ASTM D4563-02(2022)

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: D4563 − 02 (Reapproved 2022)
Standard Test Method for
Determination by Atomic Absorption Spectroscopy of
Titanium Dioxide Content of Pigments Recovered From
Whole Paint
This standard is issued under the fixed designation D4563; 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 E288 Specification for Laboratory Glass Volumetric Flasks
1.1 This test method covers the atomic absorption (AA)
3. Summary of Test Method
analysis of titanium dioxide content in pigments recovered
3.1 The specimen is prepared for analysis by ashing at
from whole paint. It is applicable to quality control situations
450 °C followed by digestion with sulfuric acid and ammo-
where the same type of product is repeatedly analyzed.
nium sulfate as in Test Methods D1394. The titanium content
1.2 The values stated in SI units are to be regarded as
is determined by atomic absorption spectroscopy using a
standard. No other units of measurement are included in this
specimen similar to that previously analyzed by theAluminum
standard.
Reduction Method in Test Methods D1394.
1.3 This standard does not purport to address all of the
3.2 By utilizing the pigment analyzed in Test Methods
safety concerns, if any, associated with its use. It is the
D1394 as an atomic absorption standard, several hundred TiO
responsibility of the user of this standard to establish appro-
determinations can be made. TheAAtechnique is much faster
priate safety, health, and environmental practices and deter-
than the technique in Test Methods D1394 for multiple
mine the applicability of regulatory limitations prior to use.
determinations and uses only acids. This keeps reagents and
Specific hazard statements are given in Section 7.
time to a minimum.
1.4 This international standard was developed in accor-
dance with internationally recognized principles on standard-
4. Significance and Use
ization established in the Decision on Principles for the
4.1 This test method may be used in quality control labo-
Development of International Standards, Guides and Recom-
ratories when the repeated analysis of titanium dioxide in
mendations issued by the World Trade Organization Technical
similar paints may be required. Reagents and time are kept to
Barriers to Trade (TBT) Committee.
a minimum when this test method is used in place of wet
chemical analysis such as in Test Methods D1394. However,
2. Referenced Documents
reproducibility and repeatability are not as good as in Test
2.1 ASTM Standards:
Methods D1394.
D1193 Specification for Reagent Water
D1394 Test Methods for Chemical Analysis of White Tita-
5. Apparatus
nium Pigments
5.1 Atomic Absorption Spectrophotometer, consisting of
E180 Practice for Determining the Precision of ASTM
5.1.1 Atomizer and nitrous oxide burner,
Methods for Analysis and Testing of Industrial and Spe-
5.1.2 Gas-pressure regulator and metering devices for ni-
cialty Chemicals (Withdrawn 2009)
trous oxide and acetylene,
5.1.3 Titanium hollow cathode lamp with regulated
constant-current supply,
This test method is under the jurisdiction of ASTM Committee D01 on Paint
5.1.4 Monochromator and associated optics,
and Related Coatings, Materials, andApplications and is the direct responsibility of
Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials. 5.1.5 Photosensitive detector connected to an electronic
Current edition approved Dec. 1, 2022. Published December 2022. Originally
amplifier,
approved in 1986. Last previous edition approved in 2015 as D4563 – 02 (2015).
5.1.6 Readout device.
DOI: 10.1520/D4563-02R22.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
5.2 Muffle Furnace, capable of maintaining 450 °C 6
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
25 °C.
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
5.3 Circulating Oven, maintained at 105 °C 6 2 °C.
The last approved version of this historical standard is referenced on
www.astm.org. 5.4 Porcelain Dishes, 90-mm diameter.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4563 − 02 (2022)
5.5 Plastic Disposable Syringe, 10-mL capacity. 7. Hazards
5.6 Agate Mortar and Pestle, 95-mm outside diameter. 7.1 Concentrated Hydrofluoric Acid—Make certain to ob-
serve manufacturer’s recommended precautions for handling.
5.7 Wide-Mouth Erlenmeyer Flask, 500-mL capacity.
7.2 Warning—Nitrous oxide and acetylene can cause
5.8 Hot Plate, with variable surface temperature control
explosions, if not used properly. See the supplier’s manual of
from10 °Caboveambientto370 °Caccuratetowithin 65 °C.
instructions for the atomic absorption instrument for proper
5.9 Burner.
operation with these gases.
5.10 Volumetric Flask, 1000 mL, plastic (see Specification
8. Calibration and Standardization
E288).
8.1 Operational instructions for atomic absorption spectro-
5.11 Paint Shaker.
photometers vary with different models. Consult the manufac-
5.12 Weighing Bottles, wide-mouth, with an external-fitting
turer’s literature for establishing optimum conditions for the
cap, and no larger than necessary for required amount of
specific instrument used.
sample.
8.2 Turn the instrument on and set the wavelength to the
5.13 Desiccator.
365.3-nm titanium line.Apply the recommended current to the
titanium hollow cathode lamp. Allow the instrument to warm
6. Reagents
upforabout15minandsettheproperslitwidth.Adjustthegas
6.1 Purity of Reagents—Reagent grade chemicals shall be
pressures and ignite the burner in accordance with instructions
used in all tests. Unless otherwise indicated, it is intended that
for using nitrous oxide and acetylene.
all reagents shall conform to the specifications of the Commit-
8.3 Aspirate the water to rinse the atomizer chamber from
tee onAnalytical Reagents of theAmerican Chemical Society,
10 min to 15 min until the burner head achieves temperature
where such specifications are available. Other grades may be
equilibrium. Set the instrument reading to zero while doing
used, provided it is first ascertained that the reagent is of
this. While aspirating the working standard from 6.7.2 set the
sufficient high purity to permit its use without reducing the
instrument to the percent TiO (determined in 6.7.1). Reaspi-
accuracy of the determination.
rate the water and reset the instrument to ZERO. Repeat this
6.2 Purity of Water—Unless otherwise indicated, references
procedure until the readings become stable.
towatershallbeunderstoodtomeanreagentwaterconforming
8.3.1 Expanding the scale of a spectrophotometer increases
to Type II of Specification D1193.
the noise level of the readout system. Therefore, if expanding
the scale to make the readout indicate 60 % TiO has this
6.3 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
effect, do not use any expansion. For instance, it is not
monium hydroxide (NH OH).
necessary to make the instrument read 60 for 60 % TiO
6.4 Ammonium Sulfate (NH ) SO ).
4 2 4
standard. It may read 30. If 60 % equals 30, a pigment giving
6.5 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro- a reading of 25 would have a TiO content of 50 %.
chloric acid (HCl).
PIGMENT CONTENT
6.6 Hydrofluoric Acid (HF)—Approximately 49 %.
6.7 Standard Pigment Solution. 9. Procedure
6.7.1 Following the procedure in Section 9 recover the
9.1 Mix the samples until homogenous, preferably on a
pigment from a paint that is similar to the unknown specimen.
mechanical shaker. If air bubbles become entrapped in the
Analyze the extracted pigment for TiO content in accordance
sample, stir by hand.
with theAluminum Reduction Method inTest Methods D1394
9.2 Draw approximately5gofthe paint under test into a
and record the percent TiO found in the pigment.
10-mL syringe and weigh to 1 mg. Transfer, by dropwise
6.7.2 Following the procedure in 12.1 – 12.5 take a speci-
addition, between 2.0 g and 4.0 g of the specimen to a tared
men of the pigment extracted in 6.7.1 into solution. Store this
porcelaindishcontainingeither2mLofwater(forwater-borne
solution for no more than 3 months in a plastic bottle marked
paint) or 2 mL of toluene (for solvent-borne paint). Reweigh
with the percent TiO as determined in 6.7.1.
the syringe to 1 mg. Swirl the dish during the addition of the
6.8 Sulfuric Acid (sp gr 1.84), concentrated sulfuric acid
paint and continue to swirl until the specimen is completely
(H SO ).
2 4
dispersed. If a water-borne paint tends to agglomerate or form
lumps that cannot be dispersed, a drop or two of concentrated
6.9 Toluene.
NH OH may help the dispersement. If the lumps persist,
discard the specimen,
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