An American National Standard

Designation: D 4530 – 03

Standard Test Method for

Determination of Carbon Residue (Micro Method)1
This standard is issued under the fixed designation D 4530; 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 (e) 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. Scope * priate safety practices and to determine the applicability of

1.1 This test method covers the determination of the amount regulatory limitations prior to use. For specific warning
of carbon residue (see Note 1) formed after evaporation and statements, see 8.2.3 and 8.4.
pyrolysis of petroleum materials under certain conditions and 2. Referenced Documents
is intended to provide some indication of the relative coke
forming tendency of such materials. 2.1 ASTM Standards:
1.2 The test results are equivalent to the Conradson Carbon D 189 Test Method for Conradson Carbon Residue of
Residue test (see Test Method D 189). Petroleum Products3
D 482 Test Method for Ash from Petroleum Products3
NOTE 1—This procedure is a modification of the original method and D 4046 Test Method for Alkyl Nitrate in Diesel Fuels by
apparatus for carbon residue of petroleum materials, where it has been
Spectrophotometry4
demonstrated that thermogravimetry is another applicable technique.2
However, it is the responsibility of the operator to establish operating D 4057 Practice for Manual Sampling of Petroleum and
conditions to obtain equivalent results when using thermogravimetry. Petroleum Products4
D 4177 Practice for Automatic Sampling of Petroleum and
1.3 This test method is applicable to petroleum products that
Petroleum Products4
partially decompose on distillation at atmospheric pressure and
E 1 Specification for ASTM Thermometers5
was tested for carbon residue values of 0.10 to 30 % (m/m).
E 133 Specification for Distillation Equipment6
Samples expected to be below 0.10 weight % (m/m) residue
2.2 IP Standard:
should be distilled to remove 90 % (V/V) of the flask charge
Specification for IP Standard Thermometers7
(see Section 9). The 10 % bottoms remaining is then tested for
carbon residue by this test method. 3. Terminology
1.4 Ash-forming constituents, as defined by Test Method
3.1 Definitions:
D 482, or non-volatile additives present in the sample will add
3.1.1 carbon residue, n—in petroleum products, the part
to the carbon residue value and be included as part of the total
remaining after a sample has been subjected to thermal
carbon residue value reported.
decomposition.
1.5 Also in diesel fuel, the presence of alkyl nitrates, such as
3.1.1.1 Discussion—The amount of residue is dependent on
amyl nitrate, hexyl nitrate, or octyl nitrate, causes a higher
the test conditions of evaporation and pyrolysis. The term may
carbon residue value than observed in untreated fuel, which
be misleading here in that the residue may contain other than
may lead to erroneous conclusions as to the coke-forming
carbon decomposition products. However, the term is retained
propensity of the fuel. The presence of alkyl nitrate in the fuel
due to its wide common usage.
may be detected by Test Method D 4046.
1.6 The values stated in SI units are to be regarded as the 4. Summary of Test Method
standard. The values given in parentheses are for information 4.1 A weighed quantity of sample is placed in a glass vial
only. and heated to 500°C under an inert (nitrogen) atmosphere in a
1.7 This standard does not purport to address all of the controlled manner for a specific time. The sample undergoes
safety concerns, if any, associated with its use. It is the coking reactions, and volatiles formed are swept away by the
responsibility of the user of this standard to establish appro-

3
Annual Book of ASTM Standards, Vol 05.01.
1 4
This test method is under the jurisdiction of ASTM Committee D02 on Annual Book of ASTM Standards, Vol 05.02.
5
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee Annual Book of ASTM Standards, Vol 14.03.
6
D02.06 on Analysis of Lubricants. Annual Book of ASTM Standards, Vol 14.04.
7
Current edition approved May 10, 2003. Published June 2003. Originally Methods for Analysis and Testing, Institute of Petroleum Standard Methods for
approved in 1985. Last previous edition approved in 2000 as D 4530–00. Petroleum and Its Products, Part I, Vol 2. Available from Institute of Petroleum, 61
2
See Fuel, Vol 63, July 1984, pp. 931–934. New Cavendish St., London, WIM 8AR, UK.

*A Summary of Changes section appears at the end of this standard.

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FIG. 1 Sample Vial Holder and Vial

nitrogen. The carbonaceous-type residue remaining is reported 6.3 Eyedropper, Syringe, or Small Rod, for sample transfer.
as a percent of the original sample as “carbon residue (micro).” 6.4 Coking Oven8 with circular heating chamber approxi-
4.1.1 When the test result is expected to be below 0.10 % mately 85 mm (33⁄8 in.) in diameter by 100-mm (4-in.) deep,
(m/m), the sample can be distilled to produce a 10 % (V/V) for top loading, with heating capability from 10 to 40°C/min
bottoms, prior to performing the test. rate to 500°C, with exhaust port 13-mm (1⁄2-in.) inside diameter
for nitrogen purge of oven chamber (inlet near top, exhaust at
5. Significance and Use bottom center) with thermocouple sensor located in oven
5.1 The carbon residue value of the various petroleum chamber next to but not touching sample vials, with lid capable
materials serves as an approximation of the tendency of the of sealing out air, and with removable condensate trap located
material to form carbonaceous type deposits under degradation at the oven chamber base. A schematic diagram is given in Fig.
conditions similar to those used in the test method, and can be 2.
useful as a guide in manufacture of certain stocks. However, 6.5 Sample Vial Holder—Cylindrical aluminum block, ap-
care needs to be exercised in interpreting the results. proximately 76 mm (3 in.) in diameter by 16-mm (5⁄8-in.) thick,
5.2 This test method offers advantages of better control of with twelve evenly spaced holes (for vials) each 13 mm (1⁄2 in.)
test conditions, smaller samples, and less operator attention in diameter by 13-mm (1⁄2-in.) deep. The holes are arranged in
compared to Test Method D 189, to which it is equivalent. a circular pattern approximately 3 mm (1⁄8 in.) from the
5.3 Up to twelve samples may be run simultaneously, perimeter. The holder has legs 6-mm (1⁄4-in.) long, with guides
including a control sample when the vial holder shown in Fig. to center in oven chamber, and an index mark on the side to use
1 is used exclusively for sample analysis. as position reference. The sample vial holder is shown in Fig.
1.
6. Apparatus 6.6 A modified version of the standard sample vial holder
6.1 Glass Sample Vials, 2-mL capacity, 12-mm outside (see Fig. 1) is required when larger glass sample vials (see 6.2)
diameter by approximately 35-mm high. are used. The modified sample vial holder is similar in nature
6.2 Larger 4 dram Glass Sample Vials, 15-mL capacity to the twelve hole vial holder, except that there are six evenly
(20.5 to 21-mm outside diameter by 70 6 1-mm high), may be
used for samples that are expected to yield residues <0.10 %
(m/m) so that a more appreciable mass difference can be 8
The sole source of supply of a satisfactory oven with associated automatic
determined. It should be noted the precision statements for the controls that performs this carbon residue test known to the committee at this time
test method were determined using the 2-mL capacity vials is ALCOR-PAC, Inc., 3234 East Pasadena Freeway, Pasadena, TX 77503. This
commercial unit is known as the MCRT. If you are aware of alternative suppliers,
only (with sample residues between 0.3 and 26 % (m/m) and please provide this information to ASTM International Headquarters. Your com-
that the precision associated with using the larger sample vials ments will receive careful consideration at a meeting of the responsible technical
has not been determined. committee 1, which you may attend.

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 D 4530 – 03

FIG. 2 Coking Oven and Lid

spaced holes (for vials) each 21.2 6 0.1 mm in diameter by 8.1.2 During weighing and filling, handle vials with forceps
approximately 16-mm deep, arranged in a circular pattern. to help minimize weighing errors. Discard the sample vials
6.7 Thermocouple, suitable for controller and temperature after use.
range of interest, with exterior temperature readout, degrees 8.1.3 It is assumed that a representative sample of the stock
Celsius. or process has been obtained for laboratory use following
6.8 Analytical Balance, with 60.1 mg sensitivity to 20 g Practice D 4057 or similar standard. Stir the sample to be
minimum weighing capacity. tested, first warming if necessary to reduce its viscosity.
6.9 Nitrogen, minimum 99.998 % purity with suitable Samples that are homogeneous liquids can be transferred
means of delivering a pressure of 0 to 200 kPa (0 to 30 psig). directly to vials using a rod, syringe, or eyedropper. Solid
Cylinders of zero grade nitrogen have been found suitable to materials may also be heated; or frozen with liquid nitrogen,
use. and then shattered to provide manageable pieces.
8.1.4 Transfer an appropriate mass of the sample (see Table
7. Sampling 1) into a tared-sample vial, reweigh to nearest 0.1 mg, and
7.1 Using the practices outlined in Practice D 4057 (manual record. Place the loaded sample vials into vial holder (up to
sampling) or Practice D 4177 (automatic sampling), ensure that twelve), noting position of each sample with respect to index
a representative sample of material to be tested is obtained. mark.
8. Procedure NOTE 2—A control sample can be included in each batch of samples
being tested. This control sample should be a typical sample that has been
8.1 Sample Preparation: tested at least 20 times in the same equipment in order to define an average
8.1.1 Determine the mass of each clean sample vial being percent carbon residue and standard deviation. Results for each batch are
used in the sample analysis, and record the mass to nearest 0.1 deemed acceptable when results for the control sample fall within the
mg. average percent carbon residue 6 three standard deviations. Control

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 D 4530 – 03
TABLE 1 Guide for Sample Size 9. Procedure for Carbon Residue on 10 % (V/V)
Expected Carbon Recommended Distillation Residue
Sample Description Residue, (m/m) % Sample Size, g
9.1 This procedure is applicable to light distillate materials,
Black, viscous or solid >5 0.15 6 0.05
Brown, viscous 1–5 0.5 6 0.1 such as ASTM No. 1 and No. 2 fuel oil or materials expected
Lube oil consistency and 0.1–<1 1.5 6 0.5 to have less than 0.1 % (m/m) carbon residue.
appearance, 10 % bottoms on
distillate material
9.2 A distillation analysis using either a 100 or 200-mL
Large vials only <0.1 5.0 6 1.0 starting volume is required in order to collect a sufficient
Small vials only <0.1 1.5 6 0.5 amount of the 10 % (V/V) residue needed in this analysis. For
a 100-mL distillation, assemble the distillation apparatus de-
scribed in Specification E 133, using flask B (125-mL bulb
volume), flask support board with 50-mm diameter opening,
results that are outside these limits indicate problems with the procedure and graduated cylinder B (100-mL capacity). For a 200-mL
or the equipment.
distillation, assemble the distillation apparatus described in
8.2 Processing of Samples: Specification E 133, using flask D (250-mL bulb volume), flask
8.2.1 With the oven at less than 100°C, place the vial holder support board with 50-mm diameter opening, and graduated
into the oven chamber and secure lid. Purge with nitrogen for cylinder C (200-mL capacity). A thermometer is not required,
at least 10 min at 600 mL/min. Then decrease the purge to 150 but the use of the ASTM High Distillation Thermometer 8F or
mL/min and heat the oven slowly to 500°C at 10°–15°C/min. 8C, as prescribed in Specification E 1, or the IP High Distilla-
tion Thermometer 6C, as prescribed in the Specification for IP
8.2.2 If the sample foams or spatters, causing loss of Thermometers, is recommended.
sample, discard and repeat the test.
9.3 Depending upon which distillation flask is used, place
NOTE 3—Spattering may be due to water that can be removed by prior either 100 or 200 mL of sample (as measured at ambient
gentle heating in a vacuum, followed by a nitrogen sweep. Alternatively, temperature) into a tared distillation flask that is held at a
a smaller sample size can be used. temperature between 13°C and ambient, and record the mass of
sample transferred (E1). Maintain the condenser bath tempera-
8.2.3 Hold oven at 500 6 2°C for 15 min. Then shut off
ture between 0 and 60°C so as to provide a sufficient
furnace power and allow oven to cool freely while under
temperature differential for sample condensation, while avoid-
nitrogen purge of 600 mL/min. When oven temperature is less
ing any solidification of waxy material in the condenser tube.
than 250°C, remove the vial holder for further cooling in
Use, without cleaning, the cylinder from which the sample was
desiccator. After the samples are removed from the oven, the
measured as the receiver, and place it so that the tip of the
nitrogen purge may be shut off. (Warning—Do not open oven condenser does not touch the wall of the cylinder. The receiver
to air at any time during the heating cycle. The introduction of temperature is required to be maintained at the same tempera-
air (oxygen) will likely cause the sample to ignite and spoil the ture (within 63°C) as the sample taken at the start of the test
test. (Because of the oven design and materials, such an in order to obtain an accurate volume measurement in the
ignition is normally not a hazard to the operator.) Open the receiving flask.
oven only after oven temperature falls below 250°C during the 9.4 Apply the heat to the flask at a uniform rate so regulated
cooling step. Maintain nitrogen flow until after the vial holder that the first drop of condensate exits from the condenser
has been removed from the oven.) (Warning—Locate the between 10 and 15 min (for 200-mL samples) or between 5 and
coking oven in laboratory exhaust hood for safe venting of 15 min (for 100-mL samples) after initial application of heat.
smoke and fumes. Alternatively, install vent line from MCRT After the first drop falls, move the receiving cylinder so that the
oven exhaust to laboratory exhaust system.) (Warning—If a tip of the condenser tube touches the wall of the cylinder. Then
vent line is used, do not connect directly to exhaust chimney to regulate the heat so that the distillation proceeds at a uniform
avoid creating negative pressure in the line.) rate of 8 to 10 mL/min (for 200-mL samples) or 4 to 5 mL/min
NOTE 4—To reduce oven temperature for the next run, remove the oven
(for 100-mL samples). For 200-mL samples, continue the
lid to allow faster cooling. As required by the procedure, the subsequent distillation until approximately 178 mL of distillate has been
test can be started when the oven has been cooled to below 100°C. collected, and then discontinue heating and allow the con-
denser to drain until 180 mL (90 % (V/V) of the charge to the
8.3 Final Weighing—Transfer sample vials (maintained in flask) has been collected in the cylinder. For 100-mL samples,
place in the vial holder) to desiccator and allow vials to cool to continue the distillation until approximately 88 mL of distillate
room temperature. Weigh the cooled vials to the nearest 0.1 mg has been collected, and then discontinue heating and allow the
and record. Handle the vials with forceps. Discard the used condenser to drain until 90 mL (90 % (V/V) of the charge to
glass sample vials. the flask) has been collected in the cylinder.
8.4 Occasionally examine the condensate trap at the bottom 9.5 Catch final drainage, if any, by immediately replacing
of the oven chamber; empty if necessary and replace. the cylinder with a suitably tared container, such as a small
(Warning—The condensate trap residue may have some Erlenmeyer flask. Add to this container, while still warm, the
carcinogenic materials present. Avoid contact with the trap distillation residue left in the distilling flask, and mix well. The
residue; dispose of it in accordance with local laboratory contents of the container then represents a 10 % (V/V) distil-
practice.) lation residue from the original product. Allow the contents of
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FIG. 3 Carbon Residue (Micro) Precision Data

the container to cool to ambient temperature before weighing NOTE 5—Precision data and Conradson carbon residue/micro carbon
the container and its contents in order to obtain an accurate residue correlation data were generated by a task force in 1983. The round
measurement. robin involved 18 laboratories, six petroleum materials in duplicate
9.6 If the distillation residue is too viscous to flow freely at analysis for both micro method and Test Method D 189 tests. The range
of values for samples was from 0.3 % to 26 % (m/m). No precision data
ambient temperature, it is necessary to warm the distillation
or correlation data exists for results obtained using 10 % bottoms or
residue to a sufficient temperature that will allow a portion of 15-mL vials, or both.
the material to be transferred into a previously weighted vial
for analysis (see Table 1). After allowing the material in the 12.2 Repeatability—The difference between two test re-
vial to cool to ambient temperature, determine the mass of the sults, obtained by the same operator with the same apparatus
test specimen to the nearest 0.1 mg and carry out the carbon under constant operating conditions on identical test material,
residue test in accordance with the procedure described in would, in the long run, in the normal and correct operation of
Section 8. the test method, exceed the values shown in Fig. 3 in only one
10. Calculation case in twenty.
12.3 Reproducibility—The difference between two single
10.1 Calculate the mass % carbon residue in the original
sample, or in the 10 % distillation bottoms as follows: and independent results, obtained by different operators work-
10.1.1 Calculate percent residue as follows: ing in different laboratories on identical test material, would, in
the long run, in the normal and correct operation of the test
~A 3 100!
% carbon residue 5 (1) method, exceed the values shown in Fig. 3 in only one case in
W
twenty.
12.4 Bias—The procedure in Test Method D 4530 for mea-
where: suring carbon residue of petroleum by the carbon residue
A = carbon residue, g, and method has no bias because the mass % of carbon residue can
W = sample used, g.
be defined only in terms of the test method.

11. Report 13. Keywords

11.1 Report the value obtained as Micro Method carbon 13.1 carbon residue; carbon residue (micro method); diesel
residue, percent or as Micro Method carbon residue on 10 % fuel; lubricating oil; petroleum products
distillation residue, percent to the nearest 0.1 % (m/m).
12. Precision and Bias 9
12.1 The precision of this test method as determined by (see
Note 5) statistical examination of interlaboratory results is as
follows:

9
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR: D02-1192.

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FIG. X1.1 Correlation of Conradson and Carbon Residue (Micro) Tests

APPENDIXES

(Nonmandatory Information)

X1. CORRELATION TO OTHER METHODS

X1.1 A correlation (see Fig. X1.1) has been derived and nonparametric analysis show that, considering the preci-
between the carbon residue test by the micro method and the sions of both tests, there is no difference between the two
Conradson carbon residue test (see Test Method D 189) in a methods. The data generated by the carbon residue test by the

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cooperative program involving 18 laboratories and six petro- micro method are statistically equivalent to the Conradson
leum materials. carbon residue test, except for better precision in the micro
X1.2 Statistical analysis using modified Student’s t tests method residue test.

X2. HELPFUL HINTS FOR THE ANALYST

X2.1 An exhaust system should be provided that will X2.4 The final residue should be less than about 50 mg and
remove the small amount of smoke produced during carbon preferably around 25 mg. If too much sample is taken, the
residue testing. Any suction line used to draw the smoke away material may boil over during heating, especially with high
should not be connected directly to the MCRT chimney. Allow residue oils. Use the equation and the table given in this test
a small space between the chimney and the suction line. This method as a guide for recommended sample masses to be
prevents a negative pressure from being created within the taken.
apparatus.
X2.2 The sample vials should be handled only with gloved X2.5 If there is spattering or foaming of samples during the
hands or forceps. initial heating stage, this may be due to the presence of water
in the sample. A smaller sample size can be used, or the water
X2.3 The large 4 dram vials should be used only for light can be removed by gentle heating in vacuum, followed by a
oils and the samples that are expected to yield residues less nitrogen sweep.
than 0.10 m/m %.

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 D 4530 – 03
SUMMARY OF CHANGES

Subcommittee D02.06 has identified the location of selected changes to this standard since the last issue
(D 4530–00) that may impact the use of this standard.

(1) Updated 6.2. (7) Deleted 10.1.2.

(2) Updated 6.3. (8) Updated 11.1 to allow reporting of 10 % distillation residue
(3) Updated address of the vendor in Footnote 8. results.
(4) Deleted use of only cylinders as a source of nitrogen in 6.9.
(9) Changed Appendix X1 title.
(5) Simplified sample requirements in 8.1.3.
(6) Added 9.6 for guidance on handling viscous distillation (10) Added new Appendix X2 to provide helpful hints to the
residue. analyst for running this test.

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