ASTM E415-99a

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Designation:E415–99a
Standard Test Method for
Optical Emission Vacuum Spectrometric Analysis of Carbon
and Low-Alloy Steel
This standard is issued under the fixed designation E 415; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope hearth, or electric furnaces and analysis of processed material.
It is designed for either chill-cast or rolled and forged speci-
1.1 This test method covers the simultaneous determination
mens. The reference materials and specimens should be of
of 20 alloying and residual elements in carbon and low-alloy
similar metallurgical condition and composition.
steels in the concentration ranges shown (Note 1).
1.4 This standard does not purport to address all of the
Concentration Range, %
A B
safety concerns, if any, associated with its use. It is the
Element Applicable Range, % Quantitative Range, %
responsibility of the user of this standard to establish appro-
Aluminum 0 to 0.075 0.02 to 0.075
priate safety and health practices and determine the applica-
Arsenic 0 to 0.1 0.05 to 0.1
bility of regulatory limitations prior to use.
Boron 0 to 0.007 0.002 to 0.007
Calcium 0 to 0.003 0.001 to 0.003
Carbon 0 to 1.1 0.08 to 1.1
2. Referenced Documents
Chromium 0 to 2.25 0.02 to 2.25
2.1 ASTM Standards:
Cobalt 0 to 0.18 0.008 to 0.18
Copper 0 to 0.5 0.04 to 0.5
E 30 Test Methods for Chemical Analysis of Steel, Cast
Manganese 0 to 2.0 0.10 to 2.0
Iron, Open-Hearth Iron, and Wrought Iron
Molybdenum 0 to 0.6 0.03 to 0.6
E 135 Terminology Relating to Analytical Chemistry for
Nickel 0 to 5.0 0.02 to 5.0
Niobium 0 to 0.085 0.02 to 0.085
Metals, Ores, and Related Materials
Nitrogen 0 to 0.015 0.004 to 0.015
E 158 Practice for Fundamental Calculations to Convert
Phosphorous 0 to 0.085 0.02 to 0.085
Intensities into Concentrations in Optical Emission Spec-
Silicon 0 to 1.15 0.07 to 1.15
Sulfur 0 to 0.055 0.01 to 0.055
trochemical Analysis
Tin 0 to 0.045 0.01 to 0.045
E 305 Practice for Establishing and Controlling Spectro-
Titanium 0 to 0.2 0.004 to 0.2
chemical Analytical Curves
Vanadium 0 to 0.3 0.004 to 0.3
Zirconium 0 to 0.05 0.02 to 0.05
E 350 Test Methods for ChemicalAnalysis of Carbon Steel,
Low-Alloy Steel, Silicon Electrical Steel, Ingot Iron, and
A 4
Applicable range in accordance with Guide E 1763 for results reported in
Wrought Iron
accordance with Practice E 1950.
E 406 Practice for Using Controlled Atmospheres in Spec-
B
Quantitative range in accordance with Practice E 1601.
trochemical Analysis
NOTE 1—The concentration ranges of the elements listed have been
E 1019 Test Methods for Determination of Carbon, Sulfur,
established through cooperative testing of reference materials. Included,
Nitrogen, and Oxygen in Steel and in Iron, Nickel, and
in addition to the original data of Test Method E 415 – 71, are data from
Cobalt Alloys
cooperative testing of a broader range of reference materials to expand the
E 1329 Practice for Verification and Use of Control Charts
element concentration ranges.
in Spectrochemical Analysis
1.2 This test method covers analysis of specimens having a
E 1601 Practice for Conducting an Interlaboratory Study to
diameter adequate to overlap the bore of the spark stand
Evaluate the Performance of an Analytical Method
opening (to effect an argon seal). The specimen thickness
E 1763 Guide for Interpretation and Use of Results from
should be between 10 and 38 mm.
Interlaboratory Testing of Chemical Analysis Methods
1.3 This test method covers the routine control analysis of
E 1806 Practice for Sampling Steel and Iron for Determi-
preliminary and ladle tests from either basic oxygen, open-
nation of Chemical Composition
E 1950 Practice for Reporting Results from Methods of
This test method is under the jurisdiction of ASTM Committee E-1 on Chemical Analysis
Analytical Chemistry for Metals, Ores and Related Materials and is the direct
responsibility of Subcommittee E01.01 on Iron, Steel, and Ferroalloys.
Current edition approved Nov. 10, 1999. Published April 2000. Originally
published as E 415 – 71. Last previous edition E 415 – 99.
Discontinued 1995, see 1994 Annual Book of ASTM Standards, Vol. 03.05.
Supporting data for this test method have been filed at ASTM Headquarters as
Annual Book of ASTM Standards, Vol. 03.05.
RR:E2-1004.
Annual Book of ASTM Standards, Vol. 03.06
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
E415
3. Terminology operated at a vacuum of 25 µm of mercury or below. The
primary slit width is 20 to 50 µm. Secondary slit width is 50 to
3.1 For definitions of terms used in this test method, refer to
200 µm.
Terminology E 135.
6.5 Measuring System, consisting of photomultipliers hav-
4. Summary of Test Method
ing individual voltage adjustments, capacitors in which the
output of each photomultiplier is stored, a voltage measuring
4.1 The most sensitive lines of arsenic, boron, carbon,
system to register the voltages on the capacitors either directly
nitrogen, phosphorus, sulfur, and tin lie in the vacuum ultra-
or indirectly, and the necessary switching arrangements to
violet region. The absorption of the radiation by air in this
provide the desired sequence of operation.
region is overcome by evacuating the spectrometer and flush-
ing the spark chamber with argon. A capacitor discharge is
6.6 Vacuum Pump, capable of maintaining a vacuum of 25
produced between the flat, ground surface of the disk specimen
µm Hg.
and a conically shaped electrode. The discharge is terminated
NOTE 3—A pump with a displacement of at least 0.23 m /min (8
at a predetermined intensity time integral of a selected iron
ft /min) is usually adequate.
line, or at a predetermined time, and the relative radiant
energies or concentrations of the analytical lines are recorded.
6.7 Flushing System, consisting of argon tanks, a pressure
regulator, and a gas flowmeter. Automatic sequencing shall be
5. Significance and Use
provided to actuate the flow of argon at a given flow rate for a
5.1 This test method for the spectrometric analysis of metals
given time interval and to start the excitation at the end of the
and alloys is primarily intended to test such materials for
flush period. Means of changing the flow rate of argon shall be
compliance with compositional specifications. It is assumed
provided. The flushing system shall be in accordance with
that all who use this test method will be analysts capable of
Practice E 406.
performing common laboratory procedures skillfully and
safely. It is expected that work will be performed in a properly
7. Reagents and Materials
equipped laboratory.
7.1 Counter Electrodes—The counter electrodes shall be
6.4-mm ( ⁄4-in.) diameter, hard-drawn, fine, silver rods,
6. Apparatus
1.5-mm ( ⁄16-in.) thoriated, tungsten rods, or other material
6.1 Sample Preparation Equipment:
provided it can be shown experimentally that equivalent
6.1.1 Sample Mold, capable of producing castings that are
precisionandbiasisobtained.Machinetherodstoa90or120°
homogeneous and free from voids and porosity. Refer to
cone.
Practice E 1806 for steel sampling procedures. The following
mold types have been found to produce acceptable samples:
NOTE 4—A black deposit builds up on the tip of the electrode, thus
6.1.1.1 Cast Iron Mold—A mold 70 mm (2 ⁄4 in.) deep, 64
reducing the overall intensity of the spectral radiation. In general this
mm (2 ⁄2 in.) in diameter at the top of the mold, and 57 mm condition will not affect analytical performance for the first 40 or 50
excitations, after which time a freshly prepared counter electrode should
(2 ⁄4in.) in diameter at the bottom of the mold. The wall
1 be installed. The number of acceptable excitations on an electrode varies
thickness of the mold is approximately 32 mm (1 ⁄4 in.).
from one instrument to another, and should be established in each
6.1.1.2 Refractory Mold Ring—Amold that has a minimum
laboratory. With a thoriated tungsten electrode, it has been reported that a
inside diameter of 32 mm (1 ⁄4 in.) and a minimum height of 25
hundred or more excitations can usually be made before replacement.
mm (1 in.).The ring is placed on a flat surface of a copper plate
7.2 Inert Gas, Argon, in accordance with Practice E 406.
approximately 50 mm (2 in.) thick.
6.1.1.3 Book-Type Steel or Copper Mold, to produce a
1 1
8. Reference Materials
chill-cast disk 64 mm (2 ⁄2 in.) in diameter and 13 mm ( ⁄2 in.)
thick.
8.1 Certified Reference Materials (CRMs) are available
6.2 Excitation Source, capable of providing a triggered
from the National Institute of Standards and Technology and
capacitor discharge having source parameters meeting the
other sources. These cover all or part of the concentration
requirements of 11.1.
ranges listed in 1.1. They are valuable in establishing prelimi-
6.3 Spark Chamber, automatically flushed with argon. The
nary working curves and determining the precision of the
spark chamber shall be mounted directly on the spectrometer,
instrument. However, because of differences between these
and shall be provided with a spark stand to hold a flat specimen
CRMs and the production specimens prepared by the sampling
and a lower electrode of rod form.
procedures recommended for this test method, curves based on
CRMs may (in very unusual circumstances) need to be
NOTE 2—Clean the excitation chamber when the counter electrode is
replaced. Clean the lens or protective window after approximately 200 to correctedwithvaluesfromreferencematerialsmadebynormal
300 excitations to minimize transmission losses.
production sampling techniques and analyzed in accordance
with Test Methods E 30, E 350, and E 1019.
6.4 Spectrometer, having a reciprocal linear dispersion of
0.60 nm/mm, or better, in the first order and a focal length of 8.2 Reference Materials—Periodically check the instrument
0.75 to 3 m. Its approximate range shall be from 120.0 to 400.0 for drift. For this purpose, verifiers and standardants are
nm. Masks shall be provided in the spectrometer to eliminate employed. These reference materials shall be homogeneous
scattered radiation. The spectrometer shall be provided with an and contain appropriate amounts of each element, covering the
air inlet and a vacuum outlet. The spectrometer shall be concentration range of elements contained in the specimens.
E415
TABLE 1 Internal Standard and Analytical Lines
9. Preparation of Specimens and Reference Materials
Line
B
9.1 Use cast or rolled and forged samples. Cut a 13 to
Element Wavelength, nm Possible Interference
A
Classification
25-mm ( ⁄2 to 1-in.) thick slice from the sample or obtain an
Aluminum 394.40 I V, Mn, Mo, Ni
initial smooth flat surface by machining at least 1.3 mm (0.05
308.22 I V, Mn
in.) off the original surface using a lathe or grinder. Make
Arsenic 197.20 I Mo, W
193.76 I Mn
certain that the specimens are homogeneous and free from
Boron 182.64 I S, Mn, Mo
voids and pits in the region to be excited (Note 5). Rough grind
182.59 I W, Mn, Cu
the cut surface by grinding on a belt surfacer, either wet or dry,
Calcium 396.85 II Nb
Carbon 193.09 I Al
with 50 to 80-grit abrasive belt. Obtain the final surface by dry
Chromium 298.92 II Mn, V, Ni, Nb, Mo
grinding. A finer abrasive belt, such as 120-grit, may be used
267.72 II Mn, Mo, W
for final dry grinding, but is not essential (Note 6).
Cobalt 345.35 I Cr, Mo
228.62 II Ni, Cr
NOTE 5—Specimen porosity is undesirable because it leads to the
Copper 327.40 I Nb
improper “diffuse-type” rather than the desired “concentrated-type” dis- 213.60 II Mo, Cr
Iron (IS) 271.44 II
charge. The specimen surface should be kept clean because the specimen
273.07 II Co
is the electron emitter, and electron emission is inhibited by oily, dirty
Manganese 293.31 II Cr, Mo, Ni
surfaces.
255.86 II Zr
NOTE 6—Reference materials and specimens shall be refinished dry on
Molybdenum 379.83 II Mn
a belt sander before being re-excited on the same area. 277.54 I Cu, V, Co, Mn
386.41 I V, Cr
Nickel 231.60 II Co, Ti
10. Preparation of Apparatus
227.02 II Nb, W
Niobium 319.50 II Mo, Al, V
NOTE 7—The instructions given herein apply to most spectrometers;
Nitrogen 149.26 I Fe, Ti, Si, Mn, Cu, Ni
however, some settings and adjustments may need to be varied, and
and nitride forming
additional preparation of the equipment may be required. It is not within
elements such as Ti
the scope of an ASTM test method to prescribe the minute details of the
Phosphorus 178.29 I Mo
apparatus preparation which may differ not only for each manufacturer, Silicon 288.16 I Mo, Cr, W
251.61 I Fe, V
but also for different equipment from the same manufacturer. For a
Sulfur 180.73 I Mn
description of and further details of operation of a particular spectrometer,
Tin 189.99 II Mn, Mo, Al
refer to the manufacturer’s handbook.
Titanium 337.28 II Nb
324.20 II Nb
10.1 Program the spectrometer to accommodate the internal
Vanadium 310.23 II Fe, Mo, Nb, Ni
standard lines and one of the analytical lines for each element
311.07 II Mn, Ti, Fe
Zirconium 343.82 II W
listed in Table 1.
A
The numerals I or II in the line classification column indicate that the line has
NOTE 8—The lines listed in Table 1 have proven satisfactory for the
been classified in a term array and definitely assigned to the normal atom (I) or to
elements and concentration ranges described in the scope. Other internal
the singly ionized atom (II).
B
standard and analytical lines, such as those listed in Table 2, may be used
Interferences are dependent upon instrument design, spectrum line choices,
provided that it can be shown experimentally that equivalent precision and and excitation conditions, and those listed require confirmation based upon
specimens selected especially to demonstrate suspected interferences.
accuracy are obtained.
10.2 Position or test the position of the spectrometer exit
TABLE 2 Other Analytical Lines
slits to ensure that peak radiation passes through each slit and
Line
B
Element Wavelength, nm Possible Interference
is incident on the photomultiplier. This shall be done initially A
Classification
and as often as necessary thereafter to maintain proper align-
Arsenic 189.04 I V, Cr
ment.
Carbon 165.81 I
NOTE 9—The manner and frequency of positioning or checking the
position of the exit slits will depend on factors such as: the type of
Copper 224.26 II Ni
spectrometer, the variety of analytical problems encountered, and the 324.75 I Mn, Nb
frequency of use. Each laboratory should establish a s
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