Measurement of Surface

Tension and Energy

Wesel, October 6th 2020, Petra Della Valentina

Topics

Theory
• Wetting behavior
• Influence of surface tension / surface free energy

Measuring and calculation methods

• Static and dynamic surface tension
• Surface free energy

Application
• Selection of surfactants depending on the application process
• Recoatability is predictable – optimization of recoatability between
solventborne-primer and waterbased-basecoat

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Topics

Theory
• Wetting behavior
• Influence of surface tension / surface free energy

Measuring and calculation methods

• Static and dynamic surface tension
• Surface free energy

Application
• Selection of surfactants depending on the application process
• Recoatability is predictable – optimization of recoatability between
solventborne-primer and waterbased-basecoat

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Theory
Surface Tension / Wetting

Good substrate wetting:

paint < substrate

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Theory
Wetting Behavior

System 1: System 2: System 3:

Surface tension 33 mN/m Surface tension 29 mN/m Surface tension 25 mN/m

Substrate: Surface tension 30 mN/m

System 1: System 2: System 3:

No substrate wetting Good substrate wetting Good substrate wetting
 Poor flow  Poor flow and leveling

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Theory
Surface Tension / Surface free Energy - More than just one value

σ = σd(disperse) + σp(polar)

σd = disperse parts σp = polar parts

Van der Waals interactions Dipol – Dipol
Hydrogen Bondings

Polar interacts only with polar – disperse only with disperse!

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Theory
Surface Tension / Surface free Energy – Wetting Behavior

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Theory
Wetting Envelope

Wetting envelope
A wettability profile of a solid, the so-called wetting
envelope, can be created by determing the surface free
energy and its polar part and its disperse part..Wettability
σtotal describes the attempt of a solid to form a common
Θ>90° interface with a liquid which comes into contact with it.

Θ=30°

Θ=0°

Calculation „wetting envelope“

of a solid phase

σpolar

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Topics

Theory
• Wetting behavior
• Influence of surface tension / surface free energy

Measuring and calculation methods

• Static and dynamic surface tension
• Surface free energy

Application
• Selection of surfactants depending on the application process
• Recoatability is predictable – optimization of recoatability between
solventborne-primer and waterbased-basecoat

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Measuring and Caculation Methods

Liquid Paint Dry Coatings film, Substrate

Static surface tension Dynamic surface tension Surface free energy
Du Noüy ring method: Bubble pressure method Contact Angle Measurement
Determination of the surface tension of a
liquid

A platinum-iridium ring is In fast application To determine the free

drawn out of the liquid processes, the surface- surface energy of solids,
while, at the same time, active substances must contact angle
the maximum force be mobile in order to measurements are carried
caused by the tension of cover the newly created out with defined liquids,
the liquid lamella during surfaces as quickly as and these measurements
the movement of the ring possible and thereby are then used to calculate
is measured keep the surface tension the free surface energy
constant. using different models
(OWRK, Wu, etc.).

90°
45°

0
° Substrate
0° <90° 90° >90° 180°

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Static Surface Tension
Du-Noüy Ring Method

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Static Surface Tension
Measurement

Surface tension is a result of intermolecular interactions within the liquid phase.

• In the liquid / gas interface, the cohesive forces are directed inwards and sidewards, resulting in a
contracting force at this interface.
• Interactions with gas phase can be neglected

Phase 2 (gas)

surface

Phase 1 (liquid)

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Static Surface Tension
Du Noüy Ring Method

Static Surface Tension

Measurement by Du Noüy ring method
The wetting of a surface with a
liquid depends on the surface tension
of the liquid.
Definition of surface tension:
work that must be applied in order to
enlarge the surface of a phase

Du Noüy ring method: .

Determination of the surface tension of
a liquid. .
A platinum-iridium ring is drawn out of
the liquid while, at the same time, the
maximum force caused by the tension
of the liquid lamella during the
movement of the ring is measured.

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Static Surface Tension
Du Noüy Ring Method

Fmax - FV
 =
L * cos 
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Static Surface Tension
Determination polar and disperse Parts of Liquids

Requirements:
• The total surface tension of the liquid is known
• The surface free energy of a solid is known and totally non-polar
• The contact angle between solid and liquid can be measured

Solid (σs = σsd = 20 mN/m)

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Dynamic Surface Tension
Bubble Pressure Method

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Dynamic Surface Tension
Examples

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Dynamic Surface Tension
Bubble Pressure Method

Dynamic Surface Tension

Measurement by Bubble Pressure Tensiometer

In fast application processes, the

surface-active substances must be
mobile in order to cover the newly
created surfaces as quickly as possible
and thereby keep the surface tension
constant.

Bubble pressure method: .

Determination of the dynamic surface
tension. .
Bubbles with different surface ages are
generated within the liquid, and the
maximum internal pressure of the
bubbles is determined.

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Dynamic Surface Tension
Bubble Pressure Method

P0 = hydrostatic pressure
Pressure (Pa)

r1 > r2 > r3 < r4 < r5

r3 = rc
rc = radius of capillary

(Pmax – P0) rc
d =
2

Time (ms)

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Surface free Energy
Contact Angle Measuement

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Surface free Energy
Measurement

Solid samples cannot adjust their surface area …

But they influence the liquid drop shape across the interface.

Phase 2 (liquid) Phase 3 (gas)

Phase 2 (liquid)

surface
surface

Phase 1
Phase 1 (solid) (solid)

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Surface free Energy
Contact Angle Measurement

Contact Angle Measurement

The hydrophobic or hydrophilic

properties of solids can be
determined with the help of the contact
angle measurement of water.
To determine the free surface energy
of solids, contact angle measurements
are carried out with defined liquids,
and these measurements are then .
used to calculate the free surface
energy using different models (OWRK, .
Wu, etc.).
In this way, the wetting behavior of
liquids on these solids can be
characterized.

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Surface free Energy
Contact Angle Measurement

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Surface free Energy
Calculation of Surface free Energy

Measurement of contact angles

of several test liquids

Selection of a
Calculation model

Surface free energy

The surface free energy is not an absolute value!

The value depends on the selection of test liquids and calculation method!
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Surface free Energy
Calculation Model: Owens,Wendt,Rabel,Kaelble,

• Most suitable method for paints and plastics

• Information of surface free energy and polar and disperse parts

10,00
9,00
8,00
7,00
6,00
5,00
4,00
3,00
2,00
1,00
0,00
0,00 0,50 1,00 1,50 2,00

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Topics

Theory
• Wetting behavior
• Influence of surface tension / surface free energy

Measuring and calculation methods

• Static and dynamic surface tension
• Surface free energy

Application
• Selection of surfactants depending on the application process
• Recoatability is predictable – optimization of recoatability between
solventborne-primer and waterbased-basecoat

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Selection of Surfactants depending on the Application Process
Task

• Measuring of the static surface tension

• Adjustment of the coating to the necessary surface tension

• Determination of the amount of surfactants used
• Differentiation of surfactants

• Measuring of the dynamic surface tension

• In the case of fast coating processes, adjustment to the necessary surface tension at the
desired application speed
• Determination of the amount of surfactants used
• Differentiation of surfactants

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Selection of Surfactants
Static Surface Tension as a Function of the Chemical Composition

30

28

26

24

22

20

18

16

14
solvent: H2O
12

10
0.2% 1.0% 0.2% 1.0% 0.2% 1.0% 0.2% 1.0%

BYK 348 BYK 3455 BYK 3450 DYNWET 800

KRÜSS K100 Measurement by DU Noüy ring method

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Selection of Surfactants
Static Surface Tension depending on the Paint System

UV PU-Dispersion 1K PU-Dispersion

50 50

45 45

40 40

35 35
control control
30 BYK-348 30 BYK-348
BYK-3455 BYK-3455
25 25

20 20

15 15

10 10
control BYK-348 BYK-3455 control BYK-348 BYK-3455

Dosierung:0.2%

KRÜSS K100 Measurement by DU Noüy ring method

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Selection of surfactants
application
Test system:
Water-borne system
applied on artificial
leather substrate, partly
modified with a
surfactant additive.

without Additive with Surfactant

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Selection of Surfactants
Dynamic Surface Tension as a Function of the Chemical Composition depending on the
Application Speed

Oberflächenspannung vs.surface
Surface tension vs. Oberflächenalter
age
70
BYK 3450 0.2% H2O
DYNWET 800 0.2% H20

65 BYK 348 0.2% H20

BYK 3455 0.2% H2O

60

55
Oberflächenspannung [mN/m]
Surface tension [mN/m]

50

45

40

35

30

25

20
7 10 50 100 500 1000 5000

Oberflächenalter
Surface age [ms][ms]

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Selection of Surfactants
Conclusion

• When using surfactants in aqueous coatings,

it is necessary to adapt the static surface tension to the respective substrate
in order to achieve good substrate wetting.

• When using surfactants for substrate wetting with fast application methods, the dynamic
surface tension can be used to optimally adapt the aqueous coating to the respective
application speed and to the substrate.

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Recoatability is predictable
Task

Optimization of recoatability of a cured solvent borne primer with a water based

base-coat by prediction of wetting behavior

Measurement and calculation methods:

• Surface free energy of the cured primer with different additives
• Surface tension ( with polar and disperse parts) of the liquid base-
coat
• Contact angle of the base-coat on primer
• Calculation of the “wetting envelope”
• Application

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Recoatability is predictable
Measuring Results

contact angle (°)

surface free disperse parts polar parts basecoat on
energy mN/m mN/m mN/m primer
sb primer control 26,8 22,6 4,2 42
sb primer + 0.1% BYK-310 25,4 20,2 5,2 51
sb-primer + 0.3% BYK-3560 31,9 22,5 9,4 32
wb-basecoat * 29,3 22,4 6,9
*surface tension liquid

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Recoatability is predictable
Optimization of Recoatability / Wetting Envelope

control BYK-310 BYK-3560

x = surface tension value of the base-coat system

Page 35 9/30/2020 Measurement of Surface Tension and Energy -- = wetting envelope of the primer system
Recoatability is predictable
Application

Dry film thickness

0 µm

Test system:
Water-borne base coat
applied onto a solvent-
borne primer surfacer,
partly modified with a
surface-active additive

20 µm
0 µm
Control 0.1% BYK-310 0.3% BYK-3560 Base Coat
Primer surfacer + additive
on total formulation

20 µm

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