1、Designation: D6130 11Standard Test Method forDetermination of Silicon and Other Elements in EngineCoolant by Inductively Coupled Plasma-Atomic EmissionSpectroscopy1This standard is issued under the fixed designation D6130; the number immediately following the designation indicates the year oforigina
2、l 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 This test method covers the determination of silicon inengine cool
3、ant by inductively coupled plasma-atomic emissionspectroscopy (ICP-AES). Silicon can be determined as low asthe range of 5 ppm by this test method. Other elements alsofound in engine coolant can be determined by this method.This test method is applicable to the determination of dissolvedor dispersed
4、 elements.1.2 This test method is applicable to both new and usedengine coolant.1.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with
5、 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.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent WaterD1176 Practice for Sampling and
6、 Preparing Aqueous Solu-tions of Engine Coolants or Antirusts for Testing PurposesE177 Practice for Use of the Terms Precision and Bias inASTM Test MethodsE691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method2.2 US EPA Standards:Method 6010, Inductively Cou
7、pled Plasma Method, SW-846, Test Methods for Evaluating Solid Waste3Method 200.7, Inductively Coupled Plasma - Atomic Emis-sion Spectrometric Method for Trace Element Analysis ofWater And Wastes, EPA-600/4-79-020, revised 198433. Summary of Test Method3.1 Elements in solution are determined, either
8、sequentiallyor simultaneously, by ICP-AES. New or used engine coolantsare prepared by dilution. Samples and standards are introducedto the nebulizer using a peristaltic pump and the aerosol isinjected into an argon-supported inductively coupled plasma.The high temperature of the plasma atomizes the
9、sample andproduces atomic emission intensities at wavelengths associatedwith the desired elements. Emission intensity is proportional toconcentration. Elemental determinations are made by compar-ing standard and sample emission intensities.4. Significance and Use4.1 Some engine coolants are formulat
10、ed with silicon con-taining additives. This test method provides a means ofdetermining the concentration of dissolved or dispersed ele-ments which give an indication of this additive content in theengine coolant.5. Interferences5.1 Interferences may be categorized as follows:5.1.1 SpectralLight emis
11、sion from spectral sources otherthan the element of interest may contribute to apparent netsignal intensity. Sources of spectral interference include directspectral line overlaps, broadened wings of intense spectrallines, ion-atom recombination continuum emission, molecularband emission and stray (s
12、cattered) light from the emission ofelements at high concentrations. Avoid overlaps by selectingalternate analytical wavelengths.5.1.2 PhysicalPhysical interferences are effects associ-ated with sample nebulization and transport processes such asviscosity and particulate contamination.1This test met
13、hod is under the jurisdiction of ASTM Committee D15 on EngineCoolants and Related Fluids and is the direct responsibility of SubcommitteeD15.04 on Chemical Properties.Current edition approved Nov. 1, 2011. Published January 2012. Originallyapproved in 1997. Last previous edition approved in 2009 as
14、D613097a (2009).DOI: 10.1520/D6130-11.2For 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.3Available from U. S. E
15、nvironmental Protection Agency, Environmental Moni-toring and Support Laboratory, Cincinnati, OH 45268.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5.1.3 BackgroundHigh background effects from scatteredlight, etc., can be compensa
16、ted for by background correctionadjacent to the analyte line.5.1.4 ChemicalChemical interferences are caused by mo-lecular compound formation, ionization effects, and thermo-chemical effects associated with sample vaporization andatomization in the plasma. Normally these effects are notpronounced an
17、d can be minimized by careful selection ofoperating conditions (incident power, plasma observation po-sition, etc.).6. Apparatus6.1 SpectrometerAn inductively coupled plasma emissionspectrometer of the simultaneous or sequential type includingRF generator, torch, nebulizer, spray chamber, recommende
18、dperistaltic pump and host computer.7. Reagents and Materials7.1 Purity of ChemicalsReagent grade or better chemicalsshall be used for preparation of all standards and samples.Other grades may be used provided it is first ascertained thatthe reagent is of sufficiently high purity to permit its usewi
19、thout lessening the accuracy of the determination.7.2 Purity of WaterReferences to water shall be under-stood to mean deionized water.7.3 Standard Stock SolutionsCertified solutions may bepurchased or prepared from high purity grade chemicals ormetals (See Method 6010, SW-846, Method 200.7). Standar
20、dscontain 1000 mg/L of the element of interest. Salts should bedried as indicated.7.4 Calibration StandardsPrepare the standards in volu-metric flasks using appropriate volumes of each stock solutionto cover the expected concentration range of the samples.Elements in multielement standards should be
21、 shown to becompatible and stable. Compensate for differences in standard/sample matrix by using an appropriate amount of ethyleneglycol and/or an internal standard. Suggested combinations andanalytical lines are in Table 1. Validate calibration standards.Monitor stability.8. Sampling8.1 Collect sam
22、ple in accordance with Practice D1176.9. Calibration and Standardization9.1 Set the up instrument according to the manufacturersinstructions. Warm it up at least 20 min.9.2 Profile and calibrate the instrument according to manu-facturers recommended procedures with the blank and stan-dards, aspirati
23、ng the standard for at least 30 s to allow theinstrument to equilibrate prior to signal integration. Watershould be run for an additional 60 s after standards containingboron. Calibration should be validated and stability of stan-dards should be monitored.10. Sample Preparation10.1 Dilute the sample
24、 with deionized water so the concen-tration of the element(s) of interest is in the linear detectionrange of the instrument. Generally a120 or150 dilution for usedengine coolant and a1100 dilution for engine coolant concen-trate are sufficient. Samples may be prepared by weight tovolume or by volume
25、 to volume. Be certain when preparingdilutions by volume that the entire sample aliquot is trans-ferred. Filter or centrifuge samples that contain particulate.11. Procedure11.1 Aspirate the prepared samples into the calibratedinstrument using the same conditions established for thecalibration proced
26、ure. Rinse sufficiently to prevent carryover.Run water an additional 60 s between samples containingboron.11.2 Run a blank and an instrument check standard (acalibration standard, calibration verification or standard enginecoolant) every ten samples or as established to be necessary forthe instrumen
27、t. Analyze a blank and check standard at the endof each run. The concentration shall be within 65 % of theexpected value. If the concentration is out of range, correct theproblem, recalibrate the instrument and rerun the samples inquestion.11.3 Matrix spikes and duplicates may be performed asquality
28、 control procedures if sample concentrations are suspectdue to contamination, spectral interferences or trace levels ofthe element of interest.11.4 Perform the corrections and calculations, includingdilution factors, using the instrument host computer.12. Report12.1 Samples prepared by weight to vol
29、ume dilution may bereported in ppm by weight or % by weight depending on theconcentration of the element of interest. Samples prepared byvolume may be reported as g/L, mg/L, g/mL, etc. These unitsmay be converted to ppm weight or % by weight using thedensity of the sample:concentration ppm by wt!5co
30、ncentration g/mL!density g/mL!(1)13. Precision and Bias13.1 The precision of this test method is based on aninterlaboratory study conducted in 2009. A total of ninelaboratories participated in this study, testing samples of sixdifferent coolants for their metals content. Every test resultrepresents
31、an individual determination, and all participantsTABLE 1 Analytical Wavelengths for ICP-AES Determination ofElements in Engine CoolantElement Wavelength, nmMixed Standard 1Silicon 251.612, 288.158, 252.851, 252.411Molybdenum 202.030, 204.598Boron 249.773Phosphorus 214.914, 178.29Mixed Standard 2Alum
32、inum 308.215, 394.401, 369.152Lead 220.353Zinc 213.856Iron 259.94, 259.837, 238.204Copper 324.754, 219.226Magnesium 279.079, 280.270, 279.553Calcium 317.933, 393.37, 396.847, 315.887Sodium 588.995, 589.592D6130 112were asked to report four replicate test results for eachmetal/coolant combination. Pr
33、actice E691 was followed for thedesign and analysis of the data; the details are given inRR:D15-1030.13.1.1 Repeatability Limit, rTwo test results obtainedwithin one laboratory shall be judged not equivalent if theydiffer by more than the r value for that material; r is the intervalrepresenting the
34、critical difference between two test results forthe same material, obtained by the same operator using thesame equipment on the same day in the same laboratory.13.1.1.1 Repeatability limits are listed in Tables 2-13.13.1.2 Reproducibility limit, RTwo test results shall bejudged not equivalent if the
35、y differ by more than the R valuefor that material; R is the interval representing the criticaldifference between two test results for the same material,obtained by different operators using different equipment indifferent laboratories.13.1.2.1 Reproducibility limits are listed in Tables 2-13.13.1.3
36、 The above terms (repeatability limit and reproduc-ibility limit) are used as specified in Practice E177.13.1.4 Any judgment in accordance with statements 13.1.1and 13.1.2 would have an approximate 95% probability ofbeing correct.13.2 BiasAt the time of the study, there was no acceptedreference mate
37、rial suitable for determining the bias for this testmethod, therefore no statement on bias is being made.13.3 The precision statement was determined through sta-tistical examination of 1,872 test results, submitted by ninelaboratories, on twelve metals, in six coolants.13.3.1 The six coolant types w
38、ere described as follows:Coolant ACoolant BCoolant CCoolant DCoolant ECoolant F13.4 To judge the equivalency of two test results, it isrecommended to choose the coolant material that is closest incharacteristics to the test material.14. Keywords14.1 engine coolant; inductively coupled plasma-atomice
39、mission spectroscopy; siliconTABLE 2 Aluminum (g/mL)MaterialAverage,AxRepeatabilityStandardDeviation, SrReproducibilityStandardDeviation, SRRepeatabilityLimit, rReproducibilityLimit, RSample A 6.4 8.0 9.7 22.4 27.2Sample B 2.9 3.0 3.2 8.3 9.0Sample C 0.5 0.7 0.7 2.0 2.1Sample D 2.9 4.4 4.9 12.4 13.9
40、Sample E 5.2 3.7 4.8 10.2 13.5Sample F 5.6 6.1 7.0 17.2 19.7AThe average of the laboratories calculated averages.D6130 113TABLE 3 Boron (g/mL)MaterialAverage,AxRepeatabilityStandardDeviation, SrReproducibilityStandardDeviation, SRRepeatabilityLimit, rReproducibilityLimit, RSample A 215.8 5.3 29.3 14
41、.7 82.1Sample B 193.5 169.5 222.7 474.6 623.5Sample C 298.8 98.2 131.6 274.8 368.5Sample D 388.8 334.9 447.3 937.6 1252.5Sample E 139.3 123.7 161.1 346.2 451.1Sample F 91.8 78.2 103.2 218.9 288.9AThe average of the laboratories calculated averages.TABLE 4 Calcium (g/mL)MaterialAverage,AxRepeatabilit
42、yStandardDeviation, SrReproducibilityStandardDeviation, SRRepeatabilityLimit, rReproducibilityLimit, RSample A 3.9 4.2 5.1 11.6 14.2Sample B 7.0 1.2 2.1 3.5 5.9Sample C 9.0 5.2 6.5 14.6 18.1Sample D 12.6 5.3 5.8 15.0 16.3Sample E 3.6 0.7 0.8 2.1 2.3Sample F 3.7 2.3 3.0 6.5 8.5AThe average of the lab
43、oratories calculated averages.TABLE 5 Copper (g/mL)MaterialAverage,AxRepeatabilityStandardDeviation, SrReproducibilityStandardDeviation, SRRepeatabilityLimit, rReproducibilityLimit, RSample A 1.4 1.6 1.8 4.4 5.1Sample B 5.0 1.3 1.6 3.8 4.4Sample C 4.8 3.8 5.0 10.7 13.9Sample D 2.9 1.3 1.8 3.6 4.9Sam
44、ple E 4.1 3.5 3.9 9.7 11.0Sample F 2.6 2.5 3.4 7.1 9.6AThe average of the laboratories calculated averages.TABLE 6 Iron (g/mL)MaterialAverage,AxRepeatabilityStandardDeviation, SrReproducibilityStandardDeviation, SRRepeatabilityLimit, rReproducibilityLimit, RSample A 7.3 0.7 4.7 2.1 13.1Sample B 41.0
45、 34.5 45.8 96.5 128.2Sample C 2.3 2.1 2.6 6.0 7.4Sample D 23.5 7.1 10.2 20.0 28.5Sample E 1.9 2.9 3.0 8.0 8.5Sample F 4.9 4.3 6.2 11.9 17.3AThe average of the laboratories calculated averages.TABLE 7 Lead (g/mL)MaterialAverage,AxRepeatabilityStandardDeviation, SrReproducibilityStandardDeviation, SRR
46、epeatabilityLimit, rReproducibilityLimit, RSample A 2.8 3.0 4.2 8.4 11.6Sample B 1.8 1.7 2.2 4.8 6.1Sample C 4.9 2.8 3.2 7.8 9.1Sample D 3.2 1.7 2.5 4.7 7.1Sample E 5.5 5.0 5.6 14.0 15.6Sample F 3.3 3.1 4.9 8.7 13.7AThe average of the laboratories calculated averages.D6130 114TABLE 8 Magnesium (g/mL
47、)MaterialAverage,AxRepeatabilityStandardDeviation, SrReproducibilityStandardDeviation, SRRepeatabilityLimit, rReproducibilityLimit, RSample A 3.4 3.7 4.6 10.2 13.0Sample B 3.0 2.1 2.4 5.9 6.9Sample C 2.4 1.6 2.1 4.5 5.8Sample D 2.2 1.7 2.0 4.6 5.7Sample E 1.6 1.4 1.7 3.8 4.6Sample F 2.9 2.5 4.0 7.0
48、11.3AThe average of the laboratories calculated averages.TABLE 9 Molybdenum (g/mL)MaterialAverage,AxRepeatabilityStandardDeviation, SrReproducibilityStandardDeviation, SRRepeatabilityLimit, rReproducibilityLimit, RSample A 389.2 4.9 19.5 13.7 54.7Sample B 114.1 73.7 105.6 206.4 295.7Sample C 10.0 8.
49、4 11.5 23.6 32.2Sample D 417.7 64.7 97.2 181.0 272.3Sample E 5.9 4.9 6.8 13.8 19.0Sample F 307.8 204.2 285.2 571.8 798.6AThe average of the laboratories calculated averages.TABLE 10 Potassium (g/mL)MaterialAverage,AxRepeatabilityStandardDeviation, SrReproducibilityStandardDeviation, SRRepeatabilityLimit, rReproducibilityLimit, RSample A 4060.2 478.8 567.7 1340.5 1589.7Sample B 2695.7 2257.9 2721.0 6322.1 7618.8Sample C 1150.5 652.4 848.9 1826.6 2376.8Sample D 3136.5 383.6 447.4 1074.0 1252.6Sample E 1219.8 368.6 462.3 1032.1 1294.6S
