Volatile Matter in The Analysis Sample of Coal and Coke: Standard Test Method For
Volatile Matter in The Analysis Sample of Coal and Coke: Standard Test Method For
Volatile Matter in The Analysis Sample of Coal and Coke: Standard Test Method For
1. Scope cokes that lose solid particles as described above. These are
1.1 This test method determines the percentage of gaseous defined as sparking fuels because particles escaping at the
products, exclusive of moisture vapor, in the analysis sample higher temperatures can become incandescent and spark as
which are released under the specific conditions of the test. they are emitted.
1.2 This test method for determination of volatile matter is 4. Summary of Test Method
empirical; because of its empirical nature, strict adherence to
basic principals and permissible procedures is required to 4.1 Volatile matter is determined by establishing the loss in
obtain valid results. weight resulting from heating a coal or coke under rigidly
1.3 This standard does not purport to address all of the controlled conditions. The measured weight loss, corrected for
safety concerns, if any, associated with its use. It is the moisture as determined in Test Method D 3173 establishes the
responsibility of the user of this standard to establish appro- volatile matter content. Two procedures are described to permit
priate safety and health practices and determine the applica- conformity with differences in sample behavior.
bility of regulatory limitations prior to use. 4.2 In this empirical test method, the use of platinum
1.4 The values stated in SI units are to be regarded as the crucibles shall be considered the standard reference method for
standard. volatile matter. Platinum crucibles shall be used in determining
the volatile matter of coke and volatile matter determined for
2. Referenced Documents classification of coals by rank. Volatile matter determinations
2.1 ASTM Standards: 2 by some laboratories using alternate nickel-chromium alloy
D 346 Practice for Collection and Preparation of Coke crucibles having the physical dimensions specified in 6.1 have
Samples for Laboratory Analysis been shown to differ from those obtained using platinum
D 2013 Practice for Preparing Coal Samples for Analysis crucibles. A laboratory utilizing nickel-chromium crucibles
D 3173 Test Method for Moisture in the Analysis Sample of shall first determine if a relative bias exists between the use of
Coal and Coke nickel-chromium and platinum crucibles on the coals being
tested using the test method set forth in Annex A. Where a
3. Terminology relative bias is shown to exist, the volatile matter determined
3.1 Definition: using nickel-chromium crucibles shall be corrected by a factor
3.1.1 sparking fuels—within the context of this test method, determined through comparison of volatile matter results from
fuels that do not yield a coherent cake as residue in the volatile both crucible types on coals being tested or analysis of samples
matter determination but do evolve gaseous products at a rate of known proximate analysis.
sufficient to mechanically carry solid particles out of the
5. Significance and Use
crucible when heated at the standard rate. Such coals normally
include all low-rank noncaking coals and lignites but can also 5.1 Volatile matter, when determined as herein described,
include those anthracites, semianthracites, bituminous, and can be used to establish the rank of coals, to indicate coke yield
on carbonization process, to provide the basis for purchasing
and selling, or to establish burning characteristics.
1
This test method is under the jurisdiction of ASTM Committee D05 on Coal
and Coke and is the direct responsibility of Subcommittee D05.21 on Methods of 6. Apparatus
Analysis.
Current edition approved March 1, 2007. Published April 2007. Originally
6.1 Platinum Crucible, with closely fitting cover, for coal.
approved in 1973. Last previous edition approved in 2002 as D 3175 – 02. The crucible shall be of not less than 10 or more than 20-mL
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or capacity, not less than 25 or more than 35 mm in diameter, and
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM not less than 30 or more than 35 mm in height.
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
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D 3175 – 07
6.2 Platinum Crucible, with closely fitting cover, for coke. than 35 mm in diameter, and not less than 30 or more than 35
The crucible shall be of 10-mL capacity, with capsule cover mm in height. Nickel-chromium crucibles shall be heat-treated
having thin flexible sides fitting down into crucible. Or the for 4 h at 500°C to ensure that they are completely oxidized
double-crucible method can be used, in which the sample is prior to use.
placed in 10-mL platinum crucible, which is then covered with 6.4 Vertical Electric Tube Furnace, for coal or coke. The
another crucible of such a size that it will fit closely to the sides electric furnace shall be a vertical tube furnace. The furnace
of the outer crucible and its bottom will rest 8.5 to 12.7 mm (1⁄3 can be of the form shown in Fig. 1. It shall be regulated to
to 1⁄2 in.) above the bottom of the outer crucible. maintain a temperature of 950 6 20°C in the crucible, as
6.3 Alternate Crucible Materials, Nickel-chromium cru- measured by a thermocouple positioned in the furnace. The
cible with closely fitting cover. The crucible shall not be less furnace shall accommodate sparking coals and meet the
than 10 or more than 20 mL capacity, not less than 25 or more specifications set forth in 7.3.2.
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D 3175 – 07
6.5 Balance, sensitive to 0.1 mg. Test Method D 3173, is the volatile matter. All analyses by this
test method shall be so marked when reported to indicate that
7. Procedure the modified procedure was used.
7.1 The sample shall be the material pulverized to No. 60 NOTE 2—If a tubular furnace of the Fieldner type (Fig. 1) is used for the
(250-µm) sieve in accordance with Practice D 2013 or Practice determination of volatile matter, the preliminary gradual heating can be
D 346. accomplished by moving the crucible to predetermined positions in the
7.2 Procedure for Nonsparking Coals and Cokes: cooler top zone of the furnace. Due to variations in the heating charac-
7.2.1 Weigh 1 g of the sample in a weighed platinum teristics of the furnace, the operator shall predetermine by thermocouple
the proper positions to meet a preliminary heating rate as specified in
crucible, close with a cover which fits closely enough so that 7.3.2. A mechanical device to lower the crucible into the furnace can be
the carbon deposit from bituminous, subbituminous, and lig- used to facilitate control of the lowering operation.
nite coals does not burn away from the underside, place on
platinum or Nichrome-wire supports and insert directly into the 8. Calculation
furnace chamber, which shall be maintained at a temperature of 8.1 Calculate the weight loss percent as follows:
950 6 20°C, and lower immediately to the 950°C zone.
Weight loss, % 5 [~A 2 B!/A] 3 100 (1)
Regulation of the temperature to within the prescribed limits is
critical. After the more rapid discharge of volatile matter has where:
subsided, as shown by the disappearance of the luminous A = weight of sample used, g, and
flame, or in the case of coke, after 2 or 3 min, inspect the B = weight of sample after heating, g.
crucible (see Note 1) to verify that the lid is still properly 8.2 Calculate the volatile matter percent in the analysis
sealed. If necessary, reseat the lid to guard against the admis- samples as follows:
sion of air into the crucible. Do this as rapidly as possible by Volatile matter in analysis sample , % 5 C 2 D (2)
raising the crucible to the top of the furnace chamber, reposi-
tion the lid to more perfectly seal the crucible, then lower the where:
crucible immediately back to the 950°C zone. After heating for C = weight loss, %, and
a total of exactly 7 min, remove the crucible from the furnace D = moisture, %.
and without disturbing the cover, allow it to cool. Coke should
be cooled in a desiccator. Weigh as soon as cold. The 9. Precision and Bias
percentage loss of weight minus the percentage moisture 9.1 The precision of this test method for the determniation
equals the volatile matter. With some strongly caking low- of Volatile Matter in Coal are shown in Table 1. Repeatability
volatile and medium-volatile bituminous coals, the coke button and Reproducibility limits for this test method were determined
can be broken with explosive violence due to the liberation of using only platinum crucibles. Repeatability and Reproducibil-
volatile matter within the button. This is usually designated as ity limits for nickel-chromium crucibles have not been deter-
popping. Such popping can blow the lid off the crucible and mined.
cause mechanical losses of the coked material. When such 9.1.1 Repeatability Limit (r)—The value below which the
popping is observed, the determination shall be rejected and absolute difference between two test results of separate and
the test repeated until popping does not occur. consecutive test determinations, carried out on the same
NOTE 1—Inspection of the crucible can be aided by the use of a mirror
sample, in the same laboratory, by the same operator, using the
held above the furnace well. same apparatus on samples taken at random from a single
quantity of homogeneous material, can be expected to occur
7.3 Modified Procedure for All Sparking Fuels: with a probability of approximately 95 %.
7.3.1 Fuels that do not cake or cake weakly when volatile 9.1.2 Reproducibility Limit (R)—The value below which the
matter is determined shall be watched closely for sparking absolute difference between two test results carried out in
during the heating period (see Note 2); also, at the end of the different laboratories, using samples taken at random from a
test the crucible cover shall be inspected for ash deposits, and single quantity of material that is as homogeneous as possible,
the presence of such deposits shall be considered as evidence can be expected to occur with a probability of approximately
of sparking. 95 %.
7.3.2 All fuels that spark when the volatile matter is
determined by the methods described in 7.1 shall be treated as
follows: The sample shall be given a preliminary gradual TABLE 1 Concentrations Range and Limits for Repeatability and
heating such that a temperature of 600 6 50°C is reached in 6 Reproducibility of Volatile Matter in Coal
min (Note 2). After this preliminary heating the sample shall be Rank, % Repeatability Reproducibility
heated for exactly 6 min at 950 6 20°C. If sparking is then Limit, Limit,
r R
observed, the determination shall be rejected and the test
repeated until no sparking occurs either during the preliminary
High-temperature coke 0.2 0.4
heating or during the 6-min period at 950°C. Remove the Anthracite 0.3 0.6
crucible from the furnace, cool on a metal cooling block, and Semianthracite, bituminous,
weigh. To ensure uniformity of results, keep the cooling period low-temperature coke 0.5 1.0
Subbituminous 0.7 1.4
constant and do not prolong beyond 15 min. The percentage Lignite 1.0 2.0
loss in weight minus the percent moisture in accordance with
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D 3175 – 07
9.2 Bias—Since this is an empirical test method when chromium crucibles shall be determined in the laboratory on
utilizing platinum crucibles, the degree of absolute bias can not coal being tested using the test method set forth in Annex A.
be determined. Bias between the use of platinum and nickel-
ANNEX
A1. METHOD FOR DETERMINING RELATIVE BIAS BETWEEN PLATINUM AND NICKEL-CHROMIUM ALLOY
CRUCIBLES
A1.1 Scope TABLE A1.1 Factors for Maximum Difference That Could Escape
Undetected 5% of the TimeA
A1.1.1 This method describes the procedure for determin-
n g
ing the component of relative bias between platinum and
10 1.29
alternate nickel-chromium alloy crucibles. 11 1.22
12 1.15
A1.2 Apparatus 13 1.10
14 1.05
A1.2.1 All Apparatus and equipment shall conform to the 15 1.01
apparatus and equipment specifications given in the “Appara- 16 0.97
17 0.94
tus” Section of Test Method D 3175 with the additional 18 0.91
requirement that temperatures shall be measured with a Type K 19 0.88
or N thermocouple with a standard tolerance of 6 2.2 Cº. 20 0.85
21 0.83
22 0.81
A1.3 Procedure 23 0.79
24 0.77
A1.3.1 Apply one of the two alternate methods given in the 25 0.76
“Procedure” section of ASTM D3175 to a minimum of twenty 26 0.74
27 0.72
pairs of the materials being tested, one member of each pair 28 0.71
consisting of a one-gram analysis sample in a platinum 29 0.70
crucible, and the other member of each pair consisting of a 30 0.68
31 0.67
one-gram analysis sample of the same material in a nickel- 32 0.66
chromium alloy crucible. 33 0.65
A1.3.2 The following additional limitations apply: 34 0.64
35 0.63
A1.3.2.1 The materials in the study group shall all be of the 36 0.62
same groupings listed in Table 1: 37 0.61
38 0.60
1. Anthracite 39 0.59
2. Semianthracite, Bituminous 40 0.59
3. Subbituminous A
Multiply standard deviation of the Differences by g for Number of Differences
4. Lignite
A1.3.2.2 The range of volatile matter contents within the A1.4 Assessment and Uses of Relative Bias Test Results
study group shall not exceed 10% absolute. If the range of A1.4.1 Compute the differences between the matched pairs,
volatile matter routinely analyzed and within the same Table 1 subtracting the result obtained with the platinum crucible from
grouping exceeds 10% absolute, analyze multiple groups to the result obtained with the nickel-chromium alloy crucible
accommodate the expected range of volatile matter. Apply the results. Calculate the mean and the standard deviation of the
appropriate relative bias to samples within the same volatile differences. Multiply the standard deviation of the differences
matter range. The relative bias shall be applicable only to by the value of y corresponding to the number of pairs (0.85 for
analyses performed in the laboratory in which it is originally 20 pairs) from Table A1.1 This is the limit of bias at the 95%
determined. confidence level that could accidentally pass undetected by
A1.3.2.3 All values determined in any experiment upon reason of statistical error. If this limit exceeds one-half the
members of the study group shall be used in the statistical repeatability limits in Table 1, do not use nickel-chromium
analysis (unless there is undeniable evidence that the data to be alloy crucibles for volatile determinations. If this limit is less
rejected is technically invalid). than one-half the repeatability limits in Table 1, nickel-
A1.3.2.4 All materials within the study group shall be chromium alloy crucibles can be used provided the results
analyzed the same number of times. obtained with nickel-chromium alloy crucibles are corrected by
A1.3.2.5 Confirmatory analyses for each study group (re- subtracting algebraically the test mean of the differences from
determination of relative bias) shall be conducted at least once nickel-chromium crucible results. Subtracting a negative value
per year to ascertain that normal wear of equipment (crucibles, algebraically corresponds to adding the absolute value.
thermocouples, furnace, etc.) does not result in changes to the A1.4.2 Once the relative bias testing is concluded and
conclusions of the experiment. See Table A1.2 as an example. acceptable results obtained, if the corrected volatile value
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D 3175 – 07
TABLE A1.2 Example of Data for a Relative Bias Experiment obtained on any subsequent test specimen falls outside the
Sample ID VM-NiCr VM-Pt NiCr-Pt range of values determined on the samples used in conducting
1 37.66 37.14 0.52 the relative bias test (the range of values being that determined
2 41.98 41.83 0.15 with Pt crucibles), because the value is outside of the method
3 39.50 38.89 0.61
4 40.35 39.93 0.42 validation range, discard the results and perform the determi-
5 40.35 40.09 0.26 nation with a platinum crucible.
6 39.77 39.30 0.47
7 33.90 33.43 0.47 A1.4.3 For client and audit purposes, maintain records of all
8 36.18 35.74 0.44 relative bias studies and volatile matter tests in such a manner
9 33.81 33.65 0.16
10 36.36 36.09 0.27
that it can be ascertained how the values were corrected.
11 38.19 37.41 0.78
12 41.06 40.68 0.38
13 42.29 41.70 0.59
14 34.73 34.34 0.39
15 42.03 41.87 0.16
16 38.01 37.47 0.54
17 40.55 39.76 0.79
18 37.51 37.15 0.36
19 38.09 37.83 0.26
20 40.78 40.68 0.10
21 41.84 41.84 0.00
22 38.44 38.14 0.30
23 41.69 41.53 0.16
MEAN 0.37
SD 0.21
SD*0.79 0.16
MINIMUM 33.43
MAXIMUM 41.87
From Table A1.1, with n = 23, y = 0.79 and from Table A1.2, the standard
deviation of the differences (SD) of the 23 sets is 0.21. The limit of bias is the
product of these two values, SD * y = 0.21% * 0.79 = 0.16%. The limit of the
bias cannot exceed 1⁄2 of the repeatability value given in Table A1.1 for the rank
of coal being considered. The example category is “Semianthracite, Bituminous”
for which the repeatability limit, r, is 0.5% (absolute) and, therefore, for which 1⁄2
r = 0.25%. The determined limit of bias for the data set in Table A1.2 is 0.16%,
and this value is less than 1⁄2 r = (0.25%). This set of data passes the relative
bias experiment and nickel-chromium crucibles may be used in testing these
types of materials (with volatile matter values in the range from 33.43% thru
41.87%
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