1、Designation: D1619 11D1619 16Standard 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 pare
2、ntheses 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 U.S. Department of Defense.1. Scope1.1 These test methods cover the determination of the sulfur conten
3、t of carbon black. The following test methods are included: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 as standard. No other units of measurement a
4、re included in this standard.1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations p
5、rior to use.2. Referenced Documents2.1 ASTM Standards:2D1509 Test Methods for Carbon BlackHeating LossD1799 Practice for Carbon BlackSampling Packaged ShipmentsD1900 Practice for Carbon BlackSampling Bulk ShipmentsD4483 Practice for Evaluating Precision for Test Method Standards in the Rubber and Ca
6、rbon Black Manufacturing Industries3. Significance and Use3.1 The total sulfur content of a carbon black is useful in determining whether a material meets a customers specifications,providing data for performing a sulfur material balance around a process for environmental monitoring and reporting, a
7、nd incalculations for reconstructing a rubber composition from analytical data.4. Reagents4.1 Purity of ReagentsReagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that allreagents shall conform to the specifications of the Committee on Analytical Reagents
8、of the American Chemical Society, wheresuch specifications are available.3 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently highpurity to permit its use without lessening the accuracy of the determination.5. Sampling5.1 Samples of packaged materials shal
9、l be taken in accordance with Practice D1799 or Practice D1900.1 These test methods are under the jurisdiction of ASTM Committee D24 on Carbon Black and are the direct responsibility of Subcommittee D24.66 on Environment,Health, and Safety.Current edition approved Jan. 1, 2011Jan. 1, 2016. Published
10、 June 2011January 2016. Originally approved in 1958. Last previous edition approved in 20102011 asD1619 10.D1619 11. DOI: 10.1520/D1619-11.10.1520/D1619-16.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM
11、 Standardsvolume information, refer to the standards Document Summary page on the ASTM website.3 Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed bythe American Chemical Society, see Analar S
12、tandards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, MD.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of w
13、hat changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered t
14、he official document.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1TEST METHOD A HIGH-TEMPERATURE COMBUSTION WITH INFRARED ABSORPTION DETECTIONPROCEDURES6. Summary of Test Method6.1 The specimen is burned in a tube furnace at a mini
15、mum operating temperature of 1350C in a stream of oxygen to oxidizethe sulfur. Moisture and particulates are removed from the gas by traps filled with anhydrous magnesium perchlorate. The gasstream is passed through a cell in which sulfur dioxide is measured by an infrared (IR) absorption detector.
16、Sulfur dioxide absorbsIR energy at a precise wavelength within the IR spectrum. Energy is absorbed as the gas passes through the cell body in whichthe IR energy is being transmitted. Thus, at the detector, less energy is received. All other IR energy is eliminated from reachingthe detector by a prec
17、ise wavelength filter. Thus, the absorption of IR energy can be attributed only to sulfur dioxide whoseconcentration is proportional to the change in energy at the detector. One cell is used as both a reference and a measurementchamber. Total sulfur as sulfur dioxide is detected on a continuous basi
18、s. This test method is empirical. Therefore, the apparatusmust be calibrated by the use of standard reference materials (SRM).6.2 This test method is for use with commercially available sulfur analyzers equipped to carry out the preceding operationsautomatically and must be calibrated using standard
19、 reference material (carbon black) of known sulfur content based on the rangeof sulfur in each carbon black specimen analyzed.7. Apparatus7.1 Measurement Apparatusequipped to automatically combust the specimen.7.2 Combustion Tube, made of mullite, porcelain, or zircon, approximately 40- to 45-mm ins
20、ide diameter with a 3-mm thickwall, at least 450-mm long with provisions for routing the gasses produced by combustion through the infrared cell.7.3 Boat Pullerrod of a heat-resistant material with a bent or disk end to insert and remove boats from the combustion tube.7.4 Gravity Convection Drying O
21、ven, capable of maintaining 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 manufacturers instructions. Make a minimum of two determinations (see 10.3) tocondition the equipment prior to calibrating th
22、e system.10. Calibration10.1 Select standards having sulfur values of approximately 0.5, 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 thespecimen (see Section 11). Repeat this procedure.Adjust instrument as
23、 recommended by the manufacturer until the absence of driftis indicated.10.3 Calibration ProcedureWeigh out four specimens of the 1.0 % sulfur standard. Follow the calibration procedurerecommended by the manufacturer. Confirm the calibration by analyzing the 1.0 % sulfur standard. The value should b
24、e within theallowable limits of the known value. If not, repeat the procedure. Then weigh out and analyze two specimens, each of the othercalibration standards. Record the results after each analysis. Compare the results obtained to the known sulfur values of thespecimens. They should be within the
25、allowable limits of the known value of the respective specimen. If not, refer to themanufacturers instructions for checking linearity of the analyzer.11. Procedure11.1 Sample PreparationDry an adequate sample of the carbon black for at least 1 h in a gravity-convection oven set at 1256 5C, in an ope
26、n container of suitable dimensions, so that the depth of black is no more than 10 mm. Cool to room temperaturein a desiccator before use.11.2 Stabilize and calibrate the analyzer (see 10.1 through 10.3).11.3 Raise the furnace temperature as recommended by the manufacturer to at least 1350C. Weigh th
27、e specimen not to exceedmore than 0.5 g of carbon black. Spread the specimen evenly in a combustion boat and use a boat puller to position the specimenin the hot zone of the furnace for at least 2 min, or until completely combusted.4 Coal standards have been found to be suitable standards and are us
28、ually available from the instrument manufacturer or may be obtained fromAlpha Products forAnalysis,3090 Johnson Road, Stevensville, MI 49127, www.alpha-.D1619 162NOTE 1The analytical cycle should begin automatically as soon as sulfur is detected.11.4 When the analysis is complete, the instrument sho
29、uld indicate the sulfur value. Refer to the manufacturers recommendedprocedure.12. Report12.1 The percent sulfur value is obtained directly from the apparatus.12.2 Report results to the nearest 0.01 %.13. Precision and Bias13.1 These precision statements have been prepared in accordance with Practic
30、e D4483-99. Refer to this practice forterminology and other statistical details.13.2 The precision results in this precision and bias section give an estimate of the precision of this test method with thematerials used in the particular interlaboratory program described in Table 1. The precision par
31、ameters should not be used foracceptance or rejection testing of any group of materials without documentation that they are applicable to those particularmaterials and the specific testing protocols of the test method. Any appropriate value may be used from Table 1.13.3 A type 1 inter-laboratory pre
32、cision program was conducted as detailed in Table 1. Both repeatability and reproducibilityrepresent short term (daily) testing conditions. The testing was performed using two operators in each laboratory performing thetest once on each of two days (total of four tests). A test result is the value o
33、btained from a single determination. Acceptabledifference values were not measured. The between operator component of variation is included in the calculated values for r andR.13.4 The results of the precision calculations for this test are given in Table 1. The materials are arranged in ascending “
34、meanlevel” order. The absolute reproducibility is more independent of the mean level so the absolute repeatability, r, and reproducibility,R, are the preferred parameters.13.5 RepeatabilityThe pooled absolute repeatability, r, of this test has been established as 0.0456 %.Any other value in Table1 m
35、ay be used as an estimate of repeatability, as appropriate. The difference between two single test results (or determinations)found on identical test material under the repeatability conditions prescribed for this test will exceed the repeatability on an averageof not more than once in 20 cases in t
36、he normal and correct operation of the method. Two single test results that differ by morethan the appropriate value from Table 1 must be suspected of being from different populations and some appropriate action taken.NOTE 2Appropriate action may be an investigation of the test method procedure or a
37、pparatus for faulty operation or the declaration of a significantdifference in the two materials, samples, etc., which generated the two test results.13.6 ReproducibilityThe pooled absolute reproducibility, R, of this test has been established as 0.1931 %. Any other value inTable 1 may be used as an
38、 estimate of reproducibility, as appropriate. The difference between two single and independent testresults found by two operators working under the prescribed reproducibility conditions in different laboratories on identical testmaterial will exceed the reproducibility on an average of not more tha
39、n once in 20 cases in the normal and correct operation ofthe method. Two single test results produced in different laboratories that differ by more than the appropriate value from Table 1must be suspected of being from different populations and some appropriate investigative or technical/commercial
40、action taken.13.7 BiasIn test method terminology, bias is the difference between an average test value and the reference (true) test propertyvalue. Reference values do not exist for this test method since the value or level of the test property is exclusively defined by thetest method. Bias, therefo
41、re, cannot be determined.TABLE 1 Precision Parameters for Test Methods D1619, Method A, (Type 1 Precision)Units PercentMaterial Period Number ofLaboratories Mean Level Sr r (r) SR R (R)SRB C6 (N326) March 2003 4 0.8056 0.0150 0.0426 5.28 0.0966 0.2734 33.94HS Tread September 2003 7 1.0779 0.0123 0.0
42、349 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 4.25 0.0409 0.1157 9.69SRB A6 (N134) September 2004 9 1.2556 0.0103 0.0291 2.32
43、 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)
44、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 Values 0.0161 0.0456 3.22 0.0682 0.1931 13.63D1619 163TEST METHOD B X-RAY FLUORESCENCE14. Summary of Test Method14.1 X-ray fluorescence ma
45、y be used to determine sulfur in carbon black. Each element has an unique energy response(fluorescence) when exposed to x-ray energy that can be used to identify the element. An x-ray source excites the sulfur atoms inthe sample material. The instrument detects the excited sulfur atoms and produces
46、a numeric value.15. Apparatus15.1 X-ray Fluorescence Instrument, designed specifically for the test of trace amounts of sulfur, with x-ray source (radioisotopeor x-ray tube), detection, and numeric display. X-ray fluorescence instruments are either wavelength dispersive or energydispersive. Energy d
47、ispersive instruments have a lower detectable limit of 15 ppm while wavelength dispersive instruments havea lower detectable limit of less than 1 ppm. Since the sulfur in oil furnace type carbon blacks is usually present in percent levels,either instrument type is suitable.15.2 Gravity Convection Dr
48、ying Oven, capable of maintaining 125 6 5C.15.3 Desiccator.16. Calibration16.1 The ability of the instrument to detect an elements energy signature is strongly influenced by the sample matrix.Therefore,the materials used to calibrate the instrument need to be as similar as possible to the unknown sa
49、mple to be tested. If the unknownsample is a liquid, slurry, powder, or solid, the calibration materials need to be a similar liquid, slurry, powder, or solid. Thepreferred calibration materials will be made by (or come from) the same process as the unknown sample.16.2 X-ray fluorescence is not a primary test, but work by ASTM International Committee D24 on Carbon Black has shownthat only carbon black with suitable levels of sulfur naturally occurring (that is, coming from the carbon black manufacturingprocess.) can be used to properly ca
