Designation: D7303 − 12

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 values stated in SI units are to be regarded as the
inductively coupled plasma atomic emission spectrometry standard. The values given in parentheses are for information
(ICP-AES) technique. only.
1.1.1 The range of applicability for this test method, based 1.4 This standard does not purport to address all of the
on the interlaboratory study conducted in 2005,2 is aluminum safety concerns, if any, associated with its use. It is the
(10–600), antimony (10–2300), barium (50–800), calcium responsibility of the user of this standard to establish appro-
(20–50 000), iron (10–360), lithium (300–3200), magnesium priate safety and health practices and determine the applica-
(30–10 000), molybdenum (50–22 000), phosphorus bility of regulatory limitations prior to use. Specific warning
(50–2000), silicon (10–15 000), sodium (30–1500), sulfur statements are given in Sections 8 and 10.
(1600–28 000), and zinc (300–2200), all in mg/kg. Lower
2. Referenced Documents

http://qstandard.org/
levels of elements may be determined by using larger sample
weights, and higher levels of elements may be determined by 2.1 ASTM Standards:3
using smaller amounts of sample or by using a larger dilution D1193 Specification for Reagent Water
factor after sample dissolution. However, the test precision in D3340 Test Method for Lithium and Sodium in Lubricating
such cases has not been determined, and may be different than Greases by Flame Photometer
the ones given in Table 1. D4057 Practice for Manual Sampling of Petroleum and
1.1.2 It may also be possible to determine additional metals Petroleum Products
such as bismuth, boron, cadmium, chromium, copper, lead, D4951 Test Method for Determination of Additive Elements
manganese, potassium, titanium, etc. by this technique. in Lubricating Oils by Inductively Coupled Plasma
However, not enough data is available to specify the precision Atomic Emission Spectrometry
for these latter determinations. These metals may originate into D5185 Test Method for Determination of Additive Elements,
greases through contamination or as additive elements. Wear Metals, and Contaminants in Used Lubricating Oils
1.1.3 During sample preparation, the grease samples are and Determination of Selected Elements in Base Oils by
decomposed with a variety of acid mixture(s). It is beyond the Inductively Coupled Plasma Atomic Emission Spectrom-
scope of this test method to specify appropriate acid mixtures etry (ICP-AES)
for all possible combination of metals present in the sample. D6299 Practice for Applying Statistical Quality Assurance
But if the ash dissolution results in any visible insoluble and Control Charting Techniques to Evaluate Analytical
material, the test method may not be applicable for the type of Measurement System Performance
grease being analyzed, assuming the insoluble material con- D6792 Practice for Quality System in Petroleum Products
tains some of the analytes of interest. and Lubricants Testing Laboratories
D7260 Practice for Optimization, Calibration, and Valida-
tion of Inductively Coupled Plasma-Atomic Emission
1
This test method is under the jurisdiction of ASTM Committee D02 on Spectrometry (ICP-AES) for Elemental Analysis of Petro-
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee leum Products and Lubricants
D02.03 on Elemental Analysis.
Current edition approved June 1, 2012. Published August 2012. Originally
3
approved in 2006. Last previous edition approved in 2006 as D7303–06. DOI: For referenced ASTM standards, visit the ASTM website, www.astm.org, or
10.1520/D7303-12. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
2
Supporting data have been filed at ASTM International Headquarters and may Standards volume information, refer to the standard’s Document Summary page on
be obtained by requesting Research Report RR:D02-1608. 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

1
 D7303 − 12
TABLE 1 Precision of Grease Analysis 5.3 Test Method D3340 has been used to determine lithium
NOTE 1—X is the mean concentration in mg/kg. and sodium content of lubricating greases using flame photom-
Range,
etry. This technique is no longer widely used. This new test
Element Repeatability Reproducibility method provides a test method for multi-element analysis of
mg/kg
Aluminum 10–600 0.2163 X0.9 6.8156 X0.9 grease samples. This is the first DO2 standard available for
Antimony 10–2300 0.3051 X0.8191 4.6809 X0.8191 simultaneous multi-element analysis of lubricating greases.
Barium 50–800 0.3165 X0.7528 2.9503 X0.7528
Calcium 20–50 000 2.2853 X0.7067 3.0571 X0.7067
Iron 10–360 0.8808 X0.7475 2.5737 X0.7475 6. Interferences
Lithium 300–3200 0.0720 X1.0352 0.1476 X1.0352
Magnesium 30–10 000 0.6620 X0.6813 2.6155 X0.6813
6.1 Spectral—Spectral interferences can usually be avoided
Molybdenum 50–22 000 0.1731 X0.9474 0.4717 X0.9474 by judicious choice of analytical wavelengths. There are no
Phosphorus 50–2000 1.2465 X0.6740 4.0758 X0.6740 known spectral interferences between elements covered by this
Silicon 10–15 000 1.3859 X0.9935 4.8099 X0.9935
Sodium 30–1500 6.5760 X0.5 11.571 X0.5
test method when using the spectral lines listed in Table 2.
Sulfur 1600–28 000 1.0507 X0.8588 1.5743 X0.8588 However, if spectral interferences exist because of other
Zinc 300–2200 0.1904 X0.8607 0.5912 X0.8607 interfering elements or selection of other spectral lines, correct
for the interferences using the technique described in Test
Method D5185.
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.

http://qstandard.org/
solutions are analyzed using ICP-AES. Aqueous calibration 6.2.2 If the dry ashing in sample preparation step is used,
standards are used. The solutions are introduced to the ICP elements such as sulfur will be volatilized during combustion.
instrument by free aspiration or an optional peristaltic pump.
By comparing emission intensities of elements in the test 7. Apparatus
specimen with those measured with the calibration standards, 7.1 Analytical Balance, capable of weighing to 0.001 g or
the concentrations of elements in the test specimen can be 0.0001 g, capacity of 150 g.
calculated. 7.2 Inductively Coupled Plasma Atomic Emission
4.2 Additional information on using inductively coupled Spectrometer—Either a sequential or simultaneous spectrom-
plasma-atomic emission spectrometry can be found in Practice eter is suitable, if equipped with a quartz ICP torch and RF
D7260. generator to form and sustain the plasma. Suggested wave-
lengths for the determination of elements in dissolved grease
5. Significance and Use solutions are given in Table 2.
5.1 Lubricating greases are used in almost all bearings used
in any machinery. Lubricating grease is composed of ~90 %
TABLE 2 Suggested WavelengthsA,B for Elements Determined in
additized oil and soap or other thickening agent. There are over Grease Samples
a dozen metallic elements present in greases, either blended as Element Wavelength, nm
additives for performance enhancements or as thickeners, or in Aluminum 167.038, 308.22, 396.15, 309.27
used greases present as contaminants and wear metals. Deter- Antimony 206.83, 217.58, 231.15
mining their concentrations can be an important aspect of Barium 223.53, 233.527, 455.40, 493.41
Calcium 315.88, 317.93, 364.4, 396.85, 422.67
grease manufacture. The metal content can also indicate the Iron 238.20, 259.94
amount of thickeners in the grease. Additionally, a reliable Lithium 670.78, 610.36, 460.29
analysis technique can also assist in the process of trouble Magnesium 279.08, 279.55, 280.278, 285.21
Molybdenum 135.387, 202.03, 281.62
shooting problems with new and used grease in the field. Phosphorus 177.51, 178.29, 213.62, 214.91, 253.40
5.2 Although widely used in other sectors of the oil industry Silicon 288.16, 251.618
Sodium 589.595
for metal analysis, ICP-AES based Test Methods D4951 or Sulfur 182.04, 180.73, 182.63
D5185 cannot be used for analyzing greases because of their Zinc 202.55, 206.20, 213.86, 334.58, 481.05
insolubility in organic solvents used in these test methods. A
These wavelengths are only suggested and do not represent all possible
Hence, grease samples need to be brought into aqueous choices.
B
Wavelengths for boron, phosphorus, and sulfur below 190 nm require that a
solution by acid decomposition before ICP-AES measure- vacuum or inert gas purge optical path be used.
ments.

2
 D7303 − 12
7.3 Peristaltic Pump, (Recommended)—A peristaltic pump also commercially available. (Warning—Take all necessary
is strongly recommended to provide a constant flow of solu- precautions to prevent exposure to radiofrequency radiation.)
tion. The pumping speed must be in the range of 0.5 to 8.10 Microwave Sample Digestion System, with closed-
3 mL/min. The pump tubing must be able to withstand at least vessel silicon-free polytetrafluoroethylene (PTFE) digestion
6 h exposure to solutions. vessels. The vessels need to be capable of withstanding the
7.4 Specimen Solution Containers, of appropriate size, glass pressure generated from the digestion of 0.2 g of sample
or polyolefin vials or bottles, with screw caps without metal (pressure achieved with a 100 mL vessel and 0.2 g of sample
liners. could be in excess of 100 psi). Microwave digestions systems
with temperature and pressure monitoring are recommended
8. Reagents and Materials for safety and accuracy of sample preparation.
8.1 Purity of Reagents—Reagent grade chemicals shall be 8.11 The test method requires essentially microwave trans-
used in all tests. Unless otherwise indicated, it is intended that parent and reagent resistant suitably inert polymeric materials
all reagents conform to the specifications of the Committee on (examples are PFA or TFM) to contain acids and samples. For
Analytical Reagents of the American Chemical Society where higher pressure capabilities the vessel may be contained within
such specifications are available.4 Other grades may be used, layers of different microwave transparent materials for
provided it is first ascertained that the reagent is of sufficiently strength, durability, and safety. The vessels internal volume
high purity to permit its use without lessening the accuracy of should be at least 45 mL, capable of withstanding pressures of
the determination. at least 30 atm (30 bar or 435 psi), and capable of controlled
8.2 Sulfuric Acid, concentrated sulfuric acid, H2SO4. pressure relief. These specifications are given to provide an
(Warning—Causes severe burns. Corrosive.) appropriate, safe, and durable reaction vessel of which there
are many adequate designs by many suppliers.
8.3 Nitric Acid, concentrated nitric acid, HNO3 .
(Warning—Causes severe burns. Corrosive.) 8.12 Rotating Turntable, to insure homogeneous distribu-
tion of microwave radiation within most systems. The speed of
8.4 Hydrochloric Acid, concentrated hydrochloric acid, the turntable should be a minimum of 3 rpm.
HCl. (Warning—Causes burns.)
8.13 Combustion Dishes, Vycor or platinum evaporation
8.5 Hydrofluoric Acid, concentrated hydrofluoric acid, HF
dishes of 250 mL size.

http://qstandard.org/
(Warning—Causes severe burns.)
8.14 Volumetric Flasks, polypropylene or similar material
8.6 Aqueous Standard Solutions, individual aqueous el-
of 25 and 50 mL sizes.
emental standards with 100 mg/L concentrations of elements of
interest. These can be prepared by dissolving pure metal 8.15 Electric Muffle Furnace, capable of maintaining 525 6
compounds in water or dilute acids, or may be purchased from 25°C and sufficiently large to accommodate several 250 mL
commercial sources. beakers. The capacity of an oxygen bleed is advantageous and
8.6.1 Multi-element aqueous standards may be advanta- optional. (Warning—Take all necessary precautions to prevent
geous to use. exposure to very hot surfaces.)
8.6.2 Internal Standard, aqueous cobalt, indium, scandium, 8.16 Heating Lamp, commercial infrared heating lamp.
yttrium or other single element standard, not a component of
the grease test specimen or calibration standard, nominal 500 9. Sampling
mg/kg concentration.
9.1 The objective of sampling is to obtain a test specimen
8.7 Water, distilled or deionized water, unless otherwise that is representative of the entire quantity. Thus, take labora-
indicated, references to water shall be understood to mean Type tory samples in accordance with the instructions in Practice
II reagent grade water as defined in Specification D1193. D4057. The specific sampling technique can affect the accu-
8.8 Quality Control (QC) Samples, preferably are portions racy of this test method.
of one or more grease materials that are stable and represen-
tative of the samples of interest. These QC samples can be used 10. Preparation of Samples
to check the validity of the testing process as described in
10.1 Sulfated Ash Digestion:
Section 15.
10.1.1 Accurately weigh approximately 1 to 2 6 0.1 g of the
8.9 Microwave Oven, commercially available laboratory grease sample in a Vycor or platinum container of suitable size.
microwave digestion oven of sufficient power (for example, at Char the sample on a hot plate until it is reduced to ~0.5 g. A
least 1000 W) is suitable. The microwave digestion dishes are heat lamp may be used to assist in this process.
10.1.2 After the charred residue is cooled, add 1 to 2 mL of
concentrated sulfuric acid and carefully heat on the hot plate
4
Reagent Chemicals, American Chemical Society Specifications, American taking care to avoid spattering of the contents, and continue
Chemical Society, Washington, DC. For suggestions on the testing of reagents not heating until the fumes are no longer evolved.
listed by the American Chemical Society, see Analar Standards for Laboratory
10.1.3 Place the charred sample in a muffle furnace at 525 6
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulatory, U.S. Pharmaceutical Convention, Inc. (USPC), 25°C until the oxidation of the carbon is practically complete.
Rockville, MD. This typically takes about 2 h.

3
 D7303 − 12
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 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 to 1 g of the grease 10.2.7 Program the microwave oven to heat at 125 W for 15
sample in a polytetrafluoroethylene (PTFE) digestion vessel 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

http://qstandard.org/
perature to within 6 2.5°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
10.2.4 The analyst should be aware of the potential for a (kitchen) type microwave ovens or to use inappropriate sealed
vigorous reaction. If a vigorous reaction occurs upon the initial containers without pressure relief for microwave acid diges-
addition of reagent or the sample is suspected of containing tions by this test method. Use of laboratory-grade microwave
easily oxidizable materials, allow the sample to predigest in the equipment is required to prevent safety hazards.
uncapped digestion vessel. Heat may be added in this step for 10.2.8.3 Warning—Laboratories should not use domestic
safety considerations (for example, the rapid release of carbon (kitchen) type microwave ovens for this test method. There are
dioxide from carbonates, easily oxidized organic matter, etc.). several significant safety issues. First, when an acid such as
Once the initial reaction has ceased, the sample may continue nitric is used to effect sample digestion in microwave units in
through the digestion procedure. sealed vessels equipment, there is the potential for the acid gas
10.2.5 Seal the vessel according to the manufacturer’s vapor released to corrode the safety devices that prevent the
directions. Properly place the vessel in the microwave system microwave magnetron from shutting off when the door is

4
 D7303 − 12
opened. This can result in operator exposure to microwave Forward Power 1100–1500 W
energy. Use of a system with isolated and corrosion resistant Coolant Gas, Argon 12–17 L/min
Auxiliary Gas, Argon 0.2–1 L/min
safety devices prevents this from occurring. Nebulizer Gas, Argon 0.7–1.1 L/min
10.2.8.4 Warning—Toxic nitrogen oxide(s), hydrogen Sample Uptake Rate 1–2 mL/min
fluoride, and toxic chlorine (from the addition of hydrochloric
acid) fumes are usually produced during digestion. Therefore, 12. Preparation of Calibration Standards
all steps involving open or the opening of microwave vessels 12.1 Blank—Prepare a blank solution by adding same con-
must be performed in a properly operating fume ventilation centration of diluted acids as used in the sample dissolution
system. (usually 5 % nitric acid).
10.2.8.5 Warning—The analyst should wear protective 12.2 Working Standards—Prepare by diluting stock stan-
gloves and face protection and must not at any time permit a dard solutions (see 8.6) to appropriate levels, usually 1 to
solution containing acid to come in contact with skin or lungs. 10 mg/L concentration with dilute nitric acid solution.
10.2.9 After the heating cycle is complete, place the heating
12.3 Check Standards—Prepare instrument check standards
pressure vessels in an ice bath for at least an hour to cool.
in the same manner as working standards such that the
Quantitatively transfer the dissolved sample into a 25 mL
concentration of the elements in the check standards are similar
volumetric flask and bring it up to volume with deionized
to the concentration of elements in the test specimen solutions.
water. (Also, see Note 1.)
12.4 Internal Standard Stock Solutions (Optional):
NOTE 6—Care must be exercised when opening the pressure vessel so
that the contents do not spill out.
12.4.1 The analyst’s selection of the single element internal
NOTE 7—There may be some insoluble residue at the end of dissolution standard may be influenced by the capabilities (wavelength
steps above if the grease sample contains refractory elements such as availability, sensitivity) of the ICP-AES instrument available.
silicon, molybdenum, barium, etc. In such cases use of hydrofluoric acid The single element chosen as the internal standard should not
to dissolve the residue may be required. If HF is used, HF-resistant be a component of the grease test specimen or calibration
labware must be used during the dissolution steps. Also, an HF-resistant
ICP sample introduction system should be used if silicon is to be
standard. Table 3 lists some commonly used internal standards,
quantified and to minimize potential damage to the “solution wetted” glass their recommended wavelengths, and their approximate con-
components in the ICP. Some post-digestion organic residue may also centration for use in this test method.
remain in the microwave digestion vessels and seals. They can be 12.4.2 Prepare a stock solution of the internal standard by
identified as floating immiscible organic residue or “ring” around the weight from a 500 mg/kg single element standard material with

http://qstandard.org/
liquid level of the microwave digestion vessel, most likely leached of any
analyte and not containing any metals.
appropriate dilution with dilute acid solution. Prepare a con-
centration that is approximately 50 times the concentration
11. Preparation of ICPAES Instrument required in the grease test specimen and working standard.
Prepare fresh internal standard stock solution weekly.
11.1 Instrument—Design differences between instruments,
ICP excitation sources, and different selected analytical wave- 13. Calibration
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
11.2 Peristaltic Pump—If a peristaltic pump is used, inspect working standard, and by running standards containing higher
the pump tubing and replace it, if necessary, before starting concentrations than the working standards. Analyses of test
each day. Verify the solution uptake rate and adjust it to the specimen solutions must be performed within the linear range
desired rate. of response.
11.3 ICP Excitation Source—Initiate the plasma source at 13.2 At the beginning of the analysis of each batch of
least 30 min before performing an analysis. During this warm specimens, perform a two-point calibration consisting of the
up period, nebulize either water or a dilute (5 %) acid solution. blank and the working standard. Use the check standard to
NOTE 8—Some instrument manufacturers recommend even longer determine if each element is in calibration. When the results
warm-up periods to minimize changes in the slopes of calibration curves. obtained with the check standard are within 5 % of the
11.4 Wavelength Profiling—Perform any wavelength profil- expected concentrations for all elements, proceed with the test
ing that is specified in the normal operation of the instrument. specimen analyses. Otherwise, make any adjustments to the
11.5 Operating Parameters—Assign the appropriate operat-
TABLE 3 Internal StandardsA
ing parameters to the instrument task file so that the desired
Approximate
elements can be determined. Parameters to be included are Internal
Recommended
Concentration
Wavelengths,
element, wavelength(s), background correction points Standard
nm
for Use,
(optional), interelement correction factors (see 6.1), and inte- mg/kg

gration time. Multiple integrations (typically three) are re- Cobalt 238.892 5
Indium 230.61 10
quired for each measurement. A typical measurement time is Scandium 361.383, 255.237 1–2
10 s. Yttrium 371.029, 317.306, 224.306 1–5
NOTE 9—Typical ICP operating conditions follow. Different conditions A
Other internal standards, wavelengths, and concentrations may be used.
specific to different instruments may be used.

5
 D7303 − 12
instrument that are necessary and repeat the calibration. Repeat 16. Calculation
this procedure with check standard every five samples. 16.1 Calculate the elemental concentrations by multiplying
13.3 Calculate the calibration factors from the intensity the determined concentration in the diluted test specimen
ratios. Alternatively, use the computer programs provided by solution by the dilution factor. Calculation of concentrations
the instrument manufacturer to calibrate the instrument. can be done manually or by instrument computer software
when such a feature is available.
14. Sample Analysis
14.1 Determine the ICP detection limits for all elements of 17. Report
interest as follows: Prepare a dilute acid blank with an 17.1 Report mg/kg or mass % concentrations to three sig-
(optional) internal standard by pipetting 1000 µL of the internal nificant figures.
standard stock solution into a 50 mL volumetric flask, and fill
to the volume with dilute acid. Seal the flask and mix well. 18. Precision and Bias2
Perform ten consecutive analyses of this solution for all
elements of interest under the same conditions/parameters that 18.1 The precision of this test method was determined by
the two-point calibration standards were analyzed. With the statistical analysis of interlaboratory results. Ten participating
ICP instrument software, determine the standard deviation of laboratories analyzed nine grease samples in duplicate.
these ten results for each element of interest. The detection 18.2 The precision of this test method was determined by
limit of each element is its standard deviation multiplied by statistical analyses of interlaboratory results collected in 2005.
three. Detection limits should be determined daily after cali- Ten participating laboratories analyzed nine samples of clay,
bration. lithium, and molybdenum, etc. greases in duplicate. Some
14.2 Analyze the test specimen solutions in the same laboratories used muffle furnace ashing, while others used high
manner as the calibration standards (that is, the same integra- pressure microwave digestion systems. At the end all labs used
tion time, background correction points (optional), plasma ICP-AES for elemental measurements.
conditions, etc.). Between test specimens nebulize water for a 18.2.1 Many “less than” values were reported by some
minimum of 60 s. laboratories. Several elements had less than 30 degrees of
freedom, and in some cases half the laboratories were biased
14.3 When the concentration of any analyte exceeds the high or low.
linear range of the calibration, dilute the test specimen solution

http://qstandard.org/
to bring it into calibration range. Then reanalyze. 18.3 Repeatability—The difference between two test results,
obtained by the same operator with the same apparatus under
14.4 Analyze the check standard after every fifth test constant operating conditions on identical test material would,
specimen solution. If any result is not within 5 % of the in the long run, in the normal and correct operation of the test
expected concentration, recalibrate the instrument and reana- method, exceed the values in Table 1 only in one case in
lyze the test specimen solutions back to the previous acceptable twenty.
check standard analysis.
18.4 Reproducibility—The difference between two single
15. Quality Assurance/Quality Control (required) and independent results, obtained by different operators work-
15.1 Confirm the performance of the instrument and the test ing in different laboratories on identical test materials, would in
procedure by analyzing a quality control (QC) sample. the long run, in the normal and correct operation of the test
15.1.1 When QA/QC protocols are already established in method, exceed the values in Table 1 only in one case in
the testing facility, these may be used to confirm the reliability twenty.
of the test result. 18.5 Bias—No bias could be calculated since no reference
15.1.2 When there is no QA/C protocol established in the material for elemental content of grease is available.
testing facility, Appendix X1 can be used as the QA/QC
protocol. 19. Keywords
NOTE 10—Further guidance on the laboratory QA/QC protocols can be 19.1 additive elements; aluminum; antimony; barium; cal-
found in Guide D6792. cium; emission spectrometry; grease; ICP; inductively-coupled
15.2 Users of this test method are advised that in contractual plasma emission spectrometry; internal standard; iron; lithium;
agreements, one or more of the contracting parties can and may lubricating grease; magnesium; molybdenum; phosphorus; sili-
make Appendix X1 a mandatory practice. con; sodium; sulfur; zinc

6
 D7303 − 12
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 75).
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 75). 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,
5
ASTM MNL 7, Manual on Presentation of Data and Control Chart Analysis, Guide D6792, and MNL 75) for further guidance on QC and
6th Ed. Section 3: Control Chart for Individuals. control charting techniques.

http://qstandard.org/
SUMMARY OF CHANGES

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D7303–06) that may impact the use of this standard.

(1) Added Practice D7260 to Referenced Documents and (2) Added new 4.2.
standard text.

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website
(www.astm.org). Permission rights to photocopy the standard may also be secured from the ASTM website (www.astm.org/
COPYRIGHT/).