Defoamer

Wesel, October 2018

Adil Bilici, End Use Specialist, Protective and Marine Coatings
 Topics

• What is foam

• Foam stabilization

• Defoamers composition/mode of action

• Defoamer classes/selection

• Defoamer test methods

M&PC & GI Seminar

Adil Bilici
Page 2
 Types of Foam
Foam is a Dispersion of a Gas in a Liquid

Wet Foam Dry Foam

M&PC & GI Seminar Microfoam (10 µm - 70µm) Macrofoam (>100 µm)

Adil Bilici
Page 4
 Types of Foam
Wet Foam versus Dry Foam

M&PC & GI Seminar

Adil Bilici
Page 5
 Causes for Foam

Air from the substrate Absorbed air from fillers/pigments

(wood, concrete, ...) (other RM eg solvents, resins etc)

M&PC & GI Seminar

Incorporated air Reaction bubbles
Adil Bilici
Page 6
(caused by production process, application (e.g. carbon dioxide in PU systems)
method)
 Effect of Foam / Air in Coatings

- Poor visual appearance

- Decreased performance properties

(eg.water resistance)

- Long production time (e.g. filling of drums)

- Poor application properties

M&PC & GI Seminar

Adil Bilici
Page 7
 Pure Liquids Do not Foam!

M&PC & GI Seminar

Adil Bilici
Page 8
 Foam Stabilization by Surfactants

The lamella is stabilized by surfactants

No drainage effect

 stable foam

M&PC & GI Seminar

Adil Bilici
Page 9
 Mechanisms of Foam Stabilization

• Influence of viscosity

• Formation of electrostatic/steric repulsing double layers

• Gibbs-Marangoni-Effect / Elasticity of the System

• Retardation of gas diffusion

M&PC & GI Seminar

Adil Bilici
Page 10
 Mechanisms of Foam Stabilization
Influence of Viscosity – Bubbles Rise to Surface

Larger foam bubbles are easier to defoam, microfoam is difficult to defoam

Bubbles rise to the surface with a

velocity dependent
of the viscosity of the liquid.

r2
__
V~  Stoke's
law

V = Velocity of rise

M&PC & GI Seminar

r = Bubble radius
Adil Bilici
Page 11
 = Viscosity of liquid
 Mechanisms of Foam Stabilization
Formation of Electrostatic/Steric Repulsing Double Layers

Surfactant: non-polar tail Repulsion of surfactants prevents

polar head complete drainage of foam lamellas

M&PC & GI Seminar

Adil Bilici
Page 12
 Mechanisms of Foam Stabilization
Gibbs-Marangoni-Effect (elasticity)

Surface tension (γ) depends

on surfactant concentration
at the surface.

M&PC & GI Seminar

Transport of surfactant/water mixtures in the Higher elastic behavior means
Adil Bilici
Page 13 direction of the arrows shown stronger foam stabilization
 Mechanisms of Foam Stabilization
Gasdiffusion

The size of neighboring foam bubbles differs

 Inner pressure in small bubbles is higher than in large bubbles

p1 p2 p1 > p2

Gas diffusion: large bubbles grow at the expense of small bubbles (Ostwald ripening)

Gas diffusion can stop because of saturation of the interface with surfactant molecules

M&PC & GI Seminar

Adil Bilici
Page 14
 Mechanisms of Foam Stabilization
Gasdiffusion during Airless Application

Under high pressure a lot of microfoam appeares

Small bubbles are getting smaller

Direct after After drying

M&PC & GI Seminar
Adil Bilici application
Page 15
 Foam Prevention

Before adding a defoamer the possible reasons for foam stabilization should be eliminated

• Wetting of solid particles

• Minimizing foam stabilizing components

• Optimization of production process

• Adapt/optimize application process and type

Defoamers
M&PC & GI Seminar
Adil Bilici
Page 16
 Requirements for Defoamers

• Insolubility/incompatibility in the system to be defoamed

• Low surface tension

• Good dewetting properties

• Good spreading ability

• Insoluble / Incompatible in the system to be defoamed

Silicones, mineral oils and some polymers fulfil these criteria

There are no compatible defoamers!

M&PC & GI Seminar

Adil Bilici
Page 17
 Mode of Action Inside the Foam Lamella

Defoamer droplet
enters the lamella

• Bridging
• Spreading
• Dewetting

M&PC & GI Seminar

Adil Bilici
Page 18
 Spreading of Defoamer

Water surface marked with an inert powder. Addition of one defoamer droplet

M&PC & GI Seminar

Adil Bilici
Page 19
 Rapid spreading
 Definition: Entering and Spreading Coefficient

• Entering coefficient
E = F + int - D

• Spreading coefficient
S = F - int - D

• Defoamer:
E > 0 and S > 0

F = Surface tension of fluid

int = Interfacial tension fluid/defoamer
D = Surface tension of defoamer
M&PC & GI Seminar
Adil Bilici
Page 20
 General Composition of a Defoamer for Aqueous Systems

Mineral oil or silicone oil or incompatible polymer

Defoamers need to have a certain incompatibility!

Hydrophobic particles

Other components

M&PC & GI Seminar

Adil Bilici
Page 21
 Hydrophobic Particles
used mainly in Defoamers for Water-borne Systems

- Hydrophobic particles are finely dispersed or formed „in situ“ into the defoamer oil

- Synergy between hydrophobic particles and defoamer oil

- Rough, structured particles are more efficient then ball shaped particles

- Chemistry: hydrophobic silica, polyurea, waxes, amides, metal salts

M&PC & GI Seminar

Adil Bilici
Page 22
Hydrophobic silica
 Hydrophobic Particles
Enhanced Defoaming Effect

Foam
lamella

Destabilization due to high

hydrophobicity and dewetting

Defoamer Hydrophobic Foam stabilizing

droplet particle surfactant
M&PC & GI Seminar
Adil Bilici
Page 23
 Influence of Incorporation / Emulsification
Defoamers Droplet Size Distribution

M&PC & GI Seminar

Adil Bilici
Page 24
 Defoamer Selection

Defoaming A good defoamer is

slightly in-compatible in
Optimum the test system, but does
not cause craters and
defects
Defects

compatible/ incompatible/
soluble insoluble

Foam

Foam stabilization

M&PC & GI Seminar

Adil Bilici
Page 25
 Defoamer Selection
Influencing Parameters

Point of
addition

Defoamer
selection
Duration of
in-corporation

Dosage
Shear forces level
needed for
incorporation
M&PC & GI Seminar
Adil Bilici
Page 26
 Defoamers for Waterborn Systems

M&PC & GI Seminar

Adil Bilici
Page 27
 BYK-Defoamer Classes for Water-borne Systems

- Mineral oil defoamers

- Silicone defoamers

- Polymeric defoamers (silicone-free)

Composition of defoamers for Aqueous system

- Mineral oil, silicone oil or water insoluble polymer
- Hydrophobic particles
- Carrier
- Other ingredients (e.g fungicides, emulsifiers)

M&PC & GI Seminar

Adil Bilici
Page 28
 Defoamer Comparison

Mineral oil Silicone Polymer

Cost
+ - -
Efficiency
- + +/-
No pH sensetivity
+ - +
No gloss retention
- + +
Storage
- + +
VOC-free possibility
+ + +

M&PC & GI Seminar

Adil Bilici
Page 29
 Composition of Mineral Oil Defoamer

%
Mineral oil 85 - 95
Hydrophobic particles 1-3
Emulsifier 3-6
Modified polysiloxanes 0,5 - 3

M&PC & GI Seminar

Adil Bilici
Page 30
 Mineral Oil Defoamer

Interior paints Industrial Gloss and Emulsion Emulsion Contains

Plasters emulsions semigloss production type silicone
paints
Alkylphenol-ethoxylate-free defoamers
BYK-035
100% Yes

BYK-037 w/o Yes

BYK-038
100% Yes

BYK-039
100% No

good excellent

M&PC & GI Seminar

Adil Bilici
Page 31
 Composition of Silicone Oil Defoamer

%
Silicone oil 5-90
Hydrophobic particles 1-3
Emulsifier 3-6
Polyglycol and/or water 0-85

M&PC & GI Seminar

Adil Bilici
Page 32
 Polysiloxanes based Defoamer

CH3 CH3
CH3
(CH3)3Si O Si O Si O Si(CH3)3
(CH3)3Si O Si O Si(CH3)3
CH3
CH3 z

modification
x

Organic
Not for waterborne systems!

y
compatible incompatible

z 2 - 27 45 - 230 380 - 1500 1800 - 2900

M&PC & GI Seminar

Leveling Surface Slip Defoaming Hammertone
Adil Bilici
Page 33
 Appearance of Silicone Defoamer for Water-borne Systems

Silicone Silicone Silicone Silicone

Defoamer in plus Polyurea plus Silica Emulsion
solution

M&PC & GI Seminar

Adil Bilici
Page 34
 Silicone Defoamer for Water-borne Systems

Active Hydrophobic Carrier/Solvent

content % particles
BYK-017 100  -
Polyglycol MW >1000,
BYK-018 100 
hydrophobic
Dipropyleneglycol
BYK-019 60
Monomethylether
BYK-1719 100  -

Polyglycol MW >1000,
BYK-021 100 
hydrophobic
Polyglycol MW >1000,
BYK-022 100 
hydrophobic
BYK-023 18.5  Water/Emulsion
M&PC & GI Seminar
Adil Bilici
Page 35
 Silicone Defoamer for Water-borne Systems

Active Hydrophobic Carrier/Solvent

content % particles
Polyglycol MW <1000,
BYK-024 100 
emulsifiable
BYK-1650 27  Water/Emulsion

BYK-025 20 Dipropyleneglykol-monomethylether

BYK-028 100  Polyglycol MW >2000, emulsifiable

BYK-044 57  Water/Emulsion

BYK-093 100  Polyglycol MW >2000, emulsifiable

BYK-094 100  Polyglycol MW <1000, emulsifiable

M&PC & GI Seminar

Adil Bilici
BYK-1724 27  Water/Emulsion
Page 36
 Silicone Defoamer Selection for Water-borne Systems
Overview

BYK-044

Shear forces
BYK-1730 BYK-017
Millbase
BYK-021 BYK-018 BYK-1719

BYK-1780 BYK-022 BYK-019

BYK-1785 BYK-1723 BYK-094

Let down BYK-024 BYK-1650

BYK-1724 BYK-1611

BYK-1770 BYK-1617 BYK-1798

BYK-093

BYK-028

Post Addition BYK-025 Time of incorporation

Silicone defoamer with Silicone defoamer without

M&PC & GI Seminar
Adil Bilici
hydrophobic particles hydrophobic particles
Page 37
 Ex: Increasing the Effect of Defoamer with Surface Additive
Water-borne 2K Epoxy System

Component A Component B
0,5 % BYK-094 gives good
Distilled water 14,5 Waterborne epoxy hardener 39,0
defoaming properties on the let
OPTIGEL CK 0,2 Distilled water 42,0
down process
DISPERBYK-190 1,0 Co-solvent 18,0
BYK-021 0,1 DMP-30 1,0 0,1 %BYK-3456 surface additive
Titanium dioxide 13,0 Total 100,0 increase the effect of the
Barium sulfate 20,0 Component A: B = 100,0: 10,0 (by weight) defoamer.
Anti-corrosion pigment 5,0
Talc 7,0
Co-solvent 1,0
Combination defoamers
Waterborne epoxy binder 36,0 with surfactants can be
Anti-flash rust agent 0,6 useful to improve
BYK-094 0,5 defoaming effect.
OPTIFLO H600 VF 0,5
BYK-3456 0,1
Total 100,0

M&PC & GI Seminar

Adil Bilici
Page 38
 Silicone Defoamers for Spray Applied Systems
Especially for Airless/Airmix Application

higher BYK-1781 BYK-1780

Defoaming Properties

BYK-1785

Silicone Defoamer with

BYK-1770 hydrophobic particels

Silicone Emulsion with

hydrophobic particels

Silicone Defoamer without

hydrophobic particels
lower
lower Incompatibility higher
M&PC & GI Seminar
Adil Bilici
Page 39
 Polymer Defoamer for Water-borne Systems
General Overview

High

BYK-012
Shear Force

BYK-1740 BYK-014

BYK-1710

BYK-015

BYK-1711

BYK-011 BYK-016*
Low

Time of incorporation
M&PC & GI Seminar
Adil Bilici
*FDA-approved, specifically for printing inks and paper coatings
Page 40
 Polymeric Defoamer for Water-borne Systems
(silicone-free)

Water Water-
Alkyd PU Based
2K PU 2K Epoxy soluble Alkyd Dosage
Emulsions Emulsion
resins UV
BYK-011 0,1-1,5%
BYK-015 0,2 - 1%
BYK-1710 0,1 – 0,5%

suitable recommended

BYK-015: Anti-popping additive with defoaming properties

BYK-1710: VOC-free, AGBB compliant

M&PC & GI Seminar
Adil Bilici
Page 41
Polymeric defoamers are chemically stable in a pH range from 3-12
 Anti Popping Additives for Aqueous Systems

Increase of the popping limit of water-borne paints

 No influence on recoatability
 Reduction of the crater sensitivity
 Can improve the levelling

2K-PU Acrylate/ Alkyd emulsions HAPS-free APEO-free Dosage

Melamine
pigmented
BYKETOL-WS No No 0.5 – 3.0%
BYKETOL-AQ Yes Yes 0.5 – 3.0%

good excellent
M&PC & GI Seminar
Adil Bilici
Page 42
 Differences of Anti-Popping Additives

Polymer Emulsifier APEO-free Solvent

BYKETOL-WS A A No Butyl glycol

BYKETOL-AQ B B Yes Methoxy-propanol

BYK-LP D 21649 C B Yes Methoxy-propanol

BYK-LP D 22857 A C Yes Butyl glycol

M&PC & GI Seminar

Adil Bilici
Page 43
 Defoamer for
solvent-borne systems

M&PC & GI Seminar

Adil Bilici
Page 44
 Defoamer for Solvent-borne and Solvent-free Systems

Silicone defoamers

Silicone-free polymer defoamers

Silicone/polymer defoamers

M&PC & GI Seminar

Adil Bilici
Page 45
 Polysiloxane based Defoamer
for Solvent-borne Systems

CH3 CH3
(CH3)3Si O Si O Si O Si(CH3)3

CH3
x

modification
CH3

Organic
(CH3)3Si O Si O Si(CH3)3

CH3
x y

M&PC & GI Seminar

Adil Bilici Organic modification = Akyl, Polyether or Fluororganic modification
Page 46
 Influence of Compatibility
One Defoamer in three Different Solvents

too too good The effectiveness of defoamers

incompatible compatible balance depends on the polarity of the used
 turbid  foam stabilization  clear, no foam system.

Ethanol Xylene Butylacetat

M&PC & GI Seminar
Adil Bilici
Page 47
 Defoamer Selection for Solvent-borne Systems
General Overview

BYK-1799
BYK-066N
BYK-065

BYK-051N BYK-052N
BYK-054 BYK-1790
Shear Force

BYK-1788 BYK-A535 BYK-1794 BYK-077

BYK-085
BYK-1791
BYK-057 BYK-1798

BYK-A530

BYK-055 BYK-141 BYK-070

BYK-088

BYK-072

Silicone defoamer Silicone/Polymer defoamer Time of incorporation

M&PC & GI Seminar
Silicone free Polymer defoamer
Adil Bilici
Page 48
 Defoamer Selection for Solvent-borne and Solvent-free Systems
Recommendation GI and M&PC Systems

BYK-1799
BYK-066N

BYK-052N
BYK-054 BYK-1790
Shear Force

BYK-1788 BYK-A535 BYK-1794 BYK-077

BYK-085

BYK-057 BYK-1798

BYK-A530

BYK-141

BYK-088

Silicone defoamer Silicone/Polymer defoamer Time of incorporation

M&PC & GI Seminar
Silicone free Polymer defoamer
Adil Bilici
Page 49
 2-pack Epoxy System

Formulation Component A

Pos. Component Supplier Function Weight [g]

Without BYK-A 530 With BYK-A 530
1 Epikote 1001X75 Hexion Binder 23.0

2 Xylene Solvent 6.0

3 Dowanol PM Dow Solvent 5.0

4 GARAMITE 1958 BYK Rheology Additive 1.0

5 DISPERBYK-142 BYK W&D Additive 0.9

6 Bayferrox 130M Lanxess Pigment 4.7

7 Finntalc M 65 Mondo Minerals Filler 12.0

8 Heucophos ZPA Heubach Anticorrosion Pigment 20.0

9 EWO Sachtleben Filler 14.0

10 BYK-A 530 BYK Defoamer 0.5

11 Dowanol PM Dow Solvent 5.2

12 Xylene Solvent 7.7

100.0

Formulation Component B

Pos. Component Supplier Function Weight [g]

M&PC & GI Seminar 1 Epikure 3155 Hexion Hardener 4.6

Adil Bilici
Page 50
 BYK-1799 and BYK-1788

Defoamer for solvent-borne, high-solid and solvent-free systems.

BYK-1799 BYK-1788

Silicone containing defoamer Polymeric defoamer, Silicone free

Solvent free Solvent free

VOC free VOC free

Very strong defoaming action Very compatible

even at a low dosage
Very good in airless application
Eliminates micro- and macrofoam

M&PC & GI Seminar

Adil Bilici
Page 51
 Defoamer Selections for Solventborne 2K PU Systems
-Side reactions and foaming

Main crosslink reaction (no foaming)

• -OH + -NCO -NH-CO-O-

Side reaction (foaming)

• H2O + -NCO -NH-CO-OH -NH2 + CO2
Faster
• -NH2 + -NCO -NH-CO-NH-

Side reaction (foaming)

Faster

• -COOH + -NCO -NH-CO- + CO2

1,8 gram of water can lead 2,24 liter carbon dioxide in paint film !!!
M&PC & GI Seminar
Adil Bilici
Page 52
 Source of Side Reactions

When solvent When pigment / filler

containing water containing water

Source of
side reaction

When application at
When binder acid value
high humidity / lower
is too high
M&PC & GI Seminar
temperature (winter)
Adil Bilici
Page 53
 Reaction Foam and Defoamers

2K PU with 2K PU with
0.3% water 0.3% water 0.5% defoamer 0.5% defoamer +
inside inside + 0.5% acetic acid
0.5%
defoamer

M&PC & GI Seminar

Adil Bilici
Page 54
Additionally, faster curing speed prevent the side reactions.
 Surface Additives with Defoaming Properties

Silicones Polyacrylates

• BYK-077 • BYK-354

• •BYK-322 • BYK-352

• •BYK-323 • BYK-392

• BYK-359
• •BYK-320

M&PC & GI Seminar

Adil Bilici
Page 55
 Defoamer Test Methods

M&PC & GI Seminar

Adil Bilici
Page 56
 Defoamer Test Methods

• Measurement of density

• Stirring-in air by dissolver

• Shaking

• Rolling with porous foam roller

• Brush application

• Actual application method

M&PC & GI Seminar

Adil Bilici
Page 57
 Test Method - Measuring the Specific Density

1. Use high speed mixer to foam up the material (e.g. ink, coating, pigment concentrates)

2. Pour material into a measuring cylinder (e.g. 50ml) or use Pyknometer

50
40
30
20
10

3. Calulate density: Weight [g]

Density = = g/cm3
Volume [cm3]
M&PC & GI Seminar
Adil Bilici
Page 58
 Defoamer Test Method:
Pour – Out Test

For any type of

medium to lower
viscosity paint, easy
to see the amount of
foam and the activity
of the defoamer

M&PC & GI Seminar

Adil Bilici
Page 59
 Defoamer Test Method:
Compatibility of a Defoamer

Application on glass panel to evaluate compatibility / crater tendency

Slightly
Incompatible Incompatible Compatible
defoamer defoamer defoamer

M&PC & GI Seminar

Adil Bilici
Page 60
Black spots are defects and craters
 Defoamer Test Method:
Shaking

For low
viscosus
material,
usually used
for emulsions
in deco

M&PC & GI Seminar

Adil Bilici
Page 61
 Foam Test – Roller

M&PC & GI Seminar

Adil Bilici
Page 62
 Foam Test - Brush

M&PC & GI Seminar

Adil Bilici
Page 63
 Testing on Real Conditions
Influence on Foam of Airless Application

Every paint system performance should be tested/ controlled under actual application parameters.

Drying conditions
Horizontal Vertical

M&PC & GI Seminar

Adil Bilici
Page 64
 Summary

Foam prevention
1. Production
2. Application

Correct additive and raw material selection

1. Wetting and dispersing additives
2. Surface additives

Usage of defoamers
There is no compatible defoamers
There is no general defoamers

M&PC & GI Seminar

Adil Bilici
Page 65
Thank you for
your attention.