334.58, 481.05
additized oil and soap or other thickening agent. There are over A
These wavelengths are only suggested and do not represent all possible
a dozen metallic elements present in greases, either blended as choices.
B
Wavelengths for boron, phosphorus, and sulfur below 190 nm require that a
additives for performance enhancements or as thickeners, or in vacuum or inert gas purge optical path be used.
used greases present as contaminants and wear metals. Deter-

2
 D7303 − 17
6.2.2 If the dry ashing in sample preparation step is used, 8.7 Water, distilled or deionized water, unless otherwise
elements such as sulfur will be volatilized during combustion. indicated, references to water shall be understood to mean Type
II reagent grade water as defined in Specification D1193.
7. Apparatus
8.8 Quality Control (QC) Samples, preferably are portions
7.1 Analytical Balance, capable of weighing to 0.001 g or of one or more grease materials that are stable and represen-
0.0001 g, capacity of 150 g. tative of the samples of interest. These QC samples can be used
7.2 Inductively Coupled Plasma Atomic Emission to check the validity of the testing process as described in
Spectrometer—Either a sequential or simultaneous spectrom- Section 15.
eter is suitable, if equipped with a quartz ICP torch and RF 8.9 Microwave Oven, commercially available laboratory
generator to form and sustain the plasma. Suggested wave- microwave digestion oven of sufficient power (for example, at
lengths for the determination of elements in dissolved grease least 1000 W) is suitable. The microwave digestion dishes are
solutions are given in Table 2. also commercially available. (Warning—Take all necessary
7.3 Peristaltic Pump, (Recommended)—A peristaltic pump precautions to prevent exposure to radiofrequency radiation.)
is strongly recommended to provide a constant flow of solu- 8.10 Microwave Sample Digestion System, with closed-
tion. The pumping speed must be in the range of 0.5 mL ⁄min vessel silicon-free polytetrafluoroethylene (PTFE) digestion
to 3 mL ⁄min. The pump tubing must be able to withstand at vessels. The vessels need to be capable of withstanding the
least 6 h exposure to solutions. pressure generated from the digestion of 0.2 g of sample
7.4 Specimen Solution Containers, of appropriate size, glass (pressure achieved with a 100 mL vessel and 0.2 g of sample
or polyolefin vials or bottles, with screw caps without metal could be in excess of 100 psi). Microwave digestions systems
liners. with temperature and pressure monitoring are recommended
for safety and accuracy of sample preparation.
8. Reagents and Materials 8.11 The test method requires essentially microwave trans-
8.1 Purity of Reagents—Reagent grade chemicals shall be parent and reagent resistant suitably inert polymeric materials
used in all tests. Unless otherwise indicated, it is intended that (examples are PFA or TFM) to contain acids and samples. For
all reagents conform to the specifications of the Committee on higher pressure capabilities the vessel may be contained within
Analytical Reagents of the American Chemical Society where layers of different microwave transparent materials for
such specifications are available.6 Other grades may be used, strength, durability, and safety. The vessels internal volume
provided it is first ascertained that the reagent is of sufficiently should be at least 45 mL, capable of withstanding pressures of
high purity to permit its use without lessening the accuracy of at least 30 atm (30 bar or 435 psi), and capable of controlled
the determination. pressure relief. These specifications are given to provide an
8.2 Sulfuric Acid, concentrated sulfuric acid, H2SO4. appropriate, safe, and durable reaction vessel of which there
(Warning—Causes severe burns. Corrosive.) are many adequate designs by many suppliers.
8.3 Nitric Acid, concentrated nitric acid, HNO3 . 8.12 Rotating Turntable, to insure homogeneous distribu-
(Warning—Causes severe burns. Corrosive.) tion of microwave radiation within most systems. The speed of
the turntable should be a minimum of 3 r ⁄min.
8.4 Hydrochloric Acid, concentrated hydrochloric acid,
HCl. (Warning—Causes burns.) 8.13 Combustion Dishes, Vycor or platinum evaporation
dishes of 250 mL size.
8.5 Hydrofluoric Acid, concentrated hydrofluoric acid, HF
(Warning—Causes severe burns.) 8.14 Volumetric Flasks, polypropylene or similar material
of 25 mL and 50 mL sizes.
8.6 Aqueous Standard Solutions, individual aqueous el-
emental standards with 100 mg/L concentrations of elements of 8.15 Electric Muffle Furnace, capable of maintaining
interest. These can be prepared by dissolving pure metal 525 °C 6 25 °C and sufficiently large to accommodate several
compounds in water or dilute acids, or may be purchased from 250 mL beakers. The capacity of an oxygen bleed is advanta-
commercial sources. geous and optional. (Warning—Take all necessary precautions
8.6.1 Multi-element aqueous standards may be advanta- to prevent exposure to very hot surfaces.)
geous to use. 8.16 Heating Lamp, commercial infrared heating lamp.
8.6.2 Internal Standard, aqueous cobalt, indium, scandium,
yttrium or other single element standard, not a component of 9. Sampling
the grease test specimen or calibration standard, nominal 500 9.1 The objective of sampling is to obtain a test specimen
mg/kg concentration. that is representative of the entire quantity. Thus, take labora-
tory samples in accordance with the instructions in Practice
6
D4057. The specific sampling technique can affect the accu-
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not racy of this test method.
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia 10. Preparation of Samples
and National Formulatory, U.S. Pharmaceutical Convention, Inc. (USPC),
Rockville, MD. 10.1 Sulfated Ash Digestion:

3
 D7303 − 17
10.1.1 Accurately weigh approximately 1 g to 2 g 6 0.1 g 10.2.4 The analyst should be aware of the potential for a
of the grease sample in a Vycor or platinum container of vigorous reaction. If a vigorous reaction occurs upon the initial
suitable size. Char the sample on a hot plate until it is reduced addition of reagent or the sample is suspected of containing
to ~0.5 g. A heat lamp may be used to assist in this process. easily oxidizable materials, allow the sample to predigest in the
10.1.2 After the charred residue is cooled, add 1 mL to 2 mL uncapped digestion vessel. Heat may be added in this step for
of concentrated sulfuric acid and carefully heat on the hot plate safety considerations (for example, the rapid release of carbon
taking care to avoid spattering of the contents, and continue dioxide from carbonates, easily oxidized organic matter, etc.).
heating until the fumes are no longer evolved. Once the initial reaction has ceased, the sample may continue
10.1.3 Place the charred sample in a muffle furnace at through the digestion procedure.
525 °C 6 25 °C until the oxidation of the carbon is practically 10.2.5 Seal the vessel according to the manufacturer’s
complete. This typically takes about 2 h. directions. Properly place the vessel in the microwave system
10.1.4 If the ashing is not complete as indicated by presence according to the manufacturer’s recommended specifications
of black color of the residue, repeat step 10.1.2 to complete the and connect appropriate temperature and pressure sensors to
sulfation. vessels according to the manufacturer’s specifications.
10.1.5 Add about 5 mL of concentrated nitric, hydrochloric 10.2.6 Pressure control for a specific matrix is applicable if
or other appropriate mineral acid to the residue, and heat gently instrument conditions are established using temperature con-
to dissolve the remaining solids. trol. Because each matrix will have a different reaction profile,
10.1.6 Dilute the solution to volume with deionized water in performance using temperature control must be developed for
a 25 mL or a 50 mL volumetric flask. every specific matrix type prior to use of the pressure control
system. At the end of the microwave program, allow the
NOTE 1—The dilutions may be carried out on a weight or volume basis.
vessels to cool for a minimum of 5 min before removing them
10.2 Closed Vessel Microwave Oven Digestion: from the microwave system.
10.2.1 Accurately weigh about 0.1 g to 1 g of the grease 10.2.7 Program the microwave oven to heat at 125 W for
sample in a polytetrafluoroethylene (PTFE) digestion vessel 15 min, then ramp up to 190 W for another 15 min.
with pressure relief mechanism. Add about 4 mL of concen-
trated nitric, hydrochloric, or other appropriate mineral acid. NOTE 4—Different microwave oven models may require different
temperature ramping and holding profiles.
NOTE 2—From a safety view point when digesting samples containing NOTE 5—Care must be taken to keep internal temperature and pressure
volatile or easily oxidized organic compounds, initially weigh no more within the capability of the vessels used. Excessive heat and pressure will
than 0.10 g and observe the reaction before capping the vessel. If a cause the digestion pressure vessels to deform and potentially leak.
vigorous reaction occurs, allow the reaction to cease before capping the
vessel. If no appreciable reaction occurs, a sample weight up to 1 g can be 10.2.8 Detailed safety recommendations specific to the
used. model and manufacturer of the microwave digestion system is
NOTE 3—Some microwave oven models may be capable of simultane- beyond the scope of this test method. The user of this test
ously processing multiple sample digestion vessels. method is advised to consult the equipment manual, the
10.2.2 Temperature control of closed vessel microwave manufacturer and other literature sources for proper safe
instruments provides the main feedback control performance operation of the digestion system. The user should be advised
mechanism for the test method. Control requires a temperature that digestion of samples within the scope of this test method
sensor in one or more vessels during the entire decomposition. could rapidly generate high pressure beyond the mechanical
The microwave decomposition system should sense the tem- capacity of the vessel, which may cause a rupture of the vessel
perature to within 62.5 °C and permit adjustment of the and damage to the digestion system. (Warning—Exercise
microwave output power within 2 s. caution when handling vessels after they have been heated
10.2.3 All digestion vessels and volumetric ware must be since they may possess high internal pressures.)
carefully acid washed and rinsed with reagent water. When 10.2.8.1 Warning—The outer layers of vessels are fre-
switching between high concentration and low concentration quently not as acid or reagent resistant as the liner material and
samples, all digestion vessels (fluoropolymer liners only) must not be chemically degraded or physically damaged to
should be cleaned by leaching with hot (1:1) hydrochloric acid retain the performance and safety required. Routine examina-
(greater than 80 °C, but less than boiling) for a minimum of 2 h tion of the vessel materials may be required to ensure their safe
followed with hot (1:1) nitric acid (greater than 80 °C, but less use.
than boiling) for a minimum of 2 h and rinsed with reagent 10.2.8.2 Warning—Another safety concern relates to the
water and dried in a clean environment. This cleaning proce- use of sealed containers without pressure relief devices. Tem-
dure should also be used whenever the prior use of the perature is the important variable controlling the reaction.
digestion vessels is unknown or cross contamination from Pressure is needed to attain elevated temperatures, but must be
vessels is suspected. Polymeric or glass volumetric ware and safely contained. However, many digestion vessels constructed
storage containers should be cleaned by leaching with more from certain suitably inert polymerics may crack, burst, or
dilute acids (approximately 10 % V/V) appropriate for the explode in the unit under certain pressures. Only suitably inert
specific plastics used and then rinsed with reagent water and polymeric (such as PFA or TFM and others) containers with
dried in a clean environment. pressure relief mechanisms or containers with suitably inert
10.2.3.1 Alternate cleaning procedures may be utilized if polymeric liners and pressure relief mechanisms are considered
they are shown to be satisfactory. acceptable. Users are therefore advised not to use domestic

4
 D7303 − 17
(kitchen) type microwave ovens or to use inappropriate sealed 11.5 Operating Parameters—Assign the appropriate operat-
containers without pressure relief for microwave acid diges- ing parameters to the instrument task file so that the desired
tions by this test method. Use of laboratory-grade microwave elements can be determined. Parameters to be included are
equipment is required to prevent safety hazards. element, wavelength(s), background correction points
10.2.8.3 Warning—Laboratories should not use domestic (optional), interelement correction factors (see 6.1), and inte-
(kitchen) type microwave ovens for this test method. There are gration time. Multiple integrations (typically three) are re-
several significant safety issues. First, when an acid such as quired for each measurement. A typical measurement time is
nitric is used to effect sample digestion in microwave units in 10 s.
sealed vessels equipment, there is the potential for the acid gas NOTE 9—Typical ICP operating conditions follow. Different conditions
vapor released to corrode the safety devices that prevent the specific to different instruments may be used.
microwave magnetron from shutting off when the door is Forward Power 1100 W to 1500 W
Coolant Gas, Argon 12 L ⁄min to 17 L/min
opened. This can result in operator exposure to microwave Auxiliary Gas, Argon 0.2 L ⁄min to 1 L/min
energy. Use of a system with isolated and corrosion resistant Nebulizer Gas, Argon 0.7 L ⁄min to 1.1 L/min
safety devices prevents this from occurring. Sample Uptake Rate 1 mL ⁄min to 2 mL/min
10.2.8.4 Warning—Toxic nitrogen oxide(s), hydrogen
12. Preparation of Calibration Standards
fluoride, and toxic chlorine (from the addition of hydrochloric
acid) fumes are usually produced during digestion. Therefore, 12.1 Blank—Prepare a blank solution by adding same con-
all steps involving open or the opening of microwave vessels centration of diluted acids as used in the sample dissolution
must be performed in a properly operating fume ventilation (usually 5 % nitric acid).
system. 12.2 Working Standards—Prepare by diluting stock stan-
10.2.8.5 Warning—The analyst should wear protective dard solutions (see 8.6) to appropriate levels, usually 1 mg ⁄L to
gloves and face protection and must not at any time permit a 10 mg ⁄L concentration with dilute nitric acid solution.
solution containing acid to come in contact with skin or lungs.
12.3 Check Standards—Prepare instrument check standards
10.2.9 After the heating cycle is complete, place the heating
in the same manner as working standards such that the
pressure vessels in an ice bath for at least an hour to cool.
concentration of the elements in the check standards are similar
Quantitatively transfer the dissolved sample into a 25 mL
to the concentration of elements in the test specimen solutions.
volumetric flask and bring it up to volume with deionized
water. (Also, see Note 1.) 12.4 Internal Standard Stock Solutions (Optional):
12.4.1 The analyst’s selection of the single element internal
NOTE 6—Care must be exercised when opening the pressure vessel so
that the contents do not spill out.
standard may be influenced by the capabilities (wavelength
NOTE 7—There may be some insoluble residue at the end of dissolution availability, sensitivity) of the ICP-AES instrument available.
steps above if the grease sample contains refractory elements such as The single element chosen as the internal standard should not
silicon, molybdenum, barium, etc. In such cases use of hydrofluoric acid be a component of the grease test specimen or calibration
to dissolve the residue may be required. If HF is used, HF-resistant standard. Table 3 lists some commonly used internal standards,
labware must be used during the dissolution steps. Also, an HF-resistant
ICP sample introduction system should be used if silicon is to be
their recommended wavelengths, and their approximate con-
quantified and to minimize potential damage to the “solution wetted” glass centration for use in this test method.
components in the ICP. Some post-digestion organic residue may also 12.4.2 Prepare a stock solution of the internal standard by
remain in the microwave digestion vessels and seals. They can be weight from a 500 mg ⁄kg single element standard material
identified as floating immiscible organic residue or “ring” around the with appropriate dilution with dilute acid solution. Prepare a
liquid level of the microwave digestion vessel, most likely leached of any
analyte and not containing any metals. concentration that is approximately 50× the concentration
required in the grease test specimen and working standard.
11. Preparation of ICPAES Instrument Prepare fresh internal standard stock solution weekly.
11.1 Instrument—Design differences between instruments,
13. Calibration
ICP excitation sources, and different selected analytical wave-
lengths for individual spectrometers make it impractical to 13.1 The linear range must be established once for the
detail the operating conditions. Consult the manufacturer’s particular instrument being used. This is accomplished by
instructions for operating the instrument. running intermediate standards between the blank and the
working standard, and by running standards containing higher
11.2 Peristaltic Pump—If a peristaltic pump is used, inspect
the pump tubing and replace it, if necessary, before starting
each day. Verify the solution uptake rate and adjust it to the TABLE 3 Internal StandardsA
desired rate. Recommended
Approximate
Internal Concentration
11.3 ICP Excitation Source—Initiate the plasma source at Wavelengths,
Standard for Use,
nm
least 30 min before performing an analysis. During this warm mg/kg
up period, nebulize either water or a dilute (5 %) acid solution. Cobalt 238.892 5
NOTE 8—Some instrument manufacturers recommend even longer Indium 230.61 10
Scandium 361.383, 255.237 1–2
warm-up periods to minimize changes in the slopes of calibration curves.
Yttrium 371.029, 317.306, 224.306 1–5
11.4 Wavelength Profiling—Perform any wavelength profil- A
Other internal standards, wavelengths, and concentrations may be used.
ing that is specified in the normal operation of the instrument.

5
 D7303 − 17
concentrations than the working standards. Analyses of test 15.2 Users of this test method are advised that in contractual
specimen solutions must be performed within the linear range agreements, one or more of the contracting parties can and may
of response. make Appendix X1 a mandatory practice.
13.2 At the beginning of the analysis of each batch of 16. Calculation
specimens, perform a two-point calibration consisting of the
blank and the working standard. Use the check standard to 16.1 Calculate the elemental concentrations by multiplying
determine if each element is in calibration. When the results the determined concentration in the diluted test specimen
obtained with the check standard are within 5 % of the solution by the dilution factor. Calculation of concentrations
expected concentrations for all elements, proceed with the test can be done manually or by instrument computer software
specimen analyses. Otherwise, make any adjustments to the when such a feature is available.
instrument that are necessary and repeat the calibration. Repeat 17. Report
this procedure with check standard every five samples.
17.1 Report mg/kg or mass % concentrations to three sig-
13.3 Calculate the calibration factors from the intensity nificant figures.
ratios. Alternatively, use the computer programs provided by
the instrument manufacturer to calibrate the instrument. 18. Precision and Bias2
18.1 The precision of this test method was determined by
14. Sample Analysis statistical analysis of interlaboratory results. Ten participating
14.1 Determine the ICP detection limits for all elements of laboratories analyzed nine grease samples in duplicate.
interest as follows: Prepare a dilute acid blank with an 18.2 The precision of this test method was determined by
(optional) internal standard by pipetting 1000 µL of the internal statistical analyses of interlaboratory results collected in 2005.
standard stock solution into a 50 mL volumetric flask, and fill Ten participating laboratories analyzed nine samples of clay,
to the volume with dilute acid. Seal the flask and mix well. lithium, and molybdenum, etc. greases in duplicate. Some
Perform ten consecutive analyses of this solution for all laboratories used muffle furnace ashing, while others used high
elements of interest under the same conditions/parameters that pressure microwave digestion systems. At the end all labs used
the two-point calibration standards were analyzed. With the ICP-AES for elemental measurements.
ICP instrument software, determine the standard deviation of 18.2.1 Many “less than” values were reported by some
these ten results for each element of interest. The detection laboratories. Several elements had less than 30 degrees of
limit of each element is its standard deviation multiplied by freedom, and in some cases half the laboratories were biased
three. Detection limits should be determined daily after cali- high or low.
bration. 18.3 Repeatability—The difference between two test results,
14.2 Analyze the test specimen solutions in the same obtained by the same operator with the same apparatus under
manner as the calibration standards (that is, the same integra- constant operating conditions on identical test material would,
tion time, background correction points (optional), plasma in the long run, in the normal and correct operation of the test
conditions, etc.). Between test specimens nebulize water for a method, exceed the values in Table 1 only in one case in
minimum of 60 s. twenty.
14.3 When the concentration of any analyte exceeds the 18.4 Reproducibility—The difference between two single
linear range of the calibration, dilute the test specimen solution and independent results, obtained by different operators work-
to bring it into calibration range. Then reanalyze. ing in different laboratories on identical test materials, would in
the long run, in the normal and correct operation of the test
14.4 Analyze the check standard after every fifth test method, exceed the values in Table 1 only in one case in
specimen solution. If any result is not within 5 % of the twenty.
expected concentration, recalibrate the instrument and reana-
lyze the test specimen solutions back to the previous acceptable 18.5 Bias—No bias could be calculated since no reference
check standard analysis. material for elemental content of grease is available.
18.6 The details of the ILS work have been published by
15. Quality Assurance/Quality Control (required) Nadkarni.7
15.1 Confirm the performance of the instrument and the test 19. Keywords
procedure by analyzing a quality control (QC) sample.
19.1 additive elements; aluminum; antimony; barium; cal-
15.1.1 When QA/QC protocols are already established in
cium; emission spectrometry; grease; ICP; inductively-coupled
the testing facility, these may be used to confirm the reliability
plasma emission spectrometry; internal standard; iron; lithium;
of the test result.
lubricating grease; magnesium; molybdenum; phosphorus; sili-
15.1.2 When there is no QA/C protocol established in the
con; sodium; sulfur; zinc
testing facility, Appendix X1 can be used as the QA/QC
protocol.
7
Nadkarni, R. A., “Multielement Analysis of Lubricating Greases with Induc-
NOTE 10—Further guidance on the laboratory QA/QC protocols can be tively Coupled Plasma-Atomic Emission Spectrometry,” J. ASTM International, Vol
found in Guide D6792. 6, No. 8, 2009, pp. 102421.

6
 D7303 − 17

APPENDIX

(Nonmandatory Information)

X1. GENERIC QUALITY CONTROL STATEMENT FOR D02 TEST METHODS

X1.1 Confirm the performance of the instrument or the test stability of the testing process, and customer requirements.
procedure by analyzing a quality control (QC) sample that is, Generally, a QC sample should be analyzed each testing day
if possible, representative of the samples typically analyzed. with routine samples. The QC frequency should be increased if
a large number of samples are routinely analyzed. However,
X1.2 Prior to monitoring the measurement process, the user when it is demonstrated that the testing is under statistical
of the test method needs to determine the average value and control, the QC testing frequency may be reduced (see Practice
control limits of the QC sample (see Practice D6299 and D6792 for further guidance on reducing QC testing frequency).
MNL 78).
X1.4.1 The QC sample precision should be periodically
X1.3 Record the QC results and analyze by control charts or checked against the ASTM test method precision to ensure data
other statistically equivalent techniques to ascertain the statis- quality (see Practice D6792 for further guidance on use of Test
tical control status of the total test process (see Practice D6299 Performance Index for this purpose).
and MNL 78). Any out-of-control data should trigger investi-
gation for root cause(s). The results of this investigation may, X1.5 It is recommended that, if possible, the type of QC
but not necessarily, result in instrument recalibration. sample that is regularly tested be representative of the sample
routinely analyzed. An ample supply of QC sample material
X1.4 In the absence of explicit requirements given in the should be available for the intended period of use, and must be
test method, the frequency of QC testing is dependent on the homogenous and stable under the anticipated storage condi-
criticality of the quality being measured, the demonstrated tions.
X1.6 Refer to relevant documents (see Practice D6299,
8
ASTM MNL 7, Manual on Presentation of Data and Control Chart Analysis, Guide D6792, and MNL 78) for further guidance on QC and
6th Ed. Section 3: Control Chart for Individuals. control charting techniques.

SUMMARY OF CHANGES

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D7303 – 12) that may impact the use of this standard. (Approved June 1, 2017.)

(1) Background of this analysis work is added in new subsec-

tions 1.3 and 18.6 and their related footnotes.

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