1、Designation: D1519 95 (Reapproved 2009)1Standard Test Methods forRubber ChemicalsDetermination of Melting Range1This standard is issued under the fixed designation D1519; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of
2、last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1NOTEAdded research report information to Sections 9 and 14 editorially in November 2010.1. Scope1.1 These test methods cover the
3、determination of themelting range of commercial rubber processing chemicalseither by use of capillary melting point tubes or by differentialscanning calorimetry (DSC).1.2 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.3 This
4、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. Referenced Documents2
5、.1 ASTM Standards:2D4483 Practice for Evaluating Precision for Test MethodStandards in the Rubber and Carbon Black ManufacturingIndustriesE1 Specification for ASTM Liquid-in-Glass ThermometersE324 Test Method for Relative Initial and Final MeltingPoints and the Melting Range of Organic Chemicals3E47
6、3 Terminology Relating to Thermal Analysis and Rhe-ologyE967 Test Method for Temperature Calibration of Differen-tial Scanning Calorimeters and Differential Thermal Ana-lyzers3. Terminology3.1 Definition:3.1.1 differential scanning calorimetrysee TerminologyE473.4. Significance and Use4.1 This test
7、method may be used for research and devel-opment. It also may be used for quality assurance, provided astandard has been agreed upon between a producer and a user.4.2 For identification purposes, melting range should besupplemented by measurements of a more specific physical andchemical property.4.3
8、 This test method is not recommended for rubber chemi-cals that decompose at their melting ranges.4.4 The melting range as determined by Test MethodACapillary Tube Melting Range is not recommended as acriterion of purity of a rubber chemical.5. Sampling5.1 Grind a representative sample of the chemic
9、al to betested with a mortar and pestle, if necessary, to pass completelythrough a 150-m (No. 100) sieve. Use the sample withoutfurther treatment.TEST METHOD ACAPILLARY TUBE MELTINGRANGE6. Apparatus6.1 Melting ApparatusAny electric melting apparatus thatsatisfies the requirements of Test Method E324
10、 may be used orany suitable manually heated oil bath such as Hershberg tube.6.2 Capillary TubeThe capillary tube to contain thesample shall be a glass tube approximately 150 mm long and1.2 to 1.4 mm in internal diameter with walls 0.2 to 0.3 mmthick and closed at one end.6.3 ThermometerThe thermomet
11、er shall be of the partialimmersion type and of suitable range selected from Specifica-tion E1, or of an equivalent range as specified by the ChemicalManufacturers Association. It shall be divided into subdivi-sions of 0.5C (1F) or less. Corrections for the thermometershall be determined by calibrat
12、ion against a thermometercertified by National Institute of Standards and Technology.1These test methods are under the jurisdiction of ASTM Committee D11 onRubber and is the direct responsibility of Subcommittee D11.11 on ChemicalAnalysis.Current edition approved July 1, 2009. Published September 20
13、09. Originallyapproved in 1995. Last previous edition approved in 2004 as D1519 95 (2004)1.DOI: 10.1520/D1519-95R09E01.2For 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
14、to the standards Document Summary page onthe ASTM website.3Withdrawn. The last approved version of this historical standard is referencedon www.astm.org.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.6.4 SieveA150-m (No. 100) sieve
15、for screening thesample shall be provided.7. Procedure7.1 Select the thermometer of the proper range and supportit so that it is immersed to the immersion mark in the liquid ofthe bath.7.2 Charge the capillary glass tube with sufficient powder toform a column in the bottom of the tube about 3 to 6-m
16、m highwhen packed down as closely as possible by moderate tappingon a solid surface.7.3 Heat the bath until a temperature approximately 25Cbelow the expected melting range is reached. Then regulate therate of rise so that it averages about 3C/min for the rest of thedetermination except that the rate
17、 of rise is 1 6 0.2C/minduring the actual melting of the sample. When the temperaturehas risen to about 10C below the expected melting range,insert the capillary in the bath and adjust the height of the tubeso that the material in the capillary is beside the center of thethermometer bulb. The capill
18、ary tube is not placed in the bathpreviously, since many materials undergo decomposition uponprolonged heating. Major adjustments of the heat sourceshould be avoided during the actual melting range.7.4 Record the melting range as the temperature rangebetween which liquefaction first becomes evident
19、and thetemperature at which no further visual change is observed inthe mass.NOTE 1The initial melting temperature is the temperature at whichthe first actual formation of liquid occurs, either as a minute drop or as afilm. It is not a preliminary contraction, sintering, or darkening. It occurswell b
20、efore the formation of meniscus. The liquefaction may occur at thetop, bottom, or sides of the sample in the capillary, as well as the rear.When the latter occurs, the point may be missed, unless care is taken towatch the rear of the tube; a mirror is a convenient aid for this purpose.NOTE 2The fina
21、l melting temperature is the temperature at which nofurther liquefaction is observed.8. Report8.1 Report the results to the nearest division on the ther-mometer, after applying necessary calibration corrections.9. Precision and Bias49.1 This precision and bias section has been prepared inaccordance
22、with Practice D4483. Refer to this practice forterminology and other statistical details.9.2 The results in this precision and bias section give anestimate of the precision of the test method with the materialsused in the particular interlaboratory program as described in9.3. The precision parameter
23、s should not be used foracceptance/rejection testing of any group of materials withoutdocumentation that they are applicable to those particularmaterials and the specific testing protocols that include this testmethod.9.3 A Type 1 interlaboratory precision program was con-ducted. Repeatability is sh
24、ort term and reproducibility is shortterm. Seven laboratories participated and three materials wereused.Atest result is the value obtained from one determination.Two determinations were run on each material, and thisprotocol was repeated on each of three days. The analysis forprecision followed the
25、general procedure as set forth in Annex5 of Practice D4483. Each cell of Practice D4483 Table 1 basicdata format contained six values (three test days, two testresults each day). The estimates for the repeatability param-eters therefore contain two undifferentiated sources of varia-tion, that is, re
26、plicates within days and between days. The finalprecision parameters are given in Table 1 of this test method.9.4 The results of the precision calculations for the initialmelting point and the final melting point are arranged inascending “mean level” order, and given in Table 1.9.5 RepeatabilityThe
27、pooled repeatability, r, of this testmethod has been established as 1.58C, as given in Table 1.Two single test results obtained under normal test methodprocedures that differ by more than 1.58C must be consideredas suspect, that is, having been derived from different ornonidentical sample population
28、s. If this is the case, appropriatecorrective action should be taken.9.6 ReproducibilityThe pooled reproducibility, R, of thistest method has been established as 3.40C, as given in Table1. Two single test results obtained under normal test methodprocedures that differ by more than 3.40C must be cons
29、ideredas suspect, that is, having been derived from different ornonidentical sample populations. If this is the case, appropriatecorrective action should be taken.9.7 BiasIn test method terminology, bias is the differencebetween an average test value and the reference (or true) testproperty value. R
30、eference values do not exist for this testmethod since the value of the melting point is exclusivelydefined by the test method. Bias, therefore, cannot be deter-mined.TEST METHOD BDIFFERENTIAL SCANNINGCALORIMETRY10. Apparatus10.1 Differential Scanning Calorimeter, capable of heatinga test specimen a
31、nd a reference material at a controlled rate and4Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR:D11-1070.TABLE 1 ASTM Test Method PrecisionType 1: Test MethodD1519 Capillary Melting RangeNOTE 1This is short-term precision (days)
32、.NOTE 2These are the same chemicals used for the DSC.MaterialMeanLevel,CWithin LaboratoriesABetween LaboratoriesASr r (r) SR R (R)Initial A 47.3 0.681 1.91 4.02 1.07 3.00 6.34Initial B 98.8 0.491 1.38 1.39 1.26 3.52 3.57Initial C 176.4 0.671 1.88 1.07 1.25 3.49 1.98Final A 49.4 0.376 1.05 2.13 0.55
33、1.53 3.10Final B 101.4 0.426 1.19 1.18 1.43 3.99 3.94Final C 179.7 0.663 1.86 1.03 1.50 4.19 2.33Pooled 0.565 1.58 1.80 1.22 3.40 3.54ASr = within laboratory, standard deviation.r = repeatability in measurement units.(r) = repeatability (in percent).SR = between laboratory, standard deviation.R = re
34、producibility in measurement units.(R) = reproducibility (in percent).D1519 95 (2009)12of automatically recording the differential heat flow betweenthe samples and the reference material to the required sensi-tivity and precision.10.2 Specimen Pans, composed of aluminum or other metalof high thermal
35、 conductivity. The specimen pans must not reactwith the sample and must not melt under the temperatures ofthe test.10.3 Nitrogen, or other inert purge gas supply.10.4 Analytical Balance, with a capacity greater than 20 mg,capable of weighing to the nearest 0.01 mg.11. Calibration11.1 Using the same
36、heating rate, purge gas, and flow rate tobe used for the specimen, calibrate the temperature axis of theinstrument using the procedure in Test Method E967.12. Procedure12.1 Weigh about 10 to 20 mg of the sieved specimen intoa DSC specimen pan. Cover and seal the specimen pan andplace into the DSC sa
37、mple holder.12.2 Place an empty sealed pan into the reference sampleholder.12.3 Close the sample chamber and ensure that the purgegas flow matches that used for the calibration.12.4 Heat the specimen rapidly to 50C below the meltingtemperature and allow to equilibrate.12.5 Heat the specimen through
38、the endotherm until base-line is re-established above the melting endotherm. Heatingrate must be the same as that used for the calibration of theinstrument. Ten degrees Celsius is a commonly used rate.Record the accompanying thermal curve.12.6 Reweigh the specimen after completion of scanning,and di
39、scard. Report any mass loss observed.NOTE 3Mass loss is only one indication of suspected sample degra-dation or decomposition. Other decomposition indicators, such as colorchange, may be noted if the specimen pan is opened.12.7 From the resultant curve, measure the temperatures forthe desired points
40、 on the curve, Te, Tp(see Fig. 1) to therequired precision,where:Te= extrapolated onset temperature for fusion, C, andTp= melting peak temperature, C.13. Report13.1 Report Teand Tp, as well as heating rate used.13.2 Any side reaction (for example, thermal degradation oroxidation) also should be repo
41、rted and the reaction identified,if possible.14. Precision and Bias414.1 This precision and bias section has been prepared inaccordance with Practice D4483. Refer to this practice forterminology and other statistical details.14.2 The results in this precision and bias section give anestimate of the
42、precision of the test method with the materialsused in the particular interlaboratory program as described in14.3. The precision parameters should not be used foracceptance/rejection testing of any group of materials withoutdocumentation that they are applicable to those particularmaterials and the
43、specific testing protocols that include this testmethod.14.3 A Type 1 interlaboratory precision program was con-ducted. Repeatability is short term and reproducibility is shortterm. Eleven laboratories participated and three materials wereused.Atest result is the value obtained from one determinatio
44、n.Two determinations were run on each material, and thisprotocol was repeated on each of three days. The analysis forprecision followed the general procedure as set forth in Annex5 of Practice D4483. Each cell of Practice D4483 Table 1 basicFIG. 1 Sample Melting EndothermD1519 95 (2009)13data format
45、 contained six values (three test days, two testresults each day). The estimates for the repeatability param-eters therefore contain two undifferentiated sources of varia-tion, that is, replicates within days and between days. The finalprecision parameters are given in Table 2 of this test method.14
46、.4 The results of the precision calculations for the onsetand the peak are arranged in ascending “mean level” order, andgiven in Table 2.14.5 RepeatabilityThe pooled repeatability, r, of this testmethod has been established as 1.40C, as given in Table 2.Two single test results obtained under normal
47、test methodprocedures that differ by more than 1.40C must be consideredas suspect, that is, having been derived from different ornonidentical sample populations. If this is the case, appropriatecorrective action should be taken.14.6 ReproducibilityThe pooled reproducibility, R, of thistest method ha
48、s been established as 3.75C, as given in Table2. Two single test results obtained under normal test methodprocedures that differ by more than 3.75C must be consideredas suspect, that is, having been derived from different ornonidentical sample populations. If this is the case, appropriatecorrective
49、action should be taken.14.7 BiasIn test method terminology, bias is the differ-ence between an average test value and the reference (or true)test property value. Reference values do not exist for this testmethod since the value of the melting point is exclusivelydefined by the test method. Bias, therefore, cannot be deter-mined.15. Keywords15.1 capillary; differential scanning calorimetry (DSC);melting range; rubber chemicalsASTM International takes no position respecting the validity of any patent rights asserted in connection with a
