ASTM D3969-01(2019)e1

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.
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Designation: D3969 − 01 (Reapproved 2019)
Standard Test Method for
Zirconium in Paint Driers by EDTA Method
This standard is issued under the fixed designation D3969; 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.
ε NOTE—Footnote 4 title updated to current edition in October 2019.
1. Scope 2. Referenced Documents
1.1 This test method covers the titrimetric determination of 2.1 ASTM Standards:
zirconiuminzirconiumdriersusedinthecoatingsindustryand D600Specification for Liquid Paint Driers
utilizes the disodium salt of ethylenediaminetetraacetic acid D1193Specification for Reagent Water
dihydrate (EDTA). E180Practice for Determining the Precision of ASTM
Methods for Analysis and Testing of Industrial and Spe-
1.2 This test method is limited to the determination of the
cialty Chemicals (Withdrawn 2009)
zirconium content of a liquid zirconium drier that does not
E300Practice for Sampling Industrial Chemicals
contain other drier elements. The test method is not applicable
to drier blends and does not differentiate hafnium from
3. Summary of Test Method
zirconium.
3.1 The zirconium drier is digested with concentrated sul-
1.3 AllcationsthatcanbetitratedwithEDTAinacidmedia
furic acid and 30% hydrogen peroxide to destroy all organic
interfere and must not be present in the sample.
matter.The diluted solution is boiled with an excess of EDTA,
1.4 This test method has been tested for concentrations of 6 the pH adjusted, and the excess titrated with bismuth nitrate
and 12% zirconium, but there is no reason to believe that it is using xylenol orange as the indicator.
not suitable for higher or lower zirconium concentrations,
4. Significance and Use
provided specimen size is adjusted proportionately.
4.1 The amount of zirconium drier used in oxidizing-type
1.5 The values stated in SI units are to be regarded as
coatings significantly affects their drying properties. This test
standard. No other units of measurement are included in this
method may be used to confirm the stated content of a pure
standard.
liquid zirconium drier manufactured for use by the coatings
1.6 This standard does not purport to address all of the
industry.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
5. Apparatus
priate safety, health, and environmental practices and deter-
5.1 Centrifuge, capable of developing 1000 to 2000 g.
mine the applicability of regulatory limitations prior to use.
1.7 This international standard was developed in accor-
6. Reagents
dance with internationally recognized principles on standard-
6.1 Purity of Reagents—Reagent grade chemicals shall be
ization established in the Decision on Principles for the
used in all tests. Unless otherwise indicated, it is intended that
Development of International Standards, Guides and Recom-
all reagents shall conform to the specifications of the Commit-
mendations issued by the World Trade Organization Technical
tee onAnalytical Reagents of theAmerican Chemical Society,
Barriers to Trade (TBT) Committee.
1 2
This test method is under the jurisdiction of ASTM Committee D01 on Paint For referenced ASTM standards, visit the ASTM website, www.astm.org, or
and Related Coatings, Materials, andApplications and is the direct responsibility of contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved Oct. 1, 2019. Published October 2019. Originally the ASTM website.
approved in 1980. Last previous edition approved in 2012 as D3969–01 (2012). The last approved version of this historical standard is referenced on
DOI: 10.1520/D3969-01R19E01. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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D3969 − 01 (2019)
where such specifications are available. Other grades may be 7. Sampling
used, provided it is first ascertained that the reagent is of
7.1 Take a small sample of liquid drier from bulk using the
sufficiently high purity to permit its use without lessening the
procedure in Practice E300 appropriate for the size of the
accuracy of the determination.
container: section on Bottle Sampling for tanks and tank cars,
or section on Tube Sampling for drums and cans.
6.2 Purity of Water—Unless otherwise indicated, references
towatershallbeunderstoodtomeanreagentwaterconforming
NOTE 3—Liquid driers are normally homogeneous so that only simple
to Type II of Specification D1193.
physicaltests,suchasspecificgravityorsolidscontent,ontopandbottom
samples from tanks, are required to confirm that separation has not
6.3 Ammonium Hydroxide (sp gr 0.90)—Concentrated, am-
occurred.Agitate drums in accordance with section on Tube Sampling in
monium hydroxide (NH OH).
4 Practice E300.
6.4 Bismuth Nitrate, Standard Solution (0.05 M)—Dissolve 7.2 Examine the sample of drier for sediment or suspended
24.25 g of bismuth nitrate (Bi(NO )·5H O) in 20 to 30 mL of matter which, if present, is evidence of noncompliance with
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concentrated nitric acid (use a magnetic stirrer if possible). Specification D600.
After solution is complete, dilute to 1 L with water.
7.3 If the sample is homogeneous keep it in a stoppered
vessel to prevent solvent evaporation prior to analysis.
NOTE 1—Add the water very slowly to the acid solution, while cooling
the flask in an ice bath to prevent splattering.
8. Standardization
6.5 EDTA, Standard Solution(0.05 M)—Dissolve 18.61 g of
8.1 Zinc Chloride, Standard Solution (0.100 M)—Calculate
EDTAin 300 to 500 mL of water and dilute to 1 L. Store in a
the molarity, M , of the zinc chloride (ZnCl ) solution as
polyethylene or borosilicate glass bottle.
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follows:
6.6 Eriochrome Black-T Indicator—Triturate 0.100 g of
S
powdered Eriochrome Black-T with 100 g of sodium chloride 1
M 5 (1)
65.37
(NaCl),andstorethemixtureinatightlystopperedbottle.This
mixture remains stable for several years.
where:
S = zinc used, g, and
6.7 Formic Acid (sp gr 1.22, 90%) HCOOH.
65.37 = zinc to producea1M solution, g/L.
6.8 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
8.2 EDTA, Standard Solution (0.05 M)—Pipet 20 or 25-mL
chloric acid (HCl).
portions (use calibrated pipets) of the standard ZnCl solution
6.9 Hydrogen Peroxide (30%).
into a 250-mL Erlenmeyer flask. Add concentrated NH OH
dropwise until the precipitate which forms redissolves. Add 3
6.10 Isopropyl Alcohol (99.5%).
mL more of NH OH.Add 0.20 to 0.25 g Eriochrome Black-T
6.11 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
indicator mixture and titrate with EDTA until the solu
...