ASTM E1473-22

Standard Test Methods for Chemical Analysis of Nickel, Cobalt, and High-Temperature Alloys

SIGNIFICANCE AND USE
4.1 These test methods for the chemical analysis of metals and alloys are primarily intended as referee methods to test such materials for compliance with compositional specifications, particularly those under the jurisdiction of Committee B02 on Nonferrous Metals and Alloys. It is assumed that all who use these test methods will be trained analysts capable of performing common laboratory procedures skillfully and safely. It is expected that work will be performed in a properly equipped laboratory under appropriate quality control practices such as those described in Guide E882.
SCOPE
1.1 These test methods describe the chemical analysis of nickel, cobalt, and high-temperature alloys having chemical compositions within the following limits:    
Element  
Composition Range, %  
Aluminum  
0.005  
to  
7.00  
Beryllium  
0.001  
to  
0.05  
Boron  
0.001  
to  
1.00  
Calcium  
0.002  
to  
0.05  
Carbon  
0.001  
to  
1.10  
Chromium  
0.10  
to  
33.00  
Cobalt  
0.10  
to  
75.00  
Copper  
0.01  
to  
35.00  
Iron  
0.01  
to  
50.00  
Lead  
0.001  
to  
0.01  
Magnesium  
0.001  
to  
0.05  
Manganese  
0.01  
to  
3.0  
Molybdenum  
0.01  
to  
30.0  
Niobium (Columbium)  
0.01  
to  
6.0  
Nickel  
0.10  
to  
98.0  
Nitrogen  
0.001  
to  
0.20  
Phosphorus  
0.002  
to  
0.08  
Sulfur  
0.002  
to  
0.10  
Silicon  
0.01  
to  
5.00  
Tantalum  
0.005  
to  
1.00  
Tin  
0.002  
to  
0.10  
Titanium  
0.01  
to  
5.00  
Tungsten  
0.01  
to  
18.00  
Vanadium  
0.01  
to  
3.25  
Zinc  
0.001  
to  
0.01  
Zirconium  
0.01  
to  
2.50  
1.2 The test methods in this standard are contained in the sections indicated as follows:    
Aluminum, Total by the 8-Quinolinol Gravimetric Method
(0.20 % to 7.00 %)  
53 to 60  
Chromium by the Atomic Absorption Spectrometry Method
(0.018 % to 1.00 %)  
91 to 100  
Chromium by the Peroxydisulfate Oxidation—Titration Method
(0.10 % to 33.00 %)  
101 to 109  
Cobalt by the Ion-Exchange-Potentiometric Titration Method
(2 % to 75 %)  
25 to 32  
Cobalt by the Nitroso-R-Salt Spectrophotometric Method
(0.10 % to 5.0 %)  
33 to 42  
Copper by Neocuproine Spectrophotometric Method
(0.010 % to 10.00 %)  
43 to 52  
Iron by the Silver Reduction Titrimetric Method
(1.0 % to 50.0 %)  
118 to 125  
Manganese by the Metaperiodate Spectrophotometric Method
(0.05 % to 2.00 %)  
8 to 17  
Molybdenum by the Ion Exchange—8-Hydroxyquinoline
Gravimetric Method (1.5 % to 30 %)  
110 to 117  
Molybdenum by the Thiocyanate Spectrophotometric Method
(0.01 % to 1.50 %)  
79 to 90  
Nickel by the Dimethylglyoxime Gravimetric Method
(0.1 % to 84.0 %)  
61 to 68  
Niobium by the Ion Exchange—Cupferron Gravimetric Method
(0.5 % to 6.0 %)  
126 to 133  
Silicon by the Gravimetric Method (0.05 % to 5.00 %)  
18 to 24  
Tantalum by the Ion Exchange—Pyrogallol Spectrophotometric
Method (0.03 % to 1.0 %)  
134 to 142  
Tin by the Solvent Extraction-Atomic Absorption Spectrometry Method (0.002 % to 0.10 %)  
69 to 78  
1.3 Other test methods applicable to the analysis of nickel alloys that may be used in lieu of or in addition to this method are E1019, E1834, E1835, E1917, E1938, E2465, E2594, E2823.  
1.4 Some of the composition ranges given in ...

General Information

• Status: Published
• Publication Date: 14-Nov-2022
• ICS: 77.120.40 - Nickel, chromium and their alloys
• Technical Committee: E01 - Analytical Chemistry for Metals, Ores, and Related Materials
• Drafting Committee: E01.08 - Ni and Co and High Temperature Alloys

Relations

• Refers: ASTM E352-23 - Standard Test Methods for Chemical Analysis of Tool Steels and Other Similar Medium- and High-Alloy Steels
• Effective Date: 15-Nov-2023
• Refers: ASTM E350-23 - Standard Test Methods for Chemical Analysis of Carbon Steel, Low-Alloy Steel, Silicon Electrical Steel, Ingot Iron, and Wrought Iron
• Effective Date: 15-Nov-2023
• Refers: ASTM E2465-23 - Standard Test Method for Analysis of Ni-Base Alloys by Wavelength Dispersive X-Ray Fluorescence Spectrometry
• Effective Date: 01-Nov-2023
• Refers: ASTM E135-20 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 01-Jan-2020
• Refers: ASTM E1601-19 - Standard Practice for Conducting an Interlaboratory Study to Evaluate the Performance of an Analytical Method
• Effective Date: 01-Nov-2019
• Refers: ASTM E2465-19 - Standard Test Method for Analysis of Ni-Base Alloys by Wavelength Dispersive X-Ray Fluorescence Spectrometry
• Effective Date: 01-Oct-2019
• Refers: ASTM E135-19 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-May-2019
• Refers: ASTM E1938-13(2018) - Standard Test Method for Determination of Titanium in Nickel Alloys by Diantipyrylmethane Spectrophotometry
• Effective Date: 01-Oct-2018
• Refers: ASTM E1917-13(2018) - Standard Test Method for Determination of Phosphorus in Nickel, Ferronickel, and Nickel Alloys by Phosphovanadomolybdate Spectrophotometry
• Effective Date: 01-Oct-2018
• Refers: ASTM E351-18 - Standard Test Methods for Chemical Analysis of Cast Iron—All Types
• Effective Date: 01-Jul-2018
• Refers: ASTM E50-17 - Standard Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
• Effective Date: 01-Sep-2017
• Refers: ASTM E88-11(2017) - Standard Practice for Sampling Nonferrous Metals and Alloys in Cast Form for Determination of Chemical Composition
• Effective Date: 01-Sep-2017
• Refers: ASTM E2823-17 - Standard Test Method for Analysis of Nickel Alloys by Inductively Coupled Plasma Mass Spectrometry (Performance-Based)
• Effective Date: 01-Jan-2017
• Refers: ASTM E882-10(2016)e1 - Standard Guide for Accountability and Quality Control in the Chemical Analysis Laboratory
• Effective Date: 01-Dec-2016
• Refers: ASTM E882-10(2016) - Standard Guide for Accountability and Quality Control in the Chemical Analysis Laboratory
• Effective Date: 01-Dec-2016

Overview

ASTM E1473-22: Standard Test Methods for Chemical Analysis of Nickel, Cobalt, and High-Temperature Alloys provides comprehensive procedures for accurately determining the chemical composition of nickel, cobalt, and various high-temperature alloys. Developed by ASTM, this standard is primarily used as a referee method to ensure materials conform to specific compositional requirements, especially those under ASTM Committee B02 on Nonferrous Metals and Alloys. The methods are intended for use by trained analysts within properly equipped laboratories that follow strict quality control practices.

ASTM E1473-22 covers chemical analysis for a broad range of elements that are critical in alloy production, including but not limited to aluminum, chromium, cobalt, copper, iron, manganese, molybdenum, nickel, silicon, and vanadium. The standard brings together a set of accurate and repeatable analytic methods essential for quality assurance in the metallurgy and manufacturing industries.

Key Topics

• Scope of Application: The test methods apply to alloys with specified composition ranges for elements such as aluminum (0.005-7.00%), cobalt (0.10-75.00%), nickel (0.10-98.0%), chromium (0.10-33.00%), and more.
• Analytical Methods Included:
  • Gravimetric and spectrophotometric methods for elements like aluminum, copper, manganese, nickel, silicon, etc.
  • Atomic absorption spectrometry and titration methods for metals such as chromium and iron.
  • Ion-exchange and potentiometric titration for high-precision cobalt determinations.
• Procedure Selection: Multiple analysis methods are offered for some elements to accommodate variations in alloy composition and potential interferences. Users must choose the appropriate method based on the material’s composition.
• Safety and Quality Control: The document highlights the importance of working under proper safety conditions and using high-purity reagents. Quality control must align with guidance such as ASTM Guide E882.
• Repeatability and Reproducibility: Testing protocols have been validated through interlaboratory studies, following international standardization principles for accuracy and consistency.

Applications

ASTM E1473-22 is vital in several practical contexts, including:

• Material Certification: Serving as a referee method for confirming compliance with alloy composition specifications, crucial for product certification, material acceptance, and regulatory compliance.
• Quality Assurance and Control: Essential in the routine testing of raw materials and finished products within metal refining, alloy production, aerospace engineering, electronics, and energy sectors.
• Research and Development: Provides reliable methods for developing new alloy formulations and ensuring the repeatability of experimental results.
• Contractual and Regulatory Compliance: Used as an authority in dispute resolution, third-party inspections, and when compliance with international or regional material standards is required.

Related Standards

Several ASTM standards complement or may be used in addition to ASTM E1473-22 for the chemical analysis of nickel, cobalt, and superalloys:

• ASTM E1019: Test Methods for Determination of Carbon, Sulfur, Nitrogen, and Oxygen in Steel, Iron, Nickel, and Cobalt Alloys.
• ASTM E1834, E1835: Analysis of nickel alloys using atomic absorption spectrometry.
• ASTM E1917: Determination of phosphorus in nickel and nickel alloys.
• ASTM E1938: Determination of titanium in nickel alloys.
• ASTM E2465, E2594, E2823: Methods involving X-ray fluorescence and inductively coupled plasma techniques for analyzing nickel-base alloys.
• ASTM E882: Guide for quality control in chemical analysis laboratories.
• ISO 5725: Precision of test methods-repeatability and reproducibility for interlaboratory tests.

By adhering to ASTM E1473-22, laboratories and manufacturers can ensure the reliable and reproducible analysis of critical alloying elements, supporting high-quality outcomes in demanding industrial applications. This standard is a key resource for those seeking precise chemical analysis and material certification in the field of metallurgy.

Standards Content (Sample)

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: E1473 − 22
Standard Test Methods for
Chemical Analysis of Nickel, Cobalt, and High-Temperature
Alloys
This standard is issued under the fixed designation E1473; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope
Iron by the Silver Reduction Titrimetric Method 118 to 125
(1.0 % to 50.0 %)
1.1 These test methods describe the chemical analysis of
Manganese by the Metaperiodate Spectrophotometric Method 8 to 17
nickel, cobalt, and high-temperature alloys having chemical (0.05 % to 2.00 %)
Molybdenum by the Ion Exchange—8-Hydroxyquinoline 110 to 117
compositions within the following limits:
Gravimetric Method (1.5 % to 30 %)
Element Composition Range, % Molybdenum by the Thiocyanate Spectrophotometric Method 79 to 90
Aluminum 0.005 to 7.00
(0.01 % to 1.50 %)
Beryllium 0.001 to 0.05 Nickel by the Dimethylglyoxime Gravimetric Method 61 to 68
Boron 0.001 to 1.00 (0.1 % to 84.0 %)
Calcium 0.002 to 0.05 Niobium by the Ion Exchange—Cupferron Gravimetric Method 126 to 133
Carbon 0.001 to 1.10 (0.5 % to 6.0 %)
Chromium 0.10 to 33.00 Silicon by the Gravimetric Method (0.05 % to 5.00 %) 18 to 24
Cobalt 0.10 to 75.00 Tantalum by the Ion Exchange—Pyrogallol Spectrophotometric 134 to 142
Copper 0.01 to 35.00 Method (0.03 % to 1.0 %)
Iron 0.01 to 50.00 Tin by the Solvent Extraction-Atomic Absorption Spectrometry 69 to 78
Method (0.002 % to 0.10 %)
Lead 0.001 to 0.01
Magnesium 0.001 to 0.05
1.3 Other test methods applicable to the analysis of nickel
Manganese 0.01 to 3.0
Molybdenum 0.01 to 30.0
alloys that may be used in lieu of or in addition to this method
Niobium (Columbium) 0.01 to 6.0
are E1019, E1834, E1835, E1917, E1938, E2465, E2594,
Nickel 0.10 to 98.0
Nitrogen 0.001 to 0.20 E2823.
Phosphorus 0.002 to 0.08
Sulfur 0.002 to 0.10
1.4 Some of the composition ranges given in 1.1 are too
Silicon 0.01 to 5.00
broad to be covered by a single method, and therefore, these
Tantalum 0.005 to 1.00
test methods contain multiple methods for some elements.The
Tin 0.002 to 0.10
Titanium 0.01 to 5.00
user must select the proper test method by matching the
Tungsten 0.01 to 18.00
information given in the scope and interference sections of
Vanadium 0.01 to 3.25
Zinc 0.001 to 0.01 each test method with the composition of the alloy to be
Zirconium 0.01 to 2.50
analyzed.
1.2 The test methods in this standard are contained in the
1.5 Units—The values stated in SI units are regarded as
sections indicated as follows:
standard.
Aluminum, Total by the 8-Quinolinol Gravimetric Method 53 to 60
(0.20 % to 7.00 %)
1.6 This standard does not purport to address all of the
Chromium by the Atomic Absorption Spectrometry Method 91 to 100
safety concerns, if any, associated with its use. It is the
(0.018 % to 1.00 %)
Chromium by the Peroxydisulfate Oxidation—Titration Method 101 to 109
responsibility of the user of this standard to establish appro-
(0.10 % to 33.00 %)
priate safety, health, and environmental practices and deter-
Cobalt by the Ion-Exchange-Potentiometric Titration Method 25 to 32
mine the applicability of regulatory limitations prior to use.
(2%to75%)
Cobalt by the Nitroso-R-Salt Spectrophotometric Method 33 to 42
Specific caution and hazard statements are given in Section 7
(0.10 % to 5.0 %)
and in 13.4, 15.1.1, 15.1.2, 21.2, 22.3, 57.3, 84.2, 114.5,
Copper by Neocuproine Spectrophotometric Method 43 to 52
(0.010 % to 10.00 %)
115.14, 130.4, 130.5, 138.5, and 138.6.
1.7 This international standard was developed in accor-
1 dance with internationally recognized principles on standard-
These test methods are under the jurisdiction of ASTM Committee E01 on
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct
ization established in the Decision on Principles for the
responsibilityofSubcommitteeE01.08onNiandCoandHighTemperatureAlloys.
Development of International Standards, Guides and Recom-
Current edition approved Nov. 15, 2022. Published December 2022. Originally
mendations issued by the World Trade Organization Technical
approved in 1992. Last previous edition approved in 2016 as E1473–16. DOI:
10.1520/E1473-22. Barriers to Trade (TBT) Committee.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E1473 − 22
2. Referenced Documents tively Coupled Plasma Mass Spectrometry (Performance-
2 Based)
2.1 ASTM Standards:
2.2 Other Documents:
D1193Specification for Reagent Water
ISO 5725Precision of Test Methods—Determination of
E29Practice for Using Significant Digits in Test Data to
Repeatability and Reproducibility for Inter-Laboratory
Determine Conformance with Specifications
Tests
E50Practices for Apparatus, Reagents, and Safety Consid-
erations for Chemical Analysis of Metals, Ores, and
3. Terminology
Related Materials
E55Practice for Sampling Wrought Nonferrous Metals and 3.1 Fordefinitionsoftermsusedinthesetestmethods,refer
to Terminology E135.
Alloys for Determination of Chemical Composition
E60Practice for Analysis of Metals, Ores, and Related
4. Significance and Use
Materials by Spectrophotometry
E88Practice for Sampling Nonferrous Metals andAlloys in
4.1 These test methods for the chemical analysis of metals
Cast Form for Determination of Chemical Composition
and alloys are primarily intended as referee methods to test
E135Terminology Relating to Analytical Chemistry for
such materials for compliance with compositional
Metals, Ores, and Related Materials
specifications, particularly those under the jurisdiction of
E173Practice for Conducting Interlaboratory Studies of
Committee B02 on Nonferrous Metals and Alloys. It is
Methods for Chemical Analysis of Metals (Withdrawn
assumed that all who use these test methods will be trained
1997)
analysts capable of performing common laboratory procedures
E350Test Methods for Chemical Analysis of Carbon Steel,
skillfullyandsafely.Itisexpectedthatworkwillbeperformed
Low-Alloy Steel, Silicon Electrical Steel, Ingot Iron, and
in a properly equipped laboratory under appropriate quality
Wrought Iron
control practices such as those described in Guide E882.
E351TestMethodsforChemicalAnalysisofCastIron—All
Types 5. Apparatus, Reagents, and Instrumental Practice
E352TestMethodsforChemicalAnalysisofToolSteelsand
5.1 Apparatus—Specialized apparatus requirements are
Other Similar Medium- and High-Alloy Steels
listed in the “Apparatus” section in each test method.
E353Test Methods for Chemical Analysis of Stainless,
5.1.1 In the methods specifying spectrophotometric testing,
Heat-Resisting, Maraging, and Other Similar Chromium-
the cells utilized to contain the reference material and sample
Nickel-Iron Alloys
solutions in spectrophotometers are referred to as “absorption
E882Guide for Accountability and Quality Control in the
cells.” Please note that the radiant energy passed through the
Chemical Analysis Laboratory
cells can be measured as absorbance or transmittance. These
E1019Test Methods for Determination of Carbon, Sulfur,
methods refer to absorbance measurements. Refer to Practices
Nitrogen, and Oxygen in Steel, Iron, Nickel, and Cobalt
E60 for details.
Alloys by Various Combustion and Inert Gas Fusion
5.2 Reagents:
Techniques
5.2.1 Purity of Reagents—Unless otherwise indicated, all
E1601Practice for Conducting an Interlaboratory Study to
reagents used in these test methods shall conform to the
Evaluate the Performance of an Analytical Method
specifications of the Committee onAnalytical Reagents of the
E1834TestMethodforAnalysisofNickelAlloysbyGraph-
American Chemical Society where such specifications are
ite Furnace Atomic Absorption Spectrometry
available. Other chemicals may be used, provided it is first
E1835Test Method forAnalysis of NickelAlloys by Flame
ascertained that they are of sufficiently high purity to permit
Atomic Absorption Spectrometry
their use without adversely affecting the expected performance
E1917Test Method for Determination of Phosphorus in
of the determination, as indicated in the Precision and Bias
Nickel, Ferronickel, and Nickel Alloys by Phosphovana-
sections.
domolybdate Spectrophotometry
5.2.2 Purity of Water—Unless otherwise indicated, refer-
E1938TestMethodforDeterminationofTitaniuminNickel
ences to water shall mean reagent water conforming to Type I
Alloys by Diantipyrylmethane Spectrophotometry
orIIofSpecificationD1193.TypeIIIorIVmaybeusedifthey
E2465Test Method for Analysis of Ni-Base Alloys by
effect no measurable change in the blank or sample.
WavelengthDispersiveX-RayFluorescenceSpectrometry
E2594Test Method forAnalysis of NickelAlloys by Induc- 5.3 Spectrophotometric Practice—Spectrophotometric
tively Coupled Plasma Atomic Emission Spectrometry practice prescribed in these test methods shall conform to
(Performance-Based) Practice E60.
E2823Test Method forAnalysis of NickelAlloys by Induc-
Available fromAmerican National Standards Institute (ANSI), 25 W. 43rd St.,
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 4th Floor, New York, NY 10036, http://www.ansi.org.
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Reagent Chemicals, American Chemical Society Specifications, American
Standards volume information, refer to the standard’s Document Summary page on Chemical Society,Washington, DC, www.acs.org. For suggestions on the testing of
the ASTM website. reagents not listed by the American Chemical Society, see the United States
The last approved version of this historical standard is referenced on Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc.
www.astm.org. (USPC), Rockville, MD, http://www.usp.org.
E1473 − 22
6. Interlaboratory Studies and Rounding Calculated must transmit not more than 5% of its maximum at a
Values wavelength shorter than 530nm. The band width of the filter
should be less than 30nm when measured at 50% of its
6.1 These test methods have been evaluated in accordance
maximum transmittance. Similar restrictions apply with re-
with Practice E173 (withdrawn 1997) or ISO 5725. The
spect to the wavelength region employed when other “wide-
Reproducibility R2 of Practice E173 corresponds to the Re-
band” instruments are used.
producibility Index R of Practice E1601.The Repeatability R1
of Practice E173 corresponds to the Repeatability Index r of 12.2 The spectral transmittance curve of permanganate ions
Practice E1601. exhibits two useful minima, one at approximately 526nm, and
the other at 545nm. The latter is recommended when a
6.2 RoundingoftestresultsobtainedusingthisTestMethod
“narrow-band” spectrophotometer is used.
shall be performed in accordance with Practice E29, Rounding
Method, unless an alternative rounding method is specified by
12.3 Tungsten, when present in amounts of more than
the customer or applicable material specification. 0.5%, interferes by producing a turbidity in the final solution.
Aspecial procedure is provided for use with samples contain-
7. Hazards and Sampling
ingmorethan0.5%tungstenwhicheliminatestheproblemby
7.1 Hazards—For precautions to be observed in the use of preventing the precipitation of the tungsten.
certain reagents and equipment in these test methods, refer to
Practices E50. 13. Reagents
7.2 Sampling—For procedures to sample the material, refer
13.1 Manganese, Standard Solution (1 mL = 0.032 mg
to Practices E55 and E88. Mn)—Transfer the equivalent of 0.4000g of assayed, high-
purity manganese (purity 99.99% minimum), to a 500-mL
MANGANESE BY THE METAPERIODATE
volumetric flask and dissolve in 20mL of HNO by heating.
SPECTROPHOTOMETRIC METHOD
Cool, dilute to volume, and mix. Using a pipet, transfer 20mL
to a 500-mL volumetric flask, dilute to volume, and mix.
8. Scope
13.2 HNO -H PO Mixture—Cautiously,whilestirring,add
3 3 4
8.1 Thistestmethodcoversthedeterminationofmanganese
100mL of HNO and 400mL of H PO to 400mL of water.
3 3 4
from 0.05% to 2.00%.
Cool, dilute to 1L, and mix. Prepare fresh as needed.
9. Summary of Test Method
13.3 Potassium Metaperiodate Solution (7.5g⁄L)—Dis-
solve 7.5g of potassium metaperiodate (KIO ) in 200mL of
9.1 Manganous ions are oxidized to permanganate ions by
treatment with periodate. Tungsten, when present in amounts hot HNO (1+1), add 400mL of H PO , cool, dilute to 1L,
3 3 4
and mix.
greaterthan0.5%,iskeptinsolutionwithH PO .Solutionsof
3 4
the samples are fumed with HClO so that the effect of
13.4 Water, Pretreated with Metaperiodate—Add 20mL of
periodate is limited to the oxidation of manganese. Spectro-
KIO solution to 1Lof water, mix, heat at not less than 90°C
photometric measurements are made at 545nm.
for 20min to 30min, and cool. Use this water to dilute
solutions to volume that have been treated with KIO solution
10. Concentration Range
tooxidizemanganese,andthusavoidreductionofpermangan-
10.1 The recommended concentration range is from
ate ions by any reducing agents in the untreated water.
0.15mg to 0.8mg of manganese per 50mL of solution, using
(Caution—Avoid the use of this water for other purposes.)
a 1-cm cell (Note 1) and a spectrophotometer with a band
width of 10nm or less.
14. Preparation of Calibration Curve
NOTE1—Thistestmethodhasbeenwrittenforcellshavinga1-cmlight
14.1 Calibration Solutions—Using pipets, transfer (5, 10,
path and a “narrow-band” instrument. The concentration range depends
15, 20, and 25) mL of manganese standard solution
upon band width and spectral region used as well as cell optical path
(1mL=0.032 mgMn)to50-mLborosilicateglassvolumetric
length. Cells having other dimensions may be used, provided suitable
flasks, and, if necessary, dilute to approximately 25mL.
adjustments can be made in the amounts of sample and reagents used.
Proceed as directed in 14.3.
11. Stability of Color
14.2 Reference Solution—Transfer approximately 25mL of
11.1 The color is stable for at least 24 h.
water to a 50-mL borosilicate glass volumetric flask. Proceed
as directed in 14.3.
12. Interferences
14.3 Color Development—Add 10mL of KIO solution,
12.1 HClO treatment, which is used in the procedure,
and heat the solutions at not less than 90°C for 20min to
yields solutions which can be highly colored due to the
30min (Note 2). Cool, dilute to volume with pretreated water,
presence of hexavalent chromium Cr(VI) ions.Although these
and mix.
ions and other colored ions in the sample solution undergo no
further change in color quality upon treatment with metaperio- 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
date ion, the following precautions must be observed when
development.
filter spectrophotometers are used: Select a filter with maxi-
mum transmittance between 545nm and 565nm. The filter 14.4 Spectrophotometry:
E1473 − 22
14.4.1 Multiple-Cell Spectrophotometer—Measure the cell Transfer the solution to either a 100-mLor 500-mLvolumetric
correction using the Reference Solution (14.2) in absorption flask as directed in 15.1. Proceed to 15.1.3.
cells with a 1-cm light path and using a light band centered at 15.1.2.2 For samples whose dissolution is hastened by HF,
545nm. Using the test cell, take the spectrophotometric add8mLto10mLofH PO , 10mLof HClO , 5mLto 6mL
3 4 4
absorbance readings of the calibration solutions (14.1) versus ofH SO ,3mLto4mLofHNO ,andafewdropsofHF.Heat
2 4 3
the reference solution (14.2). moderately until the sample is decomposed, and then heat to
copious white fumes for 10min to 12min or until the
14.4.2 Single-Cell Spectrophotometer—Transfer a suitable
chromium is oxidized and the HCl is expelled, but avoid
portion of the reference solution (14.2) to an absorption cell
heating to fumes of SO . Cool, add 50mL of water, digest if
with a 1-cm light path and adjust the spectrophotometer to the 3
necessarytodissolvethesalts,cool,andtransferthesolutionto
initial setting, using a light band centered at 545nm. While
a 100-mL or 500-mL volumetric flask as directed in 15.1.
maintaining this adjustment, take the spectrophotometric ab-
Proceed to 15.1.3.
sorbance readings of the calibration solutions (14.1).
15.1.2.3 Coolthesolution,dilutetovolume,andmix.Allow
14.5 Calibration Curve—Follow the instrument manufac-
insoluble matter to settle, or dry filter through a coarse paper
turer’s instructions for generating the calibration curve. Plot
and discard the first 15mLto 20mL of the filtrate, before
the net spectrophotometric absorbance readings of the calibra-
taking aliquots.
tion solutions against the milligrams of manganese per 50mL
15.1.3 Using a pipet, transfer 20-mLaliquots to two 50-mL
of solution.
borosilicate glass volumetric flasks; treat one as directed in
15.3 and the other as directed in 15.4.1.
15. Procedure
15.2 Reagent Blank Solution—Carry a reagent blank
15.1 Test Solutions—Select and weigh a sample as follows.
through the entire procedure using the same amounts of all
Tolerance in reagents with the sample omitted.
Manganese, Sample Sample Dilution,
15.3 Color Development—Proceed as directed in 14.3.
% Mass, g Mass, mg mL
0.01 to 0.5 0.80 0.5 100
15.4 Reference Solutions:
0.45 to 1.0 0.35 0.3 100
0.85 to 2.0 0.80 0.5 500
15.4.1 Background Color Solution—To one of the sample
aliquots in a 50-mL volumetric flask, add 10mL of HNO -
15.1.1 For Samples Containing Not More Than 0.5 %
H PO mixture,andheatthesolutionatnotlessthan90°Cfor
3 4
Tungsten—(Warning—See Practices E50 for details pertain-
20min to 30min (Note 2). Cool, dilute to volume (with
ing to the special hazards associated with the use of HClO .)
untreated water), and mix.
15.1.1.1 To dissolve samples that do not require HF, add
15.4.2 Reagent Blank Reference Solution—Transfer the re-
8mLto 10mLof HCl(1+1), and heat.Add HNO as needed
agentblanksolution(15.2)tothesamesizevolumetricflaskas
to hasten dissolution, and then add 3mL to 4mL in excess.
usedforthetestsolutionsandtransferthesamesizealiquotsas
Whendissolutioniscomplete,cool,thenadd10mLofHClO ,
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 15.3 and use as reference
expelHCl.Continuefuminguntilsaltsbegintoseparate.Cool,
solution for test samples. Treat the other as directed in 15.4.1
add 50mL 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
15.5 Spectrophotometry—Establishthecellcorrectionswith
flask. Proceed to 15.1.3.
the reagent blank Reference solution to be used as a reference
15.1.1.2 For samples whose dissolution is hastened by HF,
solution for background color solutions. Take the spectropho-
add 8mLto 10mLof HCl(1+1), and heat.Add HNO and a
tometricabsorbancereadingsofthebackgroundcolorsolutions
few drops of HF as needed to hasten dissolution, and then add
and the test solutions versus the respective reagent blank
3mL to 4mL of HNO . When dissolution is complete, cool,
reference solutions as directed in 14.4.
then add 10mL of HClO , evaporate to fumes to oxidize
chromium, if present, and to expel HCl. Continue fuming until
16. Calculation
salts begin to separate. Cool, add 50mL of water, digest if
necessarytodissolvethesalts,cool,andtransferthesolutionto 16.1 Convertthenetspectrophotometricabsorbancereading
either a 100-mL or 500-mL volumetric flask as indicated in of the test solution and of the background color solution to
15.1. Proceed to 15.1.3. milligrams of manganese by means of the calibration curve.
Calculate the percent of manganese as follows:
15.1.2 For Samples Containing More Than 0.5 %
Tungsten—(Warning—See Practices E50 for details pertain-
Manganese, % 5 ~A 2 B!/~C 310! (1)
ing to the special hazards associated with the use of HClO .)
where:
15.1.2.1 To dissolve samples that do not require HF, add
A = manganese found in 50mL of the final test solution,
8mLto10mLofH PO , 10mL of HClO , 5mL to 6mL of
3 4 4
mg,
H SO , and 3mLto 4mLof HNO . Heat moderately until the
2 4 3
B = apparent manganese found in 50mL of the final back-
sample is decomposed, and then heat to copious white fumes
ground color solution, mg, and
for10minto12minoruntilthechromiumisoxidizedandthe
C = sample mass represented in 50mL of the final test
HCl is expelled but avoid heating to fumes of SO . Cool, add
solution, g.
50mL of water, and digest if necessary to dissolve the salts.
E1473 − 22
17. Precision and Bias 21.2.1 Select a lot of HClO that contains not more than
0.0002% silicon for the analysis of samples containing silicon
17.1 Precision—Nine laboratories cooperated in testing this
in the range from 0.02% to 0.10% and not more than
test method and obtained the data summarized in Table 1.
0.0004% silicon for samples containing more than 0.10% by
17.2 Bias—The accuracy of this test method has been
determining duplicate values for silicon as directed in 21.2.2 –
deemed satisfactory based upon the data for the certified
21.2.6.
reference materials in Table 1. Users are encouraged to use
21.2.2 Transfer 15mL of HClO (Note 3) to each of two
these or similar reference materials to verify that the test
400-mL beakers. To one of the beakers transfer an additional
method is performing accurately in their laboratories.
50mL of HClO . Using a pipet, transfer 20mL of sodium
silicate solution (1mL=1.00mg Si) to each of the beakers.
SILICON BY THE GRAVIMETRIC METHOD
Evaporatethesolutionstofumesandheatfor15minto20min
at such a rate that HClO refluxes on the sides of the beakers.
18. Scope
Cool sufficiently, and add 100mL of water (40°C to 50°C).
18.1 This test method covers the determination of silicon
from 0.05% to 5.00% in alloys containing not more than
NOTE3—The15-mLadditionofHClO canbefromthesamelotasthe
one to be tested. Once a lot has been established as having less than
0.1% boron.
0.0002% silicon, it should preferably be used for the 15-mL addition in
all subsequent tests of other lots of HClO .
19. Summary of Test Method
21.2.3 Addpaperpulpandfilterimmediately,usinglow-ash
19.1 After dissolution of the sample, silicic acid is dehy-
11-cm medium-porosity filter papers. Transfer the precipitates
drated by fuming with H SO or HClO . The solution is
2 4 4
to the papers, and scrub the beakers thoroughly with a
filtered,andtheimpuresilicaisignitedandweighed.Thesilica
rubber-tippedrod.Rinsethepapersandprecipitatesalternately
isthenvolatilizedwithHF.Theresidueisignitedandweighed;
with3-mLto5-mLportionsofhotHCl(1+19)andhotwater,
the loss in mass represents silica.
for a total of six times. Finally, rinse the papers twice with
20. Interferences
H SO (1+49). Transfer the papers to platinum crucibles.
2 4
21.2.4 Dry the papers and heat at 600°C until the carbon is
20.1 The elements normally present do not interfere. When
removed.Finallyigniteat1100°Cto1150°Ctoconstantmass
boron is present in amounts greater than 0.1%, the sample
(at least 30min). Cool in a desiccator and weigh.
solution requires special treatment with methyl alcohol.
However, since no boron steels were tested, this special 21.2.5 Add enough H SO (1+1) to moisten the SiO , and
2 4 2
add3mLto5mLofHF.Evaporatetodrynessandthenheatat
treatment was not evaluated and is not described in this test
method. a gradually increasing rate until H SO is removed. Ignite for
2 4
15min at 1100°C to 1150°C, cool in a desiccator, and weigh.
21. Reagents
21.2.6 Calculate the percentage of silicon as follows:
21.1 The analyst should ensure by analyzing blanks and
Silicon, % 5 @~A 2 B! 2 ~C 2 D!# 30.4674/E 3100 (2)
other checks that possible silicon contamination of reagents
where:
will not significantly bias the results.
A = initial mass of crucible plus impure SiO when 65mL
21.2 HClO —(Warning—SeePracticesE50fordetailsper-
of HClO was taken, g,
taining to the special hazards associated with the use of
B = final mass of crucible plus impurities when 65mL of
HClO .)
HClO was taken, g,
C = finalmassofcrucibleplusimpureSiO when15mLof
TABLE 1 Statistical Information—Manganese – Metaperiodate
HClO was taken, g,
Spectrophotometric Method
D = final mass of crucible plus impurities when 15mL of
Repeatability Reproducibility
Manganese
HClO was taken, g, and
Test Specimen (R , Practice (R , Practice
1 2
Found, %
E = nominal mass (80g) of 50mL of HClO .
E173) E173)
1. Nickel alloy, 77Ni-20Cr 0.074 0.002 0.008
21.3 Sodium Silicate Solution (1.00mg⁄mL Si)—Transfer
(NIST 169, 0.073 % Mn,
certified)
11.0g of sodium silicate (Na SiO ·9H O) to a 400-mLbeaker.
2 3 2
2. High-temperature alloy, 0.289 0.007 0.026
Add 150mL of water and dissolve the salt. Filter through a
68Ni-14Cr-7Al-6Mo
medium paper, collecting the filtrate in a 1-Lvolumetric flask,
(NIST 1205, 0.29 % Mn,
not certified)
dilute to volume, and mix. Store in a polyethylene bottle. Use
3. Cobalt alloy, 1.49 0.03 0.08
this solution to determine the suitability of the HClO .
41Co-20Ni-20Cr-4Mo-4W
(NIST 168, 1.50 % Mn,
21.4 Tartaric Acid Solution (20.6 g/L)—Dissolve 20.6g of
not certified)
tartaric acid (C H O ) in water, dilute to 1L, and filter.
4. Stainless steel 18Cr-9Ni 1.79 0.07 0.07 4 6 6
(NIST 101e, 1.77 % Mn,
21.5 Water—Use freshly prepared Type II water known to
certified)
be free of silicon. Water distilled from glass, demineralized in
E1473 − 22
columns containing silicon compounds, or stored for extended 22.6 Transfer the paper and precipitate to the reserved
periods in glass, or combination thereof, has been known to platinum crucible. Dry the papers and then heat the crucible at
absorb silicon. 600°Cuntilthecarbonisremoved.Finallyigniteat1100°Cto
1150°Ctoconstantmass(atleast30min).Coolinadesiccator
and weigh.
22. Procedure
22.7 Add enough H SO (1+1) to moisten the impure
22.1 Select and weigh a sample as follows. 2 4
silica (SiO ), and add 3mL to 5mL of HF. Evaporate to
Tolerance Dehydrating Acid, mL
dryness and then heat at a gradually increasing rate until
Sample in Sample H SO
2 4
Silicon, % Mass, g Mass, mg (1+4) HClO
4 H SO is removed. Ignite at 1100 °C to 1150 °C for 15 min,
2 4
0.05 to 0.10 5.0 5 150 75
cool in a desiccator, and weigh. If the sample contains more
0.10 to 1.0 4.0 4 100 60
than 0.5 % tungsten, ignite at 750 °C instead of 1100 °C to
1.0 to 2.0 3.0 3 100 50
2.0 to 5.0 2.0 2 100 40
1150 °C after volatilization of SiO .
22.1.1 Transferthesampletoa400-mLbeakerora300-mL
23. Calculation
porcelain casserole. Proceed as directed in 22.2 or 22.3.
23.1 Calculate the percent of silicon as follows:
22.2 H SO Dehydration, if tungsten is greater than 0.5 %.
2 4
Silicon, % 5 @~~A 2 B! 30.4674!/C# 3100 (3)
22.2.1 Add amounts of HCl or HNO , or mixtures and
dilutions of these acids, that are sufficient to dissolve the
where:
sample; and then add the H SO (1+4) as specified in 21.1,
2 4
A = initial mass of crucible and impure SiO,g,
and cover. Heat until dissolution is complete. Remove and
B = final mass of crucible and residue, g, and
rinse the cover glass; substitute a ribbed cover glass.
C = sample used, g.
22.2.2 Evaporate until salts begin to separate; at this point
evaporate the solution rapidly to the first appearance of fumes
24. Precision and Bias
and fume strongly for 2min to 3min. Cool sufficiently, and
24.1 Precision—Eleven laboratories cooperated in testing
add100mLofwater(40°Cto50°C).Stirtodissolvethesalts
this test method and obtained the data summarized in Table 2.
and heat, if necessary, but do not boil. Proceed immediately as
Asample with silicon content near the upper limit of the scope
directed in 22.4.
was not available for testing.
22.3 HClO Dehydration, if tungsten is less than 0.5 % or
24.2 Bias—Noinformationonthebiasofthistestmethodis
use 22.2. (Warning—See Practices E50 for details pertaining
knownbecauseatthetimeoftheinterlaboratorystudy,suitable
to the special hazards associated with the use of HClO .)
referencematerialswerenotavailable.Theuserofthismethod
22.3.1 Add amounts of HCl or HNO , or mixtures and
is encouraged to employ accepted reference materials, if
dilutions of these acids, which are sufficient to dissolve the
available, to determine the presence or absence of bias.
sample, and cover. Heat until dissolution is complete. Add
HNO to provide a total of 35mL to 40mL, followed by
COBALT BY THE ION-EXCHANGE-
HClO as specified in the table in 22.1. Remove and rinse the
POTENTIOMETRIC TITRATION METHOD
cover glass; substitute a ribbed cover glass.
25. Scope
22.3.2 Evaporate the solution to fumes and heat for 15min
to 20min at such a rate that the HClO refluxes on the sides of
25.1 This test method covers the determination of cobalt
thecontainer.Coolsufficientlyandadd100mLofwater(40°C
from 2% to 75%.
to 50°C). Stir to dissolve the salts and heat to boiling. If the
sample solution contains more than 100 mg of chromium, add,
26. Summary of Test Method
while stirring, 1mLof tartaric acid solution for each 25mg of
26.1 Cobalt is separated from interfering elements by selec-
chromium.
tive elution from an anion-exchange column using HCl. The
22.4 Add paper pulp and filter immediately, on a low-ash
11-cm medium-porosity filter paper. Collect the filtrate in a
600-mLbeaker. Transfer the precipitate to the paper and scrub
TABLE 2 Statistical Information—Silicon – Gravimetric Method
the container thoroughly with a rubber-tipped rod. Rinse the
Repeatability Reproducibility
paperandprecipitatealternatelywith3-mLto5-mLportionsof
Test Specimen Silicon Found, % (R , Practice (R , Practice
1 2
hot HCl(1+19) and hot water until iron salts are removed but
E173) E173)
for not more than a total of ten rinsings. If 22.3 was followed, HCIO Dehydration
1. Ni-base alloy 0.029 0.006 0.026
rinse the paper twice more with H SO (1+49), but do not
2 4
75Ni-12Cr-6Al-
collect these rinsings in the filtrate; discard the rinsings.
4Mo-2Cb-0.7Ti
Transfer the paper to a platinum crucible and reserve. H SO Dehydration
2 4
1. Ni-base alloy 0.030 0.007 0.030
22.5 Add 15mLof HNO to the filtrate, stir, and evaporate 75Ni-12Cr-6Al-
4Mo-2Cb-0.7Ti
as directed either in 22.2 or 22.3, depending upon the dehy-
2. Co-base alloy 1.01 0.03 0.06
drating acid used. Filter immediately, using a low-ash 9-cm
66Co-28Cr-4W-1.5Ni
100-porosity filter paper, and rinse as directed in 22.4.
E1473 − 22
cobalt is oxidized to the trivalent state with ferricyanide, and 28.2 Apparatus for Potentiometric Titrations—Instruments
the excess ferricyanide is titrated potentiometrically with for detecting the end points in pH (acid-base), oxidation-
cobalt solution.
reduction,precipitationandcomplexationtitrationsconsistofa
pair of suitable electrodes, a potentiometer, a buret, and a
27. Interferences
motor-driven stirrer. Titrations follow the principle when two
27.1 Theelementsordinarilypresentdonotinterfereiftheir
dissimilarelectrodesareplacedinasolutionthereisapotential
contents are under the maximum limits shown in 1.1.
difference between them. This potential difference depends on
the composition of the solution and changes as the titrant is
28. Apparatus
added. A high-impedance electronic voltmeter follows the
28.1 Ion-Exchange Column,approximately25mmindiam-
changes accurately. The end point of the titration may be
eter and 300mm in length, tapered at one end, and provided
determined by adding the titrant until the potential difference
with a stopcock to control the flow rate, and a second, lower
attains a predetermined value or by plotting the potential
stopcock to stop the flow. A Jones Reductor (Fig. 1), may be
difference versus the titrant volume, the titrant being added
adapted to this method. It consists of a column 19 mm in
until the end point has been passed.
diameter and 250 mm in length, of 0.853-mm to 0.599-mm
28.2.1 An elaborate or highly sensitive and accurate poten-
(20-mesh to 30-mesh) amalgamated zinc. To amalgamate the
tiometer is not necessary for potentiometric titrations because
zinc, shake 800 g of zinc (as free of iron as possible) with 400
the absolute cell voltage needs to be known only
mL of HgCl solution (25 g/L) in a 1-L flask for 2 min. Rinse
approximately, and variations of less than 1mV are not
several times with H SO (2 + 98), and then thoroughly with
2 4
significant. Such instruments should have a range of about
water. The reductor, when idle, should always be kept filled
1.5V and a readability of about 1mV. Many pH meters are
withdistilledwatertoabovethetopofthezinc.Areservoirfor
the eluants may be added at the top of the column. also suitable for potentiometric titrations.
FIG. 1 Jones Reductor
E1473 − 22
28.2.2 The electrode system must consist of a reference chloride plastic fiber at the top of the resin bed to protect it
electrode and an indicator electrode. The reference electrode from being carried into suspension when the solutions are
maintains a constant, but not necessarily a known or reproduc- added. While passing a minimum of 35mL of HCl(7+5)
iblepotentialduringthetitration.Thepotentialoftheindicator through the column, with the hydrostatic head 100mm above
electrodedoeschangeduringthetitration;further,theindicator the top of the resin bed, adjust the flow rate to not more than
electrodemustbeonethatwillquicklycometoequilibrium.In 3.0mL⁄min. Drain to 10mm to 20mm above the top of the
this procedure a platinum indicator electrode and a saturated resin bed and then close the lower stopcock.
calomel reference electrode are appropriate.
NOTE 4—The maximum limits of 0.125g of cobalt and a 0.500g
sample(30.1)inthesamplesolutionconsidertheexchangecapacityofthe
28.3 Platinum and saturated calomel electrodes.
resin, the physical dimensions of the column, and the volume of eluants.
29. Reagents
29.5 Mercuric Chloride Solution, HgCl (25g⁄L).
29.1 Ammonium Citrate Solution (200 g/L).
29.6 Potassium Ferricyanide, Standard Solution (1
mL=3.0mg of Co):
29.2 Bromine.
29.6.1 Dissolve 16.68 g of potassium ferricyanide
29.3 Cobalt, Standard Solution (1mL=1.5mg of Co):
(K Fe(CN) ) in water and dilute to 1L. Store the solution in a
3 6
29.3.1 Dry a weighing bottle in an oven at 130 °C for 1 h,
dark-colored bottle. Standardize the solution each day before
cool in a desiccator, and weigh. Transfer 3.945 g of cobalt
use as follows: Transfer from a 50-mL buret approximately
sulfate (CoSO ) that has been heated at 550 °C for1htothe
20mLof K Fe(CN) solution to a 400-mLbeaker. Record the
3 6
weighing bottle. Dry the bottle and contents at 130 °C for 1 h,
buret reading to the nearest 0.01mL. Add25 mL of water,
coolindesiccator,stopperthebottle,andweigh.Thedifference
10mL of ammonium citrate solution, and 25mL of NH OH.
in mass is the amount of CoSO taken. Transfer the weighed
Coolto5°Cto10°Candmaintainthistemperatureduringthe
CoSO to a 400-mL beaker, rinse the weighing bottle with
titration. Transfer the beaker to the potentiometric titration
water, and transfer the rinsings to the beaker. Add 150 mL of
apparatus.Whilestirring,titratetheK Fe(CN) withthecobalt
3 6
waterand20mLofHNO ,andheattodissolvethesalts.Cool,
solution (1mL=1.5mg Co) using a 50-mL buret. Titrate at a
transfer to a 1-L volumetric flask, dilute to volume, and mix.
fairlyrapidrateuntiltheendpointisapproached,andthenadd
29.3.2 Standardization—Calculate the cobalt concentration
the titrant in one-drop increments through the end point.After
as follows:
the addition of each increment, record the buret reading and
Cobalt, mg/mL=mass of CoSO , g,×0.38026
voltage when equilibrium is reached. Estimate the buret
29.4 Ion-Exchange Resin:
reading at the end point to the nearest 0.01mL.
29.4.1 Use an anion exchange resin of the alkyl quaternary
29.6.2 Calculate the cobalt equivalent as follows (29.6.2.1):
ammonium type (chloride form) consisting of spherical beads
Cobaltequivalent, mg/mL 5 A 3 B /C (4)
~ !
having a nominal cross-linkage of 8%, and 0.075-mm to
0.037-mm (200-nominal to 400-nominal mesh) size. To re- where:
move those beads greater than about 180µm in diameter as
A = cobalt standard solution required to titrate the potas-
well as the excessively fine beads, treat the resin as follows:
sium ferricyanide solution, mL,
Transferasupplyoftheresintoabeaker,coverwithwater,and
B = cobalt standard solution, mg/mL, and
allow sufficient time (at least 30min) for the beads to undergo
C = potassium ferricyanide solution, mL.
maximum swelling. Place a 180-µm (No.80) screen, 150mm
29.6.2.1 Duplicate or triplicate values should be obtained
indiameterovera2-Lbeaker.Prepareathinslurryoftheresin
for the cobalt equivalent. The values obtained should check
and pour it onto the screen. Rinse the fine beads through the
within 1g⁄Kg to 2g⁄Kg.
screen, using a small stream of water. Discard the beads
retained on the screen, periodically, if necessary, to avoid
30. Procedure
unduecloggingoftheopenings.Whenthebulkofthecollected
30.1 Proceed as directed in 30.2 – 30.7, using 0.50 g
resin has settled, decant the water and transfer approximately
samples for cobalt compositions not greater than 25%; at
100 mL of resin to a 400-mL beaker. Add 200 mL of
higher compositions, use samples that represent between
HCl(1+19),stirvigorously,allowtheresintosettlefor4min
100mg and 125 mg of cobalt weighed to the nearest 0.1 mg.
to 6min, decant 150mL to 175mL of the suspension, and
discard. Repeat the treatment with HCl(1+19) twice more
30.2 Transfer a 0.50-g sample to a 150-mL beaker. Add
and reserve the coarser resin for the column preparation.
20mLof a mixture of five parts of HCl and one part of HNO
29.4.2 Prepare the column as follows: Place a 10-mm to
(30.2.1). Cover the beaker and digest at 60°C to 70°C until
20-mmlayerofglasswoolorpolyvinylchlorideplasticfiberin
the sample is decomposed. Rinse and remove the cover. Place
the bottom of the column, and add a sufficient amount of the
a ribbed cover glass on the beaker and evaporate the solution
prepared resin to fill the column to a height of approximately
nearly to dryness, but do not bake. Cool, add 20mL of
140mm. Place a 20-mm layer of glass wool or polyvinyl
HCl(7+5), and digest at 60°C to 70°C until salts are
dissolved (approximately 10 min).
30.2.1 Other ratios and concentrations of acids, with or
Cobalt sulfate (99.9% minimum) prepared from the hexamine salt by G.
without the addition of 1mL to 2mL of HF, are used for the
Frederick Smith Chemical Co., Columbus, OH, is satisfactory for this purpose.
Available from the Dow Chemical Co., Midland, MI. decomposition of special grades of alloys.
E1473 − 22
Some alloys are decomposed more readily by a mixture of increment, record the buret reading and voltage when equilib-
5mLof bromine, 15mLof HCl, and one drop to two drops of rium is reached. Estimate the buret reading at the end point to
HF. the nearest 0.01mL.
30.3 Cool to room temperature and transfer the solution to
31. Calculation
theion-exchangecolumn.Placeabeakerunderthecolumnand
31.1 Calculate the percent of cobalt as follows:
open the lower stopcock. When the solution reaches a level
10mm to 20mm above the resin bed, rinse the original beaker
Cobalt, % 5 AB 2 CD /E 3100 (5)
@~ ! #
with 5mL to 6mL of HCl(7+5) and transfer the rinsings to
where:
the column. Repeat this at 2-min intervals until the beaker has
A = standard potassium ferricyanide solution, mL,
beenrinsedfourtimes.Rinsetheupperpartofthecolumnwith
B = cobalt equivalent of the standard potassium ferricya-
HCl(7+5)twotimesorthreetimesandallowtheleveltodrop
nide solution,
to 10mm to 20mm above the resin bed each time. Maintain
C = cobalt standard solution, mL,
theflowrateatnotmorethan3.0mL⁄minandaddHCl(7+5)
D = concentration of cobalt standard solution, mg/mL, and
to the column until a total of 175mL to 185mL of solution
(sample solution and rinsings) containing mainly chromium,
E = sample used, mg.
manganese and nickel is collected (30.3.1). When the solution
in the column reaches a level 10mm to 20mm above the resin
32. Precision and Bias
bed, discard the eluate and then use a 400-mL beaker for the
32.1 Precision—Ten laboratories cooperated in testing this
collection of the cobalt eluate.
test method and obtained the data summarized in Table 3 for
30.3.1 Topreventanylossofcobalt,theleadingedgeofthe
Specimens 4 through 8.Although samples covered by this test
cobalt band must not be allowed to proceed any farther than
method with cobalt contents near the lower limit of the scope
25mmfromthebottomoftheresin.Normally,whenthecobalt
were not available for testing, the precision data obtained for
has reached this point in the column, the chromium,
Specimens 1, 2, and 3 using the test method indicated in Table
manganese, and nickel have been removed. Elution can be
3 should apply.
stopped at this point, although the total volume collected may
32.2 Bias—The accuracy of this test method has been
be less than 175mL.
deemed satisfactory based upon the data for the certified
30.4 Add HCl(1+2) to the column and collect 165mL to
reference materials in Table 3. Users are encouraged to use
175mLofthesolutionwhilemaintainingthe3.0-mL/minflow
these or similar reference materials to verify that the test
rate. Reserve the solution. If the sample solution did not
method is performing accurately in their laboratories.
contain more than 0.200g of iron, substitute a 250-mLbeaker
and precondition the column for the next sample as follows:
COBALT BY THE NITROSO-R-SALT
Draintheremainingsolutioninthecolumnto10mmto20mm
SPECTROPHOTOMETRIC METHOD
above the resin bed, pass 35mL to 50mL of HCl(7+5)
through the column until 10mm to 20mm of the solution 33. Scope
remains above the resin bed, then close the lower stopcock. If
33.1 This test method covers the determination of cobalt
the sample solution contained more than 0.200g of iron, or if
from 0.10% to 5.0%.
the column is not to be used again within 3h, discard the resin
and recharge the column as directed in 29.4.
TABLE 3 Statistical Information—Cobalt – Ion-Exchange
30.5 Add 30mL of HNO and 15mL of HClO to the
3 4
Potentiometric Titration Method
solutionfrom30.4andevaporatetofumesofHClO .Cool,add
Cobalt Repeatability Reproducibility
25mLto35mLofwater,boilfor1minto2min,cool,andadd
Test Specimen Found, (R , Practice (R , Practice
1 2
% E173) E173)
10mL of ammonium citrate solution.
1. No. 1, E352 1.86 0.05 0.12
30.6 Using a 50-mL buret, transfer to a 400-mL beaker a
(High alloy steel, 4Mo-6W-4Cr-
sufficient volume of K Fe(CN) solution to oxidize the cobalt 2V)
3 6
2. No. 2, E352 4.82 0.08 0.11
and to provide an excess of about 5mL to 8mL. Record the
(Tool steel, 18W-4Cr-1V)
buret reading to the nearest 0.01mL. Add 50mL of NH OH
4 3. No. 3, E352 8.46 0.03 0.07
and cool to 5°C to 10°C. Transfer the beaker to the potentio- (High alloy steel, 8Co-9Mo-2W-
4Cr-2V, NIST 153a, 8.47 % Co)
metric titration apparatus and maintain the 5°C to 10°C
4. High-temperature alloy 11.27 0.06 0.16
temperature during the titration.
20Cr-13Ni-5Mo-2W-1Nb
5. Ni-base alloy 57Ni-14Cr 13.88 0.09 0.18
30.7 While stirring, add the sample solution to the solution
(NIST 349, 13.95 % Co,
from 30.6, rinse the beaker with water, and add the rinsings to
certified)
6. High-temperature alloy 19.54 0.08 0.10
the solution. For a successful titration, the sample solution
21Cr-20Ni-4Mo-3W
must be added to the excess K Fe(CN) solution. Using a
3 6
7. Co-base alloy 21Ni- 42.91 0.18 0.15
50-mL buret, titrate the excess K Fe(CN) with the cobalt 20Cr-4Mo-5W-3Nb (NIST,
3 6
167, 42.90 % Co, not certified)
solution(1mL=1.5mgCo),atafairlyrapidrateuntiltheend
8. Co-base alloy 28Cr- 60.10 0.19 0.31
point is approached, and then add the titrant in one-drop
6Mo-3Ni
increments through the end point. After the addition of each
E1473 − 22
34. Summary of Test Method 39. Preparation of Calibration Curve
34.1 The sample solution is treated with zinc oxide to 39.1 Calibration Solutions—Usingpipets,transfer(2,5,10,
removeiron,chromium,andvanadium.Nitroso-R-saltsolution 15, 20, and 25) mL of cobalt standard solution
is added to a portion of the filtrate which has been buffered (1mL=0.06mgCo)tosix100-mLvolumetricflasks,diluteto
with sodium ac
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: E1473 − 16 E1473 − 22
Standard Test Methods for
Chemical Analysis of Nickel, Cobalt, and High-Temperature
Alloys
This standard is issued under the fixed designation E1473; 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.
1. Scope
1.1 These test methods describe the chemical analysis of nickel, cobalt, and high-temperature alloys having chemical compositions
within the following limits:
Element Composition Range, %
Aluminum 0.005 to 7.00
Beryllium 0.001 to 0.05
Boron 0.001 to 1.00
Calcium 0.002 to 0.05
Carbon 0.001 to 1.10
Chromium 0.10 to 33.00
Cobalt 0.10 to 75.00
Copper 0.01 to 35.00
Iron 0.01 to 50.00
Lead 0.001 to 0.01
Magnesium 0.001 to 0.05
Manganese 0.01 to 3.0
Molybdenum 0.01 to 30.0
Niobium (Columbium) 0.01 to 6.0
Nickel 0.10 to 98.0
Nitrogen 0.001 to 0.20
Phosphorus 0.002 to 0.08
Sulfur 0.002 to 0.10
Silicon 0.01 to 5.00
Tantalum 0.005 to 1.00
Tin 0.002 to 0.10
Titanium 0.01 to 5.00
Tungsten 0.01 to 18.00
Vanadium 0.01 to 3.25
Zinc 0.001 to 0.01
Zirconium 0.01 to 2.50
1.2 The test methods in this standard are contained in the sections indicated as follows:
Aluminum, Total by the 8-Quinolinol Gravimetric Method 53 to 60
(0.20 % to 7.00 %)
Chromium by the Atomic Absorption Spectrometry Method 91 to 100
(0.018 % to 1.00 %)
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 E01.08 on Ni and Co and High Temperature Alloys.
Current edition approved April 1, 2016Nov. 15, 2022. Published May 2016December 2022. Originally approved in 1992. Last previous edition approved in 20092016 as
E1473 – 09.E1473 – 16. DOI: 10.1520/E1473-16.10.1520/E1473-22.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E1473 − 22
Chromium by the Peroxydisulfate Oxidation—Titration Method 101 to 109
(0.10 % to 33.00 %)
Cobalt by the Ion-Exchange-Potentiometric Titration Method 25 to 32
(2 % to 75 %)
Cobalt by the Nitroso-R-Salt Spectrophotometric Method 33 to 42
(0.10 % to 5.0 %)
Copper by Neocuproine Spectrophotometric Method 43 to 52
(0.010 % to 10.00 %)
Iron by the Silver Reduction Titrimetric Method 118 to 125
(1.0 % to 50.0 %)
Manganese by the Metaperiodate Spectrophotometric Method 8 to 17
(0.05 % to 2.00 %)
Molybdenum by the Ion Exchange—8-Hydroxyquinoline 110 to 117
Gravimetric Method (1.5 % to 30 %)
Molybdenum by the Thiocyanate Spectrophotometric Method 79 to 90
(0.01 % to 1.50 %)
Nickel by the Dimethylglyoxime Gravimetric Method 61 to 68
(0.1 % to 84.0 %)
Niobium by the Ion Exchange—Cupferron Gravimetric Method 126 to 133
(0.5 % to 6.0 %)
Silicon by the Gravimetric Method (0.05 % to 5.00 %) 18 to 24
Tantalum by the Ion Exchange—Pyrogallol Spectrophotometric 134 to 142
Method (0.03 % to 1.0 %)
Tin by the Solvent Extraction-Atomic Absorption Method 69 to 78
(0.002 % to 0.10 %)
Tin by the Solvent Extraction-Atomic Absorption Spectrometry Method 69 to 78
(0.002 % to 0.10 %)
1.3 Other test methods applicable to the analysis of nickel alloys that may be used in lieu of or in addition to this method are Test
Methods E1019, E1834, E1835, E1917, E1938, E2465, E2594, E2823.
1.4 Some of the composition ranges given in 1.1 are too broad to be covered by a single method, and therefore, these test methods
contain multiple methods for some elements. The user must select the proper test method by matching the information given in
the scope and interference sections of each test method with the composition of the alloy to be analyzed.
1.5 Units—The values stated in SI units are to be regarded as standard.
1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. Specific caution and hazard statements are given in Section 7 and in 13.4,
15.1.1, 15.1.2, 21.2, 22.522.3, 57.3, 84.2, 114.5, 115.4115.14, 130.4, 130.5, 138.5, and 138.6.
1.7 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.
2. Referenced Documents
2.1 ASTM Standards:
D1193 Specification for Reagent Water
E29 Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
E50 Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
E55 Practice for Sampling Wrought Nonferrous Metals and Alloys for Determination of Chemical Composition
E60 Practice for Analysis of Metals, Ores, and Related Materials by Spectrophotometry
E88 Practice for Sampling Nonferrous Metals and Alloys in Cast Form for Determination of Chemical Composition
E135 Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
E173 Practice for Conducting Interlaboratory Studies of Methods for Chemical Analysis of Metals (Withdrawn 1997)
E350 Test Methods for Chemical Analysis of Carbon Steel, Low-Alloy Steel, Silicon Electrical Steel, Ingot Iron, and Wrought
Iron
E351 Test Methods for Chemical Analysis of Cast Iron—All Types
E352 Test Methods for Chemical Analysis of Tool Steels and Other Similar Medium- and High-Alloy Steels
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
The last approved version of this historical standard is referenced on www.astm.org.
E1473 − 22
E353 Test Methods for Chemical Analysis of Stainless, Heat-Resisting, Maraging, and Other Similar Chromium-Nickel-Iron
Alloys
E354 Test Methods for Chemical Analysis of High-Temperature, Electrical, Magnetic, and Other Similar Iron, Nickel, and
Cobalt Alloys
E882 Guide for Accountability and Quality Control in the Chemical Analysis Laboratory
E1019 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
E1601 Practice for Conducting an Interlaboratory Study to Evaluate the Performance of an Analytical Method
E1834 Test Method for Analysis of Nickel Alloys by Graphite Furnace Atomic Absorption Spectrometry
E1835 Test Method for Analysis of Nickel Alloys by Flame Atomic Absorption Spectrometry
E1917 Test Method for Determination of Phosphorus in Nickel, Ferronickel, and Nickel Alloys by Phosphovanadomolybdate
Spectrophotometry
E1938 Test Method for Determination of Titanium in Nickel Alloys by Diantipyrylmethane Spectrophotometry
E2465 Test Method for Analysis of Ni-Base Alloys by Wavelength Dispersive X-Ray Fluorescence Spectrometry
E2594 Test Method for Analysis of Nickel Alloys by Inductively Coupled Plasma Atomic Emission Spectrometry (Performance-
Based)
E2823 Test Method for Analysis of Nickel Alloys by Inductively Coupled Plasma Mass Spectrometry (Performance-Based)
2.2 Other Document:Documents:
ISO 5725 Precision of Test Methods—Determination of Repeatability and Reproducibility for Inter-Laboratory Tests
3. Terminology
3.1 For definitions of terms used in these test methods, refer to Terminology E135.
4. Significance and Use
4.1 These test methods for the chemical analysis of metals and alloys are primarily intended as referee methods to test such
materials for compliance with compositional specifications, particularly those under the jurisdiction of ASTM Committee B02 on
Nonferrous Metals and Alloys. It is assumed that all who use these test methods will be trained analysts capable of performing
common laboratory procedures skillfully and safely. It is expected that work will be performed in a properly equipped laboratory
under appropriate quality control practices such as those described in Guide E882.
5. Apparatus, Reagents, and Instrumental Practice
5.1 Apparatus—Specialized apparatus requirements are listed in the “Apparatus” section in each test method.
5.1.1 In the methods specifying spectrophotometric testing, the cells utilized to contain the reference material and sample solutions
in spectrophotometers are referred to as “absorption cells.” Please note that the radiant energy passed through the cells can be
measured as absorbance or transmittance. These methods refer to absorbance measurements. Refer to Practices E60 for details.
5.2 Reagents:
5.2.1 Purity of Reagents—Unless otherwise indicated, all reagents used in these test methods shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society where such specifications are available. Other
chemicals may be used, provided it is first ascertained that they are of sufficiently high purity to permit their use without adversely
affecting the expected performance of the determination, as indicated in the Precision and Bias sections.
5.2.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water conforming to
Type I or II of Specification D1193. Type III or IV may be used if they effect no measurable change in the blank or sample.
5.3 Spectrophotometric Practice—Spectrophotometric practice prescribed in these test methods shall conform to Practice E60.
Available from American National Standards Institute (ANSI), 25 W. 43rd St., 4th Floor, New York, NY 10036, http://www.ansi.org.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC, www.chemistry.org.www.acs.org. For suggestions on the
testing of reagents not listed by the American Chemical Society, see the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC),
Rockville, MD, http://www.usp.org.
E1473 − 22
6. Interlaboratory Studies and Rounding Calculated Values
6.1 These test methods have been evaluated in accordance with Practice E173 (withdrawn 1997) or ISO 5725. The Reproducibility
R2 of Practice E173 corresponds to the Reproducibility Index R of Practice E1601. The Repeatability R1 of Practice E173
corresponds to the Repeatability Index r of Practice E1601.
6.2 Rounding of test results obtained using this Test Method shall be performed in accordance with Practice E29, Rounding
Method, unless an alternative rounding method is specified by the customer or applicable material specification.
7. Hazards and Sampling
7.1 Hazards—For precautions to be observed in the use of certain reagents and equipment in these test methods, refer to Practices
E50.
7.2 Sampling—For procedures to sample the material, refer to Practices E55 and E88.
MANGANESE BY THE METAPERIODATE SPECTROPHOTOMETRIC METHOD
8. Scope
8.1 This test method covers the determination of manganese from 0.05 % to 2.00 %.
9. Summary of Test Method
9.1 Manganous ions are oxidized to permanganate ions by treatment with periodate. Tungsten, when present in amounts greater
than 0.5 %0.5 %, is kept in solution with H PO . Solutions of the samples are fumed with HClO so that the effect of periodate
3 4 4
is limited to the oxidation of manganese. Spectrophotometric measurements are made at 545 nm.
10. Concentration Range
10.1 The recommended concentration range is from 0.15 mg to 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 or less.
NOTE 1—This test method has been written for cells having a 1-cm light path and a “narrow-band” instrument. The concentration range depends upon
band width and spectral region used as well as cell optical path length. Cells having other dimensions may be used, provided suitable adjustments can
be made in the amounts of sample and reagents used.
11. Stability of Color
11.1 The color is stable for at least 24 h.
12. Interferences
12.1 HClO treatment, which is used in the procedure, yields solutions which can be highly colored due to the presence of
hexavalent chromium Cr(VI) ions. Although these ions and other colored ions in the sample solution undergo no further change
in color quality upon treatment with metaperiodate ion, the following precautions must be observed when filter spectrophotometers
are used: Select a filter with maximum transmittance between 545 nm and 565 nm. The filter must transmit not more than 5 % of
its maximum at a wavelength shorter than 530 nm. The band width of the filter should be less than 30 nm when measured at 50 %
of its maximum transmittance. Similar restrictions apply with respect to the wavelength region employed when other “wide-band”
instruments are used.
12.2 The spectral transmittance curve of permanganate ions exhibits two useful minima, one at approximately 526 nm, and the
other at 545 nm. The latter is recommended when a “narrow-band” spectrophotometer is used.
E1473 − 22
12.3 Tungsten, when present in amounts of more than 0.5 %0.5 %, interferes by producing a turbidity in the final solution. A
special procedure is provided for use with samples containing more than 0.5 % tungsten which eliminates the problem by
preventing the precipitation of the tungsten.
13. Reagents
13.1 Manganese, Standard Solution (1 mL = 0.032 mg Mn)—Transfer the equivalent of 0.4000 g of assayed, high-purity
manganese (purity 99.99 % minimum), to a 500-mL volumetric flask and dissolve in 20 mL of HNO by heating. Cool, dilute to
volume, and mix. Using a pipet, transfer 20 mL to a 500-mL volumetric flask, dilute to volume, and mix.
13.2 HNO -H PO Mixture—Cautiously, while stirring, add 100 mL of HNO and 400 mL of H PO to 400 mL of water. Cool,
3 3 4 3 3 4
dilute to 1 L, and mix. Prepare fresh as needed.
13.3 Potassium Metaperiodate Solution (7.5 g ⁄L)—Dissolve 7.5 g of potassium metaperiodate (KIO ) in 200 mL of hot HNO
4 3
(1 + 1), add 400 mL of H PO , cool, dilute to 1 L, and mix.
3 4
13.4 Water, Pretreated with Metaperiodate—Add 20 mL of KIO solution to 1 L of water, mix, heat at not less than 90 °C for
2020 min to 30 min, and cool. Use this water to dilute solutions to volume that have been treated with KIO solution to oxidize
manganese, and thus avoid reduction of permanganate ions by any reducing agents in the untreated water. (Caution—Avoid the
use of this water for other purposes.)
14. Preparation of Calibration Curve
14.1 Calibration Solutions—Using pipets, transfer (5, 10, 15, 20, and 25) mL of manganese standard solution (1 mL = 0.032 mg
Mn) to 50-mL borosilicate glass volumetric flasks, and, if necessary, dilute to approximately 25 mL. Proceed as directed in 14.3.
14.2 Reference Solution—Transfer approximately 25 mL of water to a 50-mL borosilicate glass volumetric flask. Proceed as
directed in 14.3.
14.3 Color Development—Add 10 mL of KIO solution, and heat the solutions at not less than 90 °C for 20 min to 30 min (Note
2). Cool, dilute to volume with pretreated water, and mix.
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 development.
14.4 Spectrophotometry:
14.4.1 Multiple-Cell Spectrophotometer—Measure the cell correction using the Reference Solution (14.2) in absorption cells with
a 1-cm light path and using a light band centered at approximately 545 nm. Using the test cell, take the spectrophotometric
absorbance readings of the calibration solutions (14.1) versus the reference solution (14.2).
14.4.2 Single-Cell Spectrophotometer—Transfer a suitable portion of the reference solution (14.2) to an absorption cell with a
1-cm light path and adjust the spectrophotometer to the initial setting, using a light band centered at approximately 545 nm. While
maintaining this adjustment, take the spectrophotometric absorbance readings of the calibration solutions.solutions (14.1).
14.5 Calibration Curve—Follow the instrument manufacturer’s instructions for generating the calibration curve. Plot the net
spectrophotometric absorbance readings of the calibration solutions against the milligrams of manganese per 50 mL of solution.
15. Procedure
15.1 Test Solutions—Select and weigh a sample in accordance with the following.as follows.
15.1.1
E1473 − 22
Tolerance in
Manganese, Sample Sample Dilution,
% Weight, g Weight, mg mL
0.01 to 0.5 0.80 0.5 100
0.45 to 1.0 0.35 0.3 100
0.85 to 2.0 0.80 0.5 500
Tolerance in
Manganese, Sample Sample Dilution,
% Mass, g Mass, mg mL
0.01 to 0.5 0.80 0.5 100
0.45 to 1.0 0.35 0.3 100
0.85 to 2.0 0.80 0.5 500
15.1.1 For Samples Containing Not More Than 0.5 % Tungsten—(Warning—See Practices E50 for details pertaining to the
special hazards associated with the use of HClO .)
15.1.1.1 To dissolve samples that do not require HF, add 8 mL to 10 mL of HCl (1 + 1), and heat. Add HNO as needed to hasten
dissolution, and then add 3 mL to 4 mL in excess. When dissolution is complete, cool, then add 10 mL of HClO ;, evaporate to
fumes to oxidize chromium, if present, and to expel HCl. Continue fuming until salts begin to separate. Cool, add 50 mL of water,
and digest if necessary to dissolve the salts. Cool and transfer the solution to a 100-mL volumetric flask. Proceed to 15.1.415.1.3.
15.1.1.2 For samples whose dissolution is hastened by HF, add 8 mL to 10 mL of HCl (1 + 1), and heat. Add HNO and a few
drops of HF as needed to hasten dissolution, and then add 3 mL to 4 mL of HNO . When dissolution is complete, cool, then add
10 mL of HClO , evaporate to fumes to oxidize chromium, if present, and to expel HCl. Continue fuming until salts begin to
separate. Cool, add 50 mL of water, digest if necessary to dissolve the salts, cool, and transfer the solution to either a 100-mL or
500-mL volumetric flask as indicated in 15.1. Proceed to 15.1.415.1.3.
15.1.2 For Samples Containing More Than 0.5 % Tungsten—(Warning—See Practices E50 for details pertaining to the special
hazards associated with the use of HClO.HClO .)
15.1.2.1 To dissolve samples that do not require HF, add 8 mL to 10 mL of H PO , 10 mL of HClO , 5 mL to 6 mL of H SO ,
3 4 4 2 4
and 3 mL to 4 mL of HNO . Heat moderately until the sample is decomposed, and then heat to copious white fumes for 10 min
to 12 min or until the chromium is oxidized and the HCl is expelled,expelled but avoid heating to fumes of SO . Cool, add 50 mL
of water, and digest if necessary to dissolve the salts. Transfer the solution to either a 100-mL or 500-mL volumetric flask as
directed in 15.1. Proceed to 15.1.415.1.3.
15.1.2.2 For samples whose dissolution is hastened by HF, add 8 mL to 10 mL of H PO , 10 mL of HClO , 5 mL to 6 mL of
3 4 4
H SO , 3 mL to 4 mL of HNO , and a few drops of HF. Heat moderately until the sample is decomposed, and then heat to copious
2 4 3
white fumes for 10 min to 12 min or until the chromium is oxidized and the HCl is expelled, but avoid heating to fumes of SO .
Cool, add 50 mL of water, digest if necessary to dissolve the salts, cool, and transfer the solution to a 100-mL or 500-mL volumetric
flask as directed in 15.1.115.1. Proceed to 15.1.415.1.3.
15.1.2.3 Cool the solution, dilute to volume volume, and mix. Allow insoluble matter to settle, or dry-filter dry filter through a
coarse paper and discard the first 15 mL to 20 mL of the filtrate, before taking aliquots.
15.1.3 Using a pipet, transfer 20-mL aliquots to two 50-mL borosilicate glass volumetric flasks; treat one as directed in 15.3 and
the other as directed in 15.4.1.
15.2 Reagent Blank Solution—Carry a reagent blank through the entire procedure using the same amounts of all reagents with the
sample omitted.
15.3 Color Development—Proceed as directed in 14.3.
15.4 Reference Solutions:
15.4.1 Background Color Solution—To one of the sample aliquots in a 50-mL volumetric flask, add 10 mL of HNO -H PO
3 3 4
mixture, and heat the solution at not less than 90 °C for 20 min to 30 min (Note 2). Cool, dilute to volume (with untreated water),
and mix.
E1473 − 22
15.4.2 Reagent Blank Reference Solution—Transfer the reagent blank solution (15.2) to the same size volumetric flask as used for
the test solutions and transfer the same size aliquots as used for the test solutions to two 50-mL volumetric flasks. Treat one portion
as directed in 15.3 and use as reference solution for test samples. Treat the other as directed in 15.4.1 and use as reference solution
for background color solutions.
15.5 Spectrophotometry—Establish the cell corrections with the reagent blank Reference solution to be used as a reference
solution for background color solutions. Take the spectrophotometric absorbance readings of the background color solutions and
the test solutions versus the respective reagent blank reference solutions as directed in 14.4.
16. Calculation
16.1 Convert the net spectrophotometric absorbance reading of the test solution and of the background color solution to milligrams
of manganese by means of the calibration curve. Calculate the percent of manganese as follows:
Manganese, %5 A 2 B / C 310 (1)
~ ! ~ !
where:
A = manganese found in 50 mL of the final test solution, mg,
B = apparent manganese found in 50 mL of the final background color solution, mg, and
C = sample weight represented in 50 mL of the final test solution, g.
C = sample mass represented in 50 mL of the final test solution, g.
17. Precision and Bias
17.1 Precision—Nine laboratories cooperated in testing this test method and obtained the data summarized in Table 1.
17.2 Bias—The biasaccuracy of this test method may be judged by comparing accepted reference values with the corresponding
arithmetic average obtained by interlaboratory testing,has been deemed satisfactory based upon the data for the certified reference
materials in Table 1such as the data listed in. Users are encouraged to use Table 1.these or similar reference materials to verify
that the test method is performing accurately in their laboratories.
SILICON BY THE GRAVIMETRIC METHOD SILICON BY THE GRAVIMETRIC METHOD
18. Scope
18.1 This test method covers the determination of silicon from 0.05 % to 5.00 % in alloys containing not more than 0.1 % boron.
TABLE 1 Statistical Information—Manganese by the –
Metaperiodate Spectrophotometric Method
Repeatability Reproducibility
Manganese
Test Specimen (R , Practice (R , Practice
1 2
Found, %
E173) E173)
1. Nickel alloy, 77Ni-20Cr 0.074 0.002 0.008
(NIST 169, 0.073 % Mn,
certified)
2. High-temperature alloy, 0.289 0.007 0.026
68Ni-14Cr-7Al-6Mo
(NIST 1205, 0.29 % Mn,
not certified)
3. Cobalt alloy, 1.49 0.03 0.08
41Co-20Ni-20Cr-4Mo-4W
(NIST 168, 1.50 % Mn,
(NIST 168, 1.50 % Mn,
not certified)
4. Stainless steel 18Cr-9Ni 1.79 0.07 0.07
(NIST 101e, 1.77 % Mn,
certified)
E1473 − 22
19. Summary of Test Method
19.1 After dissolution of the sample, silicic acid is dehydrated by fuming with sulfuricH SO or HclOHClO acid. . The solution
2 4 4
is filtered, and the impure silica is ignited and weighted.weighed. The silica is then volatilized with HF. The residue is ignited and
weighed; the loss in weightmass represents silica.
20. Interferences
20.1 The elements normally present do not interfere. When boron is present in amounts greater than 0.1 %, the sample solution
requires special treatment with methyl alcohol. However, since no boron steels were tested, this special treatment was not evaluated
and is not described in this test method.
21. Reagents
21.1 The analyst should ensure by analyzing blanks and other checks that possible silicon contamination of reagents will not
significantly bias the results.
21.2 HClO —(Warning—See Practices E50 for details pertaining to the special hazards associated with the use of HClO .)
4 4
21.2.1 Select a lot of HClO that contains not more than 0.0002 % silicon for the analysis of samples containing silicon in the
range from 0.02 % to 0.10 % and not more than 0.0004 % silicon for samples containing more than 0.10 % by determining
duplicate values for silicon as directed in 21.2.2 – 21.2.6.
21.2.2 Transfer 15 mL of HClO (Note 3) to each of two 400-mL beakers. To one of the beakers transfer an additional 50 mL
of HClO . Using a pipet, transfer 20 mL of sodium silicate solution (1 mL = 1.00 mg Si) to each of the beakers. Evaporate the
solutions to fumes and heat for 15 min to 20 min at such a rate that HClO refluxes on the sides of the beakers. Cool sufficiently,
and add 100 mL of water (40 °C to 50 °C).
NOTE 3—The 15-mL addition of HClO can be from the same lot as the one to be tested. Once a lot has been established as having less than 0.0002 %
silicon, it should preferably be used for the 15-mL addition in all subsequent tests of other lots of acid.HClO .
21.2.3 Add paper pulp and filter immediately, using low-ash 11-cm medium-porosity filter papers. Transfer the precipitates to the
papers, and scrub the beakers thoroughly with a rubber-tipped rod. WashRinse the papers and precipitates alternately with 3-mL
to 5-mL portions of hot HCl (1 + 19) and hot water, for a total of six times. Finally washFinally, rinse the papers twice with
H SO (1 + 49). Transfer the papers to platinum crucibles.
2 4
21.2.4 Dry the papers and heat at 600 °C until the carbon is removed. Finally ignite at 1100 °C to 1150 °C to constant weightmass
(at least 30 min). Cool in a desiccator and weigh.
21.2.5 Add enough H SO (1 + 1) to moisten the SiO , and add 3 mL to 5 mL of HF. Evaporate to dryness and then heat at a
2 4 2
gradually increasing rate until H SO is removed. Ignite for 15 min at 1100 °C to 1150 °C, cool in a desiccator, and weigh.
2 4
21.2.6 Calculate the percentage of silicon as follows:
Silicon, %5 @~A 2 B! 2 ~C 2 D!# 30.4674/E 3100 (2)
where:
A = initial weight of crucible plus impure SiO when 65 mL of HClO was taken, g,
2 4
B = final weight of crucible plus impurities when 65 mL of HClO was taken, g,
C = final weight of crucible plus impure SiO when 15 mL of HClO was taken, g,
2 4
D = final weight of crucible plus impurities when 15 mL of HClO was taken, g, and
E = nominal weight (80 g) of 50 mL of HClO .
A = initial mass of crucible plus impure SiO when 65 mL of HClO was taken, g,
2 4
B = final mass of crucible plus impurities when 65 mL of HClO was taken, g,
C = final mass of crucible plus impure SiO when 15 mL of HClO was taken, g,
2 4
D = final mass of crucible plus impurities when 15 mL of HClO was taken, g, and
E = nominal mass (80 g) of 50 mL of HClO .
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21.3 Sodium Silicate Solution (1.00 mg ⁄mL Si)—Transfer 11.0 g of sodium silicate (Na SiO ·9H O) to a 400-mL beaker. Add
2 3 2
150 mL of water and dissolve the salt. Filter through a medium paper, collecting the filtrate in a 1-L volumetric flask, dilute to
volume, and mix. Store in a polyethylene bottle. Use this solution to determine the suitability of the HClO .
21.4 Tartaric Acid Solution (20.6 g/L)—Dissolve 20.6 g of tartaric acid (C H O ) in water, dilute to 1 L, and filter.
4 6 6
21.5 Water—Use freshly prepared Type II water known to be free of silicon. Water distilled from glass, demineralized in columns
containing silicon compounds, or stored for extended periods in glass, or combination thereof, has been known to absorb silicon.
22. Procedure
22.1 Select and weigh a sample in accordance with the following.as follows.
22.1.1
Tolerance Dehydrating Acid, mL
Sample in Sample H SO
2 4
Silicon, % Weight, g Weight, mg (1+4) HClO
0.05 to 0.10 5.0 5 150 75
0.10 to 1.0 4.0 4 100 60
1.0 to 2.0 3.0 3 100 50
2.0 to 5.0 2.0 2 100 40
Tolerance Dehydrating Acid, mL
Sample in Sample
H SO
2 4
Silicon, % Mass, g Mass, mg (1+4) HClO
0.05 to 0.10 5.0 5 150 75
0.10 to 1.0 4.0 4 100 60
1.0 to 2.0 3.0 3 100 50
2.0 to 5.0 2.0 2 100 40
22.1.1 Transfer the sample to a 400-mL beaker or a 300-mL porcelain casserole. Proceed as directed in 22.2 or 22.3.
22.2 H SO Dehydration—Dehydration, if tungsten is greater than 0.5 %.
2 4
22.2.1 Add amounts of HCl or HNO , or mixtures and dilutions of these acids, that are sufficient to dissolve the sample; and then
add the H SO (1 + 4) as specified in 21.1, and cover. Heat until dissolution is complete. Remove and rinse the cover glass;
2 4
substitute a ribbed cover glass.
22.2.2 Evaporate until salts begin to separate; at this point evaporate the solution rapidly to the first appearance of fumes and fume
strongly for 2 min to 3 min. Cool sufficiently, and add 100 mL of water (40 °C to 50 °C). Stir to dissolve the salts and heat, if
necessary, but do not boil. Proceed immediately as directed in 22.4.
22.3 HClO Acid Dehydration—Dehydration, if tungsten is less than 0.5 % or use 22.2. (Warning—See Practices E60E50 for
details pertaining to the special hazards associated with the use of HClO .)
22.3.1 Add amounts of HCl or HNO , or mixtures and dilutions of these acids, which are sufficient to dissolve the sample, and
cover. Heat until dissolution is complete. Add HNO to provide a total of 35 mL to 40 mL, followed by HClO as specified in the
3 4
table in 22.1. Remove and rinse the cover glass; substitute a ribbed cover glass.
22.3.2 Evaporate the solution to fumes and heat for 15 min to 20 min at such a rate that the HClO refluxes on the sides of the
container. Cool sufficiently and add 100 mL of water (40 °C to 50 °C). Stir to dissolve the salts and heat to boiling. If the sample
solution contains more than 100 mg of chromium, add, while stirring, 1 mL of tartaric acid solution for each 25 mg of chromium.
22.4 Add paper pulp and filter immediately, on a low-ash 11-cm medium-porosity filter paper. Collect the filtrate in a 600-mL
beaker. Transfer the precipitate to the paper,paper and scrub the container thoroughly with a rubber-tipped rod. WashRinse the
paper and precipitate alternately with 3-mL to 5-mL portions of hot HCl (1 + 19) and hot water until iron salts are removed but
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for not more than a total of ten washings.rinsings. If 22.3 was followed, washrinse the paper twice more with H SO
2 4
(1 + 49),(1 + 49), but do not collect these washingsrinsings in the filtrate; discard the washings.rinsings. Transfer the paper to a
platinum crucible and reserve.
22.5 Add 15 mL of HNO to the filtrate, stir, and evaporate as directed either in 22.2 or 22.3, depending upon the dehydrating acid
used. Filter immediately, using a low-ash 9-cm 100-porosity filter paper, and washrinse as directed in 22.4.
22.6 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 weightmass (at least 30 min). Cool in a desiccator and
weigh.
22.7 Add enough H SO (1 + 1) to moisten the impure silica (SiO ), and add 3 mL to 5 mL of HF. Evaporate to dryness and then
2 4 2
heat at a gradually increasing rate until H SO . is removed. Ignite at 1100 °C to 1150 °C for 15 min, cool in a desiccator, and weigh.
2 4
If the sample contains more than 0.5 % tungsten, ignite at 750 °C instead of 1100 °C to 1150 °C after volatilization of SiO .
23. Calculation
23.1 Calculate the percent of silicon as follows:
Silicon, %5 A 2 B 30.4674 /C 3100 (3)
@~~ ! ! #
where:
A = initial weight of crucible and impure SiO , g,
A = initial mass of crucible and impure SiO , g,
B = final weight of crucible and residue, g, and
B = final mass of crucible and residue, g, and
C = sample used, g.
24. Precision and Bias
24.1 Precision—Eleven laboratories cooperated in testing this test method and obtained the data summarized in Table 2. A sample
with silicon content near the upper limit of the scope was not available for testing.
24.2 Bias—No data are presently available to determine the accuracy of this method.information on the bias of this test method
is known because at the time of the interlaboratory study, suitable reference materials were not available. The user of this method
is encouraged to employ accepted reference materials, if available, to determine the presence or absence of bias.
COBALT BY THE ION-EXCHANGE-POTENTIOMETRIC
TITRATION METHOD
25. Scope
25.1 This test method covers the determination of cobalt from 2 % to 75 %.
TABLE 2 Statistical Information—Silicon – Gravimetric Method
Repeatability Reproducibility
Test Specimen Silicon Found, % (R , Practice (R , Practice
1 2
E173) E173)
HCIO Dehydration
1. Ni-base alloy 0.029 0.006 0.026
75Ni-12Cr-6Al-
4Mo-2Cb-0.7Ti
H SO Dehydration
2 4
1. Ni-base alloy 0.030 0.007 0.030
75Ni-12Cr-6Al-
4Mo-2Cb-0.7Ti
2. Co-base alloy 1.01 0.03 0.06
66Co-28Cr-4W-1.5Ni
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26. Summary of Test Method
26.1 Cobalt is separated from interfering elements by selective elution from an anion-exchange column using HCl. The cobalt is
oxidized to the trivalent state with ferricyanide, and the excess ferricyanide is titrated potentiometrically with cobalt solution.
27. Interferences
27.1 The elements ordinarily present do not interfere if their contents are under the maximum limits shown in 1.1.
28. Apparatus
28.1 Ion-Exchange Column, approximately 25 mm in diameter and 300 mm in length, tapered at one end, and provided with a
stopcock to control the flow rate, and a second, lower stopcock to stop the flow. A Jones Reductor (Fig. 1), may be adapted to this
method. It consists of a column 19 mm in diameter and 250 mm in length, of 20-mesh to 30-mesh 0.853-mm to 0.599-mm
(20-mesh to 30-mesh) amalgamated zinc. To amalgamate the zinc, shake 800 g of zinc (as free of iron as possible) with 400 mL
of HgCl solution (25 g/L) in a 1-L flask for 2 min. WashRinse several times with H SO (2 + 98), and then thoroughly with water.
2 2 4
The reductor, when idle, should always be kept filled with distilled water to above the top of the zinc. A reservoir for the eluants
may be added at the top of the column.
28.2 Apparatus for Potentiometric Titrations—Instruments for detecting the end points in pH (acid-base), oxidation-reduction,
precipitation and complexation titrations consist of a pair of suitable electrodes, a potentiometer, a buret, and a motor-driven stirrer.
Titrations are based on the fact that follow the principle when two dissimilar electrodes are placed in a solution there is a potential
FIG. 1 Jones Reductor
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difference between them. This potential difference depends on the composition of the solution and changes as the titrant is added.
A high-impedance electronic voltmeter follows the changes accurately. The end point of the titration may be determined by adding
the titrant until the potential difference attains a predetermined value or by plotting the potential difference versus the titrant
volume, the titrant being added until the end point has been passed.
28.2.1 An elaborate or highly sensitive and accurate potentiometer is not necessary for potentiometric titrations because the
absolute cell voltage needs to be known only approximately, and variations of less than 1 MV1 mV are not significant. Such
instruments should have a range of about 1.5 V and a readability of about 1 MV.1 mV. Many pH meters are also suitable for
potentiometric titrations.
28.2.2 The electrode system must consist of a reference electrode and an indicator electrode. The reference electrode maintains
a constant, but not necessarily a known or reproducible potential during the titration. The potential of the indicator electrode does
change during the titration; further, the indicator electrode must be one that will quickly come to equilibrium. In this procedure
a platinum indicator electrode and a saturated calomel reference electrode are appropriate.
28.3 Platinum and a saturated calomel electrodes.
29. Reagents
29.1 Ammonium Citrate Solution (200 g/L).
29.2 Bromine.
29.3 Cobalt, Standard Solution (1 mL = 1.5 mg of Co):
29.3.1 Dry a weighing bottle in an oven at 130 °C for 1 h, cool in a desiccator, and weigh. Transfer 3.945 g of cobalt sulfate
(CoSO ) that has been heated at 550 °C for 1 h to the weighing bottle. Dry the bottle and contents at 130 °C for 1 h, cool in
desiccator, stopper the bottle, and weigh. The difference in weightmass is the amount of CoSO taken. Transfer the weighed CoSO
4 4
to a 400-mL beaker, rinse the weighing bottle with water, and transfer the rinsings to the beaker. Add 150 mL of water and 20 mL
of HNO , and heat to dissolve the salts. Cool, transfer to a 1-L volumetric flask, dilute to volume, and mix.
29.3.2 Standardization—Calculate the cobalt concentration as follows:
Cobalt, mg/mL = weightmg/mL = mass of CoSO , g, × 0.38026
29.4 Ion-Exchange Resin:
29.4.1 Use an anion exchange resin of the alkyl quaternary ammonium type (chloride form) consisting of spherical beads having
a nominal crosslinkagecross-linkage of 8 %, and 200-nominal to 400-nominal mesh0.075-mm to 0.037-mm (200-nominal to
400-nominal mesh) size. To remove those beads greater than about 180 μm in diameter as well as the excessively fine beads, treat
the resin as follows: Transfer a supply of the resin to a beaker, cover with water, and allow sufficient time (at least 30 min) for the
beads to undergo maximum swelling. Place a No. 80 (180-μm)180-μm (No. 80) screen, 150 mm in diameter over a 2-L beaker.
Prepare a thin slurry of the resin and pour it onto the screen. WashRinse the fine beads through the screen, using a small stream
of water. Discard the beads retained on the screen, periodically, if necessary, to avoid undue clogging of the openings. When the
bulk of the collected resin has settled, decant the water and transfer approximately 100 mL of resin to a 400-mL beaker. Add
200 mL of HCl (1 + 19), stir vigorously, allow the resin to settle for 4 min to 6 min, decant 150 mL to 175 mL of the suspension,
and discard. Repeat the treatment with HCl (1 + 19) twice more,more and reserve the coarser resin for the column preparation.
29.4.2 Prepare the column as follows: Place a 10-mm to 20-mm layer of glass wool or polyvinyl chloride plastic fiber in the
bottom of the column, and add a sufficient amount of the prepared resin to fill the column to a height of approximately 140 mm.
Place a 20-mm layer of glass wool or polyvinyl chloride plastic fiber at the top of the resin bed to protect it from being carried
into suspension when the solutions are added. While passing a minimum of 35 mL of HCl (7 + 5)HCl (7 + 5) through the column,
with the hydrostatic head 100 mm above the top of the resin bed, adjust the flow rate to not more than 3.0 mL ⁄min. Drain to 10 mm
to 20 mm above the top of the resin bed and then close the lower stopcock.
Cobalt sulfate (99.9 % minimum) prepared from the hexamine salt by G. Frederick Smith Chemical Co., Columbus, OH, is satisfactory for this purpose.
Available from the Dow Chemical Co., Midland, MI.
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NOTE 4—The maximum limits of 0.125 g of cobalt and a 0.500 g sample (30.1) in the sample solution take into account consider the exchange capacity
of the resin, the physical dimensions of the column, and the volume of eluants.
29.5 Mercuric Chloride Solution, HgCl (25g ⁄L).
29.6 Potassium Ferricyanide, Standard Solution (1 mL = 3.0 mg of Co):
29.6.1 Dissolve 16.68 g of potassium ferricyanide (K Fe(CN) ) in water and dilute to 1 L. Store the solution in a dark-colored
3 6
bottle. Standardize the solution each day before use as follows: Transfer from a 50-mL buret approximately 20 mL of K Fe(CN)
3 6
solution to a 400-mL beaker. Record the buret reading to the nearest 0.01 mL. Add 25 mL of water, 10 mL of ammonium citrate
solution, and 25 mL of NH OH. Cool to 5 °C to 10 °C,10 °C and maintain this temperature during the titration. Transfer the beaker
to the potentiometric titration apparatus. While stirring, titrate the K Fe(CN) with the cobalt solution (1 mL = 1.5 mg Co) using
3 6
a 50-mL buret. Titrate at a fairly rapid rate until the end point is approached, and then add the titrant in one-drop increments through
the end point. After the addition of each increment, record the buret reading and voltage when equilibrium is reached. Estimate
the buret reading at the end point to the nearest 0.01 mL.
29.6.2 Calculate the cobalt equivalent as follows (Note 529.6.2.1):
Cobalt equivalent, mg/mL 5 A 3B /C (4)
~ !
where:
A = cobalt standard solution required to titrate the potassium ferricyanide solution, mL,
B = cobalt standard solution, mg/mL, and
C = potassium ferricyanide solution, mL.
NOTE 5—Duplicate or triplicate values should be obtained for the cobalt equivalent. The values obtained should check within (1 to 2) parts per thousand.
29.6.2.1 Duplicate or triplicate values should be obtained for the cobalt equivalent. The values obtained should check within
1 g ⁄Kg to 2 g ⁄Kg.
30. Procedure
30.1 Proceed as directed in 30.2 – 30.7, using 0.50 g samples for cobalt compositions not greater than 25%; at higher
compositions, use samples that represent between 100 mg and 125 mg of cobalt weighed to the nearest 0.1 mg.
30.2 Transfer a 0.50-g sample to a 150-mL beaker. Add 20 mL of a mixture of five parts of HCl and one part of HNO (Note
630.2.1). Cover the beaker and digest at 60 °C to 70 °C until the sample is decomposed. Rinse and remove the cover. Place a ribbed
cover glass on the beaker and evaporate the solution nearly to dryness, but do not bake. Cool, add 20 mL of HCl (7 + 5),
HCl (7 + 5), and digest at 60 °C to 70 °C until salts are dissolved (approximately 10 min).
NOTE 6—Other ratios and concentrations of acids, with or without the addition of 1 mL to 2 mL of HF, are used for the decomposition of special grades
of alloys.
Some alloys are decomposed more readily by a mixture of 5 mL of bromine, 15 mL of HCl, and one to two drops of HF.
30.2.1 Other ratios and concentrations of acids, with or without the addition of 1 mL to 2 mL of HF, are used for the decomposition
of special grades of alloys.
Some alloys are decomposed more readily by a mixture of 5 mL of bromine, 15 mL of HCl, and one drop to two drops of HF.
30.3 Cool to room temperature and transfer the solution to the ion-exchange column. Place a beaker under the column and open
the lower stopcock. When the solution reaches a level 10 mm to 20 mm above the resin bed, rinse the original beaker with 5 mL
to 6 mL of HCl (7 + 5)HCl (7 + 5) and transfer the rinsings to the column. Repeat this at 2-min intervals until the beaker has been
rinsed four times. WashRinse the upper part of the column with HCl (7 + 5)HCl (7 + 5) two times or three times and allow the
level to drop to 10 mm to 20 mm above the resin bed each time. Maintain the flow rate at not more than 3.0 mL ⁄min and add
HCl (7 + 5)HCl (7 + 5) to the column until a total of 175 mL to 185 mL of solution (sample solution and washings)rinsings)
containing mainly chromium, manganese and nickel is collected (Note 730.3.1). When the solution in the column reaches a level
10 mm to 20 mm above the resin bed, discard the eluate and then use a 400-mL beaker for the collection of the cobalt eluate.
E1473 − 22
NOTE 7—To prevent any loss of cobalt, the leading edge of the cobalt band must not be allowed to proceed any farther than 25 mm from the bottom of
the resin. Normally, when the cobalt has reached this point in the column, the chromium, manganese, and nickel have been removed. Elution can be
stopped at this point, although the total volume collected may be less than 175 mL.
30.3.1 To prevent any loss of cobalt, the leading edge of the cobalt band must not be allowed to proceed any farther than 25 mm
from the bottom of the resin. Normally, when the cobalt has reache
...