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Defoamer Mark Heekeren, Lab Manager Technical Service Automotive Coatings Wesel, 12. August 2015

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Defoamer

Mark Heekeren, Lab Manager Technical Service Automotive Coatings

Wesel, 12. August 2015

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7/20/2015, Page 2, Defoamer

Content

• What is foam – foam stabilization

• Mode of action of defoamers

• Defoamer classes

• Defoamer test methods

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Effect of Foam / Air

• Poor visual appearance

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

• Poor application properties

• Decreased water resistance

Defoamers are used, in order toavoid it!!!

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Types of Foam –Foam is an emulsion of a gas in a liquid

Wet Foam Dry Foam

Macrofoam (>100 µm)Microfoam (10 µm - 70µm)

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• Adsorbed air (pigments, extenders)

• Reaction bubbles (e.g., carbon dioxide in PU systems)

• Incorporated air (production, application)

• Air from the substrate (wood, concrete, ...)

Causes for Foam

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Bubbles Break at Surface*

Pure liquids do not foam !

Drainage effect

Lamella = double wall interface

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Foam Stabilization

hydrophobic

non-polar

hydrophilic

polar

Surfactant

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• Gibbs-Marangoni-Effect

• Formation of electrostatic/steric repulsing double layers

• Gasdiffusion

• Foam stabilization through solid particles

• Influence of viscosity

Mechanisms of Foam Stabilization:

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Gibbs-Marangoni-Effect (elasticity)

γγγγ

γ + ∆γγ + ∆γγ + ∆γγ + ∆γ

γ γ γ γ −−−− ∆γ∆γ∆γ∆γ

Transport of surfactant/water

mixtures in the direction of the

arrows shown

Higher elastic behavior is

stronger foam stabilization

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Electrostatic Repulsion

+

+

+

+

+

+

+

+

+

+

>10 nm

+

+

+

+

+

+

+

+

+

+

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The size of neihgbouring foam bubbles differs:

�Inner pressure in small bubbles is higher then in large bubbles

�Under high pressure more gas is dissolved as under low pressure

Gas diffusion: large bubbles grow at the expense of small bubbles

Gas diffusion can stop because of saturation of the interface with

surfactant molecules

Air and CO2 dissolve better into the liquid phase then nitrogen

Gasdiffusion

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Bubbles Rise to Surface

V = Velocity of rise

r = Bubble radius

η = Viscosity of liquid

~Vr2

η__

Foam is a dispersion of a gas in a liquid, stabilized by surface active substances

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Mode of Action

Properties of a defoamer:

• Low Surface Tension

• Good spreading ability

• Insoluble / Incompatible in the surrounding medium

silicones, mineral oils and certain polymers fulfill these criteria's

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Spreading of Defoamer

• Marking water surface

with inert powder

• Adding one droplet

of defoamer

���� Rapid spreading

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Defects

Foam

Defoamer Selection

compatible/soluble

incompatible/

insoluble

Defoaming

Foam stabilization

Optimum

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Mode of Action of Hydrophobic Particles

- Synergy between hydrophobic particles and defoamer oil

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

- Destabilization of lamella through high hydrophobicity and dewetting of the particles

- Chemistry: hydrophobic silica, polyurea , waxes

polyamides and metal salts

- Only used in water-borne systems

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Defoamers

Act at the surface

Air Release Additives

Act in the resin

Defoamers - Air Release Additives

No clear differentiation!

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Defoamer molecules

Foam stabilizing substances

Formation of microfoamafter application

Removal of surfactants and covering of the bubble surface by defoamer molecules

Increased speed of gas diffusion into the liquid phase

���� Microfoamdisappears

Different mechanism compared to bubble rupture at the surface!

Deaeration - Mode of action inside the liquidIncreasing speed of gas diffusion

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Incorporation / Emulsification of DefoamersDroplet Size Distribution

Substrate

Defoamer

Good compatibilitygood emulsification:

- Strong defoaming

- Good substrate wetting

- no cratering

Substrate

Defoamer

Too compatibleover emulsification:

- Weak defoaming

- Good substrate wetting

- no cratering

Substrate

Defoamer

Too incompatiblepoor emulsification:

- Strong defoaming

- Poor substrate wetting

- cratering

Paint

Shear ForceIncorporation time

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Foam Prevention

• Optimization of production process

• Wetting of solid particles

• Minimize utilization of foam stabilizing components

• Adjusting application conditions (if possible)

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

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Defoamer for Aqueous Systems

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Defoamer Classes for Aqueous Systems

• Mineral oil defoamers

• Silicone defoamers

• Silicone-free polymeric defoamers

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Composition of Mineral Oil Defoamers

%

Mineral oil 85 - 95

Hydrophobic particles 1 - 3

Emulsifier 3 - 6

Modified polysiloxanes 0,5 - 3

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Mineral Oil Defoamers for Emulsion Paints and Plasters

Interior paints

Plasters

Industrial

emulsions

Gloss and semigloss paints

Emulsion production

Emulsion

type

Contains silicone

BYK-035* 100% Yes

BYK-037* w/o Yes

BYK-038* 100% Yes

BYK-039* 100% No

good excellent

*Alkylphenol-ethoxylate-free

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Defoamer Classes for Aqueous Systems

• Mineral oil defoamers

• Silicone defoamers

• Silicone-free polymeric defoamers

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Composition of Silicone Oil Defoamer

%

Silicone Oil 5-90

Hydrophobic particles 1 - 3

Emulsifier 3 - 6

Polyglycol or Water 0-85

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Polydimethylsiloxane

compatible incompatible

2 - 30 45 - 230 1800 - 2900380 - 1500

DefoamingLeveling Slip Hammertone

x

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

CH3

CH3x

Not used in Aqueous

Paint Systems

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Silicone Defoamers

n

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

CH3CH3

CH3(CH2)x

Polyether

R

m

Polyether: EO, PO, EO/PO

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suitable recommended

VOC-free

Low dosage (0,1 – 0,5%)

Suitable for PVC range between 30-85%

APEO-free

No “Fogging”

Silicone Defoamers for Emulsion Paints and Plasters

Interior paints,

Plasters

Gloss and semigloss paints

Sealers, transparent systems

Emulsion production

Solids

[%]

BYK-023 18.5

BYK-1610 17.0

BYK-1615 12.5

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Silicone Defoamers for Architectural and Wood Coatings

Architectural coatings and Joinery

Wood and furniture coatings

Solids

[%]

BYK-1730 For pigmented high gloss systems, PVC 18-25 100

BYK-1770 Airless/Airmix 100

BYK-1780 100

BYK-1785 30

suitable recommended

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Defoamer selection for waterborne systemsGeneral overview

Sh

ea

r F

orc

e

Time of incorporation

Post Addition

Letdown

Millbase

Silicone defoamer with

hydrophobic particles

Silicone defoamer w/o

hydophobic particles

BYK-1770

BYK-021

BYK-019

BYK-018

BYK-028

BYK-024

BYK-025

BYK-017

BYK-022

BYK-023 BYK-094

BYK-1610 BYK-1650

BYK-1730

BYK-1719

BYK-1615

BYK-044

BYK-093

BYK-1798

BYK-1785

BYK-1780

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Silicone Defoamers for Aqueous Systems

Solids

%

Hydrophobic

Particles

Carrier/Solvent

BYK-017 100 • -

BYK-018 100 •Polyglycol MW >1000,

hydrophobic

BYK-019 60Dipropyleneglycol

monomethylether

BYK-1719 100 • -

BYK-021 100 •Polyglycol MW >1000,

hydrophobic

BYK-022 100 •Polyglycol MW >1000,

hydrophobic

BYK-023 18.5 • Water/Emulsion

Polyether = PO

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Silicone Defoamers for Aqueous Systems

Solids

%

Hydrophobic

Particles

Carrier/Solvent

BYK-024 100 •

Polyglycol MW <1000,

hydrophilic/hydrophobic:

emulsifiable

BYK-1650 27 • Water/Emulsion

BYK-025 20 Dipropyleneglycol-monomethylether

BYK-028 100 • Polyglycol MW >2000, hydrophilic

BYK-044 57 • Water/Emulsion

BYK-093 100 • Polyglycol MW >2000, hydrophilic

BYK-094 100 •Polyglycol MW <1000,

hydrophilic/hydrophobic

Polyether = EO or EO/PO

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Defoamer Classes for Aqueous Systems

• Mineral oil defoamers

• Silicone defoamers

• Silicone-free polymeric defoamers

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Silicone- and Mineraloil-free Polymeric Defoamers for Water-Borne Systems

Emulsion Paints and

Plaster

PVC 30-85

Alkyd-

emulsions

Emulsion-polymerisa

tion process

Printing Inks and OPV

Acrylic/

Melamine Pigmented

Dosage

BYK-012 0,05 - 0,5%

BYK-014 0,05 - 0,5%

BYK-016 1 - 2%

BYK-1640 0,05 - 0,5%

BYK-1740 0,2-0,5%

suitable recommended

BYK-1740: Green Defoamer Based on Eco-friendly and Sustainable Raw Materials

BYK-016: FDA § 175.105, 175.300, 175.320, 176.200, 176.21 approved

BYK-1640: Polymer-Emulsion, Polyamid particles ; FDA § 175.105, 175.300 approved

Polymeric defoamers are chemically stable in a pH range from 3-12

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Polymeric Defoamers for Water-Borne Systems

2K PU 2K EpoxyAlkyd

Emulsion

Water soluble Alkyd resins

PU Emulsion

Water-Based

UV

Dosage

BYK-011 1-2%

BYK-015 0,2 - 1%

BYK-1710 0,1 – 0,5%

BYK-1711 0,1 – 0,5%

suitable recommended

Polymeric defoamers are chemically stable in a pH range from 3-12

BYK-015: Anti Popping additive with defoaming properties

BYK-1711: Enhanced BYK-011. More efficient and improved

storage stability.

BYK-1710: VOC-free. AGBB Conform

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Polymeric-Defoamers for Waterborne Systems

Sh

ea

r F

orc

e

Post Addition

Letdown

Millbase

BYK-1740

BYK-016*

BYK-014

BYK-1711

BYK-015

BYK-1710

BYK-012

*FDA-approved, specifically for printing inks and paper coatings

Time of

incorporation

BYK-011

BYK-1640

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Silicone-free and Mineral Oil Free Anti Popping Additives for Aqueous Systems

2K-PU Acrylate/

Melamine pigmented

Alkyd emulsions

HAPS-free APEO-free Dosage

BYKETOL-WS No No 0,5 – 3,0%

BYKETOL-AQ Yes Yes 0,5 – 3,0%

good excellent

• Increase the popping limit of water borne paints

• No influence on recoat ability

• Reduce the crater sensitivity

• Can improve the levelling

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Defoamers for Solvent-borne and Solvent-free Systems

• Silicone defoamers

• Silicone-free polymer defoamers

• Silicone/polymer defoamers

• Silicones and acrylates with defoaming properties

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Defects

Foam

Defoamer Selection

compatible/soluble

incompatible/

insoluble

Defoaming

Foam stabilization

Optimum

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Influence of CompatibilityOne Defoamer in Three Different Solvents

Left: too incompatible

� turbid

Middle: too compatible

� foam stabilization

Right: good balance

���� clear, no foam

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Defoamer Selection for Solvent borne and Solvent free systems General Overview

Time of incorporation

Sh

ea

r F

orc

e

Silicone defoamer Silicone/Polymer defoamer Silicone free Polymer defoamer

BYK-1798

BYK-065

BYK-141

BYK-072

BYK-070

BYK-088

BYK-066N

BYK-052

BYK-1790BYK-054

BYK-055

BYK-057

BYK-051

BYK-1791

BYK-A535 BYK-1794

BYK-A530

BYK-077

BYK-085

BYK-081

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Surface Additives with Defoaming Properties

• BYK-077

• BYK-322

• BYK-323

• BYK-320

• BYK-354

• BYK-352

• BYK-392

• BYK-359

Silicones Acrylates

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Test Methods

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Defoamer Test Methods

• Shaking

• Stirring-in air by dissolver

• Introducing air by pump

• Rolling with porous foam roller

• Brush application

• Measurement of density

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Defoamer Test Methods - Shaking

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Defoamer Test Methods - Stirring-in of Air by Dissolver

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Defoamer Test Methods - Rolling With Foam Roller

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Defoamer Test Methods - Brush Application

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Defoaming: Influencing Factors

Point of

addition

Shear forces needed

for incorporationDuration of

incorporation

Dosage

Defoamer selection

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Summary

• Foam prevention

1. Production

2. Application

• Correct additive selection

1. Wetting and dispersing additives

2. Surface additives

• Usage of defoamers

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ANTI-TERRA®, BYK®, BYK®-DYNWET®, BYK®-SILCLEAN®,

BYKANOL®, BYKETOL®, BYKOPLAST®, BYKUMEN®, DISPERBYK®,

DISPERPLAST®, LACTIMON®, NANOBYK®, SILBYK® and

VISCOBYK® are registered trademarks of BYK-Chemie.

AQUACER®, AQUAFLOUR®, AQUAMAT®, CERACOL®, CERAFAK®,

CERAFLOUR®, CERAMAT®, CERATIX® and MINERPOL® are

registered trademarks of BYK-Cera.

This information is given to the best of our knowledge. Because of the

multitude of formulations, production, and application conditions, all the

above mentioned statements have to be adjusted to the circumstances of

the processor.

No liabilities, including those for patent rights, can be derived from this

fact for individual cases.