ASTM E367-83(1997)e1
(Test Method)Standard Methods for Chemical Analysis of Ferrocolumbium
Standard Methods for Chemical Analysis of Ferrocolumbium
SCOPE
1.1 These methods cover the chemical analysis of ferrocolumbium having chemical compositions within the following limits: Element Concentration, % Aluminum 2.00 max Carbon 0.30 max Chromium 2.00 max Cobalt 0.25 max Columbium 40.00 to 75.00 Lead 0.01 max Manganese 3.00 max 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 methods appear in the following order: Sections Columbium, Tantalum, and Titanium by the Ion-Exchange Method 9 to 30
1.3 This standard does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of whoever uses this standard to consult and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific precautionary statements are given in Section 5.
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e1
Designation: E 367 – 83 (Reapproved 1997)
Standard Methods for
Chemical Analysis of Ferrocolumbium
This standard is issued under the fixed designation E 367; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
e NOTE—Keywords were added editorially in December 1997.
1. Scope for Determination of Chemical Composition
E 50 Practices for Apparatus, Reagents, and Safety Precau-
1.1 These methods cover the chemical analysis of ferro-
tions for Chemical Analysis of Metals
columbium having chemical compositions within the follow-
E 60 Practice for Photometric and Spectrophotometric
ing limits:
Methods for Chemical Analysis of Metals
Element Concentration, %
E 173 Practice for Conducting Interlaboratory Studies
Aluminum 2.00 max
ofMethods for Chemical Analysis of Metals
Carbon 0.30 max
Chromium 2.00 max
3. Significance and Use
Cobalt 0.25 max
Columbium 40.00 to 75.00
3.1 These methods for the chemical analysis of metals and
Lead 0.01 max
alloys are primarily intended to test such materials for com-
Manganese 3.00 max
pliance with compositional specifications. It is assumed that all
Phosphorus 0.05 max
Silicon 4.00 max
who use these methods will be trained analysts capable of
Sulfur 0.03 max
performing common laboratory procedures skillfully and
Tantalum 7.00 max
safely. It is expected that work will be performed in a properly
Tin 0.15 max
Titanium 5.00 max
equipped laboratory.
Tungsten 0.50 max
4. Apparatus, Reagents, and Photometric Practice
1.2 The methods appear in the following order:
4.1 Apparatus and reagents required for each determination
Sections
are listed in separate sections preceding the procedure. The
Columbium, Tantalum, and Titanium by the apparatus, standard solutions, and other reagents used in more
Ion-Exchange Method 9-30
than one procedure are referred to by number and shall
conform to the requirements prescribed in Practices E 50.
1.3 This standard does not purport to address all of the
Photometers shall conform to the requirements prescribed in
safety concerns, if any, associated with its use. It is the
Practice E 60.
responsibility of whoever uses this standard to consult and
4.2 Photometric practice prescribed in these methods shall
establish appropriate safety and health practices and deter-
conform to Practice E 60.
mine the applicability of regulatory limitations prior to use.
Specific precautionary statements are given in Section 5.
5. Safety Precautions
5.1 For precautions to be observed in the use of certain
2. Referenced Documents
reagents in these methods, refer to Practices E 50.
2.1 ASTM Standards:
A 550 Specification for Ferrocolumbium
6. Sampling
E 29 Practice for Using Significant Digits in Test Data to
6.1 For procedures for sampling the material, and for
Determine Conformance with Specifications
particle size of the sample for chemical analysis, refer to
E 32 Practices for Sampling Ferroalloys and Steel Additives
Practices E 32.
7. Rounding Off Calculated Values
These methods are under the jurisdiction of ASTM Committee E-1 on
7.1 Calculated values shall be rounded off to the desired
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct
responsibility of Subcommittee E01.01 on Iron, Steel, and Ferroalloys.
number of places as directed in 3.4 to 3.6 of Practice E 29.
Current edition approved Sept. 30, 1983. Published December 1983. Originally
published as E 367 – 70 T. Last previous edition E 367 – 74 (1979).
8. Interlaboratory Studies
Annual Book of ASTM Standards, Vol 01.02.
Annual Book of ASTM Standards, Vol 14.02. 8.1 These methods have been evaluated in accordance with
Annual Book of ASTM Standards, Vol 03.05.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
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E 367
Practice E 173, unless otherwise noted in the precision and bias fittings of polystyrene have been developed for such an
section. assembly. Inlet and outlet tubes are polyethylene; flexible
connections, where necessary, are of polyvinyl tubing. The
COLUMBIUM, TANTALUM, AND TITANIUM BY THE
flow rate is controlled by hosecocks on these flexible connec-
ION-EXCHANGE METHOD
tions. The system must be carefully assembled and checked to
avoid possible leakage of the solutions containing hydrofluoric
9. Scope
acid.
9.1 These methods cover the determination of columbium,
12.2 Plastic Ware—Polyethylene, polypropylene, or TFE-
tantalum, and titanium in ferrocolumbium in concentrations
fluorocarbon.
from 40 to 75 %, 0.25 to 7 %, and 0.05 to 5.0 %, respectively.
12.2.1 Bottles, 250-mL and 1-L capacity.
12.2.2 Graduated Cylinders, 50 and 250-mL capacity.
10. Summary of Test Method
12.2.3 Griffın-Form Beakers and Covers, 250 and 600-mL,
10.1 The sample is dissolved in a hydrochloric-hydrofluoric
and 1-L capacity.
acid mixture and transferred to an anion-exchange column.
13. Reagents
Titanium, iron, and other elements are eluted with an ammo-
nium chloride-hydrochloric-hydrofluoric acid mixture. This 13.1 Ammonium Chloride Solution (240 g/L)—Dissolve
eluate is treated with boric acid and cupferron, and the 480 g of ammonium chloride (NH Cl) in 1600 mL of water by
precipitate, containing the titanium, is ignited, fused with warming, cool, dilute to 2 L, and mix. Filter, if necessary. Use
potassium hydrogen sulfate, and leached in dilute sulfuric acid. this stock solution to prepare the solutions described in
The titanium is oxidized to the yellow pertitanate with hydro- 13.2-13.4.
gen peroxide. Photometric measurement is made at approxi-
13.2 Ammonium Chloride-Ammonium Fluoride Neutral
mately 410 nm. Columbium is removed by eluting with an Mixture—Transfer 600 mL of the NH Cl solution and 40 mL of
ammonium chloride-hydrofluoric acid mixture. Tantalum is
HF to a plastic beaker. Adjust the pH to 5 to 6 with NH OH
removed by eluting with an ammonium chloride-ammonium (approximately 80 to 85 mL will be required), dilute to 1 L with
fluoride solution adjusted to a pH of 5 to 6. The eluates are water, and mix.
treated with the boric acid to complex the fluorides, and each
NOTE 1—This solution must be prepared with care. If the pH is too low,
of the elements, columbium and tantalum, is precipitated with
the volume specified will not completely elute the tantalum; if the pH is
cupferron, ignited, and weighed as the pentoxide. For tantalum
too high, tantalum will precipitate in the column, thus leading to error in
in concentrations below 1 %, zirconium is added as a gatherer
the determinations being run as well as the one which follows.
in the cupferron separation and the tantalum is converted to the
13.3 Ammonium Chloride-Hydrochloric-Hydrofluoric Acid
pyrogallol complex. Photometric measurement is made at
Mixture—Transfer 240 mL of the NH Cl solution, 200 mL of
approximately 420 nm.
HF and 150 mL of HCl to a plastic bottle. Dilute to 1 L with
water, and mix.
11. Interferences
13.4 Ammonium Chloride-Hydrofluoric Acid Mixture—
11.1 Any bismuth present will appear in the tantalum
Transfer 600 mL of the NH Cl solution and 40 mL of HF to a
fraction, but this element is seldom present in concentrations
plastic bottle. Dilute to 1 L with water, and mix.
greater than 0.005 % in this ferroalloy. Trivalent antimony, if
13.5 Ammonium Nitrate Wash Solution (20 g/L)—Dissolve
present, is eluted with the titanium and precipitated with
20 g of ammonium nitrate (NH NO ) in water, and dilute to 1
4 3
cupferron, but it does not interfere in the photometric method
L.
for titanium.
13.6 Boric Acid (H BO ).
3 3
13.7 Cupferron Solution (60 g/L)—Reagent No. 115. This
12. Apparatus
solution should be prepared fresh as needed and cooled to 5°C
12.1 Ion-Exchange Columns—The columns must be con-
before use.
structed of polystyrene tubing approximately 300-mm long and
13.8 Cupferron Wash Solution—Add 25 mL of cupferron
25 mm in inside diameter. A suitable column can be prepared
solution (13.7) to 975 mL of cold HCl (1 + 9), and mix. Prepare
as follows: Insert a waxed, No. 5 rubber stopper containing a
as needed.
5-mm hole into the bottom of the polystyrene tube. Insert into
13.9 Hydrochloric-Hydrofluoric Acid Mixture—Add 250
the hole and flush with the upper surface of the stopper a
mL of HCl to 300 mL of water, add 200 mL of HF, dilute to 1
150-mm length of polystyrene tubing, having a 5-mm outside
L with water, and mix.
diameter and a 2-mm bore. Attach another 150-mm length of
13.10 Hydrogen Peroxide (H O ), 30 %.
2 2
this tubing to the smaller tube with an approximately 50-mm
13.11 Ion-Exchange Resin—Strongly basic anion-exchange
length of polyvinyl tubing, and control the flow rate by a
resin, 200 to 400 mesh, 8 to 10 % divinyl-benzene cross
hosecock on the polyvinyl tubing.
linkage. Since the mesh size of the resin may vary consider-
12.1.1 If a number of determinations are to be made, it is
ably from lot to lot, air-dry the resin and pass it through a No.
convenient to arrange the columns so that they can be operated
with a minimum of attention. Plastic columns equipped with
Columns available from Ledoux and Co., Inc., Teaneck, NJ, have been found
satisfactory for this purpose.
Dowex I anion-exchange resin has been found satisfactory. Comparable results
Tygon-R tubing has been found satisfactory for this purpose. may not be obtained with other resins.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
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E 367
270 (53-μm) sieve (Note 2). Most of the fines are removed solution clears (Note 4). Digest on the steam bath for 20 to 30
from the fraction passing the No. 270 sieve as follows: Prepare min to remove nitrous oxide fumes. Rinse the plastic cover and
a suspension of the resin in HCl (1 + 9). Allow the coarser wall of the beaker with the HCl-HF acid mixture, and dilute the
fraction to settle 10 to 15 min and remove the fines by solution to 70 mL with the same acid mixture.
decantation. Repeat the process several times until most of the
NOTE 4—The addition of HNO should be kept to a minimum because
very fine material has been removed from the suspension.
of its strong replacing power for columbium on the exchange column.
Approximately 6 to 8 drops will be required.
NOTE 2—Material retained on the No. 270 sieve may be used for other
purposes.
15.2 Transfer 50 mL of HCl-HF acid mixture to the column
in 5 to 10-mL increments. Drain the acid to a level 100 mm
13.12 Oxalate-Citrate-Sulfuric Acid Solution—Dissolve 35
above the resin bed, collecting the eluate in a 600-mL plastic
g of ammonium oxalate ((NH ) C O ·H O) and 35 g of
4 2 2 4 2
beaker. Transfer the sample solution in 5 to 10-mL increments
diammonium hydrogen citrate ((NH ) HC H O )in1L of
4 2 8 5 7
to the column. As the sample solution moves down the column,
H SO (1 + 39).
2 4
continue to add the small increments until all of the solution
13.13 Pyrogallol—(C H -1,2,3-(OH) ).
6 3 3
has been transferred. Wash the beaker four or five times with
13.14 Sodium Hydroxide Solution (100 g/L)—Dissolve 20 g
4-mL portions of the HCl-HF acid mixture, transferring the
of sodium hydroxide (NaOH) in 150 mL of water, cool, dilute
washings to the column. Wash the sides of the column with 10
to 200 mL, and mix. Store in a plastic bottle.
to 15 mL of the HCl-HF acid mixture followed by several
13.15 Tantalum, Standard Solution (1 mL 5 0.500 mg
washings with the NH Cl-HCl-HF acid mixture.
Ta)—Transfer 0.1221 g of tantalum pentoxide (Ta O )toa 4
2 5
15.3 Pass a total of 300 mL of the NH Cl-HCl-HF acid
platinum crucible. Add 2.5 g of potassium hydrogen sulfate
mixture through the column at a flow rate of approximately 100
(KHSO ) and heat to fuse the oxide. Dissolve the cooled melt
to 125 mL/h. Allow the solution to drain to the top of the resin.
in warm oxalate-citrate-sulfuric acid solution. Transfer to a
Remove the beaker containing the first fraction and reserve this
200-mL volumetric flask, cool, dilute to volume with oxalate-
solution for the determination of titanium. Replace the beaker
citrate-sulfuric acid solution and mix.
with another 600-mL plastic beaker.
13.16 Titanium, Standard Solution (1 mL 5 0.100 mg Ti)—
15.4 Wash the sides of the column with four or five portions
Transfer 0.0834 g of titanium dioxide (TiO ) to a platinum
(a total of about 25 mL) of the NH Cl-HF acid mixture,
crucible. Add1gof KHSO , and heat to fuse the oxide. Cool,
allowing the solution to drain to the top of the resin each time.
and dissolve the melt in 50 mL of warm H SO (1 + 9). Cool,
2 4
Pass a total of 300 mL of the NH Cl-HF acid mixture through
transfer to a 500-mL volumetric flask, dilute to volume with
the column at the flow rate specified in 15.3 (Note 5). Remove
H SO (1 + 9), and mix.
2 4
the beaker containing the second fraction and reserve this
13.17 Zirconium Solution (1 mL 5 1 mg Zr)—Dissolve 0.5
solution for the determination of columbium. Replace the
g of zirconium metal in 10 mL of HF in a plastic bottle, and
beaker with another 600-mL plastic beaker.
dilute to 500 mL. An equivalent amount of zirconyl chloride
may be substituted for the zirconium metal.
NOTE 5—This point in the preparation of the test solutions provides a
convenient and satisfactory place to stop, for example overnight, if the
14. Preparation of Ion-Exchange Column
elutions otherwise cannot be carried through as a continuous operation.
14.1 Placea6to 10-mm layer of acid-resistant poly(vinyl
15.5 Wash the sides of the column with five or six 5-mL
chloride) plastic fiber in the bottom of the column. Add the
portions of the NH Cl-NH F neutral mixture. Pass a total of
4 4
resin suspension in small portions to obtain a settled bed of the
350 mL of the NH Cl-NH F neutral mixture through the
4 4
resin 150 to 180-mm high. Wash the column with approxi-
column, at the flow rate specified in 15.3. Remove the beaker
mately 100 mL of HNO (1 + 9), and then perform three elution
containing the third fraction and reserve this solution for the
cycles with alternate additions of 100 mL of HCl (1 + 9) and
determination of tantalum as directed in Section 23 or Section
100 mL of HCl (3 + 1) to remove the remainder of the fines.
28. Prepare the column for the next sample by adding 50 mL
Finally, wash the column with 200 mL of HCl (1 + 3) to a level
of HCl (1 + 3) in 10-mL incremen
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