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AS/NZS 1050.

2:1994

Australian/New Zealand Standard

Methods for the analysis of iron


and steel

Part 2: Determination of carbon


content— Gravimetric method
AS/NZS 1050.2:1994

This Joint Australian/New Zealand Standard was prepared by Joint Technical


Committee CH/10, Analysis of Metals. It was approved on behalf of the Council of
Standards Australia on 18 May 1994 and on behalf of the Council of Standards
New Zealand on 5 August 1994. It was published on 15 August 1994.

The following interests are represented on Committee CH/10:

Aluminium Development Council


Australasian Institute of Mining and Metallurgy
Australian Lead Development Association
Bureau of Steel Manufacturers of Australia
Copper Technical Data Centre
National Association of Testing Authorities, Australia
Railways of Australia Committee
Royal Australian Chemical Institute

Additional interests participating in preparation of Standard:


Analytical laboratories
Department of Defence, Materials Research Laboratory
Steel manufacturers

Review of Standards. To keep abreast of progress in industry, Joint Australian/


New Zealand Standards are subject to periodic review and are kept up to date by the
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AS/NZS 1050.2:1994

Australian/New Zealand Standard

Methods for the analysis of iron


and steel

Part 2: Determination of carbon


content— Gravimetric method

First publi shed as part of AS K1—1925.


Second editi on 1926.
Revised and redesignated in part as AS K1.2— 1951.
Second editi on 1968.
AS K1.2 — 1968 withdrawn 1978.
Revised and redesignated AS 1050.2. — 1984.
Jointl y revised and designated as Joint Standard
AS/NZS 1050.2:1994.

PUBLISHED JOINTLY BY:

STANDARDS AUSTRALIA
1 The Crescent,
Homebush NSW 2140 Australia

STANDARDS NEW ZEALAND


Level 10, Standards House,
155 The Terrace,
Wellington 6001 New Zealand
ISBN 0 7262 9003 3
AS / NZS 1050.2:1994 2

PREFACE

This Standard was prepared by the Joint Australia /New Zealand Standards Committee
CH/10 on Analysis of Metals, to supersede AS 1050.2—1984, Methods for the analysis of
iron and steel, Part 2: Determination of carbon content (gravimetric method).
It is issued as part of a Joint Standard under the terms of the Active Cooperation
Agreement between Standards Australia and Standards New Zealand.

CONTENTS
Page

1 SCOPE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 REFERENCED DOCUMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3 PRINCIPLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
4 REAGENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
5 APPARATUS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
6 SAMPLING AND SAMPLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
7 PROCEDURE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
8 CALCULATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
9 PRECISION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
10 ACCEPTANCE OF ANALYTICAL VALUES . . . . . . . . . . . . . . . . . . . . . . . . . 7
11 TEST REPORT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

APPENDIX
A SET UP OF APPARATUS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

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3 AS / NZS 1050.2:1994

STANDARDS AUSTRALIA / STANDARDS NEW ZEALAND

Australian/New Zealand Standard


Methods for the analysis of iron and steel

Part 2: Determination of carbon content (gravimetric method)

1 SCOPE This Standard sets out a gravimetric method for the determination of the
total carbon content of all types of iron and steel, after combustion in oxygen using a high
temperature resistance furnace or high frequency induction heating. The method is
applicable to all types of iron and steel with carbon contents in the range 0.05% to 4.5%.

2 REFERENCED DOCUMENTS The following documents are referred to in this


Standard:
AS
1213 Iron and steel — Methods of sampling
2850 Chemical analysis — Interlaboratory test programs— For determining precision of
analytical method(s) — Guide to the planning and conduct
BS
4237 Report on reproducibility of methods of chemical analysis used in the iron and
steel industry

3 PRINCIPLE Carbon is oxidized to carbon dioxide by high temperature combustion


of the sample in oxygen. The exit gases are passed through a glass wool filter to remove
solid particles, then through manganese dioxide to remove sulfurous gases. The purified
gases are then passed through magnesium perchlorate to remove moisture before
collecting the carbon dioxide in a weighed carbon dioxide absorption bulb. The carbon
content of the sample is calculated from the increase in mass of the bulb.

4 REAGENTS
4.1 General requirements Only reagents of recognized analytical grade and only
distilled water or water of an equivalent purity shall be used.
4.2 Manganese dioxide, for combustion analysis Particle size range from 710 µm to
1.18 mm.
4.3 Magnesium perchlorate, anhydrous
4.4 Carbon dioxide absorbent Inert granular base impregnated with sodium
hydroxide.
4.5 Glass wool
4.6 Accelerator The accelerator shall be either lead, red lead, tin or tungsten
containing less than 0.001% carbon.
NOTES:
1 Red lead should be heated for several hours at 450°C to 480°C and transferred to a small
glass-stoppered bottle for storage. It should be reheated at 450°C to 480°C if it is stored for
several hours.
2 Metallic accelerators such as lead, tin or tungsten should be washed in a low boiling point
(<50°C) hydrocarbon and dried before use.
4.7 Oxygen Oxygen at least 99.5% pure with a minimum amount of carbonaceous
material.
4.8 Sulfuric acid (ρ20 1.84 g/mL).

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AS / NZS 1050.2:1994 4

5 APPARATUS The apparatus shall be set up as shown in Appendix A.


5.1 Oxygen supply and purification train (Figure A1) The oxygen purification train
shall consist of the following:
(a) Bulb B containing sulfuric acid (4.8).
(b) Bulb C packed with carbon dioxide absorbent (4.4).
(c) Bulb D packed with magnesium perchlorate (4.3).
(d) Safety valve E containing mercury to limit the pressure to the correct working
value.
5.2 Furnace An electric furnace (F, see Figure A1) capable of operating at a
temperature of 1100°C shall be used. The furnace may be either a tube furnace or a high
frequency induction furnace.
NOTES:
1 If a high frequency induction furnace is used, a catalyser must be placed between the glass
wool filter bulb (H, Figure A1) and the manganese dioxide bulb (I, Figure A1) to ensure
that all carbon monoxide is converted to carbon dioxide.
2 When a resistance furnace is used, combustion is facilitated by preheating the sample in the
combustion tube for 2 min to 3 min before admitting the oxygen.
3 Induction furnaces are capable of inflicting high frequency burns and high voltage shocks.
All guards must be properly maintained. The furnace must be disconnected from the power
line whenever electrical repairs or adjustments are made.
5.3 Combustion tube The combustion tube (G, Figure A1) shall be as follows:
(a) For a tube furnace, a refractory combustion tube of aluminous porcelain or mullite
with reduced exit.
(b) For a high frequency furnace, a suitable fused silica tube.
5.4 Absorption train The absorption train shall comprise the following:
(a) Glass wool filter bulb A bulb (H, Figure A1) packed with glass wool (4.5) to
remove solid particles from the gas stream.
NOTE: Midvale and Nesbitt bulbs have both proved satisfactory.
(b) Manganese dioxide bulb A bulb (I, Figure A1) packed with manganese dioxide
(4.2) to remove oxides of sulfur from the gas stream.
(c) Magnesium perchlorate bulb A bulb (J, Figure A1) packed with magnesium
perchlorate (4.3) to remove moisture from the gas stream.
(d) Carbon dioxide absorption bulb A Nesbitt bulb (K, Figure A1 and Figure A2)
packed with layers of carbon dioxide absorbent (4.4) and magnesium perchlorate
(4.3) separated by glass wool (4.5). The bulb shall be packed so that the gas stream
passes through the carbon dioxide absorbent then the magnesium perchlorate (see
Figure A2).
NOTE: The carbon dioxide absorption bulb should not be handled with bare hands at any
time.
5.5 Flowmeter A flowmeter (L, Figure A1) with a capacity of 0 to 2 L/min is
incorporated after the absorption train.
5.6 Combustion boats and cupulets Combustion boats and cupulets shall be made of
refractory clay, alundum or zircon and shall be of suitable size to hold up to 3 g of
sample. New boats and cupulets must be pre-ignited to at least 1100°C in oxygen for
15 min before use.

6 SAMPLING AND SAMPLES Samples for analysis shall be obtained as fine


millings or drillings by one of the procedures set out in AS 1213. If the sample is
contaminated with lubricant it should be washed in a low boiling point (<50°C)
fluorocarbon.

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5 AS / NZS 1050.2:1994

7 PROCEDURE
7.1 Number of determinations This method is written for a single determination only
and may be used in that form. Where replicate determinations are required, procedures for
the acceptance of results obtained are given in Clause 10.
7.2 Blank test A blank test shall be carried out in parallel with the analysis using the
same procedure as for the analysis and the same quantities of all reagents but omitting the
test sample.
7.3 Check test In each run one analysis of a certified reference material of the same
type of metal should be carried out in parallel with the analysis of the test sample and
under the same conditions. However, in cases of dispute, an analysis of a certified
reference material shall be carried out in parallel with the analysis of the test sample.
When the analysis is carried out on several samples of the same type of metal at the same
time, the analytical value of one certified reference material may be used.
NOTE: The certified reference material should be of the same type as the sample to be analysed
and the properties of the two materials should be sufficiently similar to ensure that in either
case no significant changes in the analytical procedure would become necessary.
7.4 Test portion Weigh to ±0.2 mg the test portion masses specified in Table 1.

TABLE 1
MASSES OF TEST PORTIONS
Carbon content Mass of test portion
% g
0.05 to 0.5 2.728
0.5 to 1.0 1.500
1.0 to 1.5 1.000
1.5 to 5.0 0.500

7.5 Determination
7.5.1 Combustion using a resistance furnace The procedure for combustion using a
resistance furnace shall be as follows:
(a) Set up the apparatus as shown in Figure A1.
(b) Adjust the furnace temperature to between 1050°C and 1100°C and regulate the
oxygen flow at between 300 mL/min and 325 mL/min.
(c) After 15 min detach the absorption bulb (5.4(d)) and weigh to the nearest 0.2 mg.
Replace the bulb and continue passage of oxygen for a further 15 min. Detach and
weigh the absorption bulb to the nearest 0.2 mg. Repeat the passage of oxygen and
weighing until the absorption tube reaches constant mass (difference between
successive weighings less than 0.5 mg). Record the mass (m1 ).
(d) Weigh a suitable test portion selected from Table 1 into a pre-ignited combustion
boat (5.6).
(e) Cover the test portion with approximately 1 g of accelerator (4.6).
NOTE: Some types of high chromium nickel steels require an additional aid to combustion,
e.g. the sample may be mixed with an equal mass of iron of known carbon content
(<0.005% carbon) in a similar state of dispersion to the test sample. When low carbon iron
is added as a combustion accelerator, a blank test should be carried out using the same
amount of iron and accelerator and the appropriate correction made.
(f) Bypass the oxygen stream through the mercury safety valve (5.1(d)).
(g) Attach the weighed absorption bulb (7.5.1(c)) and introduce the combustion boat
containing the test portion (7.5.1(d)) into the hot zone of the combustion tube (5.3).

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AS / NZS 1050.2:1994 6

Allow the boat to preheat for 3 min in the hot zone of the combustion tube and then
readmit the oxygen (4.7).
(h) Rapid combustion begins approximately 1 min after introduction of the oxygen and
is indicated by a reduced oxygen flow. Continue the oxygen flow for 10 min after
combustion has been completed (i.e. after the oxygen flow rate returns to its
original value) and reweigh the absorption bulb to the nearest 0.2 mg after the bulb
has reached ambient temperature. Record the mass (m 2).
7.5.2 Combustion using an induction furnace The procedure for combustion using an
induction furnace shall be as follows:
(a) Set up the apparatus as shown in Figure A1.
(b) Adjust the oxygen flow to approximately 1 L/min.
(c) Weigh the absorption bulb to constant mass by the procedure specified in
Clause 7.5.1(c). Record the mass (m1 ).
(d) Weigh a suitable test portion, selected from Table 1, into a cupulet or crucible.
Cover the test portion with approximately 1 g of accelerator (4.6).
NOTE: Some types of high chromium nickel steels require an additional aid to combustion,
e.g. the sample may be mixed with an equal mass of iron of known carbon content
(<0.005% carbon) in a state of dispersion similar to the test sample. When low carbon iron
is added as a combustion accelerator, a blank test should be carried out using the same
amount of iron and accelerator and the appropriate correction made.
(e) Open the furnace and position the cupulet on the pedestal. Close the furnace
ensuring that the cupulet is in the correct position within the heating zone.
(f) Sweep the system with oxygen for approximately 30 s.
(g) Open the stopcock of the absorption bulb and connect it to the absorption train.
(h) Turn on the power switch of the furnace, record the time (if an automatic timer is
used, adjust it for a 5 min burning period) and burn the sample for 5 min.
(i) Continue the oxygen flow for 5 min after the furnace has been turned off and
reweigh the absorption bulb to the nearest 0.2 mg after the bulb has reached
ambient temperature. Record the mass (m 2).

8 CALCULATIONS
Calculate the carbon content of the sample from the following formula:

where
m2 = mass of absorption tube after combustion of test portion, in grams
m1 = mass of absorption tube prior to combustion of test portion, in grams
mb = mass of carbon dioxide in blank, in grams
m = mass of test portion, in grams
0.2729 = conversion factor converting carbon dioxide to carbon

9 PRECISION A planned trial of this method was carried out by five analysts, each
from a different laboratory, five tests being carried out by each analyst on each of six
samples. From the results obtained the 95% confidence limits (2s) have been calculated
in accordance with BS 4237 and the repeatability, r, and reproducibility, R, have been
calculated in accordance with AS 2850 . These data are presented as Table 2.

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7 AS / NZS 1050.2:1994

TABLE 2
PRECISION DATA FOR CARBON DETERMINATIONS
Carbon Mean Components of
Reproducibility
certificate carbon standard Repeatability Reproducibility
Sample index
value content deviation
% % sb sw 2s r R
SRM 170 A 0.052 0.052 0.002 0.002 0.005 0.0056 0.0071
Basic open
hearth mild
steel
SAA 81/3 0.105 0.006 0.006 0.017 0.0168 0.0241
Carbon steel
SAA 81/5 0.513 0.007 0.015 0.033 0.0420 0.0467
Valve steel
(Cr 21, Mn 9,
Ni 4)
SAA 81/6 Tool 1.48 0.003 0.010 0.021 0.0280 0.0297
steel (Cr 12,
Mo 0.8, V 0.9)
SRM 6F 2.91 2.90 0.042 0.033 0.107 0.0924 0.1514
Cast iron
JSS 110/6 4.15 4.06 0.076 0.010 0.156 0.0280 0.2207
Pig iron

The reproducibility index, 2s, is obtained from the following formula:

and the repeatability, r, is obtained from the following formula:


r = 2.8 × s w
and reproducibility, R, is obtained from the following formula:
R = 1.415 × 2s
where
sb = the between-operator standard deviation
sw = the within-operator standard deviation
Ninety-five percent of results obtained by any one analyst should be reproducible to
within two standard deviations of the overall mean value derived from all laboratories (i.e.
× ± 2s). For further information see AS 2850.

10 ACCEPTANCE OF ANALYTICAL VALUES


10.1 Single test sample An individual result in its own right conveys limited
information concerning its analytical correctness; the use of a reference material will
assist in validating the accuracy of this result.
10.2 Replicate determinations An increased confidence in the final result may be
achieved by carrying out replicate determinations in conjunction with the use of
appropriate reference material. Where duplicate determinations have been carried out, the
difference between the results should not exceed the value of r. If this is not the case, the
usual recourse is to process further determinations. The recommended procedure is as
follows:

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AS / NZS 1050.2:1994 8

(a) Where the difference between duplicate results is greater than r, a further
determination should be carried out. All three results may be accepted if the range
of results is less than 1.2r, otherwise a fourth determination should be carried out.
(b) Where the range of four results is less than 1.3r, all may be accepted. If the range is
greater than 1.3r, but three of the four results are within a range of 1.2r, these three
may be accepted and the fourth rejected. Should neither condition apply, a fifth
determination should be carried out.
(c) When the range of the five results is less than 1.4r, all may be accepted. Otherwise,
if four of the five results lie within the range of 1.3r, these may be accepted and the
fifth rejected.
(d) Where an outlier is obtained from four or five determinations, it may be rejected but
it is invalid to reject any result on the basis of only three determinations or to reject
two results from five determinations.
(e) Should five results fail to achieve acceptability according to the above scheme, a
detailed investigation should be made into all aspects of the analytical procedure,
including instrument performance, operator technique, sample homogeneity and
preparation.
The test result finally reported is usually the mean of all acceptable results. Acceptance of
this final result is, however, conditional upon the acceptability of the result obtained for
the reference material, where such a material has been carried through the method with
the test samples.
10.3 Acceptance of reference material values If the value obtained for the reference
material does not agree to within 0.7R of its recognized value, the procedure shall be
repeated with the original and a different reference material. Test sample results shall be
acceptable when the criteria of the above clause are met, and the value of the reference
material agrees to within 0.7R of its recognized value.

11 TEST REPORT
The test report shall contain the following information:
(a) Identification of the sample.
(b) Date on which the sample was taken.
(c) Date on which the analysis was carried out.
(d) Carbon concentration in the test sample, expressed as a percentage by mass of the
sample.
(e) Identification of the reference material, if used, to validate the result.
(f) Any alternative standardization procedure used to validate the test result.
(g) The number of acceptable results from which the mean result has been calculated.
(h) Reference to this Australian/New Zealand Standard, i.e. AS/NZS 1050.2.
(i) Any unusual observations made during the course of the analysis which may have
had an effect on the result.

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9 AS / NZS 1050.2:1994

APPENDIX A
SET UP OF APPARATUS
(Normative)

LEGEND:

A = Oxygen gas cylinder


B = Bulb containing sulf uric acid
C = Bulb packed with carbon dioxide absorbent
D = Bulb packed with magnesium perchlorate
E = Mercury safety valve
F = Electr ic furnace
G = Combusti on tube
H = Glass wool fi lt er bulb
I = Bulb packed with manganese dioxide
J = Bulb packed with magnesium perchlorate
K = Bulb packed with carbon dioxide absorbent
L = Flowmeter

FIGURE A1 SET UP OF APPARATUS FOR GRAVIMETRIC DETERMINATION


OF CARBON IN STEEL

FIGURE A2 ABSORPTION BULB

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