Designation: E 1009 95 (Reapproved 2006)

Standard Practice for

Evaluating an Optical Emission Vacuum Spectrometer to
Analyze Carbon and Low-Alloy Steel1
This standard is issued under the fixed designation E 1009; 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 3.2 Definitions of Terms Specific to This Standard:

1.1 This practice covers evaluation of an optical emission 3.2.1 accuracythe closeness of a spectrochemical deter-
vacuum spectrometer to analyze carbon and low-alloy steels. It mination to an accepted reference; it is affected by imprecision
covers instruments used for the analysis of solid samples taken and bias.
from molten metal for production control or from products to 3.2.2 standard error (SE)although primarily a calculation
confirm the composition. Both pre-installation and post- that measures how well a calibration has been defined, standard
installation precision and accuracy are included in the evalua- error (SE) is used in this practice as an indicator of accuracy.
tion. It is CRM-dependent and instrument-operator dependent.
1.2 While Tables 1-3 are specific for plain carbon and Some expected maximum SE values are listed, but compari-
low-alloy steel, they could be supplemented by similar tables sons between instrument calibrations can strictly be done only
for other materials. when identical suites of calibrants are used.
1.3 This standard does not purport to address all of the 4. Summary of Practice
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 4.1 After the spectrometer is calibrated, use this practice to
priate safety and health practices and determine the applica- evaluate the instrument and its calibration. Certified reference
bility of regulatory limitations prior to use. materials are run as unknowns and precision is compared to
Table 1. Before comparing standard errors to those in Table 2,
2. Referenced Documents ascertain that the calibration does not include unrealistic
2.1 ASTM Standards: 2 inflections. Values equal to or less than those in Tables 1 and 2
E 135 Terminology Relating to Analytical Chemistry for indicate that the instrument is acceptable.
Metals, Ores, and Related Materials
5. Significance and Use
E 305 Practice for Establishing and Controlling Spectro-
chemical Analytical Curves3 5.1 Periodically throughout the useful life of an optical
E 406 Practice for Using Controlled Atmospheres in Spec- emission spectrometer it becomes necessary to evaluate its
trochemical Analysis performance. This is especially true at manufacture and during
E 528 Practices for Grounding Basic Optical Emission installation. The objective at this time is to establish whether
Spectrochemical Equipment3 the instrument meets design specifications and performs to
E 876 Practice for Use of Statistics in the Evaluation of customer specifications. A manufacturers objective may be to
Spectrometric Data3 compare production line instruments. With data on many
instruments, such an evaluation procedure would be a valuable
3. Terminology contribution to the manufacturers quality control plan.
3.1 DefinitionsFor definitions of terms used in this prac- 5.2 Use of this procedure at installation can tell the manu-
tice, refer to Terminology E 135 and Practice E 876. facturer or user whether there has been a significant change in
performance due to faulty shipping or handling of the instru-
ment. At this time, the procedure could be the beginning of a
1
This practice is under the jurisdiction of ASTM Committee E01 on Analytical quality control plan for the user. Once established, the data
Chemistry for Metals, Ores and Related Materials and is the direct responsibility of from the procedure provide a base for comparison of future
Subcommittee E01.01 on Iron, Steel, and Ferroalloys.
Current edition approved June 1, 2006. Published June 2006. Originally runs, enabling operators to detect changes in performance.
approved in 1990. Last previous edition approved in 2000 as E 1009 95 (2000). 5.3 Data produced by this practice make possible a com-
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or parison of different instruments, for example, X-ray and optical
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Standards volume information, refer to the standards Document Summary page on
emission or optical emission and atomic absorption. While the
the ASTM website.
3
Withdrawn.

Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
 E 1009 95 (2006)
data in the Tables 1-3 are valid for optical emission spectrom- TABLE 1 (a) Revised Data
eters, other instruments may produce better or worse perfor- Element
Approximate Standard
mance values. In this manner, the data could be used by Concentration, % Deviation

management to determine the suitability of a given instrument C 0.015 0.0009

C 1.03 0.012
to perform a given determination with an acceptable precision MN 0.067 0.0006
and accuracy. Mn 2.00 0.023
P 0.0032 0.0007
S 0.0024 0.0001
TABLE 1 Recommended Precision Requirements For Steel Using
Si 0.01 0.0002
An Optical Emission Vacuum SpectrometerA
Ni 0.021 0.0004
Ni 2.00 0.005
Approximate Standard CR 1.48 0.009
Element
Concentration, % Deviation Mo 0.005 0.0004
C 0.06 60.002 Mo 0.50 0.002
0.15 0.004 Cu 0.015 0.0003
0.50 0.010 Cu 0.30 0.0007
0.90 0.015 Ti 0.0055 0.0004
Mn 0.35 0.007 Al 0.004 0.0004
0.60 0.015 Al 0.04 0.0007
1.00 0.02 Nb 0.01 0.0005
1.50 0.03 Nb 0.1 0.002
P 0.006 0.0007 B 0.001 0.0001
0.04 0.0015 B 0.005 0.0001
S 0.005 0.0015 Zr 0.013 0.0007
0.04 0.002 Pb 0.002 0.0004
0.06 0.004 As 0.01 0.0003
Si 0.02 0.004 As 0.055 0.002
0.30 0.006
0.50 0.010 A
These precisions were generated from data that were collected on newer
Ni 0.03 0.002 instruments than the original data.
0.10 0.003
0.70 0.007
1.60 0.03
Cr 0.04 0.002 5.4 While this practice is directed towards optical emission
0.30 0.007 vacuum spectrometers in the analysis of carbon and low-alloy
0.80 0.015
Sn 0.003 0.0006 steel, its use is not restricted to that instrument or that matrix.
0.02 0.0015
0.05 0.002 6. Instrumentation
V 0.01 0.0015
0.03 0.002 6.1 The vacuum spectrometer shall be equipped with an
0.25 0.007 argon-flushed sample stand for point-to-plane excitation.
Mo 0.03 0.003 6.2 The excitation parameters and radiations measured shall
0.30 0.008
Cu 0.02 0.0007 be selected to meet the specified performance.
0.15 0.003
Ti 0.02 0.002 NOTE 1Ordinarily this selection is made by the vendor, or instrument
0.20 0.008 manufacturer, based on experience.
Al 0.006 0.002
0.02 0.003
6.3 Provision shall be made to compensate for spectral
0.07 0.004 interferences. More than one spectral line may be provided for
Nb 0.02 0.0015 an element, depending on element concentration or the exci-
0.07 0.003
B 0.001 0.00015
tation used, but switching of lines shall be done automatically.
0.07 0.003
Zr 0.05 0.002 7. Analysis Time
Pb 0.01 0.0015
Se 0.02 0.002
7.1 Analysis time, excluding sample preparation, shall not
A
exceed 30 s for single burns, or 60 s for multiple burns.
These precisions were generated from actual data in one laboratory; as such,
they represent what has been done with proven, homogeneous materials. NOTE 2This requirement may be waived if speed of analysis is not

2
 E 1009 95 (2006)
TABLE 2 Elements, Concentration Ranges, and Recommended 9. Purpose of Analytical Performance Tests
Acceptable Standard Error (SE) for Steel
9.1 Pre-Shipment Precision:
Approximate Concentration
Max Allowable Standard 9.1.1 Perform the tests in 10.1 to verify performance before
Element Range, %, as Covered by the
Error, %A
Certified Standards shipment so that any necessary adjustments can be made at the
C 0.02 to 1.00 0.009 factory. Preliminary calibration of the spectrometer is required
Mn 0.01 to 1.50 0.012 to assure that the concentration range specified for each
P 0.001 to 0.07 0.002
S 0.003 to 0.06 0.002 element is covered and to provide analytical curves for
Si 0.005 to 1.00 0.012 reporting analytical precision in terms of percent concentra-
Ni 0.01 to 2.00 0.014 tion.
Cr 0.01 to 1.00 0.012
Sn 0.002 to 0.10 0.002 NOTE 3Raw data output is adequate if the slope of the curve is
V 0.002 to 0.50 0.005
defined.
Mo 0.003 to 0.50 0.005
Cu 0.005 to 0.50 0.007
Ti 0.003 to 0.25 0.005
9.2 Post-Installation Precision:
Al 0.005 to 0.25 0.005 9.2.1 Repeat the tests in 10.1 to confirm previous calibra-
B
Nb 0.002 to 0.30 tions. The post-installation test shall be made by the customer
B 0.0001 to 0.04 0.001
Zr 0.01 to 1.00 B after training operators and verifying that the calibrations are
Pb 0.001 to 0.03 B satisfactory. The vendor may send a representative to consult
B
Se 0.001 to 0.05 on and witness this test.
A
These values will depend on the standards used and the distribution of their 9.3 Pre-Shipment Accuracy:
compositions throughout the range of calibration.
B
Accuracy will not be assessed for these elements due to lack of CRMs. 9.3.1 Perform the tests in 10.2. This provides a measure of
accuracy based on how closely the spectrometer response
TABLE 3 Sample Calculation of Standard Error (SE)A agrees with the certified values of the CRMs when needed
Difference
interference corrections are made.
Given, % Calculated, % d2 9.3.2 When evaluating spectrometers equipped with dedi-
(d), %
0.19 0.189 0.001 0.000001 cated computers or calculators, this test also demonstrates the
0.27 0.274 0.004 0.000016 ability of the software to (1) For curves that cover a wide
0.42 0.432 0.012 0.000144 concentration, an improvement in accuracy may be achieved
0.51 0.526 0.016 0.000256
0.99 0.987 0.003 0.000009 by defining the upper and lower concentrations separately, with
1.29 1.289 0.001 0.000001 a smooth transition from one segment to the other, (2) Define
2.33 2.338 0.008 0.000064
interelement effects, ( 3) Establish correction factors, and (4)
2.97 2.961 0.009 0.000081
A
Convert raw data output into percent concentration.
The sample SE calculation follows:
(d 2 5 0.000572
9.4 Post-Installation Accuracy:
9.4.1 Repeat the tests of 10.2 using the identical reference
(d 2/n 5 0.0000715 materials used in 9.3.1.
9.4.2 This test shall be done with trained operators and the
SE 5 =(d 2/n 5 0.008
vendor may send a representative to consult on and witness this
test.
where:
n = 8 10. Test Procedures
10.1 Precision:
10.1.1 The purchaser shall provide four to six reference
materials of proven homogeneity covering the approximate
required. The time limitation does not apply to resulfurized grades of steel concentrations listed in Table 1.
and may be changed for other special grades of steel.
10.1.2 Analyze the set of test specimens randomly at least
8. Users Responsibility for Laboratory Environment ten times during two separate 4-h periods. Each is to be a single
burn. Warm-up runs are permitted at the start of each test
8.1 Maintain laboratory temperature and humidity as re- period. Adjustment of optical alignment and standardization
quired by the spectrometer. The generally accepted ranges are shall be made at the start of each period. Standardization shall
18.5 to 24C (65 to 75F) and 20 to 50 % relative humidity. not be done more than once every 2 h thereafter.
8.2 Provide argon that meets the requirements for vacuum
10.1.3 Compute the standard deviation, s, for each element
spectrometers and is in accordance with Practice E 406. In
in each material of 10.1.1 based on the combined analyses from
some cases argon purity of 1 ppm is required.
each test period as follows:
8.3 Provide the required electrical power regulated to6 5 %
and filtered to prevent radio frequency interference. See s 5 =(d 2 /~n 2 1! (1)
Practice E 528.
8.4 Provide a radio-frequency ground in accordance with where:
Practice E 528. Modern excitation sources may not require d = deviation of each determination from the mean, and
special grounding. n = number of determinations.

3
 E 1009 95 (2006)
10.1.4 The test results are satisfactory if the precision or The value to use for f is discussed in Practice E 876. If the
imprecision, in terms of standard deviation, is equal to or less CRMs are calculated as if they were unknowns in an estab-
than that listed in Table 1. lished calibration, as directed in 10.2.4, f will be the number of
10.2 Accuracy: reference materials. If an alternate procedure is used in which
10.2.1 Select the CRMs for calibration from those listed in the CRMs are calculated from a calibration equation that they
Note 5. See also Note 6. define from a regression as given in Practice E 305, f is reduced
10.2.2 These same CRMs shall be used to calculate the by the order of the equation, the number of constants it
standard error as defined in 10.2.6. contains.
NOTE 4If this evaluation is to include an element not certified, then
10.2.7 Sample calculation of SE is given in Table 3.
the reference materials used must be from an accepted and reliable source. 10.2.8 The results of the test are satisfactory if the SE is
equal to or lower than that listed in Table 2.
10.2.3 If this procedure is to be considered an arbitration
test, the calibration reference materials must be acceptable to NOTE 5These certified reference materials have proven to be satis-
factory for calibration and calculation of SE as specified in this practice:
both parties, and both parties must have access to them. NIST (NBS) SRM 1761 to 1767, 1261, 1263 and 1264. Other certified
10.2.4 After the spectrometer is calibrated, analyze the same reference materials of similar compositions available from BAS, ISIJ, and
reference materials one time each. IRSID may also be used.
10.2.5 If adjustments to the spectrometer are required dur- NOTE 6Table 2 assumes that most of the concentrations will be in a
ing this test, discard the results and repeat the test. If the range considered to be in the straight-line portion of the analytical
evaluation of an element does not satisfy the accuracy require- curve. Not all curves have such; some have only that, depending on the
element and the range to be covered by an instrument. Some do not have
ments, the test may be repeated and the results substituted for
background while some have only that area to contend with. If it is
the first results. possible to do so, use a balance of reference materials in each region of
10.2.6 Compute the standard error, SE, as follows: background, straight-line, and reversal for the test. Weighting of reference
materials in a given extreme area, will affect the SE achieved. Table 2 is
SE 5 =(dc 2/f (2) recommended, based on the experience of one laboratory. Values can be
substituted but should be agreed upon beforehand.
where:
dc = difference between the certified and the calculated 11. Keywords
values, and 11.1 carbon steel; low-alloy steel; optical emission; vacuum
f = the degrees of freedom in the observations.
spectrometer

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or [email protected] (e-mail); or through the ASTM website
(www.astm.org).