This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: D1519 − 95 (Reapproved 2023)

Standard Test Methods for

Rubber Chemicals—Determination of Melting Range1
This standard is issued under the fixed designation D1519; 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 3. Terminology
1.1 These test methods cover the determination of the 3.1 Definitions:
melting range of commercial rubber processing chemicals 3.1.1 differential scanning calorimetry—see Terminology
either by use of capillary melting point tubes or by differential E473.
scanning calorimetry (DSC).
4. Significance and Use
1.2 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 4.1 This test method may be used for research and devel-
standard. opment. It also may be used for quality assurance, provided a
standard has been agreed upon between a producer and a user.
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the 4.2 For identification purposes, melting range should be
responsibility of the user of this standard to establish appro- supplemented by measurements of a more specific physical and
priate safety, health, and environmental practices and deter- chemical property.
mine the applicability of regulatory limitations prior to use. 4.3 This test method is not recommended for rubber chemi-
1.4 This international standard was developed in accor- cals that decompose at their melting ranges.
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the 4.4 The melting range as determined by Test Method
Development of International Standards, Guides and Recom- A—Capillary Tube Melting Range is not recommended as a
mendations issued by the World Trade Organization Technical criterion of purity of a rubber chemical.
Barriers to Trade (TBT) Committee.
5. Sampling
2. Referenced Documents 5.1 Grind a representative sample of the chemical to be
2 tested with a mortar and pestle, if necessary, to pass completely
2.1 ASTM Standards:
through a 150-µm (No. 100) sieve. Use the sample without
D4483 Practice for Evaluating Precision for Test Method
further treatment.
Standards in the Rubber and Carbon Black Manufacturing
Industries TEST METHOD A—CAPILLARY TUBE MELTING
E1 Specification for ASTM Liquid-in-Glass Thermometers RANGE
E324 Test Method for Relative Initial and Final Melting
Points and the Melting Range of Organic Chemicals 6. Apparatus
E473 Terminology Relating to Thermal Analysis and Rhe- 6.1 Melting Apparatus—Any electric melting apparatus that
ology satisfies the requirements of Test Method E324 may be used or
E967 Test Method for Temperature Calibration of Differen- any suitable manually heated oil bath such as Hershberg tube.
tial Scanning Calorimeters and Differential Thermal Ana-
lyzers 6.2 Capillary Tube—The capillary tube to contain the
sample shall be a glass tube approximately 150 mm long and
1.2 mm to 1.4 mm in internal diameter with walls 0.2 mm to
1
These test methods are under the jurisdiction of ASTM Committee D11 on 0.3 mm thick and closed at one end.
Rubber and Rubber-like Materials and is the direct responsibility of Subcommittee 6.3 Thermometer—The thermometer shall be of the partial
D11.11 on Chemical Analysis.
Current edition approved Sept. 1, 2023. Published September 2023. Originally immersion type and of suitable range selected from Specifica-
approved in 1995. Last previous edition approved in 2019 as D1519 – 95 (2019). tion E1, or of an equivalent range as specified by the Chemical
DOI: 10.1520/D1519-95R23.
2
Manufacturers Association. It shall be divided into subdivi-
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
sions of 0.5 °C (1 °F) or less. Corrections for the thermometer
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on shall be determined by calibration against a thermometer
the ASTM website. certified by National Institute of Standards and Technology.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

1
 D1519 − 95 (2023)
6.4 Sieve—A 150-µm (No. 100) sieve for screening the 9.3 A Type 1 interlaboratory precision program was con-
sample shall be provided. ducted. Repeatability is short term and reproducibility is short
term. Seven laboratories participated and three materials were
7. Procedure used. A test result is the value obtained from one determination.
7.1 Select the thermometer of the proper range and support Two determinations were run on each material, and this
it so that it is immersed to the immersion mark in the liquid of protocol was repeated on each of three days. The analysis for
the bath. precision followed the general procedure as set forth in Annex
5 of Practice D4483. Each cell of Practice D4483 Table 1 basic
7.2 Charge the capillary glass tube with sufficient powder to data format contained six values (three test days, two test
form a column in the bottom of the tube about 3 mm to 6 mm results each day). The estimates for the repeatability param-
high when packed down as closely as possible by moderate eters therefore contain two undifferentiated sources of
tapping on a solid surface. variation, that is, replicates within days and between days. The
7.3 Heat the bath until a temperature approximately 25 °C final precision parameters are given in Table 1 of this test
below the expected melting range is reached. Then regulate the method.
rate of rise so that it averages about 3 °C ⁄min for the rest of the 9.4 The results of the precision calculations for the initial
determination except that the rate of rise is 1 °C ⁄min 6 melting point and the final melting point are arranged in
0.2 °C ⁄min during the actual melting of the sample. When the ascending “mean level” order, and given in Table 1.
temperature has risen to about 10 °C below the expected
melting range, insert the capillary in the bath and adjust the 9.5 Repeatability—The pooled repeatability, r, of this test
height of the tube so that the material in the capillary is beside method has been established as 1.58 °C, as given in Table 1.
the center of the thermometer bulb. The capillary tube is not Two single test results obtained under normal test method
placed in the bath previously, since many materials undergo procedures that differ by more than 1.58 °C must be considered
decomposition upon prolonged heating. Major adjustments of as suspect, that is, having been derived from different or
the heat source should be avoided during the actual melting nonidentical sample populations. If this is the case, appropriate
range. corrective action should be taken.
7.4 Record the melting range as the temperature range 9.6 Reproducibility—The pooled reproducibility, R, of this
between which liquefaction first becomes evident and the test method has been established as 3.40 °C, as given in Table
temperature at which no further visual change is observed in 1. Two single test results obtained under normal test method
the mass. procedures that differ by more than 3.40 °C must be considered
as suspect, that is, having been derived from different or
NOTE 1—The initial melting temperature is the temperature at which the nonidentical sample populations. If this is the case, appropriate
first actual formation of liquid occurs, either as a minute drop or as a film.
It is not a preliminary contraction, sintering, or darkening. It occurs well corrective action should be taken.
before the formation of meniscus. The liquefaction may occur at the top, 9.7 Bias—In test method terminology, bias is the difference
bottom, or sides of the sample in the capillary, as well as the rear. When between an average test value and the reference (or true) test
the latter occurs, the point may be missed, unless care is taken to watch the
rear of the tube; a mirror is a convenient aid for this purpose. property value. Reference values do not exist for this test
NOTE 2—The final melting temperature is the temperature at which no method since the value of the melting point is exclusively
further liquefaction is observed. defined by the test method. Bias, therefore, cannot be deter-
mined.
8. Report
8.1 Report the results to the nearest division on the
thermometer, after applying necessary calibration corrections. TABLE 1 ASTM Test Method Precision—Type 1: Test Method
D1519 Capillary Melting Range
9. Precision and Bias3
NOTE 1—This is short-term precision (days).
9.1 This precision and bias section has been prepared in
NOTE 2—These are the same chemicals used for the DSC.
accordance with Practice D4483. Refer to this practice for
Mean Within LaboratoriesA Between LaboratoriesA
terminology and other statistical details. Material Level,
°C Sr r (r) SR R (R)
9.2 The results in this precision and bias section give an
estimate of the precision of the test method with the materials Initial A 47.3 0.681 1.91 4.02 1.07 3.00 6.34
Initial B 98.8 0.491 1.38 1.39 1.26 3.52 3.57
used in the particular interlaboratory program as described in Initial C 176.4 0.671 1.88 1.07 1.25 3.49 1.98
9.3. The precision parameters should not be used for Final A 49.4 0.376 1.05 2.13 0.55 1.53 3.10
acceptance/rejection testing of any group of materials without Final B 101.4 0.426 1.19 1.18 1.43 3.99 3.94
Final C 179.7 0.663 1.86 1.03 1.50 4.19 2.33
documentation that they are applicable to those particular Pooled 0.565 1.58 1.80 1.22 3.40 3.54
materials and the specific testing protocols that include this test A
Sr = within laboratory, standard deviation.
method. r = repeatability in measurement units.
(r) = repeatability (in percent).
SR = between laboratory, standard deviation.
R = reproducibility in measurement units.
3
Supporting data have been filed at ASTM International Headquarters and may (R) = reproducibility (in percent).
be obtained by requesting Research Report RR:D11-1070.

2
 D1519 − 95 (2023)
TEST METHOD B—DIFFERENTIAL SCANNING 12.5 Heat the specimen through the endotherm until base-
CALORIMETRY line is re-established above the melting endotherm. Heating
rate must be the same as that used for the calibration of the
10. Apparatus instrument. Ten degrees Celsius is a commonly used rate.
10.1 Differential Scanning Calorimeter, capable of heating a Record the accompanying thermal curve.
test specimen and a reference material at a controlled rate and 12.6 Reweigh the specimen after completion of scanning,
of automatically recording the differential heat flow between and discard. Report any mass loss observed.
the samples and the reference material to the required sensi-
tivity and precision. NOTE 3—Mass loss is only one indication of suspected sample
degradation or decomposition. Other decomposition indicators, such as
10.2 Specimen Pans, composed of aluminum or other metal color change, may be noted if the specimen pan is opened.
of high thermal conductivity. The specimen pans must not react 12.7 From the resultant curve, measure the temperatures for
with the sample and must not melt under the temperatures of the desired points on the curve, Te, Tp (see Fig. 1) to the
the test. required precision,
10.3 Nitrogen, or other inert purge gas supply. where:
10.4 Analytical Balance, with a capacity greater than 20 mg, Te = extrapolated onset temperature for fusion, °C, and
capable of weighing to the nearest 0.01 mg. Tp = melting peak temperature, °C.
11. Calibration 13. Report
11.1 Using the same heating rate, purge gas, and flow rate to 13.1 Report Te and Tp, as well as heating rate used.
be used for the specimen, calibrate the temperature axis of the
instrument using the procedure in Test Method E967. 13.2 Any side reaction (for example, thermal degradation or
oxidation) also should be reported and the reaction identified,
12. Procedure if possible.
12.1 Weigh about 10 mg to 20 mg of the sieved specimen 14. Precision and Bias3
into a DSC specimen pan. Cover and seal the specimen pan and
place into the DSC sample holder. 14.1 This precision and bias section has been prepared in
accordance with Practice D4483. Refer to this practice for
12.2 Place an empty sealed pan into the reference sample terminology and other statistical details.
holder.
14.2 The results in this precision and bias section give an
12.3 Close the sample chamber and ensure that the purge estimate of the precision of the test method with the materials
gas flow matches that used for the calibration. used in the particular interlaboratory program as described in
12.4 Heat the specimen rapidly to 50 °C below the melting 14.3. The precision parameters should not be used for
temperature and allow to equilibrate. acceptance/rejection testing of any group of materials without

FIG. 1 Sample Melting Endotherm

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 D1519 − 95 (2023)
documentation that they are applicable to those particular TABLE 2 ASTM Test Method Precision—Type 1: Test Method
materials and the specific testing protocols that include this test D1519 DSC
method. NOTE 1—This is short-term precision (days).
14.3 A Type 1 interlaboratory precision program was con- NOTE 2—These are the same chemicals used for the DSC.
ducted. Repeatability is short term and reproducibility is short Mean Within LaboratoriesA Between LaboratoriesA
term. Eleven laboratories participated and three materials were Material Level,
°C Sr r (r) SR R (R)
used. A test result is the value obtained from one determination.
Onset A 47.0 0.575 1.61 3.43 1.90 5.31 11.30
Two determinations were run on each material, and this Onset B 99.0 0.469 1.31 1.33 1.24 3.46 3.50
protocol was repeated on each of three days. The analysis for Onset C 176.8 0.376 1.05 0.59 1.15 3.21 1.82
precision followed the general procedure as set forth in Annex Peak A 50.7 0.682 1.91 3.77 2.15 6.02 11.88
Peak B 102.4 0.445 1.25 1.22 1.20 3.37 3.29
5 of Practice D4483. Each cell of Practice D4483 Table 1 basic Peak C 180.9 0.370 1.04 0.57 1.37 3.84 2.12
data format contained six values (three test days, two test Pooled 0.499 1.40 1.82 1.34 3.75 5.65
results each day). The estimates for the repeatability param- A
Sr = within laboratory, standard deviation.
eters therefore contain two undifferentiated sources of r = repeatability in measurement units.
variation, that is, replicates within days and between days. The (r) = repeatability (in percent).
SR = between laboratory, standard deviation.
final precision parameters are given in Table 2 of this test R = reproducibility in measurement units.
method. (R) = reproducibility (in percent).

14.4 The results of the precision calculations for the onset

and the peak are arranged in ascending “mean level” order, and as suspect, that is, having been derived from different or
given in Table 2. nonidentical sample populations. If this is the case, appropriate
14.5 Repeatability—The pooled repeatability, r, of this test corrective action should be taken.
method has been established as 1.40 °C, as given in Table 2. 14.7 Bias—In test method terminology, bias is the difference
Two single test results obtained under normal test method between an average test value and the reference (or true) test
procedures that differ by more than 1.40 °C must be considered property value. Reference values do not exist for this test
as suspect, that is, having been derived from different or method since the value of the melting point is exclusively
nonidentical sample populations. If this is the case, appropriate defined by the test method. Bias, therefore, cannot be deter-
corrective action should be taken. mined.
14.6 Reproducibility—The pooled reproducibility, R, of this
test method has been established as 3.75 °C, as given in Table 15. Keywords
2. Two single test results obtained under normal test method 15.1 capillary; differential scanning calorimetry (DSC);
procedures that differ by more than 3.75 °C must be considered melting range; rubber chemicals

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