ASTM E367-22

Standard Test Methods for Chemical Analysis of Ferroniobium

SIGNIFICANCE AND USE
4.1 These test methods for the chemical analysis of ferroniobium alloy are primarily intended to test such materials for compliance with compositional specifications such as Specification A550. 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.
SCOPE
1.1 These test methods cover the chemical analysis of ferroniobium having chemical compositions within the following limits:    
Element  
Composition, %  
Aluminum  
2.00 max  
Carbon  
0.30 max  
Chromium  
2.00 max  
Cobalt  
0.25 max  
Lead  
0.01 max  
Manganese  
3.00 max  
Niobium  
40.00 to 75.00  
Phosphorus  
0.05 max  
Silicon  
4.00 max  
Sulfur  
0.03 max  
Tantalum  
7.00 max  
Tin  
0.15 max  
Titanium  
5.00 max  
Tungsten  
0.50 max  
1.2 The test methods appear in the following order:    
Sections  
Separation of Niobium, Tantalum, and Titanium by the Ion-Exchange Test Method  
15 and 16  
Titanium by the Spectrophotometric Test Method [0.05 % to 5.0 %]  
17 – 21  
Niobium by the Gravimetric Test Method [40 % to 75 %]  
22 – 23  
Tantalum by the Gravimetric Test Method [1 % to 7 %]  
24 – 25  
Tantalum by the Spectrophotometric Test Method [0.25 % to 1 %]  
26 – 30  
1.3 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.4 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 consult and establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use. Specific hazard statements are given in Section 6, and specific warning statements in 11.1.  
1.5 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.

General Information

• Status: Published
• Publication Date: 14-Jun-2022
• ICS: 77.040.30 - Chemical analysis of metals
• Technical Committee: E01 - Analytical Chemistry for Metals, Ores, and Related Materials
• Drafting Committee: E01.01 - Iron, Steel, and Ferroalloys

Relations

• 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 E135-19 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-May-2019
• 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 E50-11(2016) - Standard Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
• Effective Date: 01-Aug-2016
• Refers: ASTM E135-16 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-May-2016
• Refers: ASTM A550-06(2015) - Standard Specification for Ferrocolumbium
• Effective Date: 15-Nov-2015
• Refers: ASTM E135-15a - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 01-Jul-2015
• Refers: ASTM E135-15 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-May-2015
• Refers: ASTM E135-14b - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-Aug-2014
• Refers: ASTM E135-14a - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 01-Apr-2014
• Refers: ASTM E135-14 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-Feb-2014
• Refers: ASTM E135-13a - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 01-Dec-2013
• Refers: ASTM E1601-12 - Standard Practice for Conducting an Interlaboratory Study to Evaluate the Performance of an Analytical Method
• Effective Date: 15-Dec-2012
• Refers: ASTM E50-11 - Standard Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
• Effective Date: 15-Oct-2011

Overview

ASTM E367-22: Standard Test Methods for Chemical Analysis of Ferroniobium provides comprehensive procedures and guidance for the accurate chemical analysis of ferroniobium alloys. Issued by ASTM International, this standard is designed to verify compliance with compositional specifications, such as Specification A550, ensuring material quality and fitness for purpose. The methods covered within facilitate the determination of key alloying and residual elements critical to the ferroniobium manufacturing and supply chain, supporting both laboratory best practices and industry requirements.

Key Topics

• Scope of Determination: The standard covers the analysis of ferroniobium alloys with a niobium content of 40 to 75% and imposes specified maximum values for elements such as aluminum, carbon, chromium, cobalt, lead, manganese, phosphorus, silicon, sulfur, tantalum, tin, titanium, and tungsten.
• Analytical Techniques:
  • Ion-exchange method: Used for the separation of niobium, tantalum, and titanium.
  • Spectrophotometric determination: Applied to quantify titanium (0.05% to 5.0%) and low levels of tantalum (0.25% to 1%).
  • Gravimetric analysis: Employed for the determination of niobium (40-75%) and higher concentrations of tantalum (1-7%).
• Supporting Practices: Guidance on sampling procedures, rounding of results, use of reagent and solution purity, safety practices, and laboratory equipment requirements.
• Precision and Bias: The document outlines the importance of using reference materials to validate the accuracy and reproducibility of results, as required for certifiable laboratory quality assurance.

Applications

ASTM E367-22 is vital for various stakeholders within the metal, ferroalloy, and steel industries where ferroniobium is used as a critical alloying addition. Its practical applications include:

• Quality Control: Ensuring ferroniobium batches comply with contractual or regulatory chemical specifications, especially during procurement and acceptance processes.
• Production Monitoring: Supporting manufacturers in controlling alloy composition, reducing variability, and maintaining process consistency.
• Research and Development: Providing reliable, referenced methods necessary for the development of new materials or alloys with customized properties.
• Certification and Traceability: Facilitating the required documentation and analytical proof needed for certification schemes, such as those driven by international trade, safety, and performance standards.
• Safety Assurance: Highlighting procedures for safe laboratory practice, particularly when dealing with hazardous reagents such as hydrofluoric acid.

Related Standards

These standards are referenced in or complement ASTM E367-22:

• ASTM A550 – Specification for Ferrocolumbium (Ferroniobium)
• ASTM D1193 – Specification for Reagent Water
• ASTM E29 – Practice for Using Significant Digits in Test Data
• ASTM E32 – Practices for Sampling Ferroalloys and Steel Additives
• ASTM E50 – Practices for Apparatus, Reagents, and Safety Considerations
• ASTM E60 – Practice for Analysis by Spectrophotometry
• ASTM E135 – Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• ASTM E1601 – Practice for Conducting an Interlaboratory Study (supersedes E173)
• ISO and WTO Principles – Developed in accordance with internationally recognized guidelines on standardization

Practical Value

Complying with ASTM E367-22 ensures that laboratories and producers can confidently assess the chemical composition of ferroniobium, underpinning the material's use in demanding steel and alloy applications. With standardized test methods verified for accuracy and precision, the standard bolsters quality control, facilitates regulatory compliance, and supports supply chain reliability in global markets.

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: E367 − 22
Standard Test Methods for
Chemical Analysis of Ferroniobium
This standard is issued under the fixed designation E367; 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 prior to use. Specific hazard statements are given in Section 6,
and specific warning statements in 11.1.
1.1 These test methods cover the chemical analysis of
1.5 This international standard was developed in accor-
ferroniobium having chemical compositions within the follow-
dance with internationally recognized principles on standard-
ing limits:
ization established in the Decision on Principles for the
Element Composition, %
Development of International Standards, Guides and Recom-
Aluminum 2.00 max
Carbon 0.30 max mendations issued by the World Trade Organization Technical
Chromium 2.00 max
Barriers to Trade (TBT) Committee.
Cobalt 0.25 max
Lead 0.01 max
2. Referenced Documents
Manganese 3.00 max
Niobium 40.00 to 75.00
2.1 ASTM Standards:
Phosphorus 0.05 max
Silicon 4.00 max A550 Specification for Ferrocolumbium (Ferroniobium)
Sulfur 0.03 max
D1193 Specification for Reagent Water
Tantalum 7.00 max
E29 Practice for Using Significant Digits in Test Data to
Tin 0.15 max
Titanium 5.00 max Determine Conformance with Specifications
Tungsten 0.50 max
E32 Practices for Sampling Ferroalloys and Steel Additives
1.2 The test methods appear in the following order: for Determination of Chemical Composition
E50 Practices for Apparatus, Reagents, and Safety Consid-
Sections
Separation of Niobium, Tantalum, and 15 and 16
erations for Chemical Analysis of Metals, Ores, and
Titanium by the Ion-Exchange Test Method
Related Materials
E60 Practice for Analysis of Metals, Ores, and Related
Titanium by the Spectrophotometric Test 17–21
Method [0.05 % to 5.0 %]
Materials by Spectrophotometry
E135 Terminology Relating to Analytical Chemistry for
Niobium by the Gravimetric Test Method 22–23
Metals, Ores, and Related Materials
[40 % to 75 %]
E173 Practice for Conducting Interlaboratory Studies of
Tantalum by the Gravimetric Test Method 24–25
Methods for Chemical Analysis of Metals (Withdrawn
[1%to7%]
1997)
Tantalum by the Spectrophotometric Test 26–30
E1601 Practice for Conducting an Interlaboratory Study to
Method [0.25 % to 1 %]
Evaluate the Performance of an Analytical Method
1.3 Units—The values stated in SI units are to be regarded
as standard. No other units of measurement are included in this
3. Terminology
standard.
3.1 For definition of terms used in this test method, refer to
1.4 This standard does not purport to address all of the
Terminology E135.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to consult and 4. Significance and Use
establish appropriate safety, health, and environmental prac-
4.1 These test methods for the chemical analysis of fer-
tices and determine the applicability of regulatory limitations
roniobium alloy are primarily intended to test such materials
1 2
These test methods are under the jurisdiction of ASTM Committee E01 on For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
responsibility of Subcommittee E01.01 on Iron, Steel, and Ferroalloys. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved June 15, 2022. Published July 2022. Originally the ASTM website.
approved in 1970. Last previous edition approved in 2016 as E367 – 16. DOI: The last approved version of this historical standard is referenced on
10.1520/E0367-22. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E367 − 22
for compliance with compositional specifications such as E1601. The Reproducibility R2 corresponds to the Reproduc-
Specification A550. It is assumed that all who use these test ibility Index R of Practice E1601. The Repeatability R1 of
methods will be trained analysts capable of performing com-
Practice E173 corresponds to the Repeatability Index r of
mon laboratory procedures skillfully and safely. It is expected Practice E1601.
that work will be performed in a properly equipped laboratory.
10. Scope
5. Apparatus, Reagents, and Spectrophotometric Practice
10.1 These test methods cover the determination of
5.1 Apparatus, standard solutions, and other reagents re-
niobium, tantalum, and titanium in ferroniobium from 40 % to
quired for each determination are listed in separate sections
75 %, 0.25 % to 7 %, and 0.05 % to 5.0 %, respectively.
preceding the procedure. Spectrophotometers shall conform to
the requirements prescribed in Practice E60.(Note 1.)
11. Summary of Test Method
NOTE 1—In these methods, cells utilized to contain the reference
material and sample solutions in spectrophotometers are referred to as
11.1 The sample is dissolved in a HCl-HF acid mixture and
“absorption cells.” Please note that the radiant energy passed through the
transferred to an anion-exchange column. Titanium, iron, and
cellscanbemeasuredasabsorbanceortransmittance.Thesemethodsrefer
to absorbance measurements. Refer to Practice E60 for details. other elements are eluted with a NH Cl-HCl-HF solution. This
eluate is treated with boric acid (H BO ) and cupferron, and
3 3
5.2 Spectrophotometric practice prescribed in these test
the precipitate, containing the titanium, is ignited, fused with
methods shall conform to Practice E60.
potassium hydrogen sulfate, and leached in dilute H SO . The
2 4
5.3 Purity of Water—Unless otherwise indicated, references
titanium is oxidized to the yellow pertitanate with hydrogen
to water shall be understood to mean reagent water conforming
peroxide. Spectrophotometric absorbance measurement is
to Type I or Type II of Specification D1193. Type III or Type
made at 410 nm. Niobium is removed by eluting with a
IV may be used if they effect no measurable change in the
NH Cl-HF solution. Tantalum is removed by eluting with a
blank or sample.
NH Cl-NH F solution adjusted to a pH of 5 to 6. The eluates
4 4
5.4 Purity of Reagents—Reagent grade chemicals shall be
are treated with the H BO to complex the fluorides, and each
3 3
used in all tests. Unless otherwise indicated, it is intended that
of the elements, niobium and tantalum, is precipitated with
all reagents conform to the specifications of the Committee on
cupferron, ignited, and weighed as the pentoxide. For tantalum
Analytical Reagents of the American Chemical Society where
below 1 %, zirconium is added as a gatherer in the cupferron
such specifications are available. Other grades may be used,
separation and the tantalum is converted to the pyrogallol
provided it is first ascertained that the reagent is of sufficiently
complex. Spectrophotometric absorbance measurement is
high purity to permit its use without lessening the accuracy of
made at 420 nm. (Warning—HF produces very serious burns
the determination.
which may or may not be painful on first contact. Such burns
often damage bone and other tissue within the body. Standard
6. Hazards
procedure is to use gloves and protective clothing when
6.1 For precautions to be observed in the use of certain
handling this reagent. After the material is added, the closed
reagents in these test methods, refer to Practices E50.
container,gloves,andallsurfacesthatmaylaterbetouchedare
rinsed with large quantities of water. Even one drop of HF on
6.2 Specific warning statements are given in 11.1.
the skin or fingernail must receive immediate first-aid and
medical attention should be promptly sought.)
7. Sampling
7.1 For procedures to sample the material, and particle size
12. Interferences
requirements of the sample, refer to Practices E32.
12.1 Any bismuth present will appear in the tantalum
8. Rounding Calculated Values
fraction, but this element is seldom present greater than
8.1 Rounding of test results obtained using this test method
0.005 % in this ferroalloy. Trivalent antimony, if present, is
shall be performed as directed in Practice E29, Rounding
eluted with the titanium and precipitated with cupferron, but it
Method, unless an alternative rounding method is specified by
does not interfere in the spectrophotometric test method for
the customer or applicable material specification.
titanium.
9. Interlaboratory Studies
13. Apparatus
9.1 These test methods have been evaluated in accordance
13.1 Ion-Exchange Columns—The columns must be con-
withPracticeE173,unlessotherwisenotedintheprecisionand
structedofpolystyrenetubingapproximately300 mminlength
bias section. Practice E173 has been replaced by Practice
and 25 mm in inside diameter. A suitable column can be
prepared as follows: Insert a waxed, No. 5 rubber stopper
containinga5 mmholeintothebottomofthepolystyrenetube.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Insert into the hole and flush with the upper surface of the
listed by the American Chemical Society, see Analar Standards for Laboratory
stopper a 150 mm length of polystyrene tubing, having a 5 mm
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
outside diameter and a 2 mm bore. Attach another 150 mm
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. length of this tubing to the smaller tube with an approximately
E367 − 22
50 mmlengthofpolyvinyltubing, andcontroltheflowrateby 14.9 Hydrochloric-Hydrofluoric Acid Solution—Add 250
a hosecock on the polyvinyl tubing. mL of HCl to 300 mL of water, add 200 mL of HF, dilute to 1
13.1.1 If a number of determinations are to be made, it is L with water, and mix.
convenient to arrange the columns so that they can be operated
14.10 Hydrogen Peroxide (H O ), 30 %.
2 2
with a minimum of attention. Plastic columns equipped with
14.11 Ion-Exchange Resin—Strongly basic anion-exchange
fittings of polystyrene have been developed for such an
resin, 0.075 mm to 0.037 mm (200 mesh to 400 mesh), 8 % to
assembly. Inlet and outlet tubes are polyethylene; flexible
10 %divinyl-benzenecrosslinkage. Sincethesizeoftheresin
connections, where necessary, are of polyvinyl tubing. The
mayvaryconsiderablyfromlottolot,air-drytheresinandpass
flow rate is controlled by hosecocks on these flexible connec-
it through a 53 µm (No. 270) sieve (Note 2). Most of the fines
tions. The system must be carefully assembled and checked to
are removed from the fraction passing the 53 µm (No. 270)
avoid possible leakage of the solutions containing HF.
sieve as follows: Prepare a suspension of the resin in HCl
13.2 Plastic Ware—Polyethylene, polypropylene, or TFE-
(1 + 9). Allow the coarser fraction to settle 10 min to 15 min
fluorocarbon.
and remove the fines by decantation. Repeat the process
13.2.1 Bottles, 250 mL and 1 L capacity.
several times until most of the very fine material has been
13.2.2 Graduated Cylinders, 50 mL and 250 mL capacity.
removed from the suspension.
13.2.3 Griffın-Form Beakers and Covers, 250 mL, 600 mL,
NOTE 2—Material retained on the 53 µm (No. 270) sieve may be used
and 1 L capacity.
for other purposes.
14.12 Oxalate-Citrate-Sulfuric Acid Solution—Dissolve 35
14. Reagents
g of ammonium oxalate ((NH ) C O ·H O) and 35 g of
4 2 2 4 2
14.1 Ammonium Chloride Solution (240 g/L)—Dissolve
diammonium hydrogen citrate ((NH ) HC H O)in1Lof
4 2 8 5 7
480 g of ammonium chloride (NH Cl) in 1600 mLof water by
H SO (1 + 39).
2 4
warming, cool, dilute to 2 L, and mix. Filter, if necessary. Use
14.13 Potassium Hydrogen Sulfate (KHSO ).
this stock solution to prepare the solutions described in 14.2 –
14.4.
14.14 Pyrogallol (C H -1,2,3-(OH) ).
6 3 3
14.2 Ammonium Chloride-Ammonium Fluoride Neutral
14.15 Sodium Hydroxide Solution(100g/L)—Dissolve20g
Solution—Transfer 600 mL of the NH Cl solution and 40 mL
of NaOH in 150 mLof water, cool, dilute to 200 mL, and mix.
of HF to a plastic beaker. Adjust the pH from 5 to 6 with
Store in a plastic bottle.
NH OH (approximately 80 mL to 85 mL will be required),
14.16 Tantalum, Standard Solution(1mL = 0.500mgTa)—
dilute to 1 L with water, and mix.
Transfer 0.1221 g of tantalum pentoxide (Ta O ) to a platinum
2 5
14.2.1 This solution must be prepared with care. If the pH is
crucible. Add 2.5 g of potassium hydrogen sulfate (KHSO )
too low, the volume specified will not completely elute the
and heat to fuse the oxide. Dissolve the cooled melt in warm
tantalum; if the pH is too high, tantalum will precipitate in the
oxalate-citrate-sulfuric acid solution. Transfer to a 200 mL
column,thusleadingtoerrorinthedeterminationsbeingrunas
volumetric flask, cool, dilute to volume with oxalate-citrate-
well as the one which follows.
sulfuric acid solution, and mix.
14.3 Ammonium Chloride-Hydrochloric-Hydrofluoric Acid
14.17 Titanium, Standard Solution (1 mL = 0.100 mg Ti)—
Solution—Transfer 240 mL of the NH Cl solution, 200 mL of
Transfer 0.0834 g of titanium dioxide (TiO ) to a platinum
HF and 150 mL of HCl to a plastic bottle. Dilute to 1 L with
crucible.Add1gof KHSO , and heat to fuse the oxide. Cool,
water, and mix.
and dissolve the melt in 50 mL of warm H SO (1 + 9). Cool,
2 4
14.4 Ammonium Chloride-Hydrofluoric Acid Solution—
transfer to a 500 mL volumetric flask, dilute to volume with
Transfer 600 mL of the NH Cl solution and 40 mL of HF to a
H SO (1 + 9), and mix.
2 4
plastic bottle. Dilute to 1 L with water, and mix.
14.18 Zirconium Solution (1 mL = 1 mg Zr)—Dissolve 0.5
14.5 Ammonium Nitrate Wash Solution (20 g/L)—Dissolve
g of zirconium metal in 10 mL of HF in a plastic bottle, and
20 g of ammonium nitrate (NH NO ) in water, and dilute to 1
4 3
dilute to 500 mL. An equivalent amount of zirconyl chloride
L.
may be substituted for the zirconium metal.
14.6 Boric Acid (H BO ).
3 3
14.7 Cupferron Solution (60 g/L)—Dissolve6gof cupfer-
SEPARATION OF NIOBIUM, TANTALUM, AND
ron in 80 mL of cold water, dilute to 100 mL, and filter. This
TITANIUM BY THE ION-EXCHANGE TEST
solution should be prepared fresh as needed and cooled to 5 °C
METHOD
before use.
15. Preparation of Ion-Exchange Column
14.8 Cupferron Wash Solution—Add 25 mL of cupferron
15.1 Place a 6 mm to 10 mm layer of acid-resistant poly-
solution(14.7)to975mLofcoldHCl(1 + 9),andmix.Prepare
(vinyl chloride) plastic fiber in the bottom of the column. Add
as needed.
Dowex I anion-exchange resin is a trademark of the Dow Chemical Company
Tygon-R tubing is a trademark of Saint-Gobain Performance Plastics Corpo- and has been found satisfactory for this purpose. Comparable results may not be
ration and has been found satisfactory for this purpose. obtained with other resins.
E367 − 22
the resin suspension in small portions to obtain a settled bed of determination of tantalum as directed in Section
...

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: E367 − 16 E367 − 22
Standard Test Methods for
Chemical Analysis of Ferroniobium
This standard is issued under the fixed designation E367; 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 cover the chemical analysis of ferroniobium having chemical compositions within the following limits:
Element Composition, %
Aluminum 2.00 max
Carbon 0.30 max
Chromium 2.00 max
Cobalt 0.25 max
Lead 0.01 max
Manganese 3.00 max
Niobium 40.00 to 75.00
Phosphorus 0.05 max
Silicon 4.00 max
Sulfur 0.03 max
Tantalum 7.00 max
Tin 0.15 max
Titanium 5.00 max
Tungsten 0.50 max
1.2 The test methods appear in the following order:
Sections
Separation of Niobium, Tantalum, and 15 and 16
Titanium by the Ion-Exchange Test Method
Titanium by the Spectrophotometric Test 17 – 21
Method [0.05 % to 5.0 %]
Niobium by the Gravimetric Test Method 22 – 23
[40 % to 75 %]
Tantalum by the Gravimetric Test Method 24 – 25
[1 % to 7 %]
Tantalum by the Spectrophotometric Test 26 – 30
Method [0.25 % to 1 %]
1.3 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this
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 responsibility
of Subcommittee E01.01 on Iron, Steel, and Ferroalloys.
Current edition approved May 1, 2016June 15, 2022. Published June 2016July 2022. Originally approved in 1970. Last previous edition approved in 20092016 as
E367 – 09.E367 – 16. DOI: 10.1520/E0367-16.10.1520/E0367-22.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E367 − 22
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of whoever uses the user of this standard to consult and establish appropriate safety safety, health, and healthenvironmental
practices and determine the applicability of regulatory limitations prior to use. Specific hazard statements are given in Section 6,
and specific warning statements in 11.1.
1.5 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:
A550 Specification for Ferrocolumbium (Ferroniobium)
D1193 Specification for Reagent Water
E29 Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
E32 Practices for Sampling Ferroalloys and Steel Additives for Determination of Chemical Composition
E50 Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
E60 Practice for Analysis of Metals, Ores, and Related Materials by Spectrophotometry
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)
E1601 Practice for Conducting an Interlaboratory Study to Evaluate the Performance of an Analytical Method
3. Terminology
3.1 For definition of terms used in this test method, refer to Terminology E135.
4. Significance and Use
4.1 These test methods for the chemical analysis of ferroniobium alloy are primarily intended to test such materials for compliance
with compositional specifications such as Specification A550. 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.
5. Apparatus, Reagents, and Spectrophotometric Practice
5.1 Apparatus, standard solutions, and other reagents required for each determination are listed in separate sections preceding the
procedure. Spectrophotometers shall conform to the requirements prescribed in Practice E60. (Note 1.)
NOTE 1—In these methods, 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 Practice E60 for details.
5.2 Spectrophotometric practice prescribed in these test methods shall conform to Practice E60.
5.3 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water conforming to
Type I or Type II of Specification D1193. Type III or Type IV may be used if they effect no measurable change in the blank or
sample.
5.4 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society where such
specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
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.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by
the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
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6. Hazards
6.1 For precautions to be observed in the use of certain reagents in these test methods, refer to Practices E50.
6.2 Specific warning statements are given in 11.1.
7. Sampling
7.1 For procedures to sample the material, and particle size requirements of the sample, refer to Practices E32.
8. Rounding Calculated Values
8.1 Calculated values shall be rounded to the desired number of places Rounding of test results obtained using this test method
shall be performed as directed in Practice E29., Rounding Method, unless an alternative rounding method is specified by the
customer or applicable material specification.
9. Interlaboratory Studies
9.1 These test methods have been evaluated in accordance with Practice E173, unless otherwise noted in the precision and bias
section. Practice E173 has been replaced by Practice E1601. The Reproducibility R2 corresponds to the Reproducibility Index R
of Practice E1601. The Repeatability R1 of Practice E173 corresponds to the Repeatability Index r of Practice E1601.
10. Scope
10.1 These test methods cover the determination of niobium, tantalum, and titanium in ferroniobium from 40 % to 75 %, 0.25 %
to 7 %, and 0.05 % to 5.0 %, respectively.
11. Summary of Test Method
11.1 The sample is dissolved in a HCl-HF acid mixture and transferred to an anion-exchange column. Titanium, iron, and other
elements are eluted with a NH Cl-HCl-HF solution. This eluate is treated with boric acid (H BO ) and cupferron, and the
4 3 3
precipitate, containing the titanium, is ignited, fused with potassium hydrogen sulfate, and leached in dilute H SO . The titanium
2 4
is oxidized to the yellow pertitanate with hydrogen peroxide. Spectrophotometric absorbance measurement is made at 410 nm.
Niobium is removed by eluting with a NH Cl-HF solution. Tantalum is removed by eluting with a NH Cl-NH F solution adjusted
4 4 4
to a pH of 5 to 6. The eluates are treated with the H BO to complex the fluorides, and each of the elements, niobium and tantalum,
3 3
is precipitated with cupferron, ignited, and weighed as the pentoxide. For tantalum below 1 %, zirconium is added as a gatherer
in the cupferron separation and the tantalum is converted to the pyrogallol complex. Spectrophotometric absorbance measurement
is made at 420 nm. (Warning—HF produces very serious burns which may or may not be painful on first contact. Such burns often
damage bone and other tissue within the body. Standard procedure is to use gloves and protective clothing when handling this
reagent. After the material is added, the closed container, gloves, and all surfaces that may later be touched are rinsed with large
quantities of water. Even one drop of HF on the skin or fingernail must receive immediate first-aid and medical attention should
be promptly sought.)
12. Interferences
12.1 Any bismuth present will appear in the tantalum fraction, but this element is seldom present greater than 0.005 % in this
ferroalloy. Trivalent antimony, if present, is eluted with the titanium and precipitated with cupferron, but it does not interfere in
the spectrophotometric test method for titanium.
13. Apparatus
13.1 Ion-Exchange Columns—The columns must be constructed of polystyrene tubing approximately 300-mm300 mm in length
and 25 mm in inside diameter. A suitable column can be prepared as follows: Insert a waxed, No. 5 rubber stopper containing a
5-mm5 mm hole into the bottom of the polystyrene tube. Insert into the hole and flush with the upper surface of the stopper a
150-mm150 mm length of polystyrene tubing, having a 5-mm5 mm outside diameter and a 2-mm2 mm bore. Attach another
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150-mm150 mm length of this tubing to the smaller tube with an approximately 50-mm50 mm length of polyvinyl tubing, and
control the flow rate by a hosecock on the polyvinyl tubing.
13.1.1 If a number of determinations are to be made, it is convenient to arrange the columns so that they can be operated with
a minimum of attention. Plastic columns equipped with fittings of polystyrene have been developed for such an assembly. Inlet
and outlet tubes are polyethylene; flexible connections, where necessary, are of polyvinyl tubing. The flow rate is controlled by
hosecocks on these flexible connections. The system must be carefully assembled and checked to avoid possible leakage of the
solutions containing HF.
13.2 Plastic Ware—Polyethylene, polypropylene, or TFE-fluorocarbon.
13.2.1 Bottles, 250-mL250 mL and 1-L1 L capacity.
13.2.2 Graduated Cylinders, 50-mL 50 mL and 250-mL250 mL capacity.
13.2.3 Griffın-Form Beakers and Covers, 250-mL, 600-mL,250 mL, 600 mL, and 1-L1 L capacity.
14. Reagents
14.1 Ammonium Chloride Solution (240 g/L)—Dissolve 480 g of ammonium chloride (NH Cl) in 1600 mL of water by warming,
cool, dilute to 2 L, and mix. Filter, if necessary. Use this stock solution to prepare the solutions described in 14.2 – 14.4.
14.2 Ammonium Chloride-Ammonium Fluoride Neutral Solution—Transfer 600 mL of the NH Cl solution and 40 mL of HF to
a plastic beaker. Adjust the pH from 5 to 6 with NH OH (approximately 80 mL to 85 mL will be required), dilute to 1 L with water,
and mix.
14.2.1 This solution must be prepared with care. If the pH is too low, the volume specified will not completely elute the tantalum;
if the pH is too high, tantalum will precipitate in the column, thus leading to error in the determinations being run as well as the
one which follows.
14.3 Ammonium Chloride-Hydrochloric-Hydrofluoric Acid Solution—Transfer 240 mL of the NH Cl solution, 200 mL of HF and
150 mL of HCl to a plastic bottle. Dilute to 1 L with water, and mix.
14.4 Ammonium Chloride-Hydrofluoric Acid Solution—Transfer 600 mL of the NH Cl solution and 40 mL of HF to a plastic
bottle. Dilute to 1 L with water, and mix.
14.5 Ammonium Nitrate Wash Solution (20 g/L)—Dissolve 20 g of ammonium nitrate (NH NO ) in water, and dilute to 1 L.
4 3
14.6 Boric Acid (H BO ).
3 3
14.7 Cupferron Solution (60 g/L)—Dissolve 6 g of cupferron in 80 mL of cold water, dilute to 100 mL, and filter. This solution
should be prepared fresh as needed and cooled to 5 °C before use.
14.8 Cupferron Wash Solution—Add 25 mL of cupferron solution (14.7) to 975 mL of cold HCl (1 + 9), and mix. Prepare as
needed.
14.9 Hydrochloric-Hydrofluoric Acid Solution—Add 250 mL of HCl to 300 mL of water, add 200 mL of HF, dilute to 1 L with
water, and mix.
14.10 Hydrogen Peroxide (H O ), 30 %.
2 2
14.11 Ion-Exchange Resin—Strongly basic anion-exchange resin, 200 0.075 mm to 0.037 mm (200 mesh to 400 mesh,mesh), 8 %
Tygon-R tubing is a trademark of Saint-Gobain Performance Plastics Corporation and has been found satisfactory for this purpose.
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to 10 % divinyl-benzene cross linkage. Since the mesh size of the resin may vary considerably from lot to lot, air-dry the resin
and pass it through a No. 270 (53-μm)53 μm (No. 270) sieve (Note 2). Most of the fines are removed from the fraction passing
the No. 270 53 μm (No. 270) sieve as follows: Prepare a suspension of the resin in HCl (1 + 9). Allow the coarser fraction to settle
10 min to 15 min and remove the fines by decantation. Repeat the process several times until most of the very fine material has
been removed from the suspension.
NOTE 2—Material retained on the No. 270 53 μm (No. 270) sieve may be used for other purposes.
14.12 Oxalate-Citrate-Sulfuric Acid Solution—Dissolve 35 g of ammonium oxalate ((NH ) C O ·H O) and 35 g of diammonium
4 2 2 4 2
hydrogen citrate ((NH ) HC H O ) in 1 L of H SO (1 + 39).
4 2 8 5 7 2 4
14.13 Potassium Hydrogen Sulfate (KHSO ).
14.14 Pyrogallol (C H -1,2,3-(OH) ).
6 3 3
14.15 Sodium Hydroxide Solution (100 g/L)—Dissolve 20 g of NaOH in 150 mL of water, cool, dilute to 200 mL, and mix. Store
in a plastic bottle.
14.16 Tantalum, Standard Solution (1 mL = 0.500 mg Ta)—Transfer 0.1221 g of tantalum pentoxide (Ta O ) to a platinum
2 5
crucible. Add 2.5 g of potassium hydrogen sulfate (KHSO ) and heat to fuse the oxide. Dissolve the cooled melt in warm
oxalate-citrate-sulfuric acid solution. Transfer to a 200-mL200 mL volumetric flask, cool, dilute to volume with oxalate-citrate-
sulfuric acid solution, and mix.
14.17 Titanium, Standard Solution (1 mL = 0.100 mg Ti)—Transfer 0.0834 g of titanium dioxide (TiO ) to a platinum crucible.
Add 1 g of KHSO , and heat to fuse the oxide. Cool, and dissolve the melt in 50 mL of warm H SO (1 + 9). Cool, transfer to
4 2 4
a 500-mL500 mL volumetric flask, dilute to volume with H SO (1 + 9), and mix.
2 4
14.18 Zirconium Solution (1 mL = 1 mg Zr)—Dissolve 0.5 g of zirconium metal in 10 mL of HF in a plastic bottle, and dilute
to 500 mL. An equivalent amount of zirconyl chloride may be substituted for the zirconium metal.
SEPARATION OF NIOBIUM, TANTALUM, AND TITANIUM BY THE ION-EXCHANGE TEST METHOD
15. Preparation of Ion-Exchange Column
15.1 Place a 6-mm6 mm to 10-mm10 mm layer of acid-resistant poly(vinyl chloride) plastic fiber in the bottom of the column.
Add the resin suspension in small portions to obtain a settled bed of the resin 150-mm150 mm to 180-mm180 mm in height. Wash
the column with approximately 100 mL of HNO (1 + 9), and then perform three elution cycles with alternate additions of 100
mL of HCl (1 + 9) and 100 mL of HCl (3 + 1) to remove
...