ASTM E354-21e1

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.
´1
Designation: E354 − 21
Standard Test Methods for
Chemical Analysis of High-Temperature, Electrical,
Magnetic, and Other Similar Iron, Nickel, and Cobalt Alloys
This standard is issued under the fixed designation E354; 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.
ε NOTE—Editorial corrections were made in Table 5 in February 2022.
1. Scope
Carbon, Total, by the Combustion-Thermal Conductivity Method—
124 – 134
Discontinued 1986
1.1 These test methods cover the chemical analysis of
Carbon, Total, by the Combustion Gravimetric Method (0.05 % to
79–89
1.10 %)—Discontinued 2014
high-temperature, electrical, magnetic, and other similar iron,
Chromium by the Atomic Absorption Spectrometry Method
nickel, and cobalt alloys having chemical compositions within
165 – 174
(0.006 % to 1.00 %)
the following limits:
Chromium by the Peroxydisulfate Oxidation—Titration Method
175 – 183
(0.10 % to 33.00 %)
Composition
Element
Chromium by the Peroxydisulfate-Oxidation Titrimetric Method—
Range, %
116 – 123
Discontinued 1980
Cobalt by the Ion-Exchange-Potentiometric Titration Method (2 %
Aluminum 0.005 to 18.00
53 – 60
to 75 %)
Beryllium 0.001 to 0.05
Cobalt by the Nitroso-R-Salt Spectrophotometric Method (0.10 %
Boron 0.001 to 1.00
61 – 70
to 5.0 %)
Calcium 0.002 to 0.05
Copper by Neocuproine Spectrophotometric Method (0.01 % to
Carbon 0.001 to 1.10
90 – 99
10.00 %)
Chromium 0.10 to 33.00
Copper by the Sulfide Precipitation-Electrodeposition Gravimetric
Cobalt 0.10 to 75.00
71 – 78
Method (0.01 % to 10.00 %)
Columbium (Niobium) 0.01 to 6.0
Iron by the Silver Reduction Titrimetric Method (1.0 % to 50.0 %) 192 –199
Copper 0.01 to 10.00
Manganese by the Metaperiodate Spectrophotometric Method
Iron 0.01 to 85.00
9 – 18
(0.05 % to 2.00 %)
Magnesium 0.001 to 0.05
Molybdenum by the Ion Exchange—8-Hydroxyquinoline Gravi-
Manganese 0.01 to 3.0
184 – 191
metric Method (1.5 % to 30 %)
Molybdenum 0.01 to 30.0
Molybdenum by the Thiocyanate Spectrophotometric Method
Nickel 0.10 to 84.0
153 – 164
(0.01 % to 1.50 %)
Nitrogen 0.001 to 0.20
Nickel by the Dimethylglyoxime Gravimetric Method (0.1 % to
Phosphorus 0.002 to 0.08
135 – 142
84.0 %)
Silicon 0.01 to 5.00
Phosphorus by the Molybdenum Blue Spectrophotometric Method
Sulfur 0.002 to 0.10
19 – 30
(0.002 % to 0.08 %)
Tantalum 0.005 to 10.0
Silicon by the Gravimetric Method (0.05 % to 5.00 %) 46 – 52
Titanium 0.01 to 5.00
Sulfur by the Gravimetric Method—Discontinued
Tungsten 0.01 to 18.00
Former 30 – 36
Vanadium 0.01 to 3.25
Sulfur by the Combustion-Iodate Titration Method (0.005 % to
Zirconium 0.01 to 2.50
37 – 45
0.1 %)—Discontinued 2014
1.2 The test methods in this standard are contained in the Sulfur by the Chromatographic Gravimetric Method—Discontinued
108 – 115
sections indicated below:
Tin by the Solvent Extraction–Atomic Absorption Spectrometry
143 – 152
Sections Method (0.002 % to 0.10 %)
1.3 Methods for the determination of carbon and sulfur not
Aluminum, Total, by the 8-Quinolinol Gravimetric Method (0.20 %
100 – 107
to 7.00 %)
included in this standard can be found in Test Methods E1019.
1.4 Some of the composition ranges given in 1.1 are too
broad to be covered by a single method and therefore this
These test methods are under the jurisdiction of ASTM Committee E01 on
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct
standard contains multiple methods for some elements. The
responsibility of Subcommittee E01.01 on Iron, Steel, and Ferroalloys.
user must select the proper method by matching the informa-
Current edition approved March 1, 2021. Published April 2021. Originally
tion given in the Scope and Interference sections of each
approved in 1968. Last previous edition approved in 2014 as E354 – 14. DOI:
10.1520/E0354-21E01. method with the composition of the alloy to be analyzed.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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E354 − 21
1.5 Units—The values stated in SI units are to be regarded 2.2 Other Document:
as standard. ISO 5725 Precision of Test Methods—Determination of Re-
peatability and Reproducibility for Inter-Laboratory Tests
1.6 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
3. Terminology
responsibility of the user of this standard to establish appro-
3.1 For definitions of terms used in these test methods, refer
priate safety, health, and environmental practices and deter-
to Terminology E135.
mine the applicability of regulatory limitations prior to use.
Specific hazards statements are given in Section 6 and in
4. Significance and Use
special “Warning” paragraphs throughout these test methods.
4.1 These test methods for the chemical analysis of metals
1.7 This international standard was developed in accor-
and alloys are primarily intended as referee methods to test
dance with internationally recognized principles on standard-
such materials for compliance with compositional
ization established in the Decision on Principles for the
specifications, particularly those under the jurisdiction of the
Development of International Standards, Guides and Recom-
ASTM Committee A01 on Steel, Stainless Steel and Related
mendations issued by the World Trade Organization Technical
Alloys. It is assumed that all who use these test methods will
Barriers to Trade (TBT) Committee.
be trained analysts capable of performing common laboratory
proceduresskillfullyandsafely.Itisexpectedthatworkwillbe
2. Referenced Documents
performed in a properly equipped laboratory under appropriate
2.1 ASTM Standards:
quality control practices such as those described in Guide
D1193 Specification for Reagent Water
E882.
E29 Practice for Using Significant Digits in Test Data to
5. Apparatus, Reagents, and Instrumental Practice
Determine Conformance with Specifications
E50 Practices for Apparatus, Reagents, and Safety Consid-
5.1 Apparatus—Specialized apparatus requirements are
erations for Chemical Analysis of Metals, Ores, and listed in the “Apparatus” section in each method.
Related Materials 5.1.1 In the methods specifying spectrophotometric testing,
E60 Practice for Analysis of Metals, Ores, and Related thecellsutilizedtocontainthereferencematerialsolutionsand
Materials by Spectrophotometry sample solutions in spectrophotometers are referred to as
E135 Terminology Relating to Analytical Chemistry for “absorption cells.” Please note that the radiant energy passed
Metals, Ores, and Related Materials through the cells can be measured as absorbance or transmit-
E173 Practice for Conducting Interlaboratory Studies of tance.These methods refer to absorbance measurements. Refer
Methods for Chemical Analysis of Metals (Withdrawn to Practices E60 for details.
1998)
5.2 Reagents:
E350 Test Methods for Chemical Analysis of Carbon Steel,
5.2.1 Purity of Reagents—Reagent grade chemicals shall be
Low-Alloy Steel, Silicon Electrical Steel, Ingot Iron, and
used in all tests. Unless otherwise indicated, it is intended that
Wrought Iron
all reagents conform to the specifications of the Committee on
E351 Test Methods for ChemicalAnalysis of Cast Iron—All
Analytical Reagents of the American Chemical Society where
Types
such specifications are available. Other grades may be used,
E352 TestMethodsforChemicalAnalysisofToolSteelsand
provided it is first ascertained that the reagent is of sufficiently
Other Similar Medium- and High-Alloy Steels
high purity to permit its use without lessening the accuracy of
E353 Test Methods for Chemical Analysis of Stainless,
the determination.
Heat-Resisting, Maraging, and Other Similar Chromium-
5.2.2 Purity of Water—Unless otherwise indicated, refer-
Nickel-Iron Alloys
ences to water shall mean reagent water as conforming toType
E882 Guide for Accountability and Quality Control in the
IorTypeIIofSpecificationD1193.TypeIIIorIVmaybeused
Chemical Analysis Laboratory
if they effect no measurable change in the blank or sample.
E1019 Test Methods for Determination of Carbon, Sulfur,
5.3 Spectrophotometric Practice—Spectrophotometric
Nitrogen, and Oxygen in Steel, Iron, Nickel, and Cobalt
practice prescribed in these test methods shall conform to
Alloys by Various Combustion and Inert Gas Fusion
Practice E60.
Techniques
E1601 Practice for Conducting an Interlaboratory Study to
6. Hazards
Evaluate the Performance of an Analytical Method
6.1 For precautions to be observed in the use of certain
E1806 Practice for Sampling Steel and Iron for Determina-
reagents and equipment in these methods, refer to Practices
tion of Chemical Composition
E50.
7. Sampling
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
7.1 For procedures to sample the material, refer to Practice
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
E1806.
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
3 4
The last approved version of this historical standard is referenced on Available fromAmerican National Standards Institute (ANSI), 25 W. 43rd St.,
www.astm.org. 4th Floor, New York, NY 10036, http://www.ansi.org.
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E354 − 21
8. Interlaboratory Studies and Rounding Calculated 545nmand565nm.Thefiltermusttransmitnotmorethan5 %
Values ofitsmaximumatawavelengthshorterthan530nm.Theband
width of the filter should be less than 30 nm when measured at
8.1 These test methods have been evaluated in accordance
50 % of its maximum transmittance. Similar restrictions apply
with Practice E173 (withdrawn 1997) or ISO 5725. Practice
with respect to the wavelength region employed when other
E173 has been replaced by Practice E1601. The
“wide-band” instruments are used.
Reproducibility, R2, of Practice E173 corresponds to the
Reproducibility Index, R, of Practice E1601. The 13.2 The spectral transmittance curve of permanganate ions
Repeatability, R1, of Practice E173 corresponds to the Repeat- exhibits two useful minima, one at approximately 526 nm, and
ability Index, r, of Practice E1601. the other at 545 nm. The latter is recommended when a
“narrow-band” spectrophotometer is used.
8.2 Rounding of test results obtained using this test method
shall be performed as directed in Practice E29, Rounding
13.3 Tungsten,whenpresentinamountsofmorethan0.5 %
Method, unless an alternative rounding method is specified by interferes by producing a turbidity in the final solution. A
the customer or applicable material specification.
special procedure is provided for use with samples containing
more than 0.5 % tungsten which eliminates the problem by
MANGANESE BY THE METAPERIODATE
preventing the precipitation of the tungsten.
SPECTROPHOTOMETRIC METHOD
14. Reagents
9. Scope
14.1 Manganese, Standard Solution (1 mL = 0.032 mg
9.1 This method covers the determination of manganese
Mn)—Transfer the equivalent of 0.4000 g of assayed, high-
from 0.05 % to 2.00 %.
purity manganese (purity: 99.99 % minimum), to a 500-mL
9.2 This international standard was developed in accor-
volumetric flask and dissolve in 20 mL of HNO by heating.
dance with internationally recognized principles on standard-
Cool, dilute to volume, and mix. Using a pipet, transfer 20 mL
ization established in the Decision on Principles for the
to a 500-mL volumetric flask, dilute to volume, and mix.
Development of International Standards, Guides and Recom-
14.2 Nitric-Phosphoric Acid Mixture—Cautiously, while
mendations issued by the World Trade Organization Technical
stirring,add100mLofHNO and400mLofH PO to400mL
Barriers to Trade (TBT) Committee. 3 3 4
of water. Cool, dilute to 1 L, and mix. Prepare fresh as needed.
10. Summary of Method
14.3 Potassium Metaperiodate Solution(7.5g/L)—Dissolve
10.1 Manganous ions are oxidized to permanganate ions by 7.5 g of potassium metaperiodate (KIO ) in 200 mL of hot
treatment with periodate. Tungsten, when present at composi-
HNO (1 + 1), add 400 mL of H PO , cool, dilute to 1 L, and
3 4
tions greater than 0.5 %, is kept in solution with H PO .
mix.
3 4
Solutions of the samples are fumed with HClO so that the
14.4 Water, Pretreated with Metaperiodate—Add 20 mL of
effect of periodate is limited to the oxidation of manganese.
KIO solution to 1 L of water, mix, heat at not less than 90 °C
Spectrophotometric absorbance measurements are made at
for 20 min to 30 min, and cool. Use this water to dilute
545 nm.
solutions to volume that have been treated with KIO solution
to oxidize manganese, and thus avoid reduction of permangan-
11. Concentration Range
ate ions by any reducing agents in the untreated water.
11.1 The recommended concentration range is 0.15 mg to
Caution—Avoid the use of this water for other purposes.
0.8 mg of manganese per 50 mL of solution, using a 1-cm cell
(Note 1) and a spectrophotometer with a band width of 10 nm
15. Preparation of Calibration Curve
or less.
15.1 Calibration Solutions—Using pipets, transfer 5 mL, 10
NOTE 1—This method has been written for cells having a 1-cm light
mL,15mL,20mL,and25mLofmanganesestandardsolution
path and a “narrow-band” instrument. The concentration range depends
(1 mL = 0.032 mg Mn) to 50-mLborosilicate glass volumetric
upon band width and spectral region used as well as cell optical path
flasks, and, if necessary, dilute to approximately 25 mL.
length. Cells having other dimensions may be used, provided suitable
adjustments can be made in the amounts of sample and reagents used. Proceed as directed in 15.3.
15.2 Reference Solution—Transfer approximately 25 mL of
12. Stability of Color
water to a 50-mL borosilicate glass volumetric flask. Proceed
12.1 The color is stable for at least 24 h.
as directed in 15.3.
15.3 Color Development—Add 10 mL of KIO solution,
13. Interferences
and heat the solutions at not less than 90 °C for 20 min to 30
13.1 HClO acid treatment, which is used in the procedure,
min(Note2).Cool,dilutetovolumewithpretreatedwater,and
yields solutions which can be highly colored due to the
mix.
presenceofCr(VI)ions.Althoughtheseionsandothercolored
ions in the sample solution undergo no further change in color NOTE 2—Immersing the flasks in a boiling water bath is a preferred
means of heating them for the specified period to ensure complete color
quality upon treatment with metaperiodate ion, the following
development.
precautions must be observed when filter spectrophotometers
are used: Select a filter with maximum transmittance between 15.4 Spectrophotometry:
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E354 − 21
15.4.1 Multiple-Cell Spectrophotometer—Measure the cell 16.1.2.2 For samples whose dissolution is hastened by HF:
correction using the Reference Solution (15.2) in absorption Add8mLto10mLofH PO , 10 mLof HClO ,5mLto6mL
3 4 4
cells with a 1-cm light path and using a light band centered at ofH SO ,3mLto4mLofHNO ,andafewdropsofHF.Heat
2 4 3
545 nm. Using the test cell, take the spectrophotometric moderately until the sample is decomposed, and then heat to
absorbance readings of the calibration solutions versus the
copious white fumes for 10 min to 12 min or until the
Reference Solution (15.2). chromium is oxidized and the HCl is expelled, but avoid
heating to fumes of SO . Cool, add 50 mL of water, digest, if
15.4.2 Single-Cell Spectrophotometer—Transfer a suitable
necessary, to dissolve the salts, cool, and transfer the solution
portion of the Reference Solution (15.2) to an absorption cell
to a 100-mL or 500-mL volumetric flask as directed in 16.1.
with a 1-cm light path and adjust the spectrophotometer to the
initial setting, using a light band centered at 545 nm. While Proceed to 16.1.3.
maintaining this adjustment, take the spectrophotometric ab-
16.1.2.3 Coolthesolution,dilutetovolume,andmix.Allow
sorbance readings of the calibration solutions.
insoluble matter to settle, or dry-filter through a coarse paper
and discard the first 15 mL to 20 mL of the filtrate, before
15.5 Calibration Curve—Follow the instrument manufac-
taking aliquots.
turer’s instructions for generating the calibration curve. Plot
16.1.3 Using a pipet, transfer 20-mL aliquots to two 50-mL
the net spectrophotometric absorbance readings of the calibra-
borosilicate glass volumetric flasks; treat one as directed in
tion solutions against the milligrams of manganese per 50 mL
16.3 and the other as directed in 16.4.1.
of solution.
16.2 Reagent Blank Solution—Carry a reagent blank
16. Procedure
through the entire procedure using the same amounts of all
reagents with the sample omitted.
16.1 Test Solutions—Select and weigh a sample as follows:
Tolerance in
16.3 Color Development—Proceed as directed in 15.3.
Manganese, Sample Sample Dilution,
% Mass, g Mass, mg mL
16.4 Reference Solutions:
16.4.1 Background Color Solution—To one of the sample
0.01 to 0.5 0.80 0.5 100
0.45 to 1.0 0.35 0.3 100
aliquots in a 50-mL volumetric flask, add 10 mL of HNO -
0.85 to 2.0 0.80 0.5 500
H PO mixture, and heat the solution at not less than 90 °C for
3 4
16.1.1 For Samples Containing Not More Than 0.5 %
20 min to 30 min (Note 2). Cool, dilute to volume (with
Tungsten:
untreated water), and mix.
16.1.1.1 To dissolve samples that do not require HF, add 8
16.4.2 Reagent Blank Reference Solution—Transfer the re-
mL to 10 mL of HCl (1 + 1), and heat. Add HNO as needed
agent blank solution (16.2) to the same size volumetric flask as
to hasten dissolution, and then add 3 mL to 4 mL in excess.
used for the test solutions and transfer the same size aliquots as
When dissolution is complete, cool, then add 10 mLof HClO ;
used for the test solutions to two 50-mL volumetric flasks.
evaporate to fumes to oxidize chromium, if present, and to
Treat one portion as directed in 16.3 and use as reference
expel HCl. Continue fuming until salts begin to separate. Cool,
solution for test samples. Treat the other as directed in 16.4.1
add 50 mL of water, and digest if necessary to dissolve the
and use as reference solution for Background Color Solutions.
salts. Cool and transfer the solution to a 100-mL volumetric
16.5 Spectrophotometry—Establish the cell corrections with
flask. Proceed to 16.1.3.
the Reagent Blank Reference solution to be used as a reference
16.1.1.2 For samples whose dissolution is hastened by HF,
solution for Background Color solutions. Take the spectropho-
add 8 mL to 10 mL of HCl (1 + 1), and heat. Add HNO and
tometric absorbance readings of the Background Color Solu-
afewdropsofHFasneededtohastendissolution,andthenadd
tionsandthetestsolutionsversustherespectiveReagentBlank
3mLto4mLofHNO . When dissolution is complete, cool,
Reference Solutions as directed in 15.4.
then add 10 mL of HClO , evaporate to fumes to oxidize
chromium, if present, and to expel HCl. Continue fuming until
17. Calculation
salts begin to separate. Cool, add 50 mL of water, digest if
necessarytodissolvethesalts,cool,andtransferthesolutionto 17.1 Convertthenetspectrophotometricabsorbancereading
either a 100-mL or 500-mL volumetric flask as indicated in
of the test solution and of the background color solution to
16.1. Proceed to 16.1.3. milligrams of manganese by means of the calibration curve.
Calculate the percentage of manganese as follows:
16.1.2 For Samples Containing More Than 0.5 % Tungsten:
16.1.2.1 To dissolve samples that do not require HF, add 8
Manganese, % 5 ~A 2 B!/~C 310! (1)
mL to 10 mL of H PO , 10 mL of HClO,5mLto6mLof
3 4 4
where:
H SO ,and3mLto4mLofHNO . Heat moderately until the
2 4 3
A = manganese, mg, found in 50 mL of the final test
sample is decomposed, and then heat to copious white fumes
solution,
for 10 min to 12 min or until the chromium is oxidized and the
B = apparent manganese, mg, found in 50 mL of the final
HCl is expelled, but avoid heating to fumes of SO . Cool, add
background color solution, and
50 mL of water, and digest, if necessary, to dissolve the salts.
C = sample mass, g, represented in 50 mL of the final test
Transfer the solution to either a 100-mLor 500-mLvolumetric
solution.
flask as directed in 16.1. Proceed to 16.1.3.
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E354 − 21
TABLE 1 Statistical Information—Manganese by the
23. Interferences
Metaperiodate Spectrophotometric Method
23.1 None of the elements usually present interfere except
Man-
arsenic,whichisremovedbyvolatilizationasthebromide.The
ganese Repeatability Reproducibility
Test Specimen
Found, (R , E173) (R , E173)
interference of tungsten at compositions greater than 0.5 % is
1 2
%
avoidedbyproceedingdirectlywithasmallsamplemassrather
1. Nickel alloy, 77Ni-20Cr 0.074 0.002 0.008
than an aliquot portion of a larger sample.
(NIST 169, 0.073 Mn)
2. High-temperature alloy 0.289 0.007 0.026
68Ni-14Cr-7Al-6Mo
24. Apparatus
(NIST 1205, 0.29 Mn)
3. Cobalt alloy 41Co- 1.49 0.03 0.08
24.1 Glassware must be phosphorus and arsenic-free. Boil
20Ni-20Cr-4Mo-4W (NIST
the glassware with HCl and rinse with water before use. It is
168, 1.50 Mn)
recommended that the glassware used for this determination be
4. Stainless steel 18Cr-9Ni 1.79 0.03 0.07
(NIST 101e, 1.77 Mn)
reserved for this use only. Many detergents contain phosphorus
and must not be used for cleaning purposes.
18. Precision and Bias
25. Reagents
18.1 Precision—Nine laboratories cooperated in testing this
25.1 Ammonium Molybdate Solution (20 g/L)—Cautiously,
method and obtained the data summarized in Table 1.
while stirring and cooling, add 300 mLof H SO to 500 mLof
2 4
18.2 Bias—The accuracy of this test method has been water and cool. Add 20 g of ammonium heptamolybdate
((NH ) Mo O ·4 H O), cautiously dilute to 1 L, and mix.
deemed satisfactory based upon the data for the certified
4 6 7 24 2
reference materials in Table 1. Users are encouraged to use
25.2 Ammonium Molybdate-Hydrazine Sulfate Solution—
these or similar reference materials to verify that the test
Dilute 250 mL of the ammonium molybdate solution to 600
method is performing accurately in their laboratories.
mL, add 100 mL of the hydrazine sulfate solution, dilute to 1
L, and mix. Do not use a solution that has stood for more than
PHOSPHORUS BY THE MOLYBDENUM BLUE
1h.
SPECTROPHOTOMETRIC METHOD
25.3 Hydrazine Sulfate Solution (1.5 g/L)—Dissolve 1.5 g
19. Scope
of hydrazine sulfate ((NH ) ·H SO ) in water, dilute to 1 L,
2 2 2 4
19.1 This method covers the determination of phosphorus and mix. Discard any unused solution after 24 h.
from 0.002 % to 0.08 %.
25.4 Phosphorus Standard Solution A (1 mL = 1.0 mg
19.2 This international standard was developed in accor-
P)—Transfer 2.292 g of anhydrous disodium hydrogen phos-
dance with internationally recognized principles on standard-
phate (Na HPO ), previously dried to constant mass at 105 °C,
2 4
ization established in the Decision on Principles for the
to a 500-mL volumetric flask; dissolve in about 100 mL of
Development of International Standards, Guides and Recom-
water, dilute to volume, and mix.
mendations issued by the World Trade Organization Technical
25.5 Phosphorus Standard Solution B (1 mL = 0.01 mg
Barriers to Trade (TBT) Committee.
P)—Using a pipet, transfer 10 mL of Solution A (1 mL = 1.0
mg P) to a 1-L volumetric flask, add 50 mL of HClO (1 + 5),
20. Summary of Method 4
dilute to volume, and mix.
20.1 The sample is dissolved in mixed acids and the
25.6 Phosphorus Standard Solution C (1 mL = 0.10 mg
solutionisfumedwithHClO .Ammoniummolybdateisadded
P)—Using a pipet, transfer 50 mL of Solution A (1 mL = 1.0
to react with the phosphorus to form the heteropoly phospho-
mg P) to a 500-mL volumetric flask, add 50 mL of HClO (1
molybdate. This species is then reduced with hydrazine sulfate
+ 5), dilute to volume, and mix.
to form the molybdenum blue complex. Spectrophotometric
absorbance measurement is made at 650 nm or 825 nm,
25.7 Sodium Sulfite Solution (100 g/L)—Dissolve 100 g of
depending upon the concentration.
sodium sulfite (Na SO ) in water, dilute to 1 L, and mix.
2 3
21. Concentration Range
26. Preparation of Calibration Curve for Concentrations
21.1 The recommended concentration range is from 0.005
from 0.005 mg/100 mL to 0.05 mg/100 mL
mg to 0.05 mg of phosphorus per 100 mL of solution when
26.1 Calibration Solutions—Using pipets, transfer 5 mL, 10
measuredat825nmandfrom0.05mgto0.3mgofphosphorus
mL, 15 mL, 25 mL, and 50 mL of Phosphorus Standard
per 100 mL of solution when measured at 650 nm, using a
Solution B (1 mL = 0.01 mg P) to 100-mL volumetric flasks.
1-cm cell.
Add20mLofHClO ,dilutetovolume,andmix.Usingapipet,
NOTE3—Thistestmethodhasbeenwrittenforcellshavinga1-cmlight 4
transfer 10 mL of each solution to a 100-mL borosilicate glass
path. Cells having other dimensions may be used, provided suitable
adjustments can be made in the amounts of sample and reagents used.
volumetric flask. Proceed as directed in 26.3.
22. Stability of Color 26.2 Reagent Blank—Transfer 12 mLof HClO (1+5)toa
100-mL borosilicate glass volumetric flask.
22.1 The molybdenum blue complex is stable for at least
2h. 26.3 Color Development:
´1
E354 − 21
26.3.1 Add 15 mL of Na SO solution, boil gently for 30 s, the net spectrophotometric absorbance readings of the calibra-
2 3
and add 50 mL of ammonium molybdate-hydrazine sulfate tionsolutionsagainstthemilligramsofphosphorusper100mL
solution that has been prepared within the hour. of solution.
26.3.2 Heat the solutions at not less than 90 °C for 20 min,
quickly cool, dilute to volume, and mix. 28. Procedure
NOTE 4—Immersing the flasks in a boiling water bath is the preferred
28.1 For Samples Containing Less Than 0.5 % Tungsten
means of heating them for complete color development.
and Less Than a Total of 1 % Niobium and Tantalum or 1 % of
26.4 Reference Solution—Water.
Either of the Latter Elements:
28.1.1 Test Solution:
26.5 Spectrophotometry:
28.1.1.1 Transfer a 1.0-g sample, weighed to the nearest 0.5
26.5.1 Multiple-Cell Spectrophotometer—Measure the re-
mg, to a 250-mL Erlenmeyer flask.
agent blank (which includes the cell correction) versus the
28.1.1.2 Add 15 mL of a freshly prepared mixture of 1
reference solution (26.4) using absorption cells with a 1-cm
volume of HNO
and 3 volumes of HCl, slowly and in small
light path and using a light band centered at 825 nm. Using the
portions. When the reaction has ceased, add 10 mL of HClO
test cell, take the spectrophotometric absorbance readings of
and evaporate to fumes. Remove the flask immediately to
the calibration solutions versus the reference solution.
avoid undue loss of HClO , cool, and add 20 mL of HBr (1 +
26.5.2 Single-Cell Spectrophotometer—Transfer a suitable
4). Evaporate the solution to copious white fumes and then,
portion of the reference solution (26.4) to an absorption cell
without delay, fume strongly enough to cause the white fumes
with a 1-cm light path and adjust the spectrophotometer to the
tocleartheneckoftheflask,andcontinueatthisratefor1min.
initial setting using a light band centered at 825 nm. While
28.1.1.3 Coolthesolution,add60mLofHClO (1+5),and
maintaining this adjustment, take the spectrophotometric ab-
swirl to dissolve the salts. Transfer to a 100-mL volumetric
sorbance readings of the reagent blank solution and of the
flask, cool, dilute to volume, and mix. Allow insoluble matter
calibration solutions.
to settle or dry filter the solution. Using a pipet, transfer 10-mL
26.6 Calibration Curve—Follow the instrument manufac-
portions to two 100-mL borosilicate glass volumetric flasks;
turer’s instructions for generating the calibration curve. Plot
treat one as directed in 28.1.3 and the other as directed in
the net spectrophotometric absorbance readings of the calibra-
28.1.4.2.
tionsolutionsagainstthemilligramsofphosphorusper100mL
28.1.2 Reagent Blank Solution—Carry a reagent blank
of solution.
through the entire procedure using the same amount of all
reagents with the sample omitted.
27. Preparation of Calibration Curve for Concentrations
28.1.3 Color Development—Proceed with one of the 10-mL
from 0.05 mg/100 mL to 0.30 mg/100 mL
portions obtained in 28.1.1.3, as directed in 26.3.
28.1.4 Reference Solutions:
27.1 Calibration Solutions—Using pipets, transfer 5 mL, 10
28.1.4.1 Water—Use this as the reference solution for the
mL,15mL,20mL,25mL,and30mLofPhosphorusStandard
reagent blank solution.
Solution C (1 mL = 0.10 mg P) to 100-mL volumetric flasks.
28.1.4.2 Background Color Reference Solution—Add 15
Add20mLofHClO ,dilutetovolume,andmix.Usingapipet,
mL of Na SO solution to the second 10-mL portion obtained
transfer 10 mL of each solution to a 100-mL borosilicate glass 2 3
in 28.1.1.3. Boil gently for 30 s, add 50 mLof H SO (3 + 37),
volumetric flask. 2 4
cool, dilute to volume, and mix. Use this as the reference
27.2 Reagent Blank—Proceed as directed in 26.2.
solution for the test solution.
27.3 Color Development—Proceed as directed in 26.3. 28.1.5 Spectrophotometry—Take the spectrophotometric
absorbance readings of the reagent blank solution and of the
27.4 Reference Solution—Water.
test solution (using the respective reference solutions) as
27.5 Spectrophotometry:
directed in 26.5 or 27.5 depending upon the estimated compo-
27.5.1 Multiple-Cell Spectrophotometer—Measure the re-
sition of phosphorus in the sample.
agent blank (which includes the cell correction) versus the
28.2 For Samples Containing More Than 0.5 % Tungsten
reference solution (27.4) using absorption cells with a 1-cm
and More Than a Total of 1 % Columbium and Tantalum or
light path and a light band centered at 650 nm. Using the test
1 % of Either of the Latter Elements:
cell, take the spectrophotometric absorbance readings of the
28.2.1 Test Solution:
calibration solutions versus the reference solution.
28.2.1.1 Transfer 0.100-g samples, weighed to the nearest
27.5.2 Single-Cell Spectrophotometer—Transfer a suitable
0.1 mg, to two 100-mL Erlenmeyer flasks.
portion of the reference solution (27.4) to an absorption cell
28.2.1.2 Add 5 mL of a mixture of 1 volume of HNO and
with a 1-cm light path and adjust the spectrophotometer to the
3 volumes of HCl. When the reaction has ceased, add 2.5 mL
initial setting using a light band (no change) centered at 650
of HClO and 5 mL of HBr (1 + 4). Evaporate the solutions to
nm. While maintaining this adjustment, take the spectrophoto-
copious white fumes; then, without delay, fume strongly
metricabsorbancereadingsofthereagentblanksolutionandof
enough to cause the white fumes to clear the neck of the flasks,
the calibration solutions.
and continue at this rate for 1 min.
27.6 Calibration Curve—Follow the instrument manufac- 28.2.1.3 Cool the solutions, and add 10 mL of water. Filter
turer’s instructions for generating the calibration curve. Plot through a 9-cm fine paper collecting the filtrate in a 100-mL
´1
E354 − 21
TABLE 2 Statistical Information—Phosphorus—Molybdenum
SULFUR BY THE GRAVIMETRIC METHOD
Blue—Spectrophotometric Method
(This method, which consisted of Former Sections 30 through
Phosphorus Repeatability Reproducibility
Test Specimen
Found,% (R , E173) (R , E173)
1 2 36, was discontinued in 1988.)
1. Cobalt-base alloy 41Co-20- 0.008 0.005 0.006
Ni-20Cr-4Mo-4W-3Nb
(NIST 168, 0.008 P)
SULFUR BY THE COMBUSTION-IODATE
TITRATION METHOD
(This method, which consisted of Sections 37 through 45, was
discontinued in 2014.)
borosilicate glass volumetric flask. Wash the paper and in-
soluble matter 5 times with 3-mL portions of water. Treat one
solution as directed in 28.2.3 and the other as directed in
SILICON BY THE GRAVIMETRIC METHOD
28.2.4.
46. Scope
28.2.2 Reagent Blank Solution—Proceed as directed in
28.2.1.2 and 28.2.1.3.
46.1 This method covers the determination of silicon from
28.2.3 Color Development—Proceed as directed in 26.3.
0.05 % to 5.00 % in alloys containing not more than 0.1 %
28.2.4 Reference Solutions:
boron.
28.2.4.1 Water—Use this as the reference solution for the
46.2 This international standard was developed in accor-
reagent blank solution.
dance with internationally recognized principles on standard-
28.2.4.2 Background Color Reference Solution—Add 15
ization established in the Decision on Principles for the
mL of Na SO solution to the second 10-mL portion obtained
2 3
Development of International Standards, Guides and Recom-
in 28.2.1.3. Boil gently for 30 s, add 50 mLof H SO (3 + 37),
2 4
mendations issued by the World Trade Organization Technical
cool, dilute to volume, and mix. Use this as the reference
Barriers to Trade (TBT) Committee.
solution for the test solution.
28.2.5 Spectrophotometry—Proceed as directed in 28.1.5.
47. Summary of Test Method
47.1 After dissolution of the sample, silicic acid is dehy-
29. Calculation
drated by fuming with H SO or HClO . The solution is
2 4 4
29.1 Convertthenetspectrophotometricabsorbancereading
filtered,andtheimpuresilicaisignitedandweighed.Thesilica
of the test solution and of the reagent blank solution to
isthenvolatilizedwithHF.Theresidueisignitedandweighed;
milligrams of phosphorus by means of the appropriate calibra-
the loss in mass represents silica.
tion curve. Calculate the percent of phosphorus as follows:
48. Interferences
Phosphorus,% 5 A 2 B ⁄ C 3 D (2)
~ ! ~ !
48.1 The elements normally present do not interfere. When
where:
boron is present in amounts greater than 0.1 %, the sample
A = phosphorus found in 100 mL of the final test solution,
solution requires special treatment with methyl alcohol.
mg,
49. Reagents
B = phosphorus found in 100 mL of the final reagent blank
solution, mg, and
49.1 The analyst should ensure by analyzing blanks and
C = sample represented in 100 mL of the final test solution,
other checks that possible silicon contamination of reagents
g.
will not significantly bias the results.
49.2 Perchloric Acid:
30. Precision and Bias
49.2.1 Select a lot of HClO that contains not more than
30.1 Precision—Eightlaboratoriescooperatedintestingthis
0.0002 % silicon for the analysis of samples containing silicon
method and obtained the data summarized in Table 2.
in the range from 0.02 % to 0.10 % and not more than
30.2 Bias—Only one certified reference was tested so lim- 0.0004 % silicon for samples containing more than 0.10 % by
ited information is available on the accuracy of this method. determining duplicate values for silicon as directed in 49.2.2 –
See Table 2. Users are encouraged to use this or similar 49.2.6.
reference materials to verify that the test method is performing 49.2.2 Transfer 15 mL of HClO (Note 5) to each of two
accurately in their laboratories. 400-mL beakers. To one of the beakers, transfer an additional
´1
E354 − 21
50 mL of HClO . Using a pipet, transfer 20 mL of Na SiO 50. Procedure
4 2 3
solution (1 mL= 1.00 mg Si) to each of the beakers. Evaporate
50.1 Select and weigh a sample as follows:
the solutions to fumes and heat for 15 min to 20 min at such a
Tolerance in Dehydrating Acid, mL
rate that HClO refluxes on the sides of the beakers. Cool
Sample Sample H SO
2 4
sufficiently, and add 100 mL of water (40 °C to 50 °C). Silicon, % Mass, g Mass, mg (1+4) HClO
NOTE 5—The 15-mLaddition of HClO can be from the same lot as the 0.05 to 0.10 5.0 5 150 75
one to be tested. Once a lot has been established as having less than 0.10 to 1.0 4.0 4 100 60
1.0 to 2.0 3.0 3 100 50
0.0002 % silicon, it should preferably be used for the 15-mL addition in
2.0 to 5.0 2.0 2 100 40
all subsequent tests of other lots of acid.
Transfer the sample to a 400-mL beaker or a 300-mL
49.2.3 Add paper pulp and filter immediately, using low-ash
porcelain casserole. Proceed as directed in 50.2 or 50.3.
11-cm medium-porosity filter papers. Transfer the precipitates
to the papers, and scrub the beakers thoroughly with a
50.2 Sulfuric Acid Dehydration, if tungsten is greater than
rubber-tipped rod. Wash the papers and precipitates alternately 0.5 %.
with 3-mLto 5-mLportions of hot HCl (1 + 19) and hot water,
50.2.1 Add amounts of HCl or HNO , or mixtures and
foratotalof6times.FinallywashthepaperstwicewithH SO dilutions of these acids, that are sufficient to dissolve the
2 4
(1 + 49). Transfer the papers to platinum crucibles.
sample; and then add the H SO (1 + 4) as specified in 50.1,
2 4
49.2.4 Dry the papers and heat at 600 °C until the carbon is and cover. Heat until dissolution is complete. Remove and
removed. Finally ignite at 1100 °C to 1150 °C to constant mass
rinse the cover glass; substitute a ribbed cover glass.
(at least 30 min). Cool in a desiccator and weigh. 50.2.2 Evaporate until salts begin to separate; at this point
49.2.5 Add enough H SO (1 + 1) to moisten the SiO , and
evaporate the solution rapidly to the first appearance of fumes
2 4 2
add 3 mL to 5 mL of HF. Evaporate to dryness and then heat andfumestronglyfor2minto3min.Coolsufficiently,andadd
at a gradually increasing rate until H SO is removed. Ignite
100 mLof water (40 °C to 50 °C). Stir to dissolve the salts and
2 4
for 15 min at 1100 °C to 1150 °C, cool in a desiccator, and heat, if necessary, but do not boil. Proceed immediately as
weigh. directed in 50.4.
49.2.6 Calculate the percent of silicon as follows:
50.3 Perchloric Acid Dehydration, if tungsten is less than
Silicon,% 5 @~A 2 B! 2 ~C 2 D!# 30.4674 ⁄E 3100 (3)
0.5 % or use 50.2.
50.3.1 Add amounts of HCl or HNO , or mixtures and
where:
dilutions of these acids, which are sufficient to dissolve the
A = initialmassofcrucibleplusimpureSiO when65mLof
sample, and cover. Heat until dissolution is complete. Add
HClO was taken, g,
HNO to provide a total of 35 mL to 40 mL, followed by
B = final mass of crucible plus impurities when 65 mL of
HClO as specified in the table in 50.1. Remove and rinse the
HClO was taken, g,
cover glass; substitute a ribbed cover glass.
C = initialmassofcrucibleplusimpureSiO when15mLof
50.3.2 Evaporate the solution to fumes and heat for 15 min
HClO was taken, g,
to 20 min at such a rate that the HClO refluxes on the sides of
D = final mass of crucible plus impurities when 15 mL of
thecontainer.Coolsufficientlyandadd100mLofwater(40°C
HClO was taken, g, and
to 50 °C). Stir to dissolve the salts and heat to boiling. If the
E = nominal mass (80 g) of 50 mL of HClO .
sample solution contains more than 100 mg of chromium, add,
49.3 Sodium Silicate Solution—Transfer 11.0 g of sodium
while stirring, 1 mL of tartaric acid solution for each 25 mg of
silicate (Na SiO ·9H O) to a 400-mL beaker. Add 150 mL of
2 3 2
chromium.
water and dissolve the salt. Filter through a medium paper,
50.4 Add paper pulp and filter immediately, on a low-ash
collecting the filtrate in a 1-L volumetric flask, dilute to
11-cm medium-porosity filter paper. Collect the filtrate in a
volume, and mix. Store in a polyethylene bottle. Use this
600-mLbeaker. Transfer the precipitate to the paper, and scrub
solution to determine the suitability of the HClO .
the container thoroughly with a rubber-tipped rod. Wash the
49.4 Tartaric Acid Solution (20.6 g/L)—Dissolve 20.6 g of
paperandprecipitatealternatelywith3-mLto5-mLportionsof
tartaric acid (C H O ) in water, dilute to 1 L, and filter.
4 6 6
hot HCl (1 + 19) and hot water until iron salts are removed but
49.5 Water—Use freshly prepared Type II water known to for not more than a total of ten washings. If the perchloric acid
be free of silicon. Water distilled from glass, demineralized in dehydration method was followed, wash the paper twice more
columns containing silicon compounds, or stored for extended with H SO (1 + 49), but do not collect these washings in the
2 4
periods in glass, or combination thereof, has been known to filtrate; discard the washings. Transfer the paper to a platinum
absorb silicon. crucible and reserve.
´1
E354 − 21
TABLE 3 Statistical Information—Silicon—Gravimetric Method
Silicon
Repeatability Reproducibility
Test Specimen Found,
(R , E173) (R , E173)
1 2
%
HCIO Dehydration
1. Ni-base alloy 75Ni- 0.029 0.006 0.026
12Cr-6A1-4Mo-2Nb-0.7Ti
H SO Dehydration
2 4
1. Ni-base alloy 75Ni- 0.030 0.007 0.030
12Cr-6A1-4Mo-2Nb-0.7Ti
2. Co-base alloy 66Co- 1.01 0.03 0.06
28Cr-4W-1.5Ni
50.5 Add 15 mL of HNO to the filtrate, stir, and evaporate
as directed in either 50.2 or 50.3, depending upon the dehy-
drating acid used. Filter immediately, using a low-ash, 9-cm-
100-porosity filter paper, and wash as directed in 50.4.
50.6 Transfer the paper and precipitate to the reserved
platinum crucible. Dry the papers and then heat the crucible at
600 °C until the carbon is removed. Finally ignite at 1100 °C
to 1150 °C to constant mass (at least 30 min). Cool in a
desiccator and weigh.
50.7 Add enough H SO (1 + 1) to moisten the impure
2 4
SiO , and add 3 mL to 5 mL of HF. Evaporate to dryness and
thenheatatagraduallyincreasingrateuntilH SO isremoved.
2 4
Ignite at 1100 °C to 1150 °C for 15 min, cool in a desiccator,
and weigh. If the sample contains more than 0.5 % tungsten,
ignite at 750 °C instead of 1100 °C to 1150 °C after
volatilization of SiO .
51. Calculation
FIG. 1 Jones Reductor
51.1 Calculate the percent of silicon as follows:
Silicon,% 5 @~~A 2 B! 3 0.4674! ⁄ C # 3100 (4)
53.2 This international standard was developed in accor-
where: dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
A = initial mass of crucible and impure SiO,g,
Development of International Standards, Guides and Recom-
B = final mass of crucible and residue, g, and
mendations issued by the World Trade Organization Technical
C = sample used, g.
Barriers to Trade (TBT) Committee.
52. Precision and Bias
54. Summary of Test Method
52.1 Precision—Eleven laboratories cooperated in testing
54.1 Cobalt is separated from interfering elements by selec-
this method and obtained the data summarized in Table 3.A
tive elution from an anion-exchange column using HCl. The
sample with silicon composition near the upper limit of the
cobalt is oxidized to the trivalent state with ferricyanide, and
scope was not available for testing.
the excess ferricyanide is titrated potentiometrically with
52.2 Bias—No information on the bias of this method is
cobalt solution.
knownbecauseatthetimeoftheinterlaboratorystudy,suitable
reference materials were not available or were not tested. The
55. Interferences
userofthismethodisencouragedtoemployacceptedreference
55.1 The elements ordinarily present do not interfere if their
materials, if available, to determine the presence or absence of
compositions are under the maximum limits shown in 1.1.
bias.
56. Apparatus
COBALT BY THE ION-EXCHANGE—
56.1 Ion-Exchange Column, approximately 25 mm in diam-
POTENTIOMETRIC TITRATION METHOD
eter and 300 mm in length, tapered at one end, and provided
with a stopcock to control the flow rate, and a second, lower
53. Scope
stopcock to stop the flow. A Jones Reductor (Fig. 1) may be
53.1 This method covers the determination of cobalt from adapted to this method. A reservoir for the eluants may be
2 % to 75 %. added at the top of the column.
´1
E354 − 21
NOTE 6—The maximum limits of 0.125 g of cobalt and 0.500 g in the
56.2 pH meter, with a platinum and a saturated calomel
sample solution take into account the exchange capacity of the resin, the
electrode.
physical dimensions of the column, and the volume of eluants.
57. Reagents
57.4 Potassium Ferricyanide, Standard Solution (1 mL =
3.0 mg of Co):
57.1 Ammonium Citrate Solution (200 g/l)—Dissolve 200 g
57.4.1 Dissolve 16.68 g of potassium ferricyanide
of di–ammonium hydrogen citrate in water and dilute to 1 L.
(K Fe(CN) ) in water and dilute to 1 L. Store the solution in a
3 6
57.2 Cobalt, Standard Solution (1 mL = 1.5 mg of Co):
dark-colored bottle. Standardize the solution each day before
57.2.1 Preparation—Dry a weighing bottle in an oven at
use as follows: Transfer from a 50-mL buret approximately 20
130 °C for 1 h, cool in a desiccator, and weigh. Transfer
mL of K Fe(CN) solution to a 400-mL beaker. Record the
3 6
3.945 g of cobalt sulfate (CoSO ) that has been heated at
buret reading to the nearest 0.01 mL. Add 25 mL of water, 10
550°C for1htothe weighing bottle. Dry the bottle and
mLof ammoniu
...