ASTM D4017-02

Standard Test Method for Water in Paints and Paint Materials by Karl Fischer Method

SIGNIFICANCE AND USE
Control of water content is often important in controlling the performance of paint and paint ingredients, and it is critical in controlling volatile organic compound (VOC) content.
Paint materials are often insoluble in common Karl Fischer solvents such as methanol. Pyridine has been found to be a nearly universal solvent for these materials; however, the Karl Fischer reaction is too slow in that solvent at room temperature. To speed it up, 1-ethylpiperidine is added at 5 % as a buffer, or “catalyst”.
For nonpyridine based reagents, a number of different solvent systems are available to increase solubility and to minimize interferences from ketones and aldehydes.
SCOPE
1.1 This test method is applicable to all paints and paint materials, including resins, monomers, and solvents, with the exception of aldehydes and certain active metals, metal oxides, and metal hydroxides. While the evaluation was limited to pigmented products containing amounts of water in the 30 to 70% range, there is reason to believe that higher and lower concentrations can be determined by this test method.
1.2  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 establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific hazard statements are given in Section 7.

General Information

• Status: Historical
• Publication Date: 09-Jan-2002
• ICS: 87.040 - Paints and varnishes
• Technical Committee: D01 - Paint and Related Coatings, Materials, and Applications
• Drafting Committee: D01.21 - Chemical Analysis of Paints and Paint Materials

Relations

• Replaces: ASTM D4017-96a - Standard Test Method for Water in Paints and Paint Materials by Karl Fischer Method
• Effective Date: 10-Jan-2002
• Replaced By: ASTM D4017-02(2008)e1 - Standard Test Method for Water in Paints and Paint Materials by Karl Fischer Method
• Effective Date: 01-Feb-2008
• Referred By: ASTM D7358-07(2018) - Standard Test Method for Water Content of Paints by Quantitative Calcium Hydride Reaction Test Kit
• Effective Date: 10-Jan-2002
• Referred By: ASTM D4143-16(2022) - Standard Guide for Testing Latex Vehicles
• Effective Date: 10-Jan-2002
• Referred By: ASTM D6336-11(2021) - Standard Practice for Evaluation of Flushing Vehicles for Pigment Wetting Using a Vacuum Modified Sigma Blade Mixer
• Effective Date: 10-Jan-2002
• Referred By: ASTM D5325-03(2021) - Standard Test Method for Determination of Weight Percent Volatile Content of Water-Borne Aerosol Paints
• Effective Date: 10-Jan-2002
• Referred By: ASTM D6886-18 - Standard Test Method for Determination of the Weight Percent Individual Volatile Organic Compounds in Waterborne Air-Dry Coatings by Gas Chromatography
• Effective Date: 10-Jan-2002
• Referred By: ASTM D3960-05(2018) - Standard Practice for Determining Volatile Organic Compound (VOC) Content of Paints and Related Coatings
• Effective Date: 10-Jan-2002
• Referred By: ASTM E1868-10(2021) - Standard Test Methods for Loss-On-Drying by Thermogravimetry
• Effective Date: 10-Jan-2002
• Referred By: ASTM D2827-19 - Standard Specification for Styrene Monomer
• Effective Date: 10-Jan-2002
• Referred By: ASTM D7768-12(2018) - Standard Test Method for Speciated Organic Volatile Content of Waterborne Multi-Component Coatings by Gas Chromatography
• Effective Date: 10-Jan-2002
• Referred By: ASTM D6511/D6511M-18 - Standard Test Methods for Solvent Bearing Bituminous Compounds
• Effective Date: 10-Jan-2002
• Referred By: ASTM D5324-16(2022) - Standard Guide for Testing Water-Borne Architectural Coatings
• Effective Date: 10-Jan-2002
• Referred By: ASTM D7270-07(2021) - Standard Guide for Environmental and Performance Verification of Factory-Applied Liquid Coatings
• Effective Date: 10-Jan-2002
• Referred By: ASTM E203-23 - Standard Test Method for Water Using Volumetric Karl Fischer Titration
• Effective Date: 10-Jan-2002

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation:D4017–02
Standard Test Method for
1
Water in Paints and Paint Materials by Karl Fischer Method
This standard is issued under the fixed designation D4017; 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 (e) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the Department of Defense.
1. Scope electrometric end point. The sluggish reaction with water in
pyridine is accelerated with a chemical catalyst,
1.1 This test method is applicable to all paints and paint
1-ethylpiperidine.
materials, including resins, monomers, and solvents, with the
3.1.1 Karl Fischer reagent is a mixture of iodine, amine,
exceptionofaldehydesandcertainactivemetals,metaloxides,
sulfur dioxide, and an alcohol. In the reaction with water,
and metal hydroxides. While the evaluation was limited to
iodine is reduced to hydrogen iodide. Once all the water is
pigmented products containing amounts of water in the 30 to
consumed, the appearance of free iodine is detected electro-
70% range, there is reason to believe that higher and lower
chemically and the titration is stopped. The following depicts
concentrations can be determined by this test method.
the chemistry that takes place:
1.2 This standard does not purport to address all of the
ROH+SO +RN↔ (RNH)SO R
safety concerns, if any, associated with its use. It is the 2 3
HO+I +(RNH)SO R+2RN→ (RNH)SO R+2(RNH)I
2 2 3 4
responsibility of the user of this standard to establish appro-
3.2 In classical Karl Fischer titrations the base used is
priate safety and health practices and determine the applica-
pyridine, and the solvent either methanol or methoxy ethanol.
bility of regulatory limitations prior to use. Specific hazard
In order to accelerate the reaction when pyridine is used,
statements are given in Section 7.
1-ethylpiperidine is used as a catalyst/buffer. The additional
2. Referenced Documents buffer capacity is usually already built in to most nonpyridine
6
based reagents such as hydranal (see Hydranal Manual).
2.1 ASTM Standards:
2
D1193 Specification for Reagent Water
4. Significance and Use
D3960 Practice for Determining Volatile Organic Com-
3
4.1 Control of water content is often important in control-
pound (VOC) Content of Paint and Related Coatings
ling the performance of paint and paint ingredients, and it is
E180 Practice for Determining the Precision of ASTM
critical in controlling volatile organic compound (VOC) con-
Methods for Analysis and Testing of Industrial and Spe-
4
tent.
cialty Chemicals
4.2 Paint materials are often insoluble in common Karl
E203 TestMethodforWaterUsingVolumetricKarlFischer
4
Fischer solvents such as methanol. Pyridine has been found to
Titration
be a nearly universal solvent for these materials; however, the
2.2 Other Standard:
Karl Fischer reaction is too slow in that solvent at room
EPA Federal Reference Method 24—Determination of
temperature. To speed it up, 1-ethylpiperidine is added at 5%
Volatile Matter Content, Density, Volume Solids, and
5
as a buffer, or “catalyst”.
Weight Solids of Surface Coatings
4.3 For nonpyridine based reagents, a number of different
3. Summary of Test Method
solvent systems are available to increase solubility and to
minimize interferences from ketones and aldehydes.
3.1 The material is dissolved in a suitable solvent, and
titrated directly with standardized Karl Fischer reagent, to an
5. Apparatus
5.1 Karl Fischer Apparatus, manual or automatic, encom-
passed by the description in Test Method E203. Apparatus
1
This test method is under the jurisdiction of ASTM Committee D01 on Paint
shouldbeequippedwitha25-mLburet,ClassA,orequivalent.
and Related Coatings, Materials, andApplications and is the direct responsibility of
5.2 Syringe, 100-µL capacity, with needle.
Subcommittee D01.21 on ChemicalAnalysis of Paints and Paint Materials. Current
edition approved Jan. 10, 2002. Published March 2002. Originally published as 5.3 Syringes,1-mLand10-mLcapacity,withoutneedle,but
D4017–81. Last previous edition D4017–96a.
equipped with caps.
2
Annual Book of ASTM Standards, Vol 11.01.
3
Annual Book of ASTM Standards, Vol 06.01.
4
Annual Book of ASTM Standards, Vol 15.05.
5 6
Available from the Superintendent of Documents, U.S. Government Printing AvailablefromHoechstCelaneseCorporation,HydranalTechnicalCenter,U.S.
Office, Washington, DC 20402. Highway 43, Bucks, AL 36512.
Copyright ©ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA19428-2959, United States.
1

---------------------- Page: 1 ----------------------
D4017–02
6. Reagents 8.1.1 Add enough fresh solvent to cover the electro
...