ASTM E1409-13(2021)

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: E1409 − 13 (Reapproved 2021)
Standard Test Method for
Determination of Oxygen and Nitrogen in Titanium and
Titanium Alloys by Inert Gas Fusion
This standard is issued under the fixed designation E1409; 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 3. Terminology
1.1 This test method covers the determination of oxygen in 3.1 Definitions—For definitions of terms used in this
titanium and titanium alloys in mass fractions from 0.01 % to method, refer to Terminology E135.
0.5 % and the determination of nitrogen in titanium and
titanium alloys in mass fractions from 0.003 % to 0.11 %. 4. Summary of Test Method
1.2 This standard does not purport to address all of the
4.1 This test method is intended for use with automated,
safety concerns, if any, associated with its use. It is the
commercially available, inert gas fusion analyzers. These
responsibility of the user of this standard to establish appro-
analyzers typically measure both oxygen and nitrogen simul-
priate safety, health, and environmental practices and deter-
taneously or sequentially utilizing parallel measurement sys-
mine the applicability of regulatory limitations prior to use.
tems.
Specific warning statements are given in 8.8.
4.2 The test sample, plus flux, is fused in a graphite crucible
1.3 This international standard was developed in accor-
under a flowing inert gas stream at a temperature sufficient to
dance with internationally recognized principles on standard-
release oxygen and nitrogen. Oxygen combines with carbon to
ization established in the Decision on Principles for the
form carbon monoxide (CO) and nitrogen is released as N .
Development of International Standards, Guides and Recom-
Depending on instrument design, the CO may be oxidized to
mendations issued by the World Trade Organization Technical
carbon dioxide (CO ). The CO or CO , or both, are swept by
2 2
Barriers to Trade (TBT) Committee.
the inert gas stream into either an infrared or thermal conduc-
tivity detector. The detector response generated by analysis of
2. Referenced Documents
the test sample is compared to the response generated by
2.1 ASTM Standards:
analysis of reference materials and the result is displayed as
E50 Practices for Apparatus, Reagents, and Safety Consid-
percent oxygen. The nitrogen is swept by the inert gas stream
erations for Chemical Analysis of Metals, Ores, and
into a thermal conductivity detector. The detector response
Related Materials
generated by analysis of the test sample is compared to the
E135 Terminology Relating to Analytical Chemistry for
response generated by analysis of reference materials and the
Metals, Ores, and Related Materials
result is displayed as percent nitrogen.
E173 Practice for Conducting Interlaboratory Studies of
4.3 Inatypicalinstrumentforthedeterminationofnitrogen,
Methods for Chemical Analysis of Metals (Withdrawn
the sample gases are swept with inert gas through heated rare
1998)
earth/copper oxide that converts CO to CO and hydrogen (H )
2 2
E1601 Practice for Conducting an Interlaboratory Study to
to water (H O). The CO is absorbed on sodium hydroxide
2 2
Evaluate the Performance of an Analytical Method
impregnated on clay, and the H O is removed with magnesium
perchlorate. The nitrogen, as N , enters the measuring cell and
the thermistor bridge output is integrated and processed to
This test method is under the jurisdiction of ASTM Committee E01 on
display percent nitrogen.
Analytical Chemistry for Metals, Ores, and Related Materials and is the direct
responsibility of Subcommittee E01.06 on Ti, Zr, W, Mo, Ta, Nb, Hf, Re.
5. Significance and Use
Current edition approved Dec. 1, 2021. Published February 2022. Originally
approved in 1991. Last previous edition approved in 2013 as E1409 – 13. DOI:
5.1 This test method is primarily intended as a test for
10.1520/E1409-13R21.
compliance with compositional specifications. It is assumed
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
that all who use this test method will be trained analysts
Standards volume information, refer to the standard’s Document Summary page on
capable of performing common laboratory procedures skill-
the ASTM website.
fully and safely. It is expected that the work will be performed
The last approved version of this historical standard is referenced on
www.astm.org. in a properly equipped laboratory.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E1409 − 13 (2021)
6. Interferences 8.8 Titanium Sample Pickle Solution—Three parts 30 %
hydrogen peroxide (H O ) and 1 part 48 % HF. Other pickle
2 2
6.1 The elements usually present in titanium and its alloys
solutions may be substituted if there are data supporting the
do not interfere but there is some evidence to suggest that low
effectiveness of the solution on removing contaminants. For
purity flux can cause some adsorption of the released oxygen.
example, substituting concentrated HNO for 30 % H O has
3 2 2
been found effective (see Note 3). (Warning—HF causes
7. Apparatus
serious burns that may not be immediately painful; refer to the
7.1 Instrument—Fusion and measurement apparatus, auto-
paragraph about HF in the Hazards Section of Practices E50.)
matic oxygen and nitrogen determinator consisting of an
NOTE 3—In 2004, alternative sample preparation procedures (Section
electrode furnace, provision for scrubbing impurities from
12) were tested by seven laboratories. Three laboratories processed the
analytical gas stream; infrared or thermal conductivity mea-
sample materials by pickling their samples in HF-H O (8.8). Two
2 2
surement system(s), or both, and auxiliary gas purification
laboratories utilized the HF-HNO alternative pickle solution (8.8). Two
systems (Note 1).
laboratories utilized abrasion (in this case diamond saw and shear) in
accordance with 12.2. The prepared samples were distributed among the
NOTE 1—Several models of commercial oxygen and nitrogen determi-
laboratories for analysis. Six laboratories analyzed these samples in
nators are available and presently in use by industry. Each has its own
randomorderunderasingleoperator,single-day,singlecalibrationsample
unique design characteristics and operational requirements. Consult the
run. The results of this testing are given in Tables X1.1 and X2.1 for
instrument manufacturer’s instruction manual for operational details.
oxygen and nitrogen, respectively. In both cases, the analysis of variance
(ANOVA) indicates that there is no significant difference at the 95 % level
7.2 Graphite Crucibles—The crucibles must be made of
of confidence for either oxygen or nitrogen due to the preparation
high-puritygraphiteandbeofthedimensionsrecommendedby
technique.
the instrument manufacturer.
7.3 Flux—Flux must be made of high-purity nickel. If
9. Hazards
nickel baskets are used, the dimensions must meet the require-
9.1 Use care when handling hot crucibles and operating
ments of the automatic sample drop, if present, on the
furnaces to avoid personal injury by either burn or electrical
instrument. (See Note 2.) Ultra high-purity nickel flux is
shock.
commerciallyavailableandmayeliminatetheneedtocleanthe
9.2 For precautions to be observed in the use of HF and
flux before using it.
other reagents in this test method, refer to Practices E50.
NOTE2—Insomeinstruments,nitrogenandoxygenarerunsequentially
andplatinumistherequiredfluxfornitrogen.High-purityplatinumcanbe
10. Preparation of Apparatus
substituted for nickel in the same ratio of flux to sample.
10.1 Assemble the apparatus as recommended by the manu-
7.4 Tweezers or Crucible Tongs, made of solvent and acid
facturer. Make the required power, gas, and water connections.
resistant material.
Turnontheinstrumentandallowsufficienttimetostabilizethe
equipment.
8. Reagents
8.1 Acetone—Low residue reagent grade or higher purity. 10.2 Change the chemical reagents and filters as required.
Test the furnace and analyzer to ensure the absence of leaks
8.2 Graphite Powder (optional)—High-purity as specified
(Note 4). A minimum of two test runs using a sample as
by the instrument manufacturer.
directed in 14.3 and 14.4 is recommended to condition the
8.3 Inert Gas—Use the purity and type specified by the
newly changed filters. This should be done before attempting
instrument manufacturer.
to calibrate the system or to determine the value of the blank.
8.4 Magnesium Perchlorate, Anhydrous —Used in the in-
NOTE 4—Typical leak checks should be 0.0 mm Hg to 1.5 mm Hg. The
strument to absorb water. Use the purity specified by the
maximum allowable leak check should follow the manufacturer’s recom-
instrument manufacturer. mendation.
8.5 Nickel Flux Cleaning Solution—An acid solution ca-
11. Nickel Flux Preparation
pable of removing surface contamination from the nickel flux.
Asolution made by combining 75 mLof acetic acid, 25 mLof 11.1 Ultra high-purity nickel is commercially available that
does not require the nickel cleaning procedure below. Its
HNO , and 2 mL of HCl has been found suitable for this
purpose. sufficiency must be verified by satisfactory blank determina-
tions. If ultra high-purity nickel is not used, the nickel must be
8.6 Copper Oxide or Rare Earth/Copper Oxide—Reagent
cleaned to remove contamination (11.2).
used in some instruments to oxidize CO to CO for detection.
Use the purity specified by the instrument manufacturer. 11.2 Immerse the flux in freshly prepared nickel flux clean-
5 ing solution for 50 s to 60 s, then rinse in running water for 2
8.7 Sodium Hydroxide on Clay —Reagent used in some
min to 3 min. Pour flux onto paper towels to remove excess
instruments to absorb CO . Use a purity specified by the
water. Place flux in sealable glass container, rinse with acetone
instrument manufacturer.
and decant. To prevent new oxidation from forming, the flux
may be stored under fresh acetone until used. (See Note 5.)
Known commercially as Anhydrone. NOTE 5—The fluxing agent must be of proper size to be introduced
Known commercially as Ascarite II. through the sample drop mechanism and into the graphite crucible.
E1409 − 13 (2021)
12. Sample Preparation part of the continuous analysis cycle used with the automatic
sample drop, or as the first step in a two-stage cycle associated
12.1 Remove the surface of the sample either mechanically
with the manual addition of the sample to the crucible.)
(12.2) or chemically (12.3). Start with a sample of sufficient
size that the final sample after surface removal will be between
NOTE 6—The use of graphite powder is optional. In some instruments
theadditionofgraphitepowder(0.01gto1.0gdependingoncruciblesize
0.100 g and 0.150 g.
and style) is designed to optimize furnace performance and facilitate the
12.2 To mechanically remove the sample surface, abrade
release of nitrogen from the test sample. Refer to the instrument
with a clean file or similar abrasive device to remove contami- manufacturer’s instructions for recommended graphite powder additions
(Note 1). If graphite powder is used, it must be employed consistently for
nation. Other methods, such as shearing, saw cutting, or
blanks, samples, and reference materials.
turningdownonalathe,maybeemployedforreducingsample
size and removing the surface of the sample. Regardless of the 13.4 Determination of Blank—Proceed as directed in 14.2
method used, the sample must not be allowed to overheat, as and 14.3 with a graphite crucible containing graphite powder
this will adversely affect the results of the analysis. Indications (Note 1 and Note 6) and analyze the nickel flux without a
that the sample has overheated while being worked may sample. Determine the average blank of three to five individual
include discoloration of the metal or the sample becoming too runs and enter this value into the appropriate mechanism of the
analyzer. If each individual result is within 5 µg of the average,
hottohandlewithouttools.Rinsethesampleinacetoneandair
dry. Weight to 60.001 g. Proceed to 12.4. the blank is acceptable. Alternatively, a maximum value may
be used. Values of 0.0005 % for oxygen and 0.00007 % for
12.3 To chemically remove surface contamination, follow
nitrogen have been found adequate. Higher limits may be
12.3.1 and 12.3.2.
appropriate, particularly for reporting results that are not near
12.3.1 Leach the test sample in the titanium sample pickle
the lower end of the scope. If other values are used, data
solution. (Warning—See 8.8.) (see Note 3) until the surface is
showing that they are acceptable must be on file. Problems
clean. This will normally require approximately 5 s from the
withinconsistentorhighblankvaluesmustbecorrectedbefore
timeoftheinitialvigorousreactionbetweenthesampleandthe
the analysis can be continued. If the unit does not have
solution.
provision for automatic blank compensation, then the blank
12.3.2 Immediately remove the reacting test sample and
value must be manually subtracted from the total result prior to
rinse it twice with water and once with acetone and allow to air
any other calculation. Refer to the manufacturer’s instructions
dry. Weigh to 60.001 g.
for proper blanking procedures (Note 6).
12.4 All subsequent operations on the test sample and flux
13.5 Calibration—Follow the calibration procedure recom-
must be done without introducing contamination to either. Use
mended by the manufacturer using titanium reference materi-
only clean tweezers or crucible tongs and never let the test
als.
sample or flux contact the analyst’s skin. In the event this does
13.5.1 Foreachnon-zerocalibrationpoint,weighatitanium
happen, rinse the sample and nickel with acetone and air dry
reference material to the nearest milligram, place it with nickel
before analysis.
flux into an outgassed graphite crucible containing graphite
powder if appropriate (Note 6).
13. Calibration
13.5.2 Proceed as directed in 14.3 and 14.4.
13.1 Reference Materials—Select only titanium or titanium
13.5.3 Repeat 13.5.1 and 13.5.2. Analyze three to five
alloy reference materials such that the high point on the
specimens of each titanium reference material. For each
calibration curves will represent an amount of oxygen and
reference material used to calibrate, calculate the average of
nitrogen that is approximately equal to or greater than the
these results, and compare the average to the certified value for
amount expected in the samples. The accuracy of the test
the reference material. Adjust the instrument output to match
method is dependent upon the accuracy of the methods used to
the certified value unless the average already agrees with the
certify the oxygen and nitrogen values of the reference
certified value within the range of the uncertainty given on the
materials, as well as upon their homogeneity. Thus, wherever
certificate. (Note 7.)
possible, reference materials used to confirm instrument cali-
NOTE 7—Some instruments have expanded computer capabilities that
brationshouldbetraceabletocertifiedreferencematerialsfrom
allow multi-point calibration which may improve the accuracy of the
a national or international metrological institute.
calibration over the single point calibration as tested in the current
interlaboratory study (ILS). Either calibration type may be used.
13.2 Gas Dosing—Automatic and manual gas dosing, rec-
ommendedbysomemanufacturers,canbeusedtocalibratethe
13.5.4 Confirm the calibration by analyzing another speci-
instrument, but instrument response must be verified by cali-
men of the reference material after the calibration procedure is
bration with titanium reference materials because of the fusion
complete. The result should agree with the certified value
characteristics of the furnace/sample combination.
within a suitable confidence interval (Note 8). If the result
agrees with the certified value within the uncertainty provided
13.3 Initial Adjustment of Measurement System (that is,
on the certificate of analysis, the calibration is acceptable.
“warm-up”)—Place a titanium material
...