T 565 pm-96

PROVISIONAL METHOD 1996

1996 TAPPI

The information and data contained in this document were prepared

by a technical committee of the Association. The committee and the
Association assume no liability or responsibility in connection with the
use of such information or data, including but not limited to any
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Contact angle of water droplets on corona-treated

polymer film surfaces

1. Scope

This test method covers the measurement of the contact angle of water droplets on corona-treated polymer film
surfaces with subsequent estimation of the films wetting tension.

NOTE 1: While no round-robin testing has been done to confirm the applicability of the test method to either flame or plasma-treated surfaces,
theoretically the method could be applied to those treatment methods.

NOTE 2: There is currently no ISO standard that duplicates this test method.

2. Summary

In this test method, drops of water are placed on the surface of the film sample and the contact angle values are
measured, and then averaged. The estimate of the films wetting tension is then found in a conversion chart. Any
polymer film can be tested.

3. Significance

3.1 The ability of polymer films to retain inks, coatings, adhesives, etc., is primarily dependent upon the
character of their surfaces, and can be improved by one of several surface-treating techniques. The electrical discharge
treatment, such as corona treatment, as well as flame, chemical and plasma treatment, has been found to increase the
wetting tension of a polymer film surface by increasing the surface polarity. The stronger the treatment, the higher the
polarity. (Warning: Excessive treatment can lead to weak boundary layers and a loss of adhesion.) The higher the polar
component, the more actively the surface reacts with different polar interfaces. It is therefore possible to relate the
wetting tension of a polymer film surface to its ability to accept and retain inks, coatings, adhesives, etc., if the ink,
coating or adhesive contains the necessary polar functionalities. Wetting tension in itself is not a completely acceptable
measure of ink, adhesive adhesion, or coating.
3.2 The wetting tension of polymer films belong to a group of physical parameters for which no standard
of accuracy exists. The wetting tension of a polymer cannot be measured directly because solids do not measurably
change shape in reaction to surface energy. Many indirect methods have been proposed (1). Different test methods tend
to produce different results on the same materials. Practical determination of a solids surface energy utilizes the
interaction of the solid with test liquids.
3.3 Although in the industry, the level of surface treatment of polymer films has been traditionally defined
with the units of wetting tension, dyne/cm (mN/m), the values are derived from a subjective interpretation of the observed
test liquid behavior. Such determinations cannot be used nor considered as standards for wetting tension.

Approved by the Extrusion Coating Committee of the Polymers, Laminations & Coatings Division
TAPPI
T 565 pm-96 Contact angle of water droplets on corona-treated polymer film surfaces / 2

3.4 The surface energy of a solid material consists of two components, dispersive and polar. Water, will
interact with different polymers, treated or untreated, according to the polar and dispersion forces acting upon it, but will
not chemically react with the polymer. A water droplet will assume a shape in response to the surface energy and polarity
of the films surface. As a result, different polymers which are treated to different levels can be considered a homologous
series in terms of their interaction with water. So each time a film is subjected to surface treatment, a new member of
the homologous series of polymers is produced. For such a series, the water droplet will assume a shape in response to
the particular surface energy and polarity of the films surface.
3.5 For such a series, an empirical equation exists which describes a relationship between the wetting tension
and cosine of contact angles of a test liquid, such as water. That equation can be used to estimate the wetting tension
of the substrate from the water contact angle values. See Appendix A.1.
3.6 The conversion chart for estimating the range of wetting tension of the substrate from the contact angle
values is shown in Appendix A.2. This conversion chart is shown for the purpose of providing a bridge between
previous test data obtained using TAPPI T 698 cm-91 Test Method. Otherwise, contact angle values should be used for
defining the films surface. Because of the use of several test methods for determining the wetting tensions, as well as
variability of the results, it is impossible to equate a water contact value to a single wetting tension value. For the
purpose of this test standard, each water contact angle value is equated to a range of wetting tension values.
3.7 The following ranges of water contact angle values can be used as a guide for defining typical
polyolefin materials for different levels of surface treatment:

marginal or no treatment >90

(under approx. 34 dynes/cm)
low treatment 85 to 90
(approx. 36 to 34 dynes/cm)
medium treatment 78 to 84
(approx. 39 to 36 dynes/cm)
high treatment 71 to 77
(approx. 43 to 40 dynes/cm)
very high treatment <71
(above approx. 43 dynes/cm)

The suitability of the test for specification acceptance and manufacturing control and end use of polymer films
will have to be established through capability studies.
3.8 Almost all materials have variations in surface energy as one moves from point to point. Non-uniform
treatment of film with corona treaters may also add variability to the results. Therefore, the surface energy of a specimen
must be described by the average wetting tension and its variability over the sample surface.

4. Applicable document

4.1 ASTM Standards

4.2 D 618 Standard Practice for Conditioning Plastics and Electrical Insulating Materials for Testing
D 2578 Test Method for Wetting Tension of Polyethylene and Polypropylene Films
D 724-94 Standard Test Method for Surface Wettability of Paper (Angle-of-Contact Method)
D 5946-96 Test Method Corona-Treated Polymer Films Using Water Contact Angle Measurements

5. Definitions

5.1 Surface energy (mN/m), n - for a given solid, defines molecular forces of its interaction with other
interfaces; it is measured as free energy per unit area.
5.2 Wetting tension,
c (mN/m), n - for a given solid, is accepted to be equal to the surface tension of the
liquid which just exhibits a zero contact angle on the solid; it is used as an estimate of the solids surface energy.

NOTE 2: A different unit of measurement is used in the industry for surface energy and wetting tension - dyne/cm; 1 mN/m = 1 dyne/cm.

5.3 Polarity, n - in surface chemistry, value which quantifies concentration of polar functional groups on the
polymer surface and is measured as a polar component of surface energy over the total surface energy value.
3 / Contact angle of water droplets on corona-treated polymer film surfaces T 565 pm-96

5.4 Static contact angle, 0 (degrees), n - is defined as the angle between the substrate surface and the tangent
line drawn to the droplet surface at the three-phase point, when a liquid drop is resting on a plane solid surface.
5.4.1 Discussion - Contact angle values can be determined:
a) by measuring the contact angle directly with a protractor by using tangential alignment of a cursor line,
b) by measuring the angle between the substrate surface and the line from the three-phase point to the
apex of the droplet, and then multiplying the obtained number by 2 to calculate the contact angle (2), or
c) from the dimensions of the droplets image as (3)
0 = 2*arc tan (H/R)
where H is the height of a droplets image and R is the half of its width.
The method (a) is biased due to the subjective nature of finding a tangent to the droplet image at the three
phase point; if the method (a) is to be used, the bias of each operators measurements must be determined; the methods
(b) and (c) are generally free of bias.
5.5 Surface tension of a liquid, n - definition to be determined later.

6. Interferences

6.1 The wetting tension of a polymer film in contact with a drop of liquid in the presence of air is a function
of the surface energies of both the air-film and film-liquid interfaces, any trace of surface-active impurities in the test
liquid or on the film may affect the results. It is, therefore, important that the portion of the film surface to be tested not
be touched or rubbed, that all equipment be scrupulously clean, and that water purity be carefully guarded. Glass
apparatus in particular is likely to be contaminated with detergents having very low surface tension unless specific
precautions are taken to ensue their absence such as cleaning with chromic sulfuric acid and rinsing with distilled water.
6.2 The presence of slip, antistatic, or antiblocking and other additives can change the surface of the film
as these additives bloom out to the surface with time.
6.3 Finely embossed films add more variability to the measurements.
6.4 Polymer films are known to generate static electricity charges when they are processed. Corona treatment
usually exacerbates this problem, while flame treated samples do not display static charges. The film sample for surface
measurement may carry the static charge generated in processing or may acquire a charge by friction when sliding over
the specimen holder surface.
The static charges may cause errors in contact angle measurements. These errors occur as the
electrostatic field generated by the charged sample pulls the water droplet to the film surface stronger that it would be
in the absence of charges.
To avoid measurement errors, the film sample must be kept free of static buildup before and during
measurements by placing an air ionizer, also known as a static eliminator, in the vicinity of the specimen holder. These
devices produce air ions of positive and negative polarity. The charged object in the vicinity of the ionizer will attract
ions of the opposite polarity and will be neutralized.
6.5 Transfer of a droplet onto the measured surface must be accomplished following the procedure described
in Section 11 of this method. Improper transfer techniques increase variability of measurements.
6.6 Contact angle measuring method using tangential alignment of the cursor line of a protractor, as described
in 5.4.1 (a), is biased due to the subjective nature of finding a tangent to the droplet image at the three-phase point. The
smaller the measured contact angle the larger the error. If this method is to be used, the bias of each operators
measurements must be determined.

7. Apparatus

7.1 Contact angle meter, or goniometer. The apparatus for measuring contact angles must contain: (a) liquid
dispenser capable of suspending a precise droplet of the specified volume from the tip of the dispenser, (b) sample holder
which can stretch a film sample flat without wrinkles and distortions, (c) provisions for bringing the sample toward the
suspended droplet in a controlled manner to accomplish droplet transfer onto the measured surface, (d) means for
projecting a silhouette image of the drop with minimal distortions. The apparatus must have means for direct angle
measurements, such as a protractor, or direct measurements of the droplets dimensions, such as a grid and/or a scale,
or a video camera with a video interface card to digitize the image of the droplet for subsequent calculations.
T 565 pm-96 Contact angle of water droplets on corona-treated polymer film surfaces / 4

8. Reagents and materials

8.1 Deionized ultra filtered water should be used for testing purposes. The test liquid must be kept in
scrupulously clean containers.

9. Sampling

9.1 The minimum amount of film required for this test is an approximately 25-mm wide and 300-mm long
sample strip. If a sample is taken from a roll the direction of the sample relative to the machine direction of the web must
be noted.
9.2 Extreme care must be taken to prevent the surface of the film sample from being touched or handled in
the areas upon which the test is to be made.
9.3 The number of measurements per film sample can be determined using published tables for sampling
plans. Complete tables can be found in most books on quality control (4). The recommended number of readings per
sample is ten.
9.4 For the purpose of determining the wetting tension profile across the width of the roll, one contact angle
measurement can be taken for each inch of the sample.

10. Conditioning

10.1 Conditioning is not generally required for routine QA or process control measurements as conditioning
may affect the measured value and misrepresent the actual conditions.
10.2 Conditioning is required for interlaboratory measurements intended to compare the results. Condition
the test specimens at 23 2C (73.4 3.6) and 50 5% relative humidity for not less than 40 h prior to test in
accordance with TAPPI T 402 Standard Conditioning and Testing Atmospheres of Paper, Board, Pulp Handsheets and
Related Products, for those tests where conditioning is required. In cases of disagreement, the tolerances shall be 1C
( 1.8F) and 2% relative humidity.
10.3 Test Conditions. Special test conditions are not generally required for routine QA or process control
measurements.
10.4 Test Conditions for Interlaboratory Studies. Whenever possible, conduct tests in the standard laboratory
atmosphere of 23 2C (73.4 3.6F and 50 5% relative humidity, unless otherwise specified in the test methods.
In cases of disagreement, the tolerances shall be 1C ( 1.8F) and 2% relative humidity.

11. Procedure

11.1 Place a sample strip onto the specimen holder of the instrument. Make sure the film sample is lying flat
without wrinkles and distortions.
11.2 Suspend a 5-8 microliter droplet at the end of a syringe needle. Bring the surface with the mounted
sample upward until it touches the pendant drop. Then lower the surface with the sample to complete droplet transfer.
Do not drop or squirt droplets on the surface. See Fig. 1.
11.3 Follow the instrument manufacturers instructions for a maximum time between dropping of the water
droplet and the measurement.
11.4 Advance the sample to place the next droplet onto a previously untouched area.
11.5 Take ten contact angle measurements on the sample.

12. Calculation and interpretation of results

12.1 Calculation
12.1.1 Calculate the average of the 10 measurements.
12.1.2 Calculate the standard deviation of the measurements.
12.1.3 Example of ten contact angle measurements is found below:
5 / Contact angle of water droplets on corona-treated polymer film surfaces T 565 pm-96

1. 66 6. 72
2. 72 7. 72
3. 66 8. 72
4. 72 9. 69
5. 73 10. 69

Average contact angle: 70. This result corresponds to the lower end of the very high treatment level. Standard
deviation: 2.4.
12.2 Interpretation of the results. Look up the conversion chart to find the estimate of wetting tension range
which can be attributed to the measured contact angle values.
12.3 Example: In the conversion chart in Appendix A.2, the 70 contact angle corresponds to a wetting tension
range of 46 mN/m.

13. Report

Report the instrument used, the number of readings, the average value of the contact angle measurements and the
standard deviation, the wetting tension value found in the conversion chart, temperature, humidity and any comments
and observations.

14. Precision and bias

14.1 Precision:
14.1.1 Instrument error depends on the instrument used. Instrument error can be assessed by measuring a
uniform surface such as solidified paraffin wax and calculating the standard deviation of the measurements.
14.1.2 Precision of the test. Table 1 is based on an interlaboratory study conducted in 1995 per ASTM Practice
E 691 involving four materials and eight laboratories1. Each test result was the average of ten individual determinations.
Each laboratory obtained three test results for each material on two days. The results demonstrate that the precision of
the results is generally independent on the treatment level (wetting tension) of the film.

NOTE 3: Caution - The following explanations of r and R are only intended to present a meaningful way of considering the approximate
precision of this test method. The data in Table 1 should not be rigorously applied to the acceptance or rejection of material, as those
data are specific to the interlaboratory study and may not be representative of other lots, conditions, materials, or laboratories. Users
of this test method should apply the principles outlined in ASTM Practice E 691 to generate data specific to their laboratory and
materials, or between specific laboratories. The principles 14.1.3 through 14.2 would then be valid for such data.

14.1.3 Concept of r and R - If Sr and SR have been calculated from a large enough body of data, and for test
results that were averages of ten test determinations:
14.1.3.1 Repeatability, r (Single operator) - The two test results should be judged not equivalent if they differ by
more than the r contact-angle degrees for that treatment level.
14.1.3.2 Reproducibility, R (Multilaboratory) - The two test results should be judged not equivalent if they differ
by more than the R contact-angle degrees for that treatment level.
14.1.3.3 Any judgement per 14.1.3.1 and 14.1.3.2 would have an approximate 95% (0.95) probability of being
correct.
14.2 Bias - No statement can be made about the bias of the test method because contact angle is defined in
terms of the test method.

15. Keywords

Contact angle, Polymers, Films, Corona discharge, Surface treatment, Tension, Water, Goniometers, Surface
energy

16. Additional information

Effective date of issue: December 10, 1996.

1
Supporting data are available from ASTM Headquarters, Request RR:D20-19; 5946-96
T 565 pm-96 Contact angle of water droplets on corona-treated polymer film surfaces / 6

Appendix A.1

A.1.1 When a drop of liquid rests on the surface of a solid, and a gas is in contact with both, the forces acting
at the interfaces must balance. These forces can be represented by various surface tensions acting in the direction of the
surfaces and it follow that:

GL cos 0 =
GS -
SL

where:

0 = angle of contact of the edge of the drop with the solid surface,

GL = surface tension of the gas-liquid interface,

GS = surface tension of the gas-solid interface,

SL = surface tension of the solid-liquid interface.
When the air is saturated with vapors of the liquid,
GL will be the surface tension of the liquid.
A.1.2 For the polymer series described in Section 3.4, a unique condition exists where films treated to different
levels can be considered a homologous polymer series. For such a series, the relationship between cos 0 of water
droplets and wetting tension
c was found to be linear (5)

c = k1
GL - (1 cos 0)/k2,

where the parameters k1 and k2 are constants.
A.1.2.1 In this form the relationship can be used to estimate the wetting tension of corona-treated surfaces from
the water contact angle data. In this case the value
GL is fixed at 72 mN/m for water, while the contact angle and its
cosine will be changing depending on the surface energy of the substrate.
A.1.2.2 Since the wetting tension of a polymer film belongs to a group of physical parameters for which no
standard of accuracy exists, a range of values for wetting tension corresponding to a given water contact angle value is
used to correlate the contact angle data to the wetting tension. The values of k1 and k2 range from 0.75 to 0.9 for k1 and
from 0.35 to 0.46 for k2. The conversion chart is shown in Appendix A.2.

Literature cited

1. S. Wu, Polymer Interface and Adhesion, Marcel Dekker, Inc., New York, 1982.
2. U.S. Patent 5,268,733.
3. ASTM D 724-94 Standard Test Method.
4. J.A. Duncan, Quality Control and Industrial Statistics, 3d ed., Irwin, Homewood, IL, 1965.
5. M. Blitshteyn, Wetting tension measurements on corona-treated polymer films, TAPPI Journal, 78 (3), 138-143
(March 1995).

Fig. 1 Water droplet transfer technique.

7 / Contact angle of water droplets on corona-treated polymer film surfaces T 565 pm-96

Table 1. Interlaboratory study results

Treatment Average contact Repeatability Reproducibility

Material power angle (degrees standard standard r R
(watt/sq. ft./min.) deviation, Sr deviation, SR

HDPE film 10 68.99 1.608.44 2.84039 4.50 7.95

w/EVA backing

HDPE film 2 69.39 2.41652 3.11040 6.77 8.71

w/EVA backing

HDPE film 1 75.03 2.15706 3.08072 6.04 8.63

w/EVA backing

Polypropylene pre-treated 85.00 1.95980 4.03218 5.49 11.29

film

Appendix A.2

Water Contact Angle Test for Wetting Tension (WCAT)

Conversion Chart
Water Wetting Water Wetting
Contact Angle Tension Contact Angle Tension
(degrees) (dyne/cm) (degrees) (dyne/cm)
41 62 71 45
42 62 72 44
43 61 73 44
44 61 74 43
45 60 75 42
46 60 76 42
47 59 77 41
48 59 78 40
49 58 79 40
50 58 80 39
51 57 81 38
52 57 82 38
53 56 83 37
54 56 84 36
55 55 85 35
56 54 86 35
57 54 87 34
58 53 88 33
59 53 89 33
60 52 90 32
61 51 91 31
62 51 92 31
63 50 93 30
64 50 94 29
65 49 95 29
66 48 96 28
67 48 97 27
68 47 98 26
69 46 99 26
70 46 100 25

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Technical Divisions Administrator.