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: D1331 − 20

Standard Test Methods for

Surface and Interfacial Tension of Solutions of Paints,
Solvents, Solutions of Surface-Active Agents, and Related
Materials1
This standard is issued under the fixed designation D1331; 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 Material Safety Data Sheets are available for reagents and
1.1 These test methods cover the determination of surface materials. Review them for hazards prior to usage.
tension and interfacial tension of a variety of liquid materials, 1.8 This international standard was developed in accor-
including but not restricted to paints, solvents, and solutions of dance with internationally recognized principles on standard-
surface-active agents, as defined in Terminology D459. Four ization established in the Decision on Principles for the
methods are covered as follows: Development of International Standards, Guides and Recom-
Method A—Surface Tension by du Noüy ring; mendations issued by the World Trade Organization Technical
Method B—Interfacial Tension by du Noüy ring; Barriers to Trade (TBT) Committee.
Method C—Surface Tension by Wilhelmy plate; and 2. Referenced Documents
Method D—Interfacial Tension by Wilhelmy plate.
2.1 ASTM Standards:2
iTeh Standards
1.2 Method A originally was written primarily to cover
aqueous solutions of surface-active agents, but is also appli-
D459 Terminology Relating to Soaps and Other Detergents
E177 Practice for Use of the Terms Precision and Bias in

(https://standards.iteh.ai)
cable to aqueous paints, nonaqueous solutions (including ASTM Test Methods
paints) and mixed solvent solutions. E691 Practice for Conducting an Interlaboratory Study to

than one solute component may be Document

present, including solute Preview
1.3 Method B is applicable to two-phase solutions. More Determine the Precision of a Test Method

components that are not in themselves surface-active. 3. Terminology

1.4 Method C is applicable to surface active liquids and, 3.1 Definitions of Terms Specific to This Standard:
unlike du Noüy ring, no buoyancy corrections are needed and ASTM D1331-20
3.1.1 du Noüy ring, n—platinum wire ring.
https://standards.iteh.ai/catalog/standards/sist/a4624a22-bd8c-4efd-83f0-fdcf017c7716/astm-d1331-20
results are not affected by moderate viscosities (1-10 Pa-sec) of 3.1.2 Wilhelmy plate, n—flat, thin plate made of glass or
the liquid. It is the recommended method for use with paints platinum.
and resin solutions.
4. Summary of Test Methods
1.5 Method D is applicable to two-phase solutions and
mixtures. 4.1 du Noüy Ring Methods—The ring is suspended from a
tensiometer or balance. The test liquid is brought into contact
1.6 The values stated in SI units are to be regarded as with the ring until the latter is covered. For interfacial tension
standard. No other units of measurement are included in this measurements, the ring must be at the interface between the
standard. two liquids. The ring is then slowly withdrawn until a
1.7 This standard does not purport to address all of the maximum force is attained, from which the surface or interfa-
safety concerns, if any, associated with its use. It is the cial tension may be calculated.
responsibility of the user of this standard to establish appro-
4.2 Wilhelmy Plate Methods—The plate is suspended from a
priate safety, health, and environmental practices and deter-
tensiometer or balance. The test liquid or interface between two
mine the applicability of regulatory limitations prior to use.
liquids is brought into contact with the bottom of the plate,
causing the plate to be pulled down into the liquid by the
1
These test methods are under the jurisdiction of ASTM Committee D01 on surface tension force. The force applied to the plate from above
Paint and Related Coatings, Materials, and Applications and are the direct
responsibility of Subcommittee D01.24 on Physical Properties of Liquid Paints &
2
Paint Materials. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 1, 2020. Published January 2021. Originally contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
approved in 1954. Last previous edition approved in 2014 as D1331 – 14. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D1331-20. the ASTM website.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

1
 D1331 − 20
is then increased to bring the bottom edge of the plate level 9. Calibration of Apparatus
with the flat surface of the liquid. The force acting on the plate 9.1 Calibrate the tensiometer or balance according to the
is measured and used to calculate the surface tension of the manufacturer’s directions.
liquid or the interfacial tension between two liquid phases.
10. Procedure
5. Significance and Use 10.1 After the tensiometer has been calibrated, check the
5.1 These methods provide data that are useful in evaluating level and insert the cleaned platinum ring (Note 1) that will be
the effectiveness of surface active agents in reducing surface used in the measurement. Check the plane of the ring, and set
tension. In addition, surface tension data can predict interac- the dial and vernier at zero. Adjust the rear adjusting screw so
tions between liquids and solid surfaces or other liquids and that the index level of the arm is opposite the reference mark
can be used to establish wetting properties of paints, solvents, on the mirror, that is, the ring system is at the zero position.
and other liquids. NOTE 1—Extreme care must be taken to have the sample vessel and
5.2 A number of laboratories have found the Wilhelmy plate platinum ring clean. Contamination of the liquid surface by dust or other
to be easier to use, easier to clean and generally better for use atmospheric impurities during measurement should be avoided.
with pigmented paints. 10.2 Place the solution to be tested (Note 2), contained in
the thoroughly cleaned vessel (Note 1), on the sample platform.
6. Interferences Raise the sample platform by means of its adjusting screw until
the ring is just submerged.
6.1 The du Noüy ring is difficult to clean when used with
pigmented paints. Paints high in titanium dioxide have a NOTE 2—For surface active agents: since the surface tension of a
tendency to coat the ring with a layer that is almost impossible solution is a function of the concentration, care must be taken that the
concentration is adjusted and recorded within known limits. The presence
to remove. If left on the ring, this layer of material affects the
of solutes other than the surface-active agent should be ascertained and
surface tension values that are measured. reported qualitatively and quantitatively, insofar as possible. This includes
6.2 Paint measurements with the du Noüy ring are affected hardness components in the water. Care should be taken that the solution
is physically homogeneous. Measurements made near or above the cloud
iTeh Standards
by viscosity above a level of 10 Poise (1 Pa-sec). Many
coatings have a viscosity at rest greater than that level. Above
10 P, the resistance of the ring to being pulled is as much due
point or other critical solubility points can be in serious error. This is
particularly true when the solute is a surface-active material.

(https://standards.iteh.ai)
to viscosity as to surface tension.
10.3 Lower the platform slowly, at the same time applying
torsion to the wire by means of the dial-adjusting screw. These
simultaneous adjustments must be carefully proportioned so

RING
Document Preview
METHOD A—SURFACE TENSION BY DU NOÜY that the ring system remains constantly in its zero position. As
the breaking point is approached, the adjustments must be
made more carefully and more slowly. Record the force
7. Apparatus ASTM D1331-20reading from the dial or the digital display when the ring
detaches from the surface.
https://standards.iteh.ai/catalog/standards/sist/a4624a22-bd8c-4efd-83f0-fdcf017c7716/astm-d1331-20
7.1 du Noüy Tensiometer—Either the du Noüy precision
tensiometer or the du Noüy interfacial tensiometer, equipped 10.4 Make at least two measurements. Additional measure-
with either the 4 or the 6-cm circumference platinum ring, as ments shall be made if indicated by the over-all variation
furnished by the manufacturer, may be used. The tensiometer obtained, the total number of readings to be determined by the
shall be placed on a sturdy support that is free from vibrations magnitude of that variation.
and other disturbances such as wind, sunlight, and heat. The 10.5 Record the temperature of the solution and the age of
wire of the ring shall be in one plane, free of bends or the surface at the time of testing. Since the submerging of the
irregularities, and circular. When set in the instrument, the ring (10.2) may constitute a significant disturbance of the
plane of the ring shall be horizontal, that is, parallel to the surface, take the age as the elapsed time between submersion
surface plane of the liquid being tested. and breakaway of the ring. The accuracy of this time observa-
7.2 Sample Container—The vessel for holding the liquid tion may be indicated in the usual manner. In most cases an
shall be not less than 6 cm in diameter, and sufficiently large to accuracy of 65 s is reasonable, and sufficient for this test
ensure that the contact angle between the ring and the interface method.
is zero.
11. Calculation and Report
8. Preparation of Apparatus 11.1 The dial reading, obtained from a measurement carried
out in the foregoing manner with a calibrated instrument, is
8.1 Clean all glassware thoroughly. The use of fresh actually the pull per linear centimetre on the ring (both inner
chromic-sulfuric acid cleaning mixture, followed by a thor- and outer circumference being considered) at the break-point,
ough rinsing in distilled water, is recommended. expressed in dynes. This value, called the uncorrected surface
8.2 Clean the platinum ring by rinsing thoroughly in a tension, must be multiplied by a correcting factor, F, to give the
suitable solvent and in distilled water, before taking a set of corrected surface tension. F is a function of the contours of the
measurements. Allow the ring to dry, and then heat to white liquid surface in the neighborhood of the ring at the instant of
heat in the oxidizing portion of a gas flame. breakaway. It can be numerically specified in terms of R, the

2
 D1331 − 20
mean radius, in centimetres, of the ring; r, the radius, in 12.1.2 Use fresh solutions and a freshly cleaned ring for
centimetres, of the wire from which the ring is made; and V, the each determination.
maximum volume of liquid elevated above the free surface of 12.1.3 When operating with a liquid heavier than the
the liquid. For liquids of low surface tension, such as surface- aqueous solution, place the two-layer system in the sample
active agents, F is, in general, appreciably less than unity. It vessel and place the ring in the upper (aqueous) layer. Make the
must, therefore, be ascertained and applied. Values of F in measurement by turning the torsion wire counter-clockwise
terms of two compounded parameters, R3/V and R/r have been and simultaneously keeping the ring system in the zero
compiled and tabulated by Harkins and Jordan.3 In order to position, as in the measurement of surface tension, until the
look up F in the tables, the values of these two parameters must ring breaks through the interface.
be calculated. Values for R and r are furnished by the 12.1.4 When operating with a liquid (oil) lighter than the
manufacturer with each ring. The value of V is calculated from aqueous solution, first place the aqueous solution in the sample
the following equation: vessel and immerse the ring therein. Carefully pour the oil on
V 5 M/ ~ D 2 d ! (1) top of the aqueous solution to form the two-layer system.
Contact between the oil and the ring should be avoided during
where: this operation. After allowing sufficient time for the interfacial
M = weight of liquid raised above the free surface of the tension to come to its equilibrium value (Note 3), make the
liquid, measurement in the same manner as that used for measuring
D = density of liquid, and surface tension.
d = density of air saturated with vapor of the liquid.
NOTE 3—Since the interfacial energy of a newly formed liquid-liquid
To calculate M, multiply the tensiometer dial reading by the interface generally requires some time to reach its equilibrium value, it is
factor which converts this reading into grams pull on the ring. advisable to wait at least 5 min after the interface is formed before taking
The factor D can be measured by the usual procedures, and the a measurement.
value d can be obtained from published data. The corrected
13. Calculation and Report
surface tension in dynes per centimetre is obtained by multi-
plying the uncorrected surface tension value by F. 13.1 As in the case of surface tension, a correction factor, F,
iTeh Standards
11.2 Unless specified, the surface tension values reported
shall be corrected values. Report also the temperature at which
must be multiplied by the dial reading (pull on the ring in
dynes) in order to obtain the corrected value for interfacial

(https://standards.iteh.ai)
tension. Values for F have been published by Zuidema and
the measurement was made. If it is desired to report the surface
Waters.4 The factor F is, in this case, a function of the densities
tension value of an aqueous solution at some standard
of the two liquids as well as of R and r, the radius of the ring
Document Preview
temperature, for example, 25°C, and the measurement was
actually made at a temperature within about 3°C of this value
(that is, 22 to 28°C), a correction factor of 0.14 dynes/cm·°C
and that of the wire, respectively.
13.2 Unless specified, interfacial tension values reported
may be used. Subtract this correction factor from the surface shall be corrected values. Report and adequately specify the
tension when the temperature of the test is lower ASTM D1331-20
than the nature of the nonaqueous liquid (oil) used in the determination.
https://standards.iteh.ai/catalog/standards/sist/a4624a22-bd8c-4efd-83f0-fdcf017c7716/astm-d1331-20
reported temperature, and add it to the surface tension when the Also report the temperature at which the determination was
temperature of the test is higher than the reported temperature. made. In contrast to surface tension values, interfacial tension
This value for the correction factor is not valid for nonaqueous values cannot adequately be corrected for small temperature
liquids, and should be used only where the solvent is prepon- deviations by means of a simple formula.
derantly water.
METHOD B—INTERFACIAL TENSION BY DU NOÜY METHOD C—SURFACE TENSION BY WILHELMY
RING PLATE

14. Apparatus
12. Procedure
14.1 Balance or Tensiometer with provision for attaching a
12.1 Determine interfacial tension as described in Section
Wilhelmy plate.
10 for surface tension, with the following modifications:
12.1.1 Always move the ring from the aqueous side of the 14.2 Thin Platinum or Glass Plate (microscope slides and
interface through to the nonaqueous side. With liquids lighter cover slips have been used) with a means of connecting it to the
than water, it is accordingly possible to use the precision balance or tensiometer.
tensiometer as well as the interfacial tensiometer. With liquids
heavier than water, where the ring must be pushed downward, 15. Preparation of Apparatus
the interfacial tensiometer should be used. 15.1 Clean all glassware thoroughly. The use of fresh
chromic-sulfuric acid cleaning mixture, followed by a thor-
ough rinsing in distilled water, is recommended.
3
Harkins, W. D., and Jordan, H. F., “A Method for Determination of Surface and
Interfacial Tension from the Maximum Pull on a Ring,” Journal Am. Chemical Soc.,
4
Vol 52, 1930, p. 1751. These tables are also published in Physical Methods of Zuidema, H. H., and Waters, G. W., “A Ring Method for Determination of
Organic Chemistry, Interscience Publishers, Inc., New York, NY, Vol 1, 1945, pp. Interfacial Tension,” Industrial and Engineering Chemistry, Analytical Edition, Vol
182–184. 13, 1941, p. 312.

3
 D1331 − 20
15.2 Clean platinum or glass plate by rinsing thoroughly in correction factors are necessary for this method and the fluid
a suitable solvent and distilled water. density does not need to be known.
15.3 For a correct surface tension the surface of the plate
must be roughened and with no bright spots on the plate. METHOD D—INTERFACIAL TENSION BY
WILHELMY PLATE
16. Procedure
16.1 After the tensiometer or balance has been calibrated, 18. Procedure
check the level and insert the cleaned platinum or glass plate 18.1 Determine interfacial tension as described in the pro-
that will be used in the measurement. Extreme care must be cedure for surface tension (Section 16), with the following
taken to have the sample vessel and platinum or glass plate modifications:
clean. Contamination of the liquid surface by dust or other 18.1.1 Always remove the plate from the aqueous side of
atmospheric impurities during measurement should be the interface through to the nonaqueous side. With liquids
avoided. lighter than water, it is accordingly possible to use the precision
16.2 Check that the lower edge of the plate is exactly plane tensiometer as well as the interfacial tensiometer. With liquids
by ensuring the light gap between the edge of the plate and the heavier than water, where the plate must be pushed downward,
surface is uniform. the interfacial tensiometer should be used.
18.1.2 Use fresh solutions and a freshly cleaned plate for
16.3 Place the liquid to be tested, contained in the thor-
each determination.
oughly cleaned vessel (16.1), on the sample platform. For
18.1.3 When operating with a liquid heavier than the
surface active agents: since the surface tension of a solution is
aqueous solution, place the two-layer system in the sample
a function of the concentration, care must be taken that the
vessel and place the plate in the upper (aqueous) layer. Make
concentration is adjusted and recorded within known limits.
the measurement by turning the torsion wire counter-clockwise
The presence of solutes other than the surface-active agent
and simultaneously keeping the plate system in the zero
should be ascertained and reported qualitatively and
position, as in the measurement of the surface tension.
iTeh Standards
quantitatively, insofar as possible. This includes hardness
18.1.4 When operating with a liquid (oil) lighter than the
components in the water. Care should be taken that the solution
aqueous solution, first place the aqueous solution in the sample
is physically homogeneous. Measurements made near or above
(https://standards.iteh.ai)
vessel and immerse the plate therein. Carefully pour the oil on
the cloud point or other critical solubility points can be in
top of the aqueous solution to form the two-layer system.
serious error. This is particularly true when the solute is a
Contact between the oil and the plate should be avoided during
surface-active material.
Document Preview
16.4 Rinse the platform to just below the plate. Tare the
this operation. After allowing the sufficient time for the
interfacial tension to come to its equilibrium value (Note 4),
force measuring system to zero. make the measurement in the same manner as that used for
16.5 Rinse the sample platform until the plate ASTM measuring surface tension.
D1331-20
is just
submerged and turn the mechanical drag pointer to set it at the
https://standards.iteh.ai/catalog/standards/sist/a4624a22-bd8c-4efd-83f0-fdcf017c7716/astm-d1331-20
reference mark.
NOTE 4—Since the interfacial energy of a newly formed liquid-liquid
interface generally requires some time to reach its equilibrium value, it is
advisable to wait at least 5 min after the interface is formed before taking
16.6 Raise platform around another 5 mm to ensure the a measurement.
wetting of the plate and then lower platform until the drag
pointer is pointing exactly to the reference mark again. 19. Calculations and Report
16.7 Record the force reading from the dial or the digital 19.1 Calculate surface tension as in 17.1.
display.
19.2 Report and adequately specify the nature of the non-
16.8 Make at least two measurements. Additional measure- aqueous liquid (oil) used in the determination. Also report the
ments shall be made if indicated by the overall variation temperature at which the determination was made. In contrast
obtained, the total number of readings to be determined by the to surface tension values, interfacial tension values cannot
magnitude of that variation. adequately be corrected for small temperature deviations by
means of a simple formula.
17. Calculation
17.1 The surface tension, γ, is computed from the force 20. Precision and Bias
measurement, f, using: 20.1 The precision of these test methods is based on an
γ 5 f⁄ $ @ 2 ~ 1 1 t ! # % · cos θ interlaboratory study of ASTM D1331, Standard Test Methods
for Surface and Interfacial Tension of Solutions of Paints,
where: Solvents, Solutions of Surface-Active Agents, and Related
l = length of plate Materials, conducted in 2018. A total of eight volunteer
t = thickness laboratories were asked to test four different materials. Every
The contact angle θ is often assumed to be zero for common “test result” represents an individual determination, and all
liquids on clean glass or platinum plates, but one should be participants were instructed to report three replicate test results
aware of the error caused by a non-zero contact angle. No other for each material. Practice E691 was followed for the design