ASTM E1019-18

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: E1019 − 18
Standard Test Methods for
Determination of Carbon, Sulfur, Nitrogen, and Oxygen in
Steel, Iron, Nickel, and Cobalt Alloys by Various
Combustion and Inert Gas Fusion Techniques
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
Sections
Carbon, Total, by the Combustion and Infrared 10–20
1.1 These test methods cover the determination of carbon,
Absorption or Thermal Conductivity Detection Test
Method
sulfur, nitrogen, and oxygen, in steel, iron, nickel, and cobalt
alloys having chemical compositions within the following
Nitrogen by the Inert Gas Fusion and Thermal Conduc- 32–42
limits:
tivity Detection Test Method
Element Mass Fraction Range, %
Oxygen by the Inert Gas Fusion and Infrared Absorp- 43–54
Aluminum 0.001 to 18.00
tion or Thermal Conductivity Detection Test Method
Antimony 0.002 to 0.03
Arsenic 0.0005 to 0.10
Sulfur by the Combustion-Infrared Absorption Detection 55–65
Beryllium 0.001 to 0.05
Test Method
Bismuth 0.001 to 0.50
Boron 0.0005 to 1.00
Sulfur by the Combustion–Infrared Absorption Test 21–31
Cadmium 0.001 to 0.005
Method (Potassium Sulfate Calibration) – Discontinued
Calcium 0.001 to 0.05
Carbon 0.001 to 4.50
Cerium 0.005 to 0.05
1.3 The values stated in SI units are to be regarded as
Chromium 0.005 to 35.00
standard. No other units of measurement are included in this
Cobalt 0.01 to 75.0
standard.
Niobium 0.002 to 6.00
Copper 0.005 to 10.00
1.4 This standard does not purport to address all of the
Hydrogen 0.0001 to 0.0030
Iron 0.01 to 100.0 safety concerns, if any, associated with its use. It is the
Lead 0.001 to 0.50
responsibility of the user of this standard to establish appro-
Magnesium 0.001 to 0.05
priate safety, health, and environmental practices and deter-
Manganese 0.01 to 20.0
mine the applicability of regulatory limitations prior to use.
Molybdenum 0.002 to 30.00
Nickel 0.005 to 84.00
Specific hazards statements are given in Section 6.
Nitrogen 0.0005 to 0.50
1.5 This international standard was developed in accor-
Oxygen 0.0005 to 0.03
Phosphorus 0.001 to 0.90 dance with internationally recognized principles on standard-
Selenium 0.001 to 0.50
ization established in the Decision on Principles for the
Silicon 0.001 to 6.00
Development of International Standards, Guides and Recom-
Sulfur 0.002 to 0.35
Tantalum 0.001 to 10.00 mendations issued by the World Trade Organization Technical
Tellurium 0.001 to 0.35
Barriers to Trade (TBT) Committee.
Tin 0.002 to 0.35
Titanium 0.002 to 5.00
Tungsten 0.005 to 21.00 2. Referenced Documents
Vanadium 0.005 to 5.50
2.1 ASTM Standards:
Zinc 0.005 to 0.20
Zirconium 0.005 to 2.500
D1193 Specification for Reagent Water
E29 Practice for Using Significant Digits in Test Data to
1.2 The test methods appear in the following order:
Determine Conformance with Specifications
These test methods are under the jurisdiction of ASTM Committee E01 on
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct
responsibility of Subcommittee E01.01 on Iron, Steel, and Ferroalloys. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved April 15, 2018. Published June 2018. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1984. Last previous edition approved in 2011 as E1019 – 11. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/E1019-18. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E1019 − 18
E50 Practices for Apparatus, Reagents, and Safety Consid- 9. Interlaboratory Studies
erations for Chemical Analysis of Metals, Ores, and
9.1 These test methods have been evaluated in accordance
Related Materials
with Practice E173. The Reproducibility R of Practice E173
E135 Terminology Relating to Analytical Chemistry for
corresponds to the Reproducibility Index R of Practice E1601.
Metals, Ores, and Related Materials
The Repeatability R of Practice E173 corresponds to the
E173 Practice for Conducting Interlaboratory Studies of
Repeatability Index r of Practice E1601.
Methods for Chemical Analysis of Metals (Withdrawn
1998)
TOTAL CARBON BY THE COMBUSTION AND
E1601 Practice for Conducting an Interlaboratory Study to
INFRARED ABSORPTION OR THERMAL
Evaluate the Performance of an Analytical Method
CONDUCTIVITY DETECTION TEST METHOD
E1806 Practice for Sampling Steel and Iron for Determina-
tion of Chemical Composition
10. Scope
10.1 This test method covers the determination of carbon
3. Terminology
from 0.005 % to 4.5 %.
3.1 For definition of terms used in this test method, refer to
Terminology E135.
11. Summary of Test Method
11.1 The carbon is converted to carbon dioxide (CO)by
4. Significance and Use
combustion in a stream of oxygen.
4.1 These test methods for the chemical analysis of metals
11.1.1 Thermal Conductivity Test Method—The CO is
and alloys are primarily intended to test such materials for
absorbed on a suitable grade of zeolite, released by heating the
compliance with compositional specifications. It is assumed
zeolite, and swept by helium or oxygen into a chromatographic
that all who use these test methods will be trained analysts,
column. Upon elution, the amount of CO is measured in a
capable of performing common laboratory procedures skill-
thermistor-type conductivity cell. Refer to Fig. 1 for example.
fully and safely. It is expected that work will be performed in
11.1.2 Infrared (IR) Absorption, Test Method A—The
a properly equipped laboratory.
amount of CO is measured by infrared (IR) absorption. CO
2 2
absorbs IR energy at a precise wavelength within the IR
5. Apparatus and Reagents
spectrum. Energy of this wavelength is absorbed as the gas
passes through a cell body in which the IR energy is transmit-
5.1 Apparatus and reagents required for each determination
ted. All other IR energy is eliminated from reaching the
are listed in separate sections preceding the procedure.
detector by a precise wavelength filter. Thus, the absorption of
5.2 These methods were originally developed for older
IR energy can be attributed to only CO and its amount is
technology manual instrumentation with the flow schematics
measured as changes in energy at the detector. One cell is used
indicated. Current commercially available instruments are
as both a reference and a measure chamber. Total carbon, as
more automated and may have slightly different flow schemat-
CO , is measured over a period of time. Refer to Fig. 2 for
ics and should be capable of producing data meeting or
example.
exceeding the precision and bias requirements.
11.1.3 Infrared (IR) Absorption, Test Method B—The detec-
tor consists of an IR energy source, a separate measure
6. Hazards
chamberandreferencechamber,andadiaphragmactingasone
6.1 For hazards to be observed in the use of certain reagents
plate of a parallel plate capacitor. During specimen
in this test method, refer to Practices E50.
combustion, the flow of CO with its oxygen carrier gas is
routed through the measure chamber while oxygen alone
6.2 Use care when handling hot crucibles and operating
passes through the reference chamber. Energy from the IR
furnaces to avoid personal injury by either burn or electrical
source passes through both chambers, simultaneously arriving
shock.
at the diaphragm (capacitor plate). Part of the IR energy is
absorbed by the CO present in the measure chamber while
7. Sampling
none is absorbed passing through the reference chamber. This
7.1 For procedures to sample the materials, refer to those
creates an IR energy imbalance reaching the diaphragm, thus
parts of Practice E1806.
distorting it. This distortion alters the capacitance creating an
electric signal change that is amplified for measurement as
8. Rounding Calculated Values
CO . Total carbon, as CO , is measured over a period of time.
2 2
8.1 Rounding of test results obtained using these test meth-
Refer to Fig. 3 for example.
ods shall be performed as directed in Practice E29, Rounding 11.1.4 Infrared (IR) Absorption, Test Method C, Closed
Method, unless an alternative rounding method is specified by
Loop—The combustion is performed in a closed loop, where
the customer or applicable material specification.
carbon monoxide (CO) and CO are detected in the same
infrared cell. Each gas is measured with a solid state energy
detector. Filters are used to pass the appropriate IR wavelength
to each detector. In the absence of CO and CO , the energy
The last approved version of this historical standard is referenced on 2
www.astm.org. received by each detector is at its maximum. During
E1019 − 18
A—High Purity Oxygen M—CO Absorber – Zeolite
B—Oxygen Regulator (2 Stage) N—Furnace Combustion Exhaust
C—Sodium Hydroxide Impregnated Clay and Magnesium Perchlo- O—Furnace Purge Exhaust
rate
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—Chromatographic Column
H—Dust Trap T—TC Cell/Readout
I—Manganese Dioxide U—Measure Flowmeter
J—Heated CO to CO Converter (suitable catalyst) V—Reference Flowmeter
K—Magnesium Perchlorate (Note 1 in 14.4) W—Furnace Power Supply
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 Detection Test Method
combustion, the IR absorption properties of CO and CO gases 13. Apparatus
in the chamber cause a loss of energy; therefore a loss in signal
13.1 Combustion and Measurement Apparatus—See Figs.
results which is proportional to amounts of each gas in the
1-4 for examples.
closed loop. Total carbon, as CO plus CO, is measured over a
13.2 Crucibles—Use crucibles that meet or exceed the
period of time. Refer to Fig. 4 for example.
specifications of the instrument manufacturer and prepare the
11.2 This test method is written for use with commercial
crucibles by heating in a suitable furnace for not less than 40
analyzers, equipped to perform the above operations automati-
min at approximately 1000 °C. Remove from the furnace and
cally and calibrated using reference materials of known carbon
cool before use. Crucibles may be stored in a desiccator prior
content.
to use.
13.2.1 The analytical ranges for the use of untreated cru-
12. Interferences
cibles shall be determined by the testing laboratory and
12.1 The elements ordinarily present in iron, steel, nickel, supporting data shall be maintained on file to validate these
and cobalt alloys do not interfere. ranges. Heating of crucibles is particularly important when
E1019 − 18
14.3 Copper (Low Carbon) Accelerator, granular, 2.00 mm
to 0.599 mm (10 mesh to 30 mesh).
14.3.1 Theacceleratorshouldcontainnomorethan0.001 %
carbon. If necessary, wash three times with acetone by decan-
tation to remove organic contaminants and dry at room
temperature. The mm (mesh) size is critical to the inductive
coupling that heats the sample. Some manufacturers of accel-
erators may not certify the mm (mesh) size on a lot to lot basis.
These accelerators may be considered acceptable for use
without verifying the mm (mesh) size.
14.4 Magnesium Perchlorate, (known commercially as An-
hydrone) — Use the purity specified by the instrument manu-
facturer.
NOTE 1—Phosphorus pentoxide may be used by some instrument
manufacturers.
14.5 Oxygen—Purity as specified by the instrument manu-
facturer.
14.6 Platinum or Platinized Silica, heated to 350 °C for the
conversion of CO to CO . Use the form specified by the
instrument manufacturer.
NOTE 2—Copper oxide may be used by some instrument manufactur-
ers.
14.7 Sodium Hydroxide on Clay (known commercially as
A—Oxygen Cylinder G—CO-CO Converter (suitable
Ascarite II)—Use the purity specified by the instrument manu-
catalyst)
facturer.
B—Two Stage Regulator H—SO Trap
C—Sodium Hydroxide Impregnated Clay I—CO IR Cell/Readout
14.8 Tungsten (Low Carbon) Accelerator, 1.68 mm to 0.853
D—Magnesium Percholorate (Note 1 in 14.4) J—Induction Furnace
E—Regulator K—Combustion Area mm (12 mesh to 20 mesh). See 14.3.1.
F—Flow Controller L—Dust Trap
14.9 Tungsten-Tin (Low Carbon) Accelerator, 0.853 mm to
FIG. 2 Infrared Absorption Detection Test Method A
0.422 mm (20 mesh to 40 mesh) or 1.68 mm to 0.853 mm (12
mesh to 20 mesh). See 14.3.1.
15. Preparation of Apparatus
analyzing for low levels of carbon and may not be required if
15.1 Assemble the apparatus as recommended by the manu-
the material to be analyzed has higher levels of carbon such as
facturer.
that found in pig iron (3.5% or greater). Above certain carbon
mass fractions, as determined by the testing laboratory, the 15.2 Test the furnace and analyzer to ensure the absence of
non-treatment of crucibles will have no adverse effect.
leaks and make the required electrical power connections.
Prepare the analyzer for operation as directed by the manufac-
13.3 Crucible Tongs—Capable of handling recommended
turer’s instructions. Change the chemical reagents and filters at
crucibles.
the intervals recommended by the instrument manufacturer.
Make a minimum of two determinations using the specimen
14. Reagents
andacceleratorasdirectedin18.1.2and18.1.3toconditionthe
14.1 Purity of Reagents—Reagent grade chemicals shall be
instrument before attempting to calibrate the system or deter-
used in all tests. Unless otherwise indicated, it is intended that
mine the blank. Avoid the use of reference materials for
all reagents shall conform to the specifications of the Commit-
instrument conditioning.
tee onAnalytical Reagents of theAmerican Chemical Society,
15.2.1 Approximately 1.5 g of accelerator is typically re-
where such specifications are available. Other grades may be
quired for proper combustion. However, the use of 1.5 g of
used, provided it is first ascertained that the reagent is of
accelerator may not be sufficient for all instruments. The
sufficiently high purity to permit its use without lessening the
required amount is determined by the instrument used, induc-
accuracy of the determination.
tion coil spacing, position of the crucible in the induction coil,
14.2 Acetone—The residue after evaporation shall be
age and strength of the oscillator tube, and type of crucible
< 0.0005 %.
being used. Use the amount required to produce proper sample
combustion and use the same amount throughout the entire test
method.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not 16. Sample Preparation
listed by the American Chemical Society, see the United States Pharmacopeia—
16.1 The specimens should be uniform in size, but not finer
National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD
(http://www.usp.org/USPNF). than 0.422 mm (40 mesh). Specimens will typically be in the
E1019 − 18
A—Oxygen Cylinder G—Orifice
B—Two Stage Regulator H—Pressure Regulator
C—Sodium Hydroxide Impregnated Clay I—Combustion Chamber
D—Magnesium Percholorate (Note 1 in 14.4) J—CO to CO Converter (suitable catalyst)
E—Dust Trap K—SO Trap (typically cellulose)
F—IR Cell/Readout L—Measure Flow Rotameter
FIG. 3 Infrared Absorption Detection Test Method B
A—Oxygen Cylinder G—Furnace
B—Sodium Hydroxide Impregnated Clay H—Pump
C—Magnesium Perchlorate (Note 1 in 14.4) I—Flow Meter
D—Pressure Regulator J—Exhaust
E—IR Cell/Readout K—CO to CO Converter (suitable catalyst)
F—Dust Trap L—SO Trap (typically cellulose)
FIG. 4 Infrared Absorption Detection Test Method C—Closed Loop
E1019 − 18
form of chips, drillings, slugs, or solids. Specimens shall be values are equal to the total result of the accelerator and A
free of any residual lubricants and cutting fluids. It may be minus the value of A.
necessary to clean specimens to remove residual lubricants and 17.3.4 Record the average value of the last three or more
cutting fluids. Any cleaned specimens shall be rinsed in stable blank determinations.
acetone (or another suitable solvent with low residue, see 14.2) 17.3.5 If the blank readings are too high or unstable,
and dried completely before analysis. determine the cause, correct it, and repeat the steps as directed
in 17.3.1 – 17.3.4.
17. Calibration 17.3.6 Enter the average blank value in the analyzer. Refer
to the manufacturer’s instructions for specific instructions on
17.1 Calibration Reference Materials:
performing this function. Typically the instrument will elec-
NOTE3—Theaccuracyofthistestmethodislargelydependentuponthe tronically compensate for the blank value. If the unit does not
absence of bias in the values assigned to the reference materials and upon
have this function, the blank value shall be subtracted from the
the homogeneity of these materials.
total result prior to any calculation.
17.1.1 For Range I, 0.005 % to 0.10 % carbon, select three
17.4 Determination of Blank Reading—Range II—Proceed
certified reference materials containing approximately
as directed in 17.3.
0.005 %, 0.05 %, and 0.10 % carbon and designate them asA,
17.5 Determination of Blank Reading—Range III:
B, and C, respectively. An accelerator with a certified carbon
17.5.1 Transfer 0.5 g ofA, weighed to the nearest 1 mg, and
value may be used as A.
approximately 1.5 g of accelerator to a crucible.
17.1.2 For Range II, 0.10 % to 1.25 % carbon, select two
17.5.2 Proceed as directed in 17.3.2 – 17.3.6.
certified reference materials containing approximately 0.12 %
and 1.00 % carbon and designate them as BB and CC, 17.6 Calibration—Range I (0.005 % to 0.10 % Carbon):
respectively.
17.6.1 Weighfour1.0gspecimensofC,tothenearest1mg,
then place in crucibles. To each, add approximately 1.5 g of
17.1.3 For Range III, 1.25 % to 4.50 % carbon, select two
certified reference materials containing approximately 1.25 % accelerator (see 17.6.4.1).
17.6.2 Follow the calibration procedure recommended by
and 4.00 % carbon and designate them as BBB and CCC,
respectively. the manufacturer. Use C as the primary calibration reference
material (RM) and analyze at least three specimens to deter-
17.1.4 Users may determine that only one or two ranges are
mine the measurement response to be used in the calibration
necessary for calibration depending on the carbon range of
regression. Treat each specimen, as directed in 18.1.2 and
samples to be tested.
18.1.3, before proceeding to the next one.
17.2 Adjustment of Response of Measurement System:
17.6.3 Confirm the calibration by analyzing C following the
17.2.1 Modern instruments may not require adjustment of
calibration procedure. If the result agrees with the certified
the measurement system response prior to calibration. For
value within the uncertainty provided on the certificate of
these instruments proceed directly to 17.3 after the condition-
analysis, the calibration is acceptable. Also, if the certified
ing runs described in 15.2.
value falls within a prediction interval calculated as described
17.2.2 Transfer 1.0 g of B, weighed to the nearest 1 mg, and
in Eq 1, the calibration is acceptable (see Note 4). The
approximately 1.5 g of accelerator to a crucible. Some manu-
prediction interval is defined as the range of values either
facturers provide scoops that dispense approximately 1.5 g of
bounded by the mean result and (mean result – p)orbythe
accelerator. Once it is verified that the scoop delivers this
mean result and (mean result + p). Compare the certified value
approximate mass, it is acceptable to use this device for routine
of the reference material to the appropriate calculated predic-
dispensing of accelerator.
tioninterval.Ifthecertifiedvalueofthereferencematerialfalls
17.2.3 Proceed as directed in 18.1.2 and 18.1.3.
within the prediction interval, there is evidence that the
17.2.4 Repeat 17.2.2 and 17.2.3 until the absence of drift is calibration may not be biased. If the value does not fall within
indicated by stable carbon readings being obtained. Consis-
the prediction interval there may be calibration bias.
tency is indicated by consecutive runs agreeing within 0.001 %
p 5 t· 1 1 ·s (1)
carbon. If using an instrument which requires manual
S D
=
n
adjustment, adjust the signal to provide a reading within
6 0.003 % of the carbon value for the certified reference
where:
material.
p = width of the prediction interval,
n = number of replicates used in 17.6.2,
17.3 Determination of Blank Reading—Range I:
t = student’s t chosen for a one-sided interval at the 95 %
17.3.1 Add approximately 1.5 g of accelerator into a cru-
confidence level for n replicate measurements. For
cible. If required, 1.0 g ofA, weighed to the nearest 1 mg, may
example: t = 2.92 when n = 3 (degrees of freedom = 2);
be added to the crucible.
t= 2.35 when n = 4 (degrees of freedom = 3); t= 2.13,
17.3.2 Proceed as directed in 18.1.2 and 18.1.3.
when n = 5 (degrees of freedom = 4), and
17.3.3 Repeat 17.3.1 and 17.3.2 a sufficient number of times
s = standard deviation of n replicates.
to establish that low (less than 0.002 % carbon) and stable
NOTE 4—The procedure for verifying calibration reference materials
(6 0.0002 % carbon) readings are obtained. Blank values are
(RMs) outlined in the original version of this test method required the test
equal to the total result of the accelerator. IfAwas used, blank result to be compared to “the uncertainty limits of the certified value for
E1019 − 18
the calibration RM,” typically interpreted as the range defined by the
17.8.3 If not, repeat 17.8.1 and 17.8.2.
certified value plus or minus its associated uncertainty. The original
17.8.4 Weigh at least two 0.5 g specimens of BBB, weighed
version was utilized in the generation of the data in this test method’s
to the nearest 1 mg, and transfer to crucibles. To each, add
precisionandbiasstatements.Thecurrentmethodin17.6.3forconfirming
approximately 1.5 g of accelerator.
the calibration is statistically rigorous and should be used in general
17.8.5 Treat each specimen as described in 18.1.2 and
practice. As an option, the laboratory may obtain an estimate of s from a
control chart maintained as part of their quality control program. If the
18.1.3 before proceeding to the next one.
control chart contains a large number of measurements (n > 30), t may be
17.8.6 Record the results of 17.8.4 and 17.8.5 and compare
set equal to 2 at the 95 % confidence level.At its discretion, the laboratory
to the certified carbon value of BBB. The result should agree
may choose to set a smaller range for the acceptable test result.
with the certified value within a suitable confidence interval
17.6.4 Weigh at least two 1.0 g specimens of B, weighed to
(see Note 4 in 17.6.3). If the result agrees with the certified
the nearest 1 mg, and transfer them to crucibles. To each, add
value within the uncertainty provided on the certificate of
approximately 1.5 g of accelerator.
analysis, the calibration is acceptable. Also, if the certified
17.6.4.1 Theuseof1.5gofacceleratormaynotbesufficient
value falls within an interval calculated as described in Eq 1,
foralldeterminators.Therequiredamountisdeterminedbythe
the calibration is acceptable. If not, refer to manufacturer’s
analyzer used, induction coil spacing, position of the crucible
instructions for checking the linearity of the analyzer.
intheinductioncoil,ageandstrengthoftheoscillatortube,and
17.8.7 Verify the calibration when: (1) a different lot of
type of crucible being used. Use the amount required to
crucibles is used, (2) a different lot of accelerator is used, (3)
produce proper sample combustion using the same amount
the system has been in use for 4 h, (4) the oxygen supply has
throughout the entire test method.
been changed, and (5) the system has been idle for 1 h.
17.6.5 Treat each specimen as directed in 18.1.2 and 18.1.3
Verification should consist of analyzing at least one specimen
before proceeding to the next one.
of each calibration RM. Recalibrate as necessary.
17.6.6 Record the results of 17.6.4 and 17.6.5 and compare
them to the certified carbon value of B.The result should agree
18. Procedure
with the certified value within a suitable confidence interval
18.1 Procedure—Range I:
(see Note 4 in 17.6.3). If the result agrees with the certified
18.1.1 Stabilize the furnace and analyzer as directed in
value within the uncertainty provided on the certificate of
Section 15. Transfer approximately 1.0 g of specimen and
analysis, the calibration is acceptable. Also, if the certified
approximately 1.5 g of accelerator to a crucible. (See 13.2.)
value falls within an interval calculated as described in Eq 1,
18.1.2 Place the crucible into the furnace mechanism. Use
the calibration is acceptable. If not, refer to the manufacturer’s
crucible tongs to handle the crucibles.
instructions for checking the linearity of the system.
18.1.3 Refer to the manufacturer’s recommended procedure
17.7 Calibration—Range II (0.10 % to 1.25 % carbon):
regarding entry of specimen mass and blank value. Start the
17.7.1 Proceed as directed in 17.6.1 – 17.6.3, using CC.
analysis cycle.
17.7.2 Proceed as directed in 17.6.4 – 17.6.6, using BB.
18.2 Procedure—Range II—Proceed as directed in 18.1.
17.8 Calibration—Range III (1.25 % to 4.50 % carbon):
18.3 Procedure—Range III—Proceed as directed in 18.1,
17.8.1 Weigh four 0.5 g specimens of CCC, to the nearest 1
using a 0.5 g specimen.
mg,andplaceincrucibles.Toeach,addapproximately1.5gof
accelerator. Follow the calibration procedure recommended by
19. Calculation
the manufacturer. Use CCC as the primary calibration RM and
19.1 The calibration function of the equipment shall yield a
analyze at least three specimens to determine the calibration
linear plot described by Eq 2.
slope. Treat each specimen, as directed in 18.1.2 and 18.1.3,
before proceeding to the next one.
Y 5 mX1b (2)
17.8.2 Confirm the calibration by analyzing CCC following
where:
the calibration procedure. If the result agrees with the certified
Y = measurement response,
value within the uncertainty provided on the certificate of
m = slope,
analysis, the calibration is acceptable. Also, if the certified
X = calibration RM mass fraction, and
value falls within an interval calculated as described in Eq 1,
b = Y intercept.
the calibration is acceptable. See Note 4 in 17.6.3.
TABLE 1 Statistical Information—Carbon, Range I
Repeatability Reproducibility
Test Specimen Carbon Found, %
(R , Practice E173) (R , Practice E173)
1 2
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
E1019 − 18
TABLE 2 Statistical Information—Carbon, Range II
Repeatability Reproducibility
Test Specimen Carbon Found, %
(R , Practice E173) (R , Practice E173)
1 2
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
Repeatability Reproducibility
Test Specimen Carbon Found, %
(R , Practice E173) (R , Practice E173)
1 2
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
Calculation of the calibration function shall be done using a SULFUR BY THE COMBUSTION–INFRARED
linear least squares regression. Some manufacturers recom- ABSORPTION TEST METHOD (POTASSIUM
mend the use of a curve weighting factor where the calibration SULFATE CALIBRATION)
RM mass fraction is derived as 1/X. It is acceptable to use this
This test method, which consisted of Sections 21 through 31
type of curve weighting.
of this standard, was discontinued in 2018.
19.2 Since most modern commercially available instru-
ments calculate mass fractions directly, including corrections
NITROGEN BY THE INERT GAS FUSION AND
for blank and sample mass, manual calculations by the analyst
THERMAL CONDUCTIVITY DETECTION
are not required.
TEST METHOD
19.2.1 If the analyzer does not compensate for blank and
sample mass values, then use the following formula:
32. Scope
Carbon,% 5 A 2 B 3 C/D (3)
@~ ! #
32.1 This test method covers the determination of nitrogen
where:
from 0.0010 % to 0.2 %.
A = instrument reading for specimen,
32.1.1 The upper limit of the scope has been set at 0.2 %
B = instrument reading for blank,
because sufficient numbers of test materials containing higher
C = mass compensator setting, and
nitrogen contents were unavailable for testing as directed in
D = specimen mass, g.
Practice E173. However, recognizing that commercial nitrogen
determinators are capable of handling higher compositions,
20. Precision and Bias
this test method provides a calibration procedure up to 0.5 %.
20.1 Precision—Nine laboratories cooperated in testing this
Users of this test method are cautioned that use of it above
test method and obtained the data summarized in Table 1
0.2 % is not supported by interlaboratory testing. In this case,
through Table 3. Testing was performed in compliance with
laboratories should perform method validation using reference
Practice E173 (see 9.1).
materials.
20.2 Bias—The accuracy of this test method has been
33. Summary of Test Method
deemed satisfactory based upon the data for the certified
reference materials in Table 1, Table 2, and Table 3. Users are
33.1 Thespecimen,containedinasmall,single-usegraphite
encouraged to use these or similar reference materials to verify
crucible, is fused under a flowing helium atmosphere at a
that the test method is performing accurately in their labora-
minimum temperature of 1900 °C. Nitrogen present in the
tories.
sample is released as molecular nitrogen into the flowing
helium stream. The nitrogen is separated from other liberated
5 gases such as hydrogen and CO and is finally measured in a
Supporting data are available fromASTM International Headquarters. Request
RR:E01-1093. thermal conductivity cell. Refer to Figs. 5-8 for examples.
E1019 − 18
A—Helium Supply H—Electrode Furnace (Note 5 in 35.1)
B—Pressure Regulator 2 Stage I—Dust Filter
C—Sodium Hydroxide Impregnated Clay J—Heated Rare Earth Copper Oxide
D—Magnesium Perchlorate (Note 1 in 14.4) 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
1 to 4
Crucible Degas Flow
5 to 2
H
3 to 6
1 to 6
Fusion Flow
5 to 4
H
3&2
FIG. 5 Nitrogen Test Method A—Flow Diagram
33.2 This test method is written for use with commercial all reagents shall conform to the specifications of the Commit-
analyzers equipped to perform the above operations automati- tee onAnalytical Reagents of theAmerican Chemical Society,
cally and calibrated using reference materials of known nitro- where such specifications are available. Other grades may be
gen content. used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
34. Interferences
accuracy of the determination.
34.1 The elements ordinarily present in iron, steel, nickel,
36.2 Acetone—The residue after evaporation shall be
and cobalt alloys do not interfere.
<0.0005 %.
35. Apparatus
36.3 Copper—, use the purity and form specified by the
instrument manufacturer.
35.1 Fusion and Measurement Apparatus—SeeFigs.5-8for
examples.
36.4 Helium, high-purity (99.99 %).
NOTE 5—Some manufacturers may use an induction furnace
36.5 Magnesium Perchlorate, (known commercially as An-
35.2 Graphite Crucibles—Use the size crucibles recom- hydrone). Use the purity specified by the instrument manufac-
turer. See Note 1 in 14.4.
mended by the manufacturer of the instrument. Crucibles shall
be composed of high purity graphite.
36.6 Rare Earth Copper Oxide—Use the purity as specified
35.3 Crucible Tongs—Capable of handling recommended
by the instrument manufacturer.
crucibles.
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.
E1019 − 18
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 (Note 1 in 14.4) L—Electrode Furnace (Note 5 in 35.1)
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
2 to 4
Crucible Degas Flow
5 to 3
H
1 to 6
1 to 4
Fusion Flow
5 to 6
H
2&3 off
FIG. 6 Nitrogen Test Method B—Flow Diagram
37. Preparation of Apparatus 38. Sample Preparation
38.1 Practice E1806 provides some guidance for sampling
37.1 Assemble the apparatus as recommended by the manu-
and preparation of steel and iron alloys for gas analysis.
facturer.
Specimens will typically be in the form of chips, drillings,
37.2 Test the furnace and analyzer to ensure the absence of
slugs, or solids. Final specimen preparation shall be performed
leaks, and make the required electrical power and water
as directed in 38.2 or 38.3.
connections. Prepare the apparatus for operation as directed in 38.1.1 Size all specimens to permit free introduction
the manufacturer’s instructions. Change the chemical reagents
throughtheloadingdeviceoftheequipmentordirectlyintothe
and filters at the intervals recommended by the instrument graphite crucible.
manufacturer. Make a minimum of two determinations using a
38.2 If slugs or solid-form specimens are used, cut them
specimen as directed in 40.2.1 or 40.2.2 to condition the
withawater-cooledabrasivecut-offwheelorbyanothermeans
instrument before attempting to calibrate the system or to
that will prevent overheating. Abrade the surface to remove
determine the blank. Avoid the use of reference materials for
surface oxidation using a clean file, die grinder, or silicon
instrument conditioning.
carbide grinding media. Again, avoid overheating the sample.
If specimens are wet ground it will be necessary to rinse
37.2.1 Many instrument manufacturers provide a cycle time
specimensinwaterfollowedbyanacetonerinse.Samplesshall
in the analysis parameters to pre-heat the crucible (commonly
be air dried completely prior to analysis.
referred to as degassing or outgassing) before a blank can be
determined or a sample can be added to the crucible for
38.3 Clean, dry chips and millings may be analyzed without
analysis. This outgassing removes any absorbed impurities
additional preparation; however, specimens shall be free of any
from the crucible. See Figs. 5-8 for examples of crucible degas
lubricants and cutting fluids. It may be necessary to clean
flow. specimenstoremoveresiduallubricantsandcuttingfluids.Any
E1019 − 18
A—Helium Supply I—Sample Holding Chamber
B—Pressure Regulator J—Electrode Furnace (Note 5 in 35.1)
C—Heated Copper K—Dust Filter
D—Sodium Hydroxide Impregnated Clay L—Heated Rare Earth Copper Oxide
E—Magnesium Perchlorate (Note 1 in 14.4) 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
1 to 4
Crucible Degas Flow
5 to 2
H
3 to 6
1 to 6
Fusion Flow
5 to 4
H
3&2 off
FIG. 7 Nitrogen/Oxygen Test Method A—Flow Diagram
cleaned specimens shall be rinsed in acetone and dried com- 39.2.1 Modern instruments may not require adjustment of
pletely before analysis the measurement system response prior to calibration. For
these instruments proceed directly to 39.3 after performing the
38.4 Handle prepared specimens with tweezers; not with
conditioning runs described in 37.2.
bare hands.
39.2.2 Prepareanapproximate1.0gspecimenofCweighed
39. Calibration to the nearest 1 mg as directed in 38.2 or 38.3.
39.2.3 Proceed as directed in 40.2.1 or 40.2.2.
39.1 Calibration Reference Materials—See Note 3 in 17.1.
39.2.4 Repeat 39.2.2 and 39.2.3 and adjust as recommended
The presence of nitrogen as refractory nitrides in the matrix
by the manufacturer until the absence of drift is indicated by
may affect sample fusion and nitrogen evolution under stan-
consecutive runs agreeing within 0.0004 %.
dard operating conditions of the analyzer. It is therefore
recommended that when available, calibration reference mate-
39.3 Determination of Blank Reading—Ranges I and II:
rials be of the same or similar composition as the samples to be
39.3.1 Iftheinstrumentisequippedwithanelectronicblank
analyzed.
compensator, adjust to zero, and proceed with the determina-
39.1.1 For Range I of 0.0005 % to 0.10 % nitrogen, select
tion of the blank value.
at least three certified reference materials with mass fractions
39.3.2 Make three blank determinations as directed in
ranging from approximately 0.002 % to 0.10 % nitrogen and
40.2.1 or 40.2.2 with the sample omitted. Use a fresh crucible
designate them as A, B, and C respectively .
eachtime.Iftheloadingdeviceisusedtoanalyzetheunknown
39.1.2 For Range II of 0.10 % to 0.50 % nitrogen, select
or calibration sample, see 38.1.1.
three certified reference materials containing approximately
39.3.3 If the blank values exceed 0.0003 % or a spread of
0.10 %, 0.30 %, and 0.50 % nitrogen and designate them as
three consecutive values exceeds 0.0003 %, determine the
AA, BB, and CC, respectively.
cause, make necessary corrections, and repeat 39.3.1 and
39.2 Adjustment of Response of Measurement System: 39.3.2.
E1019 − 18
A—Helium Supply J—Flow Manifold
B—Pressure Regulator 2 Stage K—Sample Holding Chamber
C—Sodium Hydroxide Impregnated Clay L—Electrode Furnace (Note 5 in 35.1)
D—Magnesium Perchlorate (Note 1 in 14.4) 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
2 to 4
Crucible Degas Flow
5 to 3
H
1 to 6
1 to 4
Fusion Flow
5 to 6
H
2&3 off
FIG. 8 Nitrogen/Oxygen Test Method B—Flow Diagram
39.3.4 Record the average value of at least three blank tion is acceptable. See Note 4 in 17.6.3. If not, repeat 39.4.1
readings. and 39.4.2. The prediction interval is defined as the range of
39.3.5 Enter the average blank value in the appropriate
values either bounded by the mean result and (mean result – p)
mechanism of the analyzer. Refer to the manufacturer’s in-
or by the mean result and (mean result + p). Compare the
structions for specific instructions on performing this function.
certified value of the reference material to the appropriate
This mechanism will electronically compensate for the blank
calculated prediction interval. If the certified value of the
value. If the unit does not have this function, the average blank
reference material falls within the prediction interval, there is
value shall be subtracted from the instrument readings for
evidence that the calibration may not be biased. If the value
reference materials and specimens. See 41.2.1.
does not fall within the prediction interval there may be
39.4 Calibration Procedure—Range I:
calibration bias.
39.4.1 Prepare four 1.0 g specimens of C weighed to the
nearest 1 mg, as directed in 38.2 or 38.3. p 5 t· 1 1 ·s (4)
S D
=n
39.4.2 Follow the calibration procedure recommended by
the manufacturer using C as the primary calibration RM.
where:
Analyze C at least three times to determine the calibration
p = width of the prediction interval,
slope. Treat each specimen as directed in 40.2.1 or 40.2.2
n = number of replicates used in 39.4.2,
before proceeding to the next one.
t = student’s t chosen for the 95 % confidence level for n
39.4.3 Confirm the calibration by analyzing C after calibra-
replicate measurements. For example: t = 2.92 when n =
tion. If the result agrees with the certified value within the
3 (degrees of freedom = 2); t = 2.35 when n = 4 (degrees
uncertainty provided on the certificate of analysis, the calibra-
of freedom = 3); t = 2.13, when n = 5 (degrees of
tion is acceptable. Also, if the certified value falls within a
freedom = 4), and
prediction interval calculated as described in Eq 4, the calibra-
E1019 − 18
40.2.2.2 Place a 1.0 g specimen weighed to the nearest 1 mg
s = standard deviation of n replicates.
in the loading device. Refer to the manufacturer’s recom-
39.4.4 Prepare two 1.0 g specimens each of A, B, and C
mended procedure, including entry of sample mass.
weighed to the nearest 1 mg, as directed in 38.2 or 38.3.
40.2.2.3 Place an empty crucible in the furnace mechanism.
39.4.5 Treat each specimen as directed in 40.2.1 or 40.2.2
40.2.2.4 Start the analysis cycle, referring to the manufac-
before proceeding to the next one.
turer’s recommended procedure.
39.4.6 If the result agrees with the certified value within the
uncertainty provided on the certificate of analysis, the calibra-
41. Calculation
tion is acceptable. Also, if the certified value falls within an
41.1 The calibration function of the equipment shall yield a
interval calculated as described in Eq 4, the calibration is
linear plot described by Eq 2 in 19.1. Calculation of the
acceptable. See 39.4.3 for discussion. If not, refer to the
calibration function shall be done using a linear least squares
manufacturer’s instructions for checking the linearity of the
regression. Some manufacturers recommend the use of a curve
system.
weighting factor where the calibration RM mass fraction is
39.4.7 Verify the calibration when: (1) a different lot of
derived as 1/X. It is acceptable to use this type of curve
crucibles is used, (2) the system has been idle for 1 h, (3) the
weighting.
system has been in use for 4 h, and (4) the helium supply has
been changed. Verification should consist of analyzing at least
41.2 Since most modern commercially available instru-
onespecimenofeachcalibrationRM.Recalibrateasnecessary.
ments calculate mass fraction concentrations directly, includ-
ingcorrectionsforblankandsamplemass,manualcalculations
39.5 Calibration Procedure—Range II:
by the analyst are not required.
39.5.1 Proceed as directed in 39.4.1 – 39.4.3 using CC.
41.2.1 If the analyzer does not compensate for blank and
39.5.2 Proceed as directed in 39.4.4 – 39.4.6 using AA and
sample mass values, then the equation is:
BB. See 39.4.7.
Nitrogen,% 5 A 2 B 3 C/D (5)
@~ ! #
40. Procedure
where:
40.1 Assemble the apparatus and condition it as directed in
A = instrument reading for specimen,
Section 37. If the samples are to be analyzed in the automatic
B = instrument
...