1、Designation: D1619 11Standard Test Methods forCarbon BlackSulfur Content1This standard is issued under the fixed designation D1619; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses
2、indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.This standard has been approved for use by agencies of the Department of Defense.1. Scope1.1 These test methods cover the determination of the sulfurcontent of carbon bl
3、ack. The following test methods areincluded:SectionsTest Method A High-Temperature Combustion With In-frared Absorption Detection Procedures6 to 13Test Method B X-Ray Fluorescence 14 to 191.2 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in t
4、hisstandard.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2.
5、Referenced Documents2.1 ASTM Standards:2D1509 Test Methods for Carbon BlackHeating LossD1799 Practice for Carbon BlackSampling PackagedShipmentsD1900 Practice for Carbon BlackSampling Bulk Ship-mentsD4483 Practice for Evaluating Precision for Test MethodStandards in the Rubber and Carbon Black Manuf
6、acturingIndustries3. Significance and Use3.1 The total sulfur content of a carbon black is useful indetermining whether a material meets a customers specifica-tions, providing data for performing a sulfur material balancearound a process for environmental monitoring and reporting,and in calculations
7、 for reconstructing a rubber compositionfrom analytical data.4. Reagents4.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Ch
8、emical Society,where such specifications are available.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.5. Sampling5.1 Samples of packaged materials shall be taken in accor-d
9、ance with Practice D1799 or Practice D1900.TEST METHOD A HIGH-TEMPERATURECOMBUSTION WITH INFRARED ABSORPTIONDETECTION PROCEDURES6. Summary of Test Method6.1 The specimen is burned in a tube furnace at a minimumoperating temperature of 1350C in a stream of oxygen tooxidize the sulfur. Moisture and pa
10、rticulates are removed fromthe gas by traps filled with anhydrous magnesium perchlorate.The gas stream is passed through a cell in which sulfur dioxideis measured by an infrared (IR) absorption detector. Sulfurdioxide absorbs IR energy at a precise wavelength within theIR spectrum. Energy is absorbe
11、d as the gas passes through thecell body in which the IR energy is being transmitted. Thus, atthe detector, less energy is received. All other IR energy iseliminated from reaching the detector by a precise wavelengthfilter. Thus, the absorption of IR energy can be attributed onlyto sulfur dioxide wh
12、ose concentration is proportional to the1These test methods are under the jurisdiction of ASTM Committee D24 onCarbon Black and are the direct responsibility of Subcommittee D24.66 onEnvironment, Health, and Safety.Current edition approved Jan. 1, 2011. Published June 2011. Originally approvedin 195
13、8. Last previous edition approved in 2010 as D1619 10. DOI: 10.1520/D1619-11.2For 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 ont
14、he ASTM website.3Reagent Chemicals, American Chemical Society Specifications , AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United
15、States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.change in energy at the detector. One cell is used as both areference and a measurem
16、ent chamber. Total sulfur as sulfurdioxide is detected on a continuous basis. This test method isempirical. Therefore, the apparatus must be calibrated by theuse of standard reference materials (SRM).6.2 This test method is for use with commercially availablesulfur analyzers equipped to carry out th
17、e preceding operationsautomatically and must be calibrated using standard referencematerial (carbon black) of known sulfur content based on therange of sulfur in each carbon black specimen analyzed.7. Apparatus7.1 Measurement Apparatusequipped to automaticallycombust the specimen.7.2 Combustion Tube
18、, made of mullite, porcelain, or zircon,approximately 40- to 45-mm inside diameter with a 3-mmthick wall, at least 450-mm long with provisions for routing thegasses produced by combustion through the infrared cell.7.3 Boat Pullerrod of a heat-resistant material with a bentor disk end to insert and r
19、emove boats from the combustiontube.7.4 Gravity Convection Drying Oven, capable of maintain-ing 125 6 5C.8. Reagents8.1 Purity of Reagentssee 4.1.8.2 Magnesium Perchlorate.9. Preparation of Apparatus9.1 Assemble the apparatus according to the manufacturersinstructions. Make a minimum of two determin
20、ations (see10.3) to condition the equipment prior to calibrating thesystem.10. Calibration10.1 Select standards having sulfur values of approximately0.5, 1.0, and 1.5 % sulfur4.10.2 Adjustment of Response of Measurement SystemWeigh out approximately 0.5 g of the 1.0 % sulfur standard.Analyze the spe
21、cimen (see Section 11). Repeat this procedure.Adjust instrument as recommended by the manufacturer untilthe absence of drift is indicated.10.3 Calibration ProcedureWeigh out four specimens ofthe 1.0 % sulfur standard. Follow the calibration procedurerecommended by the manufacturer. Confirm the calib
22、ration byanalyzing the 1.0 % sulfur standard. The value should bewithin the allowable limits of the known value. If not, repeatthe procedure. Then weigh out and analyze two specimens,each of the other calibration standards. Record the results aftereach analysis. Compare the results obtained to the k
23、nownsulfur values of the specimens. They should be within theallowable limits of the known value of the respective speci-men. If not, refer to the manufacturers instructions forchecking linearity of the analyzer.11. Procedure11.1 Sample PreparationDry an adequate sample of thecarbon black for at lea
24、st1hinagravity-convection oven set at125 6 5C, in an open container of suitable dimensions, so thatthe depth of black is no more than 10 mm. Cool to roomtemperature in a desiccator before use.11.2 Stabilize and calibrate the analyzer (see 10.1 through10.3).11.3 Raise the furnace temperature as recom
25、mended by themanufacturer to at least 1350C. Weigh the specimen not toexceed more than 0.5 g of carbon black. Spread the specimenevenly in a combustion boat and use a boat puller to positionthe specimen in the hot zone of the furnace for at least 2 min,or until completely combusted.NOTE 1The analyti
26、cal cycle should begin automatically as soon assulfur is detected.11.4 When the analysis is complete, the instrument shouldindicate the sulfur value. Refer to the manufacturers recom-mended procedure.12. Report12.1 The percent sulfur value is obtained directly from theapparatus.13. Precision and Bia
27、s13.1 These precision statements have been prepared inaccordance with Practice D4483-99. Refer to this practice forterminology and other statistical details.13.2 The precision results in this precision and bias sectiongive an estimate of the precision of this test method with thematerials used in th
28、e particular interlaboratory program de-scribed in Table 1. The precision parameters should not be usedfor acceptance or rejection testing of any group of materialswithout documentation that they are applicable to those par-ticular materials and the specific testing protocols of the testmethod. Any
29、appropriate value may be used from Table 1.13.3 A type 1 inter-laboratory precision program was con-ducted as detailed in Table 1. Both repeatability and reproduc-ibility represent short term (daily) testing conditions. Thetesting was performed using two operators in each laboratoryperforming the te
30、st once on each of two days (total of fourtests). A test result is the value obtained from a singledetermination. Acceptable difference values were not mea-sured. The between operator component of variation is in-cluded in the calculated values for r and R.13.4 The results of the precision calculati
31、ons for this test aregiven in Table 1. The materials are arranged in ascending“mean level” order. The absolute reproducibility is moreindependent of the mean level so the absolute repeatability, r,and reproducibility, R, are the preferred parameters.13.5 RepeatabilityThe pooled absolute repeatabilit
32、y, r, ofthis test has been established as 0.0456 %. Any other value inTable 1 may be used as an estimate of repeatability, asappropriate. The difference between two single test results (ordeterminations) found on identical test material under therepeatability conditions prescribed for this test will
33、 exceed therepeatability on an average of not more than once in 20 casesin the normal and correct operation of the method. Two single4Coal standards have been found to be suitable standards and are usuallyavailable from the instrument manufacturer or may be obtained fromAlpha Productsfor Analysis, 3
34、090 Johnson Road, Stevensville, MI 49127, www.alpha-.D1619 112test results that differ by more than the appropriate value fromTable 1 must be suspected of being from different populationsand some appropriate action taken.NOTE 2Appropriate action may be an investigation of the test methodprocedure or
35、 apparatus for faulty operation or the declaration of asignificant difference in the two materials, samples, etc., which generatedthe two test results.13.6 ReproducibilityThe pooled absolute reproducibility,R, of this test has been established as 0.1931 %. Any othervalue in Table 1 may be used as an
36、 estimate of reproducibility,as appropriate. The difference between two single and inde-pendent test results found by two operators working under theprescribed reproducibility conditions in different laboratorieson identical test material will exceed the reproducibility on anaverage of not more than
37、 once in 20 cases in the normal andcorrect operation of the method. Two single test resultsproduced in different laboratories that differ by more than theappropriate value from Table 1 must be suspected of beingfrom different populations and some appropriate investigativeor technical/commercial acti
38、on taken.13.7 BiasIn test method terminology, bias is the differ-ence between an average test value and the reference (true) testproperty value. Reference values do not exist for this testmethod since the value or level of the test property isexclusively defined by the test method. Bias, therefore,
39、cannotbe determined.TEST METHOD B X-RAY FLUORESCENCE14. Summary of Test Method14.1 X-ray fluorescence may be used to determine sulfur incarbon black. Each element has an unique energy response(fluorescence) when exposed to x-ray energy that can be usedto identify the element. An x-ray source excites
40、 the sulfuratoms in the sample material. The instrument detects theexcited sulfur atoms and produces a numeric value.15. Apparatus15.1 X-ray Fluorescence Instrument, designed specificallyfor the test of trace amounts of sulfur, with x-ray source(radioisotope or x-ray tube), detection, and numeric di
41、splay.X-ray fluorescence instruments are either wavelength disper-sive or energy dispersive. Energy dispersive instruments havea lower detectable limit of 15 ppm while wavelength dispersiveinstruments have a lower detectable limit of less than 1 ppm.Since the sulfur in oil furnace type carbon blacks
42、 is usuallypresent in percent levels, either instrument type is suitable.15.2 Gravity Convection Drying Oven, capable of maintain-ing 125 6 5C.15.3 Desiccator.16. Calibration16.1 The ability of the instrument to detect an elementsenergy signature is strongly influenced by the sample matrix.Therefore
43、, the materials used to calibrate the instrument needto be as similar as possible to the unknown sample to be tested.If the unknown sample is a liquid, slurry, powder, or solid, thecalibration materials need to be a similar liquid, slurry, powder,or solid. The preferred calibration materials will be
44、 made by (orcome from) the same process as the unknown sample.16.2 X-ray fluorescence is not a primary test, but work byASTM International Committee D24 on Carbon Black hasshown that only carbon black with suitable levels of sulfurnaturally occurring (that is, coming from the carbon blackmanufacturi
45、ng process.) can be used to properly calibrate thetechnique. It has been determined that a standard materialcannot be made by adding elemental sulfur to carbon black.16.3 Calibrate the instrument according to the manufactur-ers instructions.16.4 Four carbon black standards have been identified5andth
46、eir respective sulfur level determined by combustion meth-ods following Test Methods D1619 Method A calibrationprocedures. They are:Material % Sulfur StandardDeviationStandard A 0.00 0.00Standard B 1.54 0.05Standard C 1.93 0.06Standard D 0.82 0.035Sulfur-in-carbon black standards A-D are available f
47、rom Laboratory Standardsand Technologies, Inc., 227 Somerset Street, Borger, TX, 79007, www.carbonstan-.TABLE 1 Precision Parameters for Test Methods D1619, Method A, (Type 1 Precision)Units PercentMaterial PeriodNumber ofLaboratoriesMean Level Sr r (r) SR R (R)SRB C6 (N326) March 2003 4 0.8056 0.01
48、50 0.0426 5.28 0.0966 0.2734 33.94HS Tread September 2003 7 1.0779 0.0123 0.0349 3.24 0.0174 0.0494 4.58SRB8E (N660) September 2008 9 1.1085 0.0067 0.0188 1.70 0.1182 0.3344 30.17SRB8B (N134) June 2009 13 1.1738 0.0117 0.0330 2.81 0.0600 0.1698 14.46SRB8A (N326) March 2008 12 1.1945 0.0179 0.0507 4.
49、25 0.0409 0.1157 9.69SRB A6 (N134) September 2004 9 1.2556 0.0103 0.0291 2.32 0.0400 0.1133 9.03N234 September 2007 10 1.3094 0.0210 0.0595 4.54 0.0616 0.1743 13.31N299 March 2006 10 1.5716 0.0113 0.0320 2.04 0.0414 0.1173 7.46N772 March 2005 9 1.8256 0.0176 0.0499 2.74 0.1026 0.2903 15.90LS Carcass March 2004 6 1.8565 0.0202 0.0573 3.09 0.0265 0.0751 4.04SRB8D (LS Carcass) March 2009 12 1.8988 0.0254 0.0718 3.78 0.0862 0.2439 12.84SRB D7 (LS Carcass) September 2006 12 1.9172 0.0142 0.0401 2.09 0.0348 0.0986 5.14Average 1.4163Pooled Va
