Determination of Carbon, Sulfur, Nitrogen, and Oxygen in Steel, Iron, Nickel, and Cobalt Alloys by Various Combustion and Fusion Techniques

Designation: E1019 − 11
Standard Test Methods for

Determination of Carbon, Sulfur, Nitrogen, and Oxygen in
Steel, Iron, Nickel, and Cobalt Alloys by Various
Combustion and Fusion Techniques1
This standard is issued under the fixed designation E1019; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope Zirconium 0.005 to 2.500
1.1 These test methods cover the determination of carbon, 1.2 The test methods appear in the following order:
sulfur, nitrogen, and oxygen, in steel, iron, nickel, and cobalt Sections
alloys having chemical compositions within the following Carbon, Total, by the Combustion–Instrumental Measurement
Test Method 10 – 20
limits: Nitrogen by the Inert Gas Fusion–Thermal Conductivity 32 – 42
Element Concentration Range, % Test Method
Aluminum 0.001 to 18.00 Oxygen by the Inert Gas Fusion Test Method 43 – 54
Antimony 0.002 to 0.03 Sulfur by the Combustion-Infrared Absorption Test Method
Arsenic 0.0005 to 0.10 (Calibration with Metal Reference Materials) 55 – 65
Beryllium 0.001 to 0.05 Sulfur by the Combustion–Infrared Absorption Test Method
Bismuth 0.001 to 0.50 (Potassium Sulfate Calibration) 21 – 31
Boron 0.0005 to 1.00
Cadmium 0.001 to 0.005
1.3 The values stated in SI units are to be regarded as
Calcium 0.001 to 0.05 standard. No other units of measurement are included in this
Carbon 0.001 to 4.50 standard.
Cerium 0.005 to 0.05
Chromium 0.005 to 35.00 1.4 This standard does not purport to address all of the
Cobalt 0.01 to 75.0 safety concerns, if any, associated with its use. It is the
Niobium 0.002 to 6.00
Copper 0.005 to 10.00
responsibility of the user of this standard to establish appro-
Hydrogen 0.0001 to 0.0030 priate safety and health practices and determine the applica-
Iron 0.01 to 100.0 bility of regulatory limitations prior to use. Specific hazards
Lead 0.001 to 0.50
Magnesium 0.001 to 0.05
statements are given in Section 6.
Manganese 0.01 to 20.0
Molybdenum 0.002 to 30.00 2. Referenced Documents
Nickel 0.005 to 84.00
Nitrogen 0.0005 to 0.50 2.1 ASTM Standards:2
Oxygen 0.0005 to 0.03 D1193 Specification for Reagent Water
Phosphorus 0.001 to 0.90 E29 Practice for Using Significant Digits in Test Data to
Selenium 0.001 to 0.50
Silicon 0.001 to 6.00 Determine Conformance with Specifications
Sulfur (Metal Reference 0.002 to 0.35 E50 Practices for Apparatus, Reagents, and Safety Consid-
Materials)
erations for Chemical Analysis of Metals, Ores, and
Sulfur (Potassium Sulfate) 0.001 to 0.600
Tantalum 0.001 to 10.00 Related Materials
Tellurium 0.001 to 0.35 E135 Terminology Relating to Analytical Chemistry for
Tin 0.002 to 0.35
Titanium 0.002 to 5.00
Metals, Ores, and Related Materials
Tungsten 0.005 to 21.00 E173 Practice for Conducting Interlaboratory Studies of
Vanadium 0.005 to 5.50 Methods for Chemical Analysis of Metals (Withdrawn
Zinc 0.005 to 0.20
1998)3
1 2
These test methods are under the jurisdiction of ASTM Committee E01 on For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
responsibility of Subcommittee E01.01 on Iron, Steel, and Ferroalloys. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved March 15, 2011. Published June 2011. Originally the ASTM website.
3
approved in 1984. Last previous edition approved in 2008 as E1019 – 08. DOI: The last approved version of this historical standard is referenced on
10.1520/E1019-11. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1
E1019 − 11
E1601 Practice for Conducting an Interlaboratory Study to chromatographic column. Upon elution, the amount of carbon
Evaluate the Performance of an Analytical Method dioxide is measured in a thermistor-type conductivity cell.
E1806 Practice for Sampling Steel and Iron for Determina- Refer to Fig. 1.
tion of Chemical Composition 11.1.2 Infrared (IR) Absorption, Test Method A—The
amount of carbon dioxide is measured by infrared (IR)
3. Terminology absorption. Carbon dioxide (CO2) absorbs IR energy at a
3.1 For definition of terms used in this test method, refer to precise wavelength within the IR spectrum. Energy of this
Terminology E135. wavelength is absorbed as the gas passes through a cell body in
which the IR energy is transmitted. All other IR energy is
4. Significance and Use eliminated from reaching the detector by a precise wavelength
4.1 These test methods for the chemical analysis of metals filter. Thus, the absorption of IR energy can be attributed to
and alloys are primarily intended to test such materials for only CO2 and its concentration is measured as changes in
compliance with compositional specifications. It is assumed energy at the detector. One cell is used as both a reference and
that all who use these test methods will be trained analysts, a measure chamber. Total carbon, as CO2, is monitored and
capable of performing common laboratory procedures skill- measured over a period of time. Refer to Fig. 2.
fully and safely. It is expected that work will be performed in 11.1.3 Infrared (IR) Absorption, Test Method B—The detec-
a properly equipped laboratory. tor consists of an IR energy source, a separate measure
chamber and reference chamber, and a diaphragm acting as one
5. Apparatus and Reagents plate of a parallel plate capacitor. During specimen
5.1 Apparatus and reagents required for each determination combustion, the flow of CO2 with its oxygen gas carrier is
are listed in separate sections preceding the procedure. routed through the measure chamber while oxygen alone
passes through the reference chamber. Energy from the IR
6. Hazards source passes through both chambers, simultaneously arriving
6.1 For hazards to be observed in the use of certain reagents at the diaphragm (capacitor plate). Part of the IR energy is
in this test method, refer to Practices E50. absorbed by the CO2 present in the measure chamber while
none is absorbed passing through the reference chamber. This
6.2 Use care when handling hot crucibles and operating creates an IR energy imbalance reaching the diaphragm, thus
furnaces to avoid personal injury by either burn or electrical distorting it. This distortion alters the fixed capacitance creat-
shock. ing an electric signal change that is amplified for measurement
as CO2. Total carbon, as CO2, is monitored and measured over
7. Sampling
a period of time. Refer to Fig. 3.
7.1 For procedures for sampling the materials, refer to those 11.1.4 Infrared (IR) Absorption, Test Method C, Closed
parts of Practice E1806. Loop—The combustion is performed in a closed loop, where
CO and CO2 are detected in the same infrared cell. Each gas is
8. Rounding Calculated Values measured with a solid state energy detector. Filters are used to
8.1 Calculated values shall be rounded to the desired num- pass the appropriate IR wavelength to each detector. In the
ber of places as directed in Practice E29. absence of CO and CO2, the energy received by each detector
is at its maximum. During combustion, the IR absorption
9. Interlaboratory Studies properties of CO and CO2 gases in the chamber cause a loss of
9.1 These test methods have been evaluated in accordance energy; therefore a loss in signal results which is proportional
with Practice E173. The Reproducibility R2 of Practice E173 to concentrations of each gas in the closed loop. Total carbon,
corresponds to the Reproducibility Index R of Practice E1601. as CO2 plus CO, is monitored and measured over a period of
The Repeatability R1 of Practice E173 corresponds to the time. Refer to Fig. 4.
Repeatability Index r of Practice E1601. 11.2 This test method is written for use with commercial
analyzers, equipped to perform the above operations automati-
TOTAL CARBON BY THE COMBUSTION cally and calibrated using steels of known carbon content.
INSTRUMENTAL MEASUREMENT TEST METHOD
12. Interferences
10. Scope 12.1 For the scope of elements typically found in materials
10.1 This test method covers the determination of carbon in to be tested by this method refer to 1.1.
concentrations from 0.005 % to 4.5 %. 13. Apparatus
11. Summary of Test Method 13.1 Combustion and Measurement Apparatus—See Figs.
11.1 The carbon is converted to carbon dioxide by combus- 1-4.
tion in a stream of oxygen. 13.2 Crucibles—Use crucibles that meet or exceed the
11.1.1 Thermal Conductivity Test Method—The carbon di- specifications of the instrument manufacturer and prepare the
oxide is absorbed on a suitable grade of zeolite, released by crucibles by heating in a suitable furnace for not less than 40
heating the zeolite, and swept by helium or oxygen into a min at approximately 1000 °C. Remove from the furnace and
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E1019 − 11
A—High Purity Oxygen M—CO2 Collection Trap

B—Oxygen Regulator (2 Stage) N—Furnace Combustion Exhaust
C—Sodium Hydroxide Impregnated Clay/Magnesium Perchlorate O—Furnace Purge Exhaust
D—Secondary Pressure Regulator P—Metal Connector To Use Oxygen As Carrier Gas
E—Flowmeter Q—High Purity Helium
F—Induction Furnace R—Helium Regulator (2 Stage)
G—Combustion Tube S—Chromagraphic Column
H—Dust Trap T—TC Cell/Readout
I—Manganese Dioxide U—Measure Flowmeter
J—Heated CO to CO2 Converter V—Reference Flowmeter
K—Magnesium Perchlorate W—Furnace Power Stat
L—Valve Manifold
* May be sealed chamber if

oxygen is carrier gas.
** Not required if oxygen is

carrier gas.
FIG. 1 Apparatus for Determination of Carbon by the Combustion Thermal Conductivity Test Method
cool before use. Crucibles may be stored in a desiccator prior tee on Analytical Reagents of the American Chemical Society,
to use. Heating of crucibles is particularly important when where such specifications are available.4 Other grades may be
analyzing for low levels of carbon and may not be required if used, provided it is first ascertained that the reagent is of
the material to be analyzed has higher levels of carbon such as sufficiently high purity to permit its use without lessening the
that found in pig iron. Above certain concentrations, as accuracy of the determination.
determined by the testing laboratory, the nontreatment of
crucibles will have no adverse effect. The analytical ranges for 14.2 Acetone—The residue after evaporation shall be
the use of untreated crucibles shall be determined by the testing < 0.0005 %.
laboratory and supporting data shall be maintained on file to 14.3 Copper (Low Carbon), granular (10 mesh to 30 mesh)
validate these ranges. (Note 1).
13.3 Crucible Tongs—Capable of handling recommended
crucibles.
4
Reagent Chemicals, American Chemical Society Specifications, American
14. Reagents Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
14.1 Purity of Reagents—Reagent grade chemicals shall be
Chemicals, BDH Ltd., Poole, Dorset, U.K. (http://uk.vwr.com), and the United
used in all tests. Unless otherwise indicated, it is intended that States Pharmacopeia—National Formulary, U.S. Pharmacopeial Convention, Inc.
all reagents shall conform to the specifications of the Commit- (USPC), Rockville, MD (http://www.usp.org/USPNF).
3
E1019 − 11
15.2 Test the furnace and analyzer to ensure the absence of
leaks and make the required electrical power connections.
Prepare the analyzer for operation in a manner consistent with
the manufacturer’s instructions. Change the chemical reagents
and filters at the intervals recommended by the instrument
manufacturer. Make a minimum of two determinations using
the specimen and accelerator as directed in 18.1.2 and 18.1.3 to
condition the instrument before attempting to calibrate the
system or determine the blank. Avoid the use of reference
materials for instrument conditioning.
16. Sample Preparation

16.1 The specimens should be uniform in size, but not finer
than 40 mesh. Specimens will typically be in the form of chips,
drillings, slugs, or solids. Specimens shall be free of any
residual lubricants and cutting fluids. It may be necessary to
clean specimens to remove residual lubricants and cutting
fluids. Any cleaned specimens shall be rinsed in acetone and
dried completely before analysis.
16.2 If necessary, wash in acetone or another suitable
solvent and dry.
17. Calibration
A—Oxygen Cylinder G—CO-CO2 Converter
B—Two Stage Regulator H—SO3 Trap 17.1 Calibration Reference Materials (Note 2):
C—Sodium Hydroxide Impregnated Clay I—CO2 IR Cell/Readout
D—Magnesium Percholorate J—Induction Furnace
17.1.1 For Range I, 0.005 % to 0.10 % carbon, select three
E—Regulator K—Combustion Area certified reference materials containing approximately
F—Flow Controller L—Dust Trap 0.005 %, 0.05 %, and 0.10 % carbon and designate them as
Calibrants A, B, and C, respectively. Some labs may use
FIG. 2 Infrared Absorption Test Method A
accelerator with a certified carbon value as Calibrant A.
17.1.2 For Range II, 0.10 % to 1.25 % carbon, select two
certified reference materials containing approximately 0.12 %
14.4 Magnesium Perchlorate, (known commercially as An- and 1.00 % carbon and designate them as Calibrants BB and
hydrone) — Use the purity specified by the instrument manu- CC, respectively.
facturer. 17.1.3 For Range III, 1.25 % to 4.50 % carbon, select two
14.5 Oxygen—Purity as specified by the instrument manu- certified reference materials containing approximately 1.25 %
facturer. and 4.00 % carbon and designate them as Calibrants BBB and
14.6 Platinum or Platinized Silica, heated to 350 °C for the CCC, respectively.
conversion of carbon monoxide to carbon dioxide. Use the NOTE 2—The uncertainty of results obtained using this test method is
form specified by the instrument manufacturer. dependent on the uncertainty of the values assigned to the calibration
reference materials. The homogeneity of the reference materials shall be
14.7 Sodium Hydroxide, on clay (known commercially as considered as well, if it was not included in the derivation of the published
Ascarite II) — Use the purity specified by the instrument uncertainty values.
manufacturer. 17.2 Adjustment of Response of Measurement System:
14.8 Tungsten (Low Carbon) Accelerator, 12 mesh to 20 17.2.1 Modern instruments may not require adjustment of
mesh (Note 1). the measurement system response prior to calibration. For
these instruments proceed directly to 17.3 after the condition-
14.9 Tungsten-Tin (Low Carbon) Accelerator, 20 mesh to 40
ing runs described in 15.2.
mesh or 12 mesh to 20 mesh.
17.2.2 Transfer 1.0 g of Calibrant B, weighed to the nearest
NOTE 1—The accelerator should contain no more than 0.001 % carbon. 1 mg, and approximately 1.5 g of accelerator to a crucible.
If necessary, wash three times with acetone by decantation to remove Some manufacturers provide scoops that dispense approxi-
organic contaminants and dry at room temperature. The mesh size is
critical to the inductive coupling which heats the sample. Some manufac-
mately 1.5 g of accelerator. Once it is verified that the scoop
turers of accelerators may not certify the mesh size on a lot to lot basis. delivers this approximate mass, it is acceptable to use this
These accelerators may be considered acceptable for use without verifying device for routine dispensing of accelerator.
the mesh size. 17.2.3 Proceed as directed in 18.1.2 and 18.1.3.
17.2.4 Repeat 17.2.2 and 17.2.3 until the absence of drift is
15. Preparation of Apparatus indicated by stable carbon readings being obtained. Consis-
15.1 Assemble the apparatus as recommended by the manu- tency is indicated by consecutive runs agreeing within 0.001 %
facturer. carbon. If using an instrument which requires manual
4
E1019 − 11
A—Oxygen Cylinder G—Orifice

B—Two Stage Regulator H—Pressure Regulator
C—Sodium Hydroxide Impregnated Clay I—Combustion Chamber
D—Magnesium Percholorate J—CO to CO2 Converter
E—Dust Trap K—SO3 Trap
F—IR Cell/Readout L—Measure Flow Rotameter
FIG. 3 Infrared Absorption Test Method B
adjustment, adjust the signal to provide a reading within 17.6 Calibration—Range I (0.005 % to 0.10 % Carbon):
6 0.003 of the certified percent carbon value for the certified 17.6.1 Weigh four 1.0 g specimens of Calibrant C, to the
reference material. nearest 1 mg, then place in crucibles. To each, add approxi-
17.3 Determination of Blank Reading—Range I: mately 1.5 g of accelerator (see Note 5).
17.3.1 Add approximately 1.5 g of accelerator into a cru- 17.6.2 Follow the calibration procedure recommended by
cible. If required, 1.0 g of Calibrant A, weighed to the nearest the manufacturer. Use Calibrant C as the primary calibrant and
1 mg, may be added to the crucible. analyze at least three specimens to determine the measurement
17.3.2 Proceed as directed in 18.1.2 and 18.1.3. response to be used in the calibration regression. Treat each
17.3.3 Repeat 17.3.1 and 17.3.2 a sufficient number of times specimen, as directed in 18.1.2 and 18.1.3, before proceeding
to establish that low (less than 0.002 % carbon) and stable to the next one.
(6 0.0002 % carbon) readings are obtained. Blank values are 17.6.3 Confirm the calibration by analyzing Calibrant C
equal to the total result of the accelerator. If Calibrant A was following the calibration procedure. The result should agree
used, blank values are equal to the total result of the accelerator with the certified value within a suitable confidence interval
and Calibrant A minus the certified value of Calibrant A. (see Note 4). If the result agrees with the certified value within
17.3.4 Record the average value of the last three or more the uncertainty provided on the certificate of analysis, the
stable blank determinations. calibration is acceptable. Also, if the certified value falls within
17.3.5 If the blank readings are too high or unstable, an interval calculated as described in Eq 1, the calibration is
determine the cause, correct it, and repeat the steps as directed acceptable.
in 17.3.1 – 17.3.4.
Test Result 2 t·s # Certified Value # Test Result1t 2 s (1)
17.3.6 Enter the average blank value in the analyzer (Note
3). Refer to the manufacturer’s instructions for specific instruc- where:
tions on performing this function. Typically the instrument will s = standard deviation of the analyses run in 17.6,
electronically compensate for the blank value. n = number of analyses (that is, 3 to 5), and
t = Student’s t value, which is for n = 3, t = 4.30; for n = 4,
NOTE 3—If the unit does not have this function, the blank value shall be
subtracted from the total result prior to any calculation. t = 3.18; for n = 5, t = 2.78 at the 95 % confidence level.
NOTE 4—The procedure for verifying calibrants outlined in the original
17.4 Determination of Blank Reading—Range II—Proceed version of this test method required the test result to be compared to “the
as directed in 17.3. uncertainty limits of the certified value for the calibrant,” typically
17.5 Determination of Blank Reading—Range III: interpreted as the range defined by the certified value plus or minus its
associated uncertainty. The original version was utilized in the generation
17.5.1 Transfer 0.5 g of Calibrant A, weighed to the nearest of the data in this test method’s precision and bias statements. The current
1 mg, and approximately 1.5 g of accelerator to a crucible. method in 17.6.3 for confirming the standardization is statistically
17.5.2 Proceed as directed in 17.3.2 – 17.3.6. rigorous and should be used in general practice. As an option, the
5
E1019 − 11
A—Oxygen Cylinder G—Furnace

B—Sodium Hydroxide Impregnated Clay H—Pump
C—Magnesium Perchlorate I—Flow Meter
D—Press Regulator J—Exhaust
E—IR Cell/Readout K—CO to CO2 Converter
F—Dust Trap L—SO3 Trap
FIG. 4 Infrared Absorption Test Method C—Closed Loop
laboratory may obtain an estimate of s from a control chart maintained as 17.7 Calibration—Range II (0.10 % to 1.25 % carbon):
part of their quality control program. If the control chart contains a large
17.7.1 Proceed as directed in 17.6.1 – 17.6.3, using Cali-
number of measurements (n > 30), t may be set equal to 2 at the 95 %
confidence level. At its discretion, the laboratory may choose to set a brant CC.
smaller range for the acceptable test result. 17.7.2 Proceed as directed in 17.6.4 – 17.6.6, using Cali-
17.6.4 Weigh at least two 1.0 g specimens of Calibrant B, brant BB.
weighed to the nearest 1 mg, and transfer them to crucibles. To 17.8 Calibration—Range III (1.25 % to 4.50 % carbon):
each, add approximately 1.5 g of accelerator. 17.8.1 Weigh four 0.5 g specimens of Calibrant CCC, to the
17.6.5 Treat each specimen as directed in 18.1.2 and 18.1.3 nearest 1 mg, and place in crucibles. To each, add approxi-
before proceeding to the next one. mately 1.5 g of accelerator. Follow the calibration procedure
17.6.6 Record the results of 17.6.4 and 17.6.5 and compare recommended by the manufacturer. Use Calibrant CCC as the
them to the certified carbon value of Calibrant B. The result primary calibrant and analyze at least three specimens to
should agree with the certified value within a suitable confi- determine the calibration slope. Treat each specimen, as
dence interval (see Note 4). If the result agrees with the directed in 18.1.2 and 18.1.3, before proceeding to the next
certified value within the uncertainty provided on the certificate one.
of analysis, the calibration is acceptable. Also, if the certified
17.8.2 Confirm the calibration by analyzing Calibrant CCC
value falls within an interval calculated as described in Eq 1,
following the calibration procedure. The result should agree
the calibration is acceptable. If not, refer to the manufacturer’s
with the certified value within a suitable confidence interval
instructions for checking the linearity of the system.
(see Note 4). If the result agrees with the certified value within
NOTE 5—The use of 1.5 g of accelerator may not be sufficient for all the uncertainty provided on the certificate of analysis, the
determinators. The required amount is determined by the analyzer used, calibration is acceptable. Also, if the certified value falls within
induction coil spacing, position of the crucible in the induction coil, age an interval calculated as described in Eq 1, the calibration is
and strength of the oscillator tube, and type of crucible being used. Use the
amount required to produce proper sample combustion using the same acceptable.
amount throughout the entire test method. 17.8.3 If not, repeat 17.8.1 and 17.8.2.
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E1019 − 11
17.8.4 Weigh at least two 0.5 g specimens of Calibrant Calculation of the calibration function shall be done using a
BBB, weighed to the nearest 1 mg, and transfer to crucibles. To linear least squares regression. Some manufacturers recom-
each, add approximately 1.5 g of accelerator. mend the use of a curve weighting factor where the calibrant
17.8.5 Treat each specimen as described in 18.1.2 and concentration is derived as 1/X. It is acceptable to use this type
18.1.3 before proceeding to the next one. of curve weighting.
17.8.6 Record the results of 17.8.4 and 17.8.5 and compare 19.2 Since most modern commercially available instru-
to the certified carbon value of Calibrant BBB. The result ments calculate mass fraction concentrations directly, includ-
should agree with the certified value within a suitable confi- ing corrections for blank and sample mass, manual calculations
dence interval (see Note 4). If the result agrees with the by the analyst are not required.
certified value within the uncertainty provided on the certificate
of analysis, the calibration is acceptable. Also, if the certified NOTE 7—If the analyzer does not compensate for blank and sample
mass values, then use the following formula:
value falls within an interval calculated as described in Eq 1,
the calibration is acceptable. If not, refer to manufacturer’s Carbon, % 5 @ ~ A 2 B ! 3 C/D # (3)
instructions for checking the linearity of the analyzer (Note 6). where:
NOTE 6—Verify the calibration when: (1) a different lot of crucibles is A = DVM (Digital Volt Meter) reading for specimen,
used, (2) a different lot of accelerator is used, (3) the system has been in B = DVM reading for blank,
use for 4 h, (4) the oxygen supply has been changed, and (5) the system C = mass compensator setting, and
has been idle for 1 h. Verification should consist of analyzing at least one D = specimen mass, g.
specimen of each calibrant. Recalibrate as necessary.
20. Precision and Bias5
18. Procedure 20.1 Precision—Nine laboratories cooperated in testing this
18.1 Procedure—Range I: test method and obtained the data summarized in Tables 1-3.
18.1.1 Stabilize the furnace and analyzer as directed in Testing was performed in compliance with Practice E173 (see
Section 15. Transfer approximately 1.0 g of specimen and 9.1).
approximately 1.5 g of accelerator to a crucible. (See 13.2.) 20.2 Bias—No information on the bias of this method is
18.1.2 Place the crucible on the furnace pedestal and raise known because at the time of the interlaboratory study, suitable
the pedestal into position. Use crucible tongs to handle the reference materials were not available. The user of this method
crucibles. is encouraged to employ accepted reference materials, if
18.1.3 Refer to the manufacturer’s recommended procedure available, to determine the presence or absence of bias.
regarding entry of specimen mass and blank value. Start the
analysis cycle.
SULFUR BY THE COMBUSTION–INFRARED
18.2 Procedure—Range II—Proceed as directed in 18.1. ABSORPTION TEST METHOD (POTASSIUM
18.3 Procedure—Range III—Proceed as directed in 18.1, SULFATE CALIBRATION)
using a 0.5 g specimen.
21. Scope
19. Calculation 21.1 This test method covers the determination of sulfur in
19.1 The calibration function of the equipment shall yield a the range of 0.001 % to 0.01 %. As written, this test method is
linear plot described by Eq 2. not applicable to cast iron samples.
Y 5 mX1b (2) 22. Summary of Test Method
where: 22.1 The sample is combusted in a stream of oxygen that
converts the sulfur in the sample to sulfur dioxide. The sulfur
Y = measurement response,
is measured using infrared absorption spectrometry
M = slope,
X = calibrant concentration, and 5
Supporting data are available from ASTM International Headquarters. Request
b = Y intercept.
RR:E01-1093.
TABLE 1 Statistical Information—Carbon, Range I

Repeatability Reproducibility
Test Specimen Carbon Found, %
(R1, Practice E173) (R2, Practice E173)
1. Electrolytic iron (NIST 365, 0.0068 C) 0.007 0.002 0.003
2. Bessemer carbon steel (NIST 8j, 0.081 C) 0.080 0.003 0.006
3. Type 304L stainless steel 18Cr-8Ni (NIST 101f, 0.014 C) 0.014 0.002 0.004
4. Type 446 stainless steel 26Cr (NIST 367, 0.093 C) 0.094 0.003 0.004
5. Nickel steel 36Ni (NIST 126b, 0.090 C) 0.092 0.003 0.004
6. Waspaloy 57Ni-20Cr-14Co-4Mo (NIST 349, 0.080 C) 0.078 0.003 0.004
7. Silicon steel (NIST 131a, 0.004 C) 0.004 0.002 0.002
8. High temperature alloy A286 26Ni-15Cr (NIST 348, 0.044 C) 0.046 0.003 0.004
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E1019 − 11
TABLE 2 Statistical Information—Carbon, Range II
1. Basic open hearth steel (NIST 11h, 0.200 C) 0.201 0.006 0.010
2. Basic open hearth carbon steel (NIST 337, 1.07 C) 1.087 0.039 0.053
3. Low alloy electric furnace steel (NIST 51b, 1.21 C) 1.224 0.039 0.048
4. High temperature nickel alloy (LE 105, 0.130 C) 0.130 0.005 0.008
5. Tool steel 8Co-9Mo-2W-4Cr-2V (NIST 153a, 0.902 C) 0.905 0.023 0.027
6. Type 416 stainless steel (NIST 133b, 0.128 C) 0.126 0.005 0.013
7. Low alloy steel 1Cr (NIST 163, 0.933 C) 0.934 0.016 0.020
TABLE 3 Statistical Information—Carbon, Range III

1. Tool steel (CISRI 150, 1.56 C) 1.550 0.027 0.049
2. Low alloy electric furnace steel (NIST 51b, 1.21 C) 1.228 0.039 0.050
3. Cast iron (LECO 501-105, 2.20 C) 2.202 0.044 0.056
4. Ductile iron (LECO 501-083, 4.24 C) 4.244 0.083 0.091
5. White iron (LECO 501-024, 3.25 C) 3.274 0.064 0.074
6. Iron (BAM 035-1, 1.31 C) 1.314 0.034 0.048
7. Ferritic stainless steel (BAM 228-1, 2.05 C) 2.040 0.027 0.055
22.1.1 Infrared Absorption Test Method A—Sulfur dioxide energy, therefore a loss in signal results which is proportional
(SO2) absorbs IR energy at a precise wavelength within the IR to the concentration of the gas in the closed loop. Total sulfur,
spectrum. Energy of this wavelength is absorbed as the gas as SO2, is measured over a period of time. Refer to Fig. 6.
passes through a cell body in which the IR energy is transmit- 22.1.3 Infrared Absorption Test Method C—The detector
ted. All other IR energy is eliminated from reaching the consists of an IR energy source, a separate measure chamber
detector by a precise wavelength filter. Therefore, the absorp- and reference chamber, and a diaphragm acting as one plate of
tion of IR energy can be attributed to only SO2 and its a parallel plate capacitor. During specimen combustion, the
concentration is measured as changes in energy at the detector. flow of SO2 with its oxygen gas carrier is routed through the
One cell is used as both a reference and a measure chamber. measure chamber while oxygen alone passes through the
Total sulfur, as SO2, is monitored and measured over a period reference chamber. Energy from the IR source passes through
of time. Refer to Fig. 5. both chambers, simultaneously arriving at the diaphragm
22.1.2 Infrared Absorption Test Method B—The combustion (capacitor plate). Part of the IR energy is absorbed by the SO2
is performed in a closed loop where SO2 is detected in an present in the measure chamber while none is absorbed passing
infrared cell. The SO2 is measured with a solid state energy through the reference chamber. This creates an IR energy
detector, and filters are used to pass the appropriate IR imbalance reaching the diaphragm, thus distorting it. This
wavelength to the detector. During combustion, the IR absorp- distortion alters the fixed capacitance creating an electric signal
tion properties of the SO2 gas in the chamber causes a loss of change that is amplified for measurement as SO2. Total SO2 is
measured over a period of time. Refer to Fig. 7.
23. Interferences
23.1 The elements ordinarily present do not interfere. For
the scope of elements typically found in materials to be tested
by this method refer to 1.1.
24. Apparatus
24.1 Combustion and Measurement Apparatus—See Figs.
5-7.
24.2 Crucibles—Use crucibles that meet or exceed the
specifications of the instrument manufacturer and prepare the
crucibles by heating in a suitable furnace for not less than 40
min at approximately 1000 °C. Remove from the furnace and
cool before use. Crucibles may be stored in a desiccator prior
to use. Above certain concentrations, as determined by the
A—Oxygen Cylinder F—Flow Controller
B—Two Stage Regulator G—IR Cell/Readout testing laboratory, the nontreatment of crucibles will have no
C—Sodium Hydroxide Impregnated Clay H—Induction Furnace adverse effect. The analytical ranges for the use of untreated
D—Magnesium Perchlorate I—Combustion Area
E—Regulator J—Dust Trap
crucibles shall be specified by the testing laboratory, and
supporting data shall be maintained on file to validate these
FIG. 5 Infrared Absorption Test Method A ranges.
8
E1019 − 11
A—Oxygen Cylinder F—Dust Trap

B—Sodium Hydroxide Impregnated Clay G—Furnace
C—Magnesium Perchlorate H—Pump
D—Press Regulator I—Flow Meter
E—IR Cell/Readout J—Exhaust
FIG. 6 Infrared Absorption Test Method B
A—Oxygen Cylinder F—IR Detector/Readout

B—Two Stage Regulator G—Orifice
C—Sodium Hydroxide Impregnated Clay H—Pressure Regulator
D—Magnesium Perchlorate I—Combustion Chamber
E—Dust Trap J—Measure Flow Rotameter
FIG. 7 Infrared Absorption Test Method C
24.3 Micropipet, (50 µL).
9
E1019 − 11
24.4 Crucible Tongs—Capable of handling recommended specimen and accelerator as directed in 29.2 and 29.3 to
crucibles. condition the instrument before attempting to calibrate the
24.5 Tin Capsules—Approximate dimensions: diameter 6 system or determine the blank. Avoid the use of reference
mm, length 20 mm. Use the purity specified by the instrument materials for instrument conditioning.
manufacturer. Wash twice with acetone and dry at approxi-
mately 90 °C for not less than 4 h prior to use.
27.1 The specimen should be uniform in size, but not finer
25. Reagents than 40 mesh. Specimens will typically be in the form of chips,
drillings, slugs, or solids. Specimens shall be free of any
25.1 Purity of Reagents—Reagent grade chemicals shall be
residual lubricants or cutting fluids, or both. It may be
used in all tests. Unless otherwise indicated, it is intended that
necessary to clean specimens to remove residual lubricants or
all reagents shall conform to the specifications of the Commit-
cutting fluids, or both. Any cleaned specimens shall be rinsed
tee on Analytical Reagents of the American Chemical Society,
in acetone and dried completely before analysis.
where such specifications are available.4 Other grades may be
used, provided it is first ascertained that the reagent is of 28. Calibration
sufficiently high purity to permit its use without lessening the
accuracy of the determination. 28.1 Calibration Reference Materials:
28.1.1 Weigh to the nearest 0.0001 g the following masses
25.2 Acetone—The residue after evaporation shall be of K2SO4 to obtain the indicated solution concentrations:
< 0.0005 %.
Sulfur Concentration
25.3 Iron (purity, 99.8 % minimum)—shall be free of sulfur Sulfur Solution K2SO4 (g) (mg/mL)
or contain a low known sulfur content. A 0.1087 0.2
B 0.2718 0.5
25.4 Magnesium Perchlorate, (known commercially as An- C 0.5435 1.0
D 1.0870 2.0
hydrone). Use the purity specified by the instrument manufac- H 0.0000 0.0
turer.
28.1.2 Dissolve each quantity of K2SO4 in 50 mL of water
25.5 Oxygen—Purity as specified by the instrument manu- in five 100-mL beakers.
facturer. 28.1.3 Transfer quantitatively each solution to a 100-mL
25.6 Potassium Sulfate (K2SO4)—Dry 20 g of K2SO4 at volumetric flask. Dilute to volume and mix.
105 °C to 110 °C for not less than 1 h to a constant mass. Cool 28.1.4 Using a pipet, transfer 50 µL of the following sulfur
in a desiccator. solutions to individual tin capsules. Prepare the number of
replicates indicated and then proceed as directed in 28.1.5.
25.7 Sodium Hydroxide, on clay (known commercially as
S, % in the Number of
Ascarite II). Use the purity specified by the instrument manu- Sulfur Solution S (µg) Test Portion Replicates
facturer. H 0 0.0000 5
A 10 0.0010 2
25.8 Tungsten Accelerator (Low Sulfur): Minus 20 mesh to B 25 0.0025 5
+40 mesh. C 50 0.0050 2
D 100 0.0100 5
25.9 Tungsten-Tin Accelerator, Minus 12 mesh to +40 mesh
or –12 mesh to +20 mesh. 28.1.5 Dry the tin capsules slowly at about 90 °C to full
dryness, and cool in a desiccator. Compress the top part of the
NOTE 8—The accelerator should contain no more than 0.001 % sulfur. tin capsule before placing in the instrument.
If necessary, wash three times with acetone by decantation to remove
organic contaminants and dry at room temperature. The mesh size is 28.2 Adjustment of Response of Measurement System:
critical to the inductive coupling that heats the sample. Some manufac- 28.2.1 Modern instruments may not require adjustment of
turers of accelerators may not certify the mesh size on a lot to lot basis. the measurement system response prior to calibration. For
These accelerators may be considered acceptable for use without verifying
the mesh size.
these instruments proceed directly to 28.3 after the condition-
ing runs described in 26.2.
25.10 Purity of Water—Unless otherwise indicated, refer- 28.2.2 Transfer one dried capsule of sulfur solution B to a
ences to water shall be understood to mean reagent water as crucible. Add approximately 1.0 g of pure iron, weighed to the
defined by Type II of Specification D1193. nearest 5 mg, and approximately 1.5 g of tungsten accelerator
to the crucible. Proceed as directed in 29.2 and 29.3.
26. Preparation of Apparatus 28.2.3 Repeat 28.2.2 until the absence of drift is indicated
26.1 Assemble the apparatus as recommended by the manu- by stable sulfur readings being obtained. Stability is indicated
facturer. by consecutive runs agreeing within 0.0002 % sulfur. Prepare
26.2 Test the furnace and analyzer to ensure the absence of more capsules of sulfur solution B if necessary. If using an
leaks, and make the required electrical power connections. instrument that requires manual adjustment, adjust the signal to
Prepare the analyzer for operation in accordance with manu- provide a reading of 0.0025 % 6 0.0003 % sulfur.
facturer’s instructions. Change the chemical reagents and 28.3 Determination of Blank Reading:
filters at the intervals recommended by the instrument manu- 28.3.1 Transfer one dried capsule of sulfur solution H to a
facturer. Make a minimum of two determinations using the crucible. Add approximately 1.0 g of pure iron, weighed to the
10
E1019 − 11
nearest 5 mg, and approximately 1.5 g of accelerator to the NOTE 10—Verify the calibration when: (1) a different lot of crucibles is
crucible. Some manufacturers provide scoops that dispense used, (2) a different lot of accelerator is used, (3) the system been idle for
1 h, (4) the system has been in use for 4 h, and (5) the oxygen supply has
approximately 1.5 g of accelerator. Once it is verified that the been changed. Verification should consist of analyzing at least one
scoop delivers this approximate mass, it is acceptable to use specimen of each calibrant. Recalibrate as necessary.
this device for routine dispensing of accelerator. Proceed as
directed in 29.2 and 29.3. 29. Procedure
28.3.2 Repeat 28.3.1 a sufficient number of times to estab-
29.1 Stabilize the furnace and analyzer as directed in
lish that low (less than 0.0005 % of sulfur) and stable (6
Section 26. Transfer approximately 1.0 g of specimen, weighed
0.0002 % of sulfur) readings are obtained. Blank values are
to the nearest 1 mg, and approximately 1.5 g of accelerator to
equal to the total result of accelerator, iron, and tin capsule of
a crucible. (See 24.2.)
solution H (purified water).
28.3.3 Record the average value of at least three consecutive 29.2 Place the crucible on the furnace pedestal and raise the
blank determinations. pedestal into position. Use crucible tongs to handle the
28.3.4 If the blank readings are too high or unstable, crucibles.
determine the cause, correct it, and repeat the steps as directed 29.3 Refer to manufacturer’s recommended procedure re-
in 28.3.1 – 28.3.3. Prepare more capsules of sulfur solution H garding entry of specimen mass and blank value. Start the
if necessary. analysis cycle.
28.3.5 Enter the average blank value in the analyzer (Note NOTE 11—This procedure is for analysis of steel samples and a new
9). Refer to the manufacturer’s instructions for specific proto- blank shall be determined using approximately 1.5 g of accelerator only.
col for performing this function. Typically the instrument will Refer to 62.3.
electronically compensate for the blank value.
30. Calculation
NOTE 9—If the unit does not have this function, the blank value shall be
subtracted from the total result prior to any calculation. 30.1 The calibration function of the equipment shall yield a
linear plot described by Eq 4. Calculation of the calibration
28.4 Calibration:
function shall be done using a linear least squares regression.
28.4.1 Transfer four dried capsules of sulfur solution D to
Some manufacturers recommend the use of a curve weighting
crucibles. Add approximately 1.0 g of pure iron, weighed to the
factor where the calibrant concentration is derived as 1/X. It is
nearest 5 mg, and approximately 1.5 g of accelerator to each
acceptable to use this type of curve weighting.
crucible.
28.4.2 Follow calibration procedure recommended by the 30.2 Since most modern commercially available instru-
manufacturer using dried capsules of sulfur solution D as the ments calculate mass fraction concentrations directly, includ-
primary calibrant, analyzing at least three specimens to deter- ing corrections for blank and sample mass, manual calculations
mine the measurement response to be used in the calibration by the analyst are not required.
regression. Treat each capsule as directed in 29.2 and 29.3 NOTE 12—If the analyzer does not compensate for blank and sample
before proceeding to the next one. mass values, then use the following formula:
28.4.3 Confirm the calibration by analyzing a capsule of
Sulfur, % 5 @ ~ A 2 B ! 3 C/D # (4)
sulfur solution D after the calibration procedure. The value
should be 0.0100 % 6 0.0005 % sulfur. If not, repeat 28.4.1 where:
and 28.4.2. A = DVM (Digital Volt Meter) reading for specimen,
28.4.4 Transfer two dried capsules of sulfur solution A, B, B = DVM reading for blank,
and C to crucibles. Add approximately 1.0 g of pure iron, C = mass compensator setting, and
D = specimen mass, g.
weighed to the nearest 5 mg, and approximately 1.5 g of
accelerator to each crucible.
31. Precision and Bias6
28.4.5 Treat each capsule as directed in 29.2 and 29.3 before
proceeding to the next one. 31.1 Precision—Twenty-five laboratories participated in
28.4.6 Record the results of 28.4.5 and compare them to the testing this method under the auspices of WG-3 of ISO
theoretical sulfur values solutions A, B, and C. If they are not
within 0.0003 % of the theoretical concentrations of sulfur in
the test portions, refer to the manufacturer’s instructions for 6
checking the linearity of the system. RR:E01-1041.
TABLE 4 Statistical Information—Sulfur

Test Specimen Sulfur Found, %
Low alloy steel (JK 24, 0.0010 S) 0.0010 0.00045 0.00051
Stainless steel (NIST 348, 0.0020 S) 0.00198 0.0005 0.00064
Silicon steel (IRSID 114-1, 0.0037 S) 0.00322 0.00051 0.0007
Plain carbon steel (JSS 240-8, 0.0060 S) 0.00549 0.00055 0.00099
Stainless steel (JSS 652-7, 0.0064 S) 0.00615 0.00084 0.00087
11
E1019 − 11
Committee TC 17/SC 1 and obtained the data summarized in laboratories should perform method validation using reference materials.
Table 4. Testing was performed in compliance with Practice
33. Summary of Test Method
E173 (refer to 9.1).
33.1 The specimen, contained in a small, single-use graphite
31.2 Bias—No information on the bias of this test method is
crucible, is fused under a flowing helium atmosphere at a
known because suitable reference materials were not available
minimum temperature of 1900 °C. Nitrogen present in the
at the time of the interlaboratory study. The user of this test
sample is released as molecular nitrogen into the flowing
method is encouraged to employ accepted reference materials,
helium stream. The nitrogen is separated from other liberated
if available, to determine the presence or absence of bias.
gases such as hydrogen and carbon monoxide and is finally
measured in a thermal conductivity cell. Refer to Figs. 8-11.
NITROGEN BY THE INERT GAS FUSION 33.2 This test method is written for use with commercial
THERMAL CONDUCTIVITY TEST METHOD analyzers equipped to perform the above operations automati-
32. Scope cally and calibrated using reference materials of known nitro-
gen content.
32.1 This test method covers the determination of nitrogen
(N) in concentrations from 0.0010 % to 0.2 % (Note 13). 34. Interferences
NOTE 13—The upper limit of the scope has been set at 0.2 % because 34.1 The elements ordinarily present do not interfere. For
sufficient numbers of test materials containing higher nitrogen contents the scope of elements typically found in materials to be tested
were unavailable for testing in accordance with Practice E173. However, by this method refer to 1.1.
recognizing that commercial nitrogen determinators are capable of han-
dling higher concentrations, this test method provides a calibration 35. Apparatus
procedure up to 0.5 %. Users of this test method are cautioned that use of
it above 0.2 % is not supported by interlaboratory testing. In this case, 35.1 Fusion and Measurement Apparatus—See Fig. 8.
A—Helium Supply H—Electrode Furnace

B—Pressure Regulator 2 Stage I—Dust Filter
C—Sodium Hydroxide Impregnated Clay J—Heated Rare Earth Copper Oxide
D—Magnesium Perchlorate K—Thermal Conductive Detector/Readout
E—Flow Control L—Flow Rotameter
F—Flow Manifold M—Charcoal
G—Sample Holding Chamber N—Flow Restrictor
Manifold Porting
Crucible Degas Flow

H 1 to 4
5 to 2
3 to 6
Fusion Flow
H 1 to 6
5 to 4
3&2
FIG. 8 Nitrogen Test Method A—Flow Diagram
12
E1019 − 11
A—Helium Supply I—Optional Gas Doser

B—Pressure Regulator 2 Stage J—Flow Manifold
C—Sodium Hydroxide Impregnated Clay K—Sample Holding Chamber
D—Magnesium Perchlorate L—Electrode Furnace
E—Flow Restrictor M—Dust Filter
F—Flow Meter N—Heated Rare Earth Copper Oxide
G—Pressure Meter O—Flow Control
H—Needle Valve P—Thermal Conductive Detector Readout
Manifold Porting
Crucible Degas Flow

H 2 to 4
5 to 3
1 to 6
Fusion Flow
H 1 to 4
5 to 6
2 & 3 off
FIG. 9 Nitrogen Test Method B—Flow Diagram
35.2 Graphite Crucibles—Use the size crucibles recom- 36.5 Magnesium Perchlorate, (known commercially as An-
mended by the manufacturer of the instrument. Crucibles shall hydrone). Use the purity specified by the instrument manufac-
be composed of high purity graphite. turer.
35.3 Crucible Tongs—Capable of handling recommended 36.6 Rare Earth Copper Oxide—Use the purity as specified
crucibles. by the instrument manufacturer.
36.7 Silica, as specified by the instrument manufacturer.
36. Reagents
36.8 Sodium Hydroxide, on clay, (known commercially as
36.1 Purity of Reagents—Reagent grade chemicals shall be Ascarite II). Use the purity as specified by the instrument
used in all tests. Unless otherwise indicated, it is intended that manufacturer.
tee on Analytical Reagents of the American Chemical Society, 37. Preparation of Apparatus
used, provided it is first ascertained that the reagent is of 37.1 Assemble the apparatus as recommended by the manu-
sufficiently high purity to permit its use without lessening the facturer.
accuracy of the determination. 37.2 Test the furnace and analyzer to ensure the absence of
36.2 Acetone—The residue after evaporation shall be leaks, and make the required electrical power and water
<0.0005 %. connections. Prepare the apparatus for operation in a manner
consistent with the manufacturer’s instructions. Change the
36.3 Copper—, use the purity and form specified by the chemical reagents and filters at the intervals recommended by
instrument manufacturer. the instrument manufacturer. Make a minimum of two deter-
36.4 Helium, high-purity (99.99 %). minations using a specimen as directed in 40.2.1 or 40.2.2 to
13
E1019 − 11
A—Helium Supply I—Sample Holding Chamber

B—Pressure Regulator J—Electrode Furnace
C—Heated Copper K—Dust Filter
D—Sodium Hydroxide Impregnated Clay L—Heated Rare Earth Copper Oxide
E—Magnesium Perchlorate M—Magnesium Perchlorate
F—Flow Control N—Silica Column
G—Flow Manifold O—Thermal Conductive Detector/Readout
H—Optional Gas Doser P—Flow Rotameter
Manifold Porting
Crucible Degas Flow

H 1 to 4
5 to 2
3 to 6
Fusion Flow
H 1 to 6
5 to 4
3 & 2 off
FIG. 10 Nitrogen/Oxygen Test Method A—Flow Diagram
condition the instrument before attempting to calibrate the lubricants and cutting fluids. It may be necessary to clean
system or to determine the blank. Avoid the use of reference specimens to remove residual lubricants and cutting fluids. Any
materials for instrument conditioning. cleaned specimens shall be rinsed in acetone and dried com-
pletely before analysis
38.4 Handle prepared specimens with tweezers; not with
38.1 Practice E1806 provides some guidance for sampling bare hands.
and preparation of steel and iron alloys for gas analysis.
Specimens will typically be in the form of chips, drillings, 39. Calibration
slugs, or solids. Final specimen preparation shall be performed 39.1 Reference Materials:
as directed in 38.2 or 38.3 (Note 14). 39.1.1 For Range I of 0.0005 % to 0.10 % nitrogen, select
NOTE 14—Size all specimens to permit free introduction through the five certified reference materials containing approximately
loading device of the equipment or directly into the graphite crucible. 0.002 %, 0.01 %, 0.03 %, 0.05 %, and 0.10 % nitrogen and
38.2 If a slug or solid-form specimens are used, cut them designate them as Calibrants A, B, C, D, and E, respectively
with a water-cooled abrasive cut-off wheel or by another means (Note 15).
that will prevent overheating. Abrade the surface to remove 39.1.2 For Range II of 0.10 % to 0.50 % nitrogen, select
surface oxidation Using a clean file, die grinder, or silicon three certified reference materials containing approximately
carbide grinding media. Again, care must be taken not to 0.10 %, 0.30 %, and 0.50 % nitrogen and designate them as
overheat the sample. If specimens are wet ground it will be Calibrants AA, BB, and CC, respectively (Note 15).
necessary to rinse specimens in water followed by an acetone NOTE 15—The uncertainty of results obtained using this test method is
rinse. Samples shall be air dried well prior to analysis. dependent on the uncertainty of the values assigned to the calibration
38.3 Clean, dry chips and millings may be analyzed without considered as well, if it was not included in the derivation of the published
additional preparation; however, specimens shall be free of any uncertainty values.
14
E1019 − 11
A—Helium Supply J—Flow Manifold

B—Pressure Regulator 2 Stage K—Sample Holding Chamber
C—Sodium Hydroxide Impregnated Clay L—Electrode Furnace
D—Magnesium Perchlorate M—Dust Filter
E—Flow Restrictor N—Heated Rare Earth Copper Oxide
F—Flow Meter O—Flow Control
G—Pressure Regulator P—IR Detector/Readout
H—Needle Valve Q—Thermal Conductive Detector Readout
I—Optional Gas Doser
Manifold Porting
Crucible Degas Flow

H 2 to 4
5 to 3
1 to 6
Fusion Flow
H 1 to 4
5 to 6
2 & 3 off
FIG. 11 Nitrogen/Oxygen Test Method B—Flow Diagram
39.2 Adjustment of Response of Measurement System: 39.3.3 If the blank values exceed 0.0003 % or a spread of
39.2.1 Modern instruments may not require adjustment of three consecutive values exceeds 0.0003 %, then determine the
the measurement system response prior to calibration. For cause, make necessary corrections, and repeat 39.3.1 and
these instruments proceed directly to 39.3 after performing the 39.3.2.
conditioning runs described in 37.2. 39.3.4 Record the average value of at least three blank
39.2.2 Prepare an approximate 1.0 g specimen of Calibrant readings.
C weighed to the nearest 1 mg as directed in 38.2 or 38.3. 39.3.5 Enter the average blank value in the appropriate
39.2.3 Proceed as directed in 40.2.1 or 40.2.2. mechanism of the analyzer (Note 17). Refer to the manufac-
39.2.4 Repeat 39.2.2 and 39.2.3 and adjust as recommended turer’s instructions for specific instructions on performing this
by the manufacturer until the absence of drift is indicated by function. This mechanism will electronically compensate for
consecutive runs agreeing within 0.0004 %. the blank value.
39.3 Determination of Blank Reading—Ranges I and II: NOTE 17—If the unit does not have this function, the average blank
39.3.1 If the instrument is equipped with an electronic blank value shall be subtracted from the DVM readings for reference materials
compensator, adjust to zero, and proceed with the determina- and specimens (Note 21).
tion of the blank value. 39.4 Calibration Procedure—Range I:
39.3.2 Make three blank determinations as directed in 39.4.1 Prepare four 1.0 g specimens of Calibrant D weighed
40.2.1 or 40.2.2 with the sample omitted. Use a fresh crucible to the nearest 1 mg, as directed in 38.2 or 38.3.
each time (Note 16). 39.4.2 Follow the calibration procedure recommended by
NOTE 16—If the loading device is used to analyze the unknown or the manufacturer using Calibrant D as the primary calibrant.
calibration sample, see Note 14. Analyze Calibrant D at least three times to determine the
15
E1019 − 11
calibration slope. Treat each specimen as directed in 40.2.1 or 40.2.2.2 Place a 1.0 g specimen weighed to the nearest 1 mg
40.2.2 before proceeding to the next one. in the loading device. Refer to the manufacturer’s recom-
39.4.3 Confirm the calibration by analyzing Calibrant D mended procedure, including entry of sample mass.
after calibration. The result should agree with the certified 40.2.2.3 Place an empty crucible on the furnace lower
value within a suitable confidence interval (Note 4). If the electrode assembly and close the furnace.
result agrees with the certified value within the uncertainty
40.2.2.4 Start the analysis cycle, referring to the manufac-
provided on the certificate of analysis, the calibration is
turer’s recommended procedure (Notes 19 and 20).
acceptable. Also, if the certified value falls within an interval
calculated as described in Eq 5, the calibration is acceptable. If NOTE 19—If the samples are to be analyzed in the automatic mode,
not, repeat 39.4.1 and 39.4.2. blank determination and calibration should also be performed in the
test result 2 t·s # certified value # test result1t·s (5) automatic mode. If samples are to be analyzed in the manual mode, blank
determination and calibration should be performed in the manual mode.
where: Solid samples may be analyzed in either automatic or manual mode, but
drillings or chips should be analyzed in the manual mode.
s = standard deviation of the analyses run in 39.4.3,
n = number of analyses (that is, 3 to 5), and NOTE 20—The presence of nitrogen as refractory nitrides in the matrix
t = student’s t value which is for n=3. t=4.30; for n=4, t= may affect sample fusion and nitrogen evolution under standard operating
conditions of the analyzer. It is therefore recommended that calibrants be
3.18; for n= 5, t=2.78 at the 95 % confidence level.
of the same or similar composition as the samples to be analyzed when
39.4.4 Prepare two 1.0 g specimens each of Calibrants A, B, available.
C, and E weighed to the nearest 1 mg, as directed in 38.2 or
38.3. 41. Calculation
39.4.5 Treat each specimen as directed in 40.2.1 or 40.2.2 41.1 The calibration function of the equipment shall yield a
before proceeding to the next one. linear plot described by Eq 6. Calculation of the calibration
39.4.6 The result should agree with the certified value function shall be done using a linear least squares regression.
within a suitable confidence interval (Note 4). If the result Some manufacturers recommend the use of a curve weighting
agrees with the certified value within the uncertainty provided factor where the calibrant concentration is derived as 1/X. It is
on the certificate of analysis, the calibration is acceptable. Also,
if the certified value falls within an interval calculated as
described in Eq 5, the calibration is acceptable. If not, refer to 41.2 Since most modern commercially available instru-
the manufacturer’s instructions for checking the linearity of the ments calculate mass fraction concentrations directly, includ-
system. ing corrections for blank and sample mass, manual calculations
NOTE 18—Verify the calibration when: (1) a different lot of crucibles is
by the analyst are not required. (Note 21).
used, (2) the system has been idle for 1 h, (3) the system has been in use
NOTE 21—If the analyzer does not compensate for blank and sample
for 4 h, and (4) the helium supply has been changed. Verification should
consist of analyzing at least one specimen of each calibrant. Recalibrate as mass values, then the equation is:
necessary. Nitrogen, % 5 @ ~ A 2 B ! 3 C/D # (6)
39.5 Calibration Procedure—Range II: where:
39.5.1 Proceed as directed in 39.4.1 – 39.4.3 using Calibrant A = DVM (Digital Volt Meter) reading for specimen,
CC. B = DVM reading for blank,
39.5.2 Proceed as directed in 39.4.4 – 39.4.6 using Cali- C = mass compensator setting, and
brants AA and BB (Note 18). D = specimen mass, g.
40. Procedure 42. Precision and Bias7

40.1 Assemble the apparatus and condition it as directed in 42.1 Precision—Nine laboratories cooperated in testing this
Section 37. test method and obtained the precision data summarized in
Tables 5-7. Testing was performed in compliance with Practice
40.2 Procedure—Ranges I and II:
E173 (refer to 9.1).
40.2.1 Manual Operation:
40.2.1.1 Set the analyzer to operate in the manual mode. 42.2 Bias—The accuracy of this test method can be inferred
40.2.1.2 Place an empty crucible on the furnace lower from the data in Tables 5-7 by comparing the certified values
electrode assembly and close the furnace. for nitrogen with the average values obtained (Note 22).
40.2.1.3 Weigh a 1.0 g specimen to the nearest 1 mg and NOTE 22—Although this test method was tested to only 0.22 %, most
refer to the manufacturer’s recommended procedure, including commercial instruments are believed to be capable of analyzing samples
entry of sample mass. containing nitrogen up to 0.5 %.
40.2.1.4 Start the analysis cycle, referring to the manufac-
turer’s recommended procedure (Note 19).
40.2.2 Automatic Operation: 7
40.2.2.1 Set the analyzer to operate in the automatic mode. RR:E01-1051.
16
E1019 − 11
TABLE 5 Statistical Information—Nitrogen, Range I (chip)
Repeatability
Nitrogen Found, Reproducibility
Test Specimen (R1, Practice
% (R2, Practice E173)
E173)
No. 1 High purity iron (Euro CRM 088.1, 0.0009 % N) 0.0010 0.0005 0.0008
No. 2 High purity iron (JSS-001, 0.0017 % N) 0.0016 0.0004 0.0010
No. 3 Carbon steel (BAM 028/1, 0.0029 % N) 0.0033 0.0007 0.0012
No. 4 Carbon steel (JK NR3B, 0.0054 % N) 0.0051 0.0005 0.0010
No. 5 Carbon steel (JK 2D, 0.0085 % N) 0.0099 0.0013 0.0015
No. 6 Tool steel (NIST 50 C, 0.012 % N) 0.012 0.0008 0.0010
No. 7 Tool steel (NIST 153a, 0.024 % N) 0.026 0.001 0.002
No. 8 Stainless steel (NIST 73c, 0.037 % N) 0.037 0.003 0.003
No. 9 Cast iron (NIST 890, 0.089 % N) 0.088 0.004 0.008
TABLE 6 Statistical Information—Nitrogen, Range II (chip)

Nitrogen Found,
Test Specimen (R1, Practice (R2, Practice
%
E173) E173)
No. 1 High-temperature alloy A661 (Car Tech, 0.1598 % N) 0.115 0.005 0.015
No. 2 Stainless steel (NIST 367, 0.168 % N) 0.158 0.005 0.017
No. 3 Valve steel (LECO 502-016, 0.218 % N) 0.203 0.009 0.020
TABLE 7 Statistical Information—Nitrogen, Range I (solid)

Nitrogen Found,
Test Specimen (R1, Practice (R2, Practice
%
E173) E173)
No. 1 Low alloy steel (NIST 1098, 0.0032 % N) 0.0041 0.0006 0.0014
No. 2 Low alloy steel (NIST 1096, 0.0040 % N) 0.0043 0.0006 0.0011
No. 3 Cast iron (ACIPCO; 0.01 % N) 0.0076 0.0011 0.0014
No. 4 Low alloy steel 4320 (TC, 0.0080 % N) 0.0083 0.0011 0.0015
No. 5 Tool steel (LSC, 0.064 % N) 0.067 0.004 0.006
No. 6 High temperature alloy Inco 600 (LTV, 0.1 % N) 0.088 0.008 0.015
No. 7 Stainless steel, Type 316 (LTV, 0.09 % N) 0.096 0.004 0.007
OXYGEN BY THE INERT GAS FUSION gen. The oxygen combines with carbon from the crucible to
TEST METHOD form carbon monoxide (CO) and is carried by the flowing inert
gas stream to either a thermal conductivity or an infrared
43. Scope detector. In some instruments the CO is converted to carbon
43.1 This test method covers the determination of oxygen in dioxide (CO2) and detected in an infrared cell as CO2. The
the concentrations from 0.001 % to 0.005 %. detector output is compared to that obtained from similar
NOTE 23—The upper limit of the scope has been set at 0.005 % because
certified reference materials and is displayed as oxygen content
sufficient numbers of test materials containing higher oxygen contents of the sample.
were unavailable for testing in accordance with Practice E173. However,
recognizing that commercial oxygen determinators are capable of han- 44.3 In a typical instrument based on thermal conductivity
dling higher concentrations, it may be that this test method can be used for detection (Fig. 12), the sample is fused in a stream of helium
oxygen concentrations outside the scope. In this case, laboratories should which carries the released gases over copper oxide which
perform method validation using reference materials. Users of this test oxidizes CO to CO2 and hydrogen to water. The water is then
method are cautioned that use of it above 0.005 % is not supported by
interlaboratory testing. absorbed by magnesium perchlorate and the remaining nitro-
gen and carbon dioxide are separated chromatographically. The
44. Summary of Test Method nitrogen is eluted from the chromatographic column within
44.1 This test method is written for use with automated, seconds and is either measured or disregarded. The oxygen (as
commercially available analyzers that are based on the inert CO2) then elutes from the column and enters the measuring cell
gas fusion principle and use a variety of gas conditioning and of the thermistor bridge. Bridge output is integrated and the
measuring techniques. Certified reference materials should be data are processed and displayed directly as percent oxygen.
used for all calibrations. 44.4 In a typical instrument based on infrared detection
44.2 The sample, contained in a small, single-use graphite (Fig. 13), the sample is fused in a stream of inert gas and the
crucible, is fused under a flowing inert gas stream at a evolved gases are passed directly into a cell through which
temperature sufficient to release oxygen, nitrogen, and hydro- infrared energy is transmitted. The absorption of infrared
17
E1019 − 11
A—Helium Supply H—Electrode Furnace

B—Pressure Regulator I—Dust Filter A—Inert Gas I—Optional Gas Doser
C—Sodium Hydroxide Impregnated J—Heated Rare Earth Copper Oxide B—Pressure Regulator 2 Stage J—Flow Manifold
Clay K—Thermal Conductive Detector/ C—Sodium Hydroxide Impregnated Clay K—Sample Holding Chamber
D—Magnesium Perchlorate Readout D—Magnesium Perchlorate L—Electrode Furnace
E—Flow Control L—Flow Rotameter E—Flow Restrictor M—Dust Filter
F—Flow Manifold M—Optional Gas Doser F—Flow Meter N—Flow Control
G—Sample Holding Chamber G—Pressure Regulator O—IR Detector/Readout
H—Needle Valve
Manifold Porting
Crucible Degas
Flow
H 2 to 4
5 to 3
Manifold Porting
Fusion Flow
H
1 to 6
1 to 4
5 to 6
Crucible Degas
Flow
H 1 to 4
5 to 2
3 to 6
2 & 3 off
FIG. 12 Apparatus for Determination of Oxygen by the Inert Gas

Fusion Flow
H 1 to 6
5 to 4
3 & 2 off
Fusion-Thermal Conductivity Test Method
FIG. 13 Apparatus for Determination of Oxygen by the Inert Gas
Fusion-Infrared Absorption Test Method
energy by the CO in the gas stream causes a reduction in the
energy received at an infrared detector. The detector response
data are processed and displayed directly as percent oxygen. 48. Reagents
45. Interferences 48.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
45.1 The elements ordinarily present do not interfere. For
the scope of elements typically found in materials to be tested
tee on Analytical Reagents of the American Chemical Society,
by this method refer to 1.1.
46. Safety Precautions used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
46.1 For precautions to be observed in the use of certain accuracy of the determination.
reagents in this test method, refer to Practices E50.
48.2 Acetone—Residue after evaporation shall be <0.0005
46.2 Use care when handling hot crucibles and operating %
furnaces to avoid personal injury by either burn or electrical
shock. 48.3 Ascarite II (Sodium Hydroxide on Clay)—Used in
some instruments to absorb residual CO2 in the inert gas
47. Apparatus stream. Use the purity specified by the instrument manufac-
47.1 Instrument—The general features of the instruments turer.
used in developing the test data accompanying this test method 48.4 Inert Gas (Helium, Argon, or Nitrogen as Specified for
are shown schematically in Figs. 12 and 13. These units are the Instrument being Used)—99.99 % purity minimum. Ultra
commercially available. high purity is recommended
47.2 Graphite Crucibles—The crucibles shall be made of 48.5 Magnesium Perchlorate (Mg(ClO4)2) (known commer-
high-purity graphite and should be those recommended by the cially as Anhydrone)—Used in most instruments as a moisture
manufacturer or their equivalent. trap. Use the purity specified by the instrument manufacturer.
18
E1019 − 11
48.6 Rare Earth Copper Oxide, as recommended by the NOTE 25—The uncertainty of results obtained using this test method is
instrument manufacturer. dependent on the uncertainty of the values assigned to the calibration
considered as well, if it was not included in the derivation of the published
49. Preparation of Apparatus uncertainty values.
49.1 Assemble the apparatus as recommended by the manu- 51.2 Gas Dosing—Automated and manual gas dosing (rec-
facturer. Make the required power, gas, and water connections. ommended by some instrument manufacturers) can be used to
Turn on the instrument and allow sufficient warm up time to calibrate the instrument, but instrument response shall be
stabilize the system. confirmed as described below using the reference materials
49.2 Change the chemical reagents and filters at the inter- described in 51.1.
vals recommended by the instrument manufacturer. Test the 51.3 Adjustment of Response of Measurement System:
furnace and the analyzer to ensure the absence of leaks. Make 51.3.1 Modern instruments may not require adjustment of
a minimum of two determinations using a sample as directed in the measurement system response prior to calibration. For
Section 52 to condition the instrument before attempting to these instruments proceed directly to 51.4 after the condition-
calibrate the system or to determine the value of the blank. ing runs described in 49.2.
Avoid the use of reference materials for instrument condition- 51.3.2 Using Calibrant B as the sample, proceed as directed
ing. in 52.2. Repeat 52.2 until the absence of drift is indicated.
Absence of drift is indicated when the last four results have a
maximum variation range of 0.0005 % oxygen. Make appro-
50.1 Use only solid specimens to minimize the potential for priate adjustments to the calibration potentiometer, if appli-
errors due to surface oxidation. Specimens shall be of the cable. Record potentiometer settings. Adjust the instrument
proper size to permit free introduction into the sample loading calibration to provide a reading within 6 0.0003 % absolute of
device, if required, and to fit in the graphite crucible. the certified value for the calibrant using the average of the last
50.2 Cut the specimens to an appropriate size using a silicon four results. Refer to the manufacturer’s instructions for the
carbide, water-cooled cut-off wheel or by other means that will specific protocol for performing this operation.
avoid overheating. Avoid oxide cutting or oxide abrading 51.4 Determination of Blank Reading—Using Calibrant A
materials. Thin, flat specimens may be stamped using a punch or a blank crucible as the sample, proceed as directed in 52.2.
and die. Abrade all surfaces of the specimen to remove all Repeat a sufficient number of times to establish that a low
traces of surface oxidation or other impurities using a clean average blank value (0.0002 % oxygen or less) and stable
file, die grinder, or silicon carbide grinding media (wet or dry). individual blank values (6 0.0001 % oxygen) are obtained.
Again care must be taken not to overheat the specimen. If wet Blank values are equal to the total result from the crucible and
grinding is done, it will be necessary to rinse specimens in Calibrant A minus the certified oxygen content of Calibrant A.
acetone and air dry well. If dry grinding is used, care must be Record the average value of four successive blank determina-
taken to avoid overheating of the specimen. For some material, tions that meet the above requirements for maximum and stable
such as plain carbon sheet steel, a rimmed or semi-killed values. If the blank readings are too high or unstable, determine
deoxidation practice is used and the oxygen may not be the cause, correct it, and repeat the steps as directed in 52.2.
uniformly distributed throughout the thickness of the sample. Enter the average blank value in the appropriate mechanism of
In these cases, the removal of too much surface material may the analyzer; refer to manufacturer’s instructions for the
cause erroneous results. specific protocol for performing this operation. This mecha-
50.3 Ensure that all pores in the surface of the sample are nism will electronically compensate for the blank value (Note
free of acetone. 26).
50.4 Do not touch the specimen with fingers during and NOTE 26—If the unit does not have this function, the blank value shall
following the final stages of cleaning. Some steel alloys may be be subtracted from the total result prior to any calculation.
prone to oxidation and it may be necessary to store these 51.5 Calibration:
prepared specimens in a desiccator. If oxidation prone alloys 51.5.1 Weigh an appropriate sample size of Calibrant C
are not analyzed within four hours of preparation, it may be (refer to manufacturer’s instructions) to the nearest 1 mg and
necessary to repeat the filing step or grinding step prior to place it in the instrument sample loading device or directly in
analysis. the outgassed crucible, following the manufacturer’s direction.
NOTE 24—Careful adherence to the sample preparation procedures
51.5.2 Follow the calibration procedure recommended by
described above is critical to obtaining accurate and precise results. The the manufacturer using Calibrant C to determine the calibration
use of small and irregular shaped samples requires a diligent effort to slope. Run samples until the maximum range from four
ensure that all surface contamination has been removed. successive samples does not exceed 0.0005 % oxygen. Treat
each sample as directed in 52.2 before proceeding to the next
51. Calibration one.
51.1 Calibration Reference Materials—Select three refer- 51.5.3 Confirm the calibration by analyzing an additional
ence materials containing approximately 0.0005 %, 0.002 %, sample of Calibrant C after the calibration procedure is
and 0.005 % oxygen and designate them as Calibrants A, B, completed. The result should agree with the certified value
and C, respectively. within a suitable confidence interval (Note 4). If the result
19
E1019 − 11
agrees with the certified value within the uncertainty provided 52.2.1.4 Start the analysis cycle, referring to the manufac-
on the certificate of analysis, the calibration is acceptable. Also, turer’s recommended procedure (Note 19).
if the certified value falls within an interval calculated as 52.2.2 Automatic Operation:
described in Eq 7, the calibration is acceptable. If the result is 52.2.2.1 Set the analyzer to operate in the automatic mode.
not acceptable, repeat the calibration procedure. 52.2.2.2 Place a 1.0 g specimen weighed to the nearest 1 mg
test result 2 t·s # certified value # test result1t·s (7) in the loading device. Refer to the manufacturer’s recom-
mended procedure, including entry of sample mass.
where: 52.2.2.3 Place an empty crucible on the furnace lower
s = standard deviation of the analyses run in 51.5.3, electrode assembly and close the furnace.
n = number of analyses (that is, 3 to 5), and 52.2.2.4 Start the analysis cycle, referring to the manufac-
t = student’s t value which is for n=3. t=4.30; for n=4, t= turer’s recommended procedure (Note 19).
3.18; for n= 5, t=2.78 at the 95 % confidence level.
NOTE 28—If the samples are to be analyzed in the automatic mode,
51.5.4 Next, weigh at least two samples of appropriate size blank determination and calibration should also be performed in the
of Calibrant B to the nearest 1 mg and transfer to the automatic mode. If samples are to be analyzed in the manual mode, blank
instrument sample loading device. Treat each sample as di- determination and calibration should be performed in the manual mode.
rected in 52.2 before proceeding to the next one. Solid samples may be analyzed in either automatic or manual mode, but
51.5.5 Record the results and compare them to the actual drillings, slugs, or chips should be analyzed in the manual mode.
certified oxygen value for Calibrant B. The result should agree
with the certified value within a suitable confidence interval 53. Calculation
(Note 4). If the result agrees with the certified value within the 53.1 The calibration function of the equipment shall yield a
uncertainty provided on the certificate of analysis, the calibra- linear plot described by the following function given in Eq 7.
tion is acceptable. Also, if the certified value falls within an Calculation of the calibration function shall be done using a
interval calculated as described in Eq 7, the calibration is linear least squares regression. Some manufacturers recom-
acceptable mend the use of a curve weighting factor where the calibrant
51.5.6 If the result is not acceptable, refer to the manufac- concentration is derived as 1/X. It is acceptable to use this type
turer’s instructions for checking the linearity of the analyzer. of curve weighting.
NOTE 27—Verify the calibration when: (1) a different lot of crucibles is 53.2 Since most modern commercially available instru-
used, (2) the system has been in use for 4 h, (3) the inert gas supply has ments calculate mass fraction concentrations directly, includ-
been changed, and (4) the system has been idle for 1 h . Verification should ing corrections for blank and sample mass, manual calculations
consist of analyzing at least one specimen of each calibrant. Recalibrate as
necessary. by the analyst are not required.
52. Procedure 54. Precision and Bias

52.1 Assemble the apparatus and condition it as directed in 54.1 Precision—Sixteen laboratories cooperated in testing
Section 37. this test method and obtained the data summarized in Table 8.
52.2 Procedure—Ranges I and II: Testing was performed in compliance with Practice E173 (refer
52.2.1 Manual Operation: to 9.1). Note that the values for R1 and R2 are based on M = 3
52.2.1.1 Set the analyzer to operate in the manual mode. (see Practice E173). This means that similar values for R1 and
52.2.1.2 Place an empty crucible on the furnace lower R2 may be expected from the averages of triplicate determina-
electrode assembly and close the furnace. tions.
52.2.1.3 Weigh a 1.0 g specimen to the nearest 1 mg and 54.2 Bias—No information on the bias of this method is
refer to the manufacturer’s recommended procedure, including known because at the time of the interlaboratory study, suitable
entry of sample mass. reference materials were not available. The user of this method
TABLE 8 Statistical Information—Oxygen (wt., %)

RepeatabilityA ReproducibilityA
Test Specimen Oxygen Found (R1, Practice E173) (R2, Practice E173)
Ni-Cr-Mo Alloy (AISI 4330) 0.00048 0.00018 0.00040
Tool Steel (M-50) 0.00056 0.00015 0.00061
Cr-Alloy Steel (52100) 0.00080 0.00022 0.00088
Carbon Steel (1070) 0.00118 0.00026 0.00065
Carbon Steel (1570) 0.00126 0.00024 0.00071
Alloy Steel (33100) 0.00139 0.00023 0.00048
Cr-Alloy Steel (52100) 0.00218 0.00034 0.00091
Ni-Cr-Mo Alloy (8622) 0.00237 0.00034 0.00076
Carbon Steel (1026) 0.00357 0.00023 0.00092
Cr-Stainless (440C) 0.00437 0.00032 0.00108
Ingot Iron (NIST-466, 0.0050 wt. % oxygen) 0.00538 0.00031 0.00081
A
M = 3, see Practice E173, 4.11 and 4.12 and Note 1.
20
E1019 − 11
is encouraged to employ accepted reference materials, if 58. Apparatus
available, to determine the presence or absence of bias. 58.1 Combustion and Measurement Apparatus—See Figs.
5-7.
SULFUR BY THE COMBUSTION–INFRARED 58.2 Crucibles—Use crucibles recommended by the manu-
ABSORPTION TEST METHOD (CALIBRATION facturer of the instrument or equivalent, and prepare the
WITH METAL REFERENCE MATERIALS) crucibles by heating them in a suitable furnace for not less than
40 min at approximately 1000 °C. Remove them from the
55. Scope furnace and cool before use. Preheated crucibles may also be
stored in a desiccator prior to use. Above certain
55.1 These test methods cover the determination of sulfur in
concentrations, as determined by the testing laboratory, the
the range of 0.002 % to 0.35 %.
nontreatment of crucibles will have no adverse effect The
analytical ranges for the use of untreated crucibles shall be
56. Summary of Test Method
specified by the testing laboratory, and supporting data shall be
56.1 The sample is combusted in a stream of oxygen that maintained on file to validate these ranges.
converts the sulfur in the sample to sulfur dioxide. The sulfur 58.3 Crucible Tongs, capable of handling recommended
is then determined by infrared absorption. crucibles.
56.1.1 Infrared Absorption: Test Method A—Sulfur dioxide
(SO2) absorbs IR energy at a precise wavelength within the IR 59. Reagents
spectrum. The energy of this wavelength is absorbed as the gas 59.1 Purity of Reagents—Reagent grade chemicals shall be
passes through a cell body in which the IR energy is transmit- used in all tests. Unless otherwise indicated, it is intended that
ted. All other IR energy is eliminated from reaching the all reagents shall conform to the specifications of the Commit-
detector by a precise wavelength filter. The absorption of IR tee on Analytical Reagents of the American Chemical Society,
energy can be therefore attributed to only SO2, and its where such specifications are available.4 Other grades may be
concentration is measured as changes in energy at the detector. used, provided it is first ascertained that the reagent is of
One cell is used as both a reference and a measure chamber. sufficiently high purity to permit its use without lessening the
Total sulfur, as SO2, is measured over a period of time. Refer accuracy of the determination.
to Fig. 5.
59.2 Acetone—The residue after evaporation shall be
56.1.2 Infrared Absorption: Test Method B—The combus-
< 0.0005 %.
tion is performed in a closed loop in which SO2 is detected in
an infrared cell. The SO2 is measured with a solid state energy 59.3 Magnesium Perchlorate, (known commercially as An-
detector, and filters are used to pass the appropriate IR hydrone). Use the purity specified by the instrument manufac-
wavelength to the detector. The IR absorption properties of turer.
SO2 gas cause a loss of signal at the detector that is propor- 59.4 Oxygen—Purity as specified by the instrument manu-
tional to the concentration of SO2 in the closed loop. Total facturer.
sulfur, as SO2, is measured over a period of time. Refer to Fig.
59.5 Sodium Hydroxide, on clay, (known commercially as
6.
Ascarite II). Use the purity specified by the instrument manu-
56.1.3 Infrared Absorption: Test Method C—The detector facturer.
consists of an IR energy source, a separate measure chamber
and reference chamber, and a diaphragm acting as one plate of 59.6 Tungsten Accelerator (Low Sulfur), 12 mesh to 20
a parallel plate capacitor. During specimen combustion, the mesh (Note 29).
flow of SO2 with its oxygen gas carrier is routed through the 59.7 Tungsten-Tin Accelerator, 20 mesh to 40 mesh or 12
measure chamber while oxygen alone passes through the mesh to 20 mesh.
reference chamber. Energy from the IR source passes through
NOTE 29—The accelerator should contain no more than 0.001 % sulfur.
both chambers, simultaneously arriving at the diaphragm If necessary, wash three times with acetone by decantation to remove
(capacitor plate). Part of the IR energy is absorbed by the SO2 organic contaminants and dry at room temperature. The mesh size is
present in the measure chamber, while none is absorbed critical to the inductive coupling which heats the sample. Some manufac-
passing through the reference chamber. This creates an IR turers of accelerators may not certify the mesh size on a lot to lot basis.
These accelerators may be considered acceptable for use without verifying
energy imbalance reaching the diaphragm and thus distorting
the mesh size.
it. This distortion alters the fixed capacitance, creating an
electric signal change that is amplified for measurement as 60. Sample Preparation
SO2. Total SO2 is monitored and measured over a period of
60.1 60.1 The specimen should be uniform in size, but not
time. Refer to Fig. 7.
finer than 40 mesh. Specimens will typically be in the form of
chips, drillings, slugs, or solids. Specimens shall be free of any
57. Interferences
residual lubricants, cutting fluids, or both. It may be necessary
57.1 The elements normally present do not interfere. . For to clean specimens to remove residual lubricants or cutting
the scope of elements typically found in materials to be tested fluids, or both. Any cleaned specimens shall be rinsed in
by this method refer to 1.1. acetone and dried completely before analysis.
21
E1019 − 11
61. Preparation of Apparatus amount required to produce proper sample combustion using the same
amount throughout the entire test method.
61.1 Assemble the apparatus as recommended by the manu-
facturer. 62.3.2 Proceed as directed in 63.1.2 and 63.1.3.
62.3.3 Repeat the steps given in 62.3.1 and 62.3.2 a suffi-
61.2 Test the furnace and analyzer to ensure the absence of
cient number of times to establish that low (less than 0.00005
leaks, and make the required electrical power connections.
% of sulfur) and stable (6 0.00001 % of sulfur) readings are
Prepare the analyzer for operation in accordance with the
obtained. Blank values are equal to the total result of the
manufacturer’s instructions. Make a minimum of two determi-
accelerator and Calibrant A minus the certified value for the
nations using a specimen and accelerator, as directed in 63.2
calibrant.
and 63.3 to condition the instrument before attempting to
calibrate the system or determine the blank. Avoid the use of 62.3.4 Record the average value of at least three blank
reference materials for instrument conditioning. determinations.
62.3.5 If the blank readings are too high or unstable,
62. Calibration determine the cause, correct it, and repeat the steps as directed
62.1 Calibrants (Note 30): in 62.3.1 – 62.3.4.
62.1.1 For Range I, 0.002 % to 0.010 % sulfur, select three 62.3.6 Enter the average blank value in the analyzer (Note
certified reference materials containing approximately 32). Refer to the manufacturer’s instructions for specific
0.001 %, 0.005 %, and 0.010 % sulfur and designate them as instructions on performing this function. This mechanism will
Calibrants A, B, and C, respectively. compensate electronically for the blank value.
62.1.2 For Range II, 0.010 % to 0.10 % sulfur, select two NOTE 32—If the unit does not have this function, the blank value shall
certified reference materials containing approximately 0.02 % be subtracted from the total result prior to any calculation.
and 0.08 % sulfur and designate them as Calibrants BB and
62.4 Determination of Blank Reading—Range II—Proceed
CC, respectively.
as directed in section 62.3.
62.1.3 For Range III, 0.10 % to 0.35 % sulfur, select two
certified reference materials containing approximately 0.10 % 62.5 Determination of Blank Reading—Range III:
and 0.40 % sulfur and designate them as Calibrants BBB and 62.5.1 Transfer 0.5 g of Calibrant A, weighed to the nearest
CCC, respectively. 1 mg, and approximately 1.5 g of accelerator to a preheated
NOTE 30—The uncertainty of results obtained using this test method is
crucible (Note 31).
dependent on the uncertainty of the values assigned to the calibration 62.5.2 Proceed as directed in 62.3.2 – 62.3.6.
considered as well, if it was not included in the derivation of the published 62.6 Calibration—Range I (0.002 % to 0.010 % Sulfur):
uncertainty values. 62.6.1 Weigh four 1.0-g test samples of Calibrant C,
62.2 Adjustment of Response of Measurement System: weighed to the nearest 1 mg, and then place them in crucibles.
62.2.1 Modern instruments may not require adjustment of Add approximately 1.5 g of accelerator (Note 31) to each.
the measurement system response prior to calibration. For 62.6.2 Follow the calibration procedure recommended by
these instruments proceed directly to 62.3 after performing the the manufacturer. Use Calibrant C as the calibrant and analyze
conditioning runs described in 61.2. at least three test samples to determine the calibration slope.
62.2.2 Transfer 1.0 g of Calibrant B, weighed to the nearest Treat each test sample as directed in 63.1.2 and 63.1.3 before
1 mg, and approximately 1.5 g of accelerator to a crucible proceeding to the next one.
(Note 31). Some manufacturers provide scoops that dispense 62.6.3 . The result should agree with the certified value
approximately 1.5 g of accelerator. Once it is verified that the within a suitable confidence interval (Note 4). If the result
scoop delivers this approximate mass, it is acceptable to use agrees with the certified value within the uncertainty provided
this device for routine dispensing of accelerator. on the certificate of analysis, the calibration is acceptable. Also,
62.2.3 Proceed as directed in 63.1.2 and 63.1.3. if the certified value falls within an interval calculated as
62.2.4 Repeat the steps given in 62.2.2 and 62.2.3 until the described in Eq 8, the calibration is acceptable. If not, repeat
absence of drift is indicated by stable sulfur readings. Consis- the steps given in 62.6.1 and 62.6.2.
tency is indicated when consecutive runs of Calibrant B repeat test result 2 t·s # certified value # test result1t·s (8)
to within 0.0002%. . Adjust the signal to provide a reading
within 6 0.0003 of the certified percent sulfur value for where:
Calibrant B. s = standard deviation of the analyses run in 62.6.3,
n = number of analyses (that is, 3 to 5), and
62.3 Determination of Blank Readings—Range I: t = student’s t value which is for n = 3, t = 4.30; for n = 4
62.3.1 Transfer 1.0 g of Calibrant A, weighed to the nearest , t = 3.18; for n = 5, t = 2.78 at the 95 % confidence level.
1 mg, and approximately 1.5 g of accelerator into a crucible
(Note 31). Some labs may use accelerator with a certified (See Note 2.)
sulfur value as Calibrant A. 62.6.4 Weigh at least two 1.0-g test samples of Calibrant B,
weighed to the nearest 1 mg, and transfer them to crucibles.
NOTE 31—The use of 1.5 g of accelerator may not be sufficient for all Add approximately 1.5 g of accelerator (Note 31) to each.
determinators. The required amount is determined by the analyzer used,
induction coil spacing, position of the crucible in the induction coil, age 62.6.5 Treat each test sample as directed in 63.1.2 and
and strength of the oscillator tube, and type of crucible being used. Use the 63.1.3 before proceeding to the next one.
22
E1019 − 11
62.6.6 Record the results of 62.6.4 and 62.6.5 and compare TABLE 9 Statistical Information, Sulfur, Range I
them to the certified sulfur value of Calibrant B. The result (0.002 % to 0.010 % S)
should agree with the certified value within a suitable confi- Certified Sulfur Repeatability Reproducibility
Test Material Value, Found, (R1, Practice (R2, Practice
dence interval (Note 4). If the result agrees with the certified % Sulfur % E173) E173)
value within the uncertainty provided on the certificate of JK NR24 0.0010 0.00103 0.00025 0.00078
analysis, the calibration is acceptable. Also, if the certified NIST 132b 0.0030 0.0027 0.00033 0.00094
value falls within an interval calculated as described in Eq 8, High Temperature ... 0.0043 0.00051 0.00118
Alloy
the calibration is acceptable. If not, refer to the manufacturer’s NIST 50c 0.0064 0.0065 0.0005 0.0024
instructions for determining the linearity of the system (Note
33).
TABLE 10 Statistical Information, Sulfur, Range II
NOTE 33—Verify the calibration when: (1) a different lot of crucibles is
(0.010 % to 0.10 % S)
used, (2) a different lot of accelerator is used, (3) the system has been idle
for 1 h, (4) the system has been in use for 4 h, and (5) the oxygen supply Test
Certified Sulfur Repeatability Reproducibility
has been changed. Verification should consist of analyzing at least one Value, Found, (R1, Practice (R2, Practice
Material
specimen of each calibrant. Recalibrate as necessary. % Sulfur % E173) E173)
NIST 890 0.015 0.0149 0.0015 0.0039
62.7 Calibration—Range II (0.010 % to 0.10 % Sulfur): NIST 163 0.027 0.0264 0.0015 0.0092
62.7.1 Proceed as directed in 62.6.1 – 62.6.3, using Cali- NIST 73c 0.036 0.0356 0.0032 0.0078
brant CC.
62.7.2 Proceed as directed in 62.6.4 – 62.6.6, using Cali-
brant BB. TABLE 11 Statistical Information, Sulfur, Range III
(0.10 % to 0.35 % S)
62.8 Calibration—Range III (0.10 % to 0.35 % Sulfur): Certified Sulfur
62.8.1 Weigh four 0.5-g test samples of Calibrant CCC, to Test Repeatability (R1, Reproducibility (R2,
Value, Found,
Material Practice E173) Practice E173)
the nearest 1 mg, and place them in crucibles. Add approxi- % Sulfur %
mately 1.5 g of accelerator (Note 31) to each. NIST 6g 0.124 0.1200 0.0076 0.0239
NIST 129c 0.245 0.2451 0.0074 0.0243
62.8.2 Follow the calibration procedure recommended by NIST 133 0.356 0.3683 0.0174 0.0373
the manufacturer. Use Calibrant CCC as the primary calibrant
and analyze at least three test samples to determine the
calibration slope. Treat each test sample as directed in 63.1.2
and 63.1.3 before proceeding to the next one. nearest 1 mg, and approximately 1.5 g of accelerator to a
62.8.3 Confirm the calibration by analyzing Calibrant CCC crucible (see 58.2) (Note 31).
following the calibration procedure. The result should agree 63.1.2 Place the crucible on the furnace pedestal and raise
with the certified value within a suitable confidence interval the pedestal into position. Use crucible tongs to handle the
(Note 4). If the result agrees with the certified value within the crucibles.
uncertainty provided on the certificate of analysis, the calibra- 63.1.3 Refer to the manufacturer’s recommended procedure
tion is acceptable. Also, if the certified value falls within an regarding the entry of test sample mass and blank value. Start
interval calculated as described in Eq 8, the calibration is the analysis cycle.
acceptable. If not, repeat the steps given in 62.8.1 and 62.8.2. 63.2 Procedure—Range II—Proceed as directed in 63.1.
62.8.4 Weigh at least two 0.5-g test samples of Calibrant
63.3 Procedure—Range III—Proceed as directed in 63.1,
BBB, weighed to the nearest 1 mg, and transfer them to
using a 0.5-g test sample.
crucibles. Add approximately 1.5 g of accelerator (Note 31) to
each. 64. Calculation
62.8.5 Treat each test sample as described in 63.1.2 and
63.1.3 before proceeding to the next one. 64.1 The calibration function of the equipment shall yield a
linear plot described by Eq 2. Calculation of the calibration
62.8.6 Record the results of 62.8.4 and 62.8.5 and compare
function shall be done using a linear least squares regression.
them to the certified sulfur value of the Calibrant BBB. The
Some manufacturers recommend the use of a curve weighting
result should agree with the certified value within a suitable
factor where the calibrant concentration is derived as 1/X. It is
confidence interval (Note 4). If the result agrees with the
certified value within the uncertainty provided on the certificate
of analysis, the calibration is acceptable. Also, if the certified 64.2 Since most modern commercially available instru-
value falls within an interval calculated as described in Eq 8, ments calculate mass fraction concentrations directly, includ-
the calibration is acceptable. If not, refer to the manufacturer’s ing corrections for blank and sample mass, manual calculations
instructions for determining the linearity of the analyzer (Note by the analyst are not required (Note 34).
33). NOTE 34—Use the following formula if the analyzer does not compen-
sate for blank and sample mass values:
63. Procedure
sulfur, % 5 @ ~ A 2 B ! 3 C/D # (9)
63.1 Procedure—Range I:
where:
63.1.1 Stabilize the furnace and analyzer as directed in
A = DVM (Digital Volt Meter) reading for test sample,
Section 59. Transfer 1.0 g of test sample, weighed to the
23
E1019 − 11
B = DVM reading for blank, NOTE 36—Although these test methods were tested to only 0.35 %,
C = mass compensator setting, and most commercial analyzers are believed to be capable of analyzing
D = test sample mass in grams. samples containing sulfur up to 0.5 %.
65. Precision and Bias 66. Keywords

65.1 Precision—Nine laboratories cooperated in testing
66.1 carbon content; cobalt alloys; combustion; determina-
these test methods and obtained the precision data summarized
tion; fusion; gas dosing; inert gas fusion; infrared absorption;
in Tables 9-11 (see Note 35). Testing was performed in
iron alloys; nickel alloys; nitrogen content; oxygen content;
compliance with Practice E173 (refer to 9.1).
steel alloys; sulfur content; thermal conductivity
NOTE 35—In Tables 9-11, all results in Ranges I and II are from nine
laboratories. The results in Range III are from eight laboratories.
65.2 Bias—The accuracy of these test methods can be
inferred from the data given in Tables 9-11 by comparing the
certified values for sulfur with the average values obtained (see
Note 36).
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24

Determination of Carbon, Sulfur, Nitrogen, and Oxygen in Steel, Iron, Nickel, and Cobalt Alloys by Various Combustion and Fusion Techniques

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Determination of Carbon, Sulfur, Nitrogen, and Oxygen in Steel, Iron, Nickel, and Cobalt Alloys by Various Combustion and Fusion Techniques

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Designation: E1019 − 11

Standard Test Methods for

1. Scope Zirconium 0.005 to 2.500

A—High Purity Oxygen M—CO2 Collection Trap

* May be sealed chamber if

** Not required if oxygen is

16. Sample Preparation

A—Oxygen Cylinder G—Orifice

FIG. 3 Infrared Absorption Test Method B

A—Oxygen Cylinder G—Furnace

FIG. 4 Infrared Absorption Test Method C—Closed Loop

TABLE 1 Statistical Information—Carbon, Range I

TABLE 3 Statistical Information—Carbon, Range III

A—Oxygen Cylinder F—Dust Trap

FIG. 6 Infrared Absorption Test Method B

A—Oxygen Cylinder F—IR Detector/Readout

FIG. 7 Infrared Absorption Test Method C

24.3 Micropipet, (50 µL).

TABLE 4 Statistical Information—Sulfur

A—Helium Supply H—Electrode Furnace

Crucible Degas Flow

FIG. 8 Nitrogen Test Method A—Flow Diagram

A—Helium Supply I—Optional Gas Doser

Crucible Degas Flow

FIG. 9 Nitrogen Test Method B—Flow Diagram

A—Helium Supply I—Sample Holding Chamber

Crucible Degas Flow

FIG. 10 Nitrogen/Oxygen Test Method A—Flow Diagram

A—Helium Supply J—Flow Manifold

Crucible Degas Flow

FIG. 11 Nitrogen/Oxygen Test Method B—Flow Diagram

40. Procedure 42. Precision and Bias7

TABLE 6 Statistical Information—Nitrogen, Range II (chip)

TABLE 7 Statistical Information—Nitrogen, Range I (solid)

A—Helium Supply H—Electrode Furnace

FIG. 12 Apparatus for Determination of Oxygen by the Inert Gas

52. Procedure 54. Precision and Bias

TABLE 8 Statistical Information—Oxygen (wt., %)

65. Precision and Bias 66. Keywords

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