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1 1 presented by Nanoparticles Improve Coating Performances Dr. Thomas Sawitowski, Manager Nanotechnology The use of Nanoadditives in plastic and coating compositesICNT, San Francisco 2005 2 Out-line Definition of Nanotechnology Current applications in coatings and compounds Scratch resistance Influence of surface treatments Nano-Additives for UV curable applications Nano-Additives for solvent-borne coatings UV-stability • Conclusions

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Page 1: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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1

presented by

Nanoparticles Improve Coating Performances

Dr. Thomas Sawitowski,

Manager Nanotechnology

“The use of Nanoadditives in plastic and coating composites“ICNT, San Francisco 2005

2

Out-line

• Definition of Nanotechnology

• Current applications in coatings and compounds• Scratch resistance

• Influence of surface treatments• Nano-Additives for UV curable applications• Nano-Additives for solvent-borne coatings

• UV-stability

• Conclusions

Page 2: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Applications / End-Uses of BYK Chemie

Pigment Concentrates Powder Coatings Can CoatingsPolyurethane Foams Compounds

Printing Inks Wood/Furniture Coatings Industrial CoatingsCoil CoatingsAutomotive OEM

Architectural CoatingsPVC Plastisols Ambient Curing Resins Thermoplastics Automotive Refinish

4

Let´s go Nano!

This is really an innovative approachBut I‘m affraid we can‘t consider it.

It‘s never done before

Page 3: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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5

Ener

gie

Nanotechnology

• Change in properties due to a change in size• Conductivity of metals ≈ 2 nm• Fluorescence of Q-dots ≈ 10 nm• Transparency of ceramics ≈ 20 nm• Colour of metals ≈ 50 nm• Stiffness of metals ≈ 250 nm• Ductility of ceramics ≈ 500 nm

0%20%40%60%80%

100%

0 1 2 3 4 5 6 7 8 9 10

Diameter [nm]

Su

rfac

eA

tom

s[%

]

• Increase in specific surface area• Reactivity• Surface energy

• Shape• Anisotropy of properties

6

Nanoparticles

• Basic Processes

Top-Down• Grinding

Bottom-up• Gas Phase Synthesis • Chemical precipitation• Sol-Gel-Chemistry• Emulsion techniques• Plasma-spraying• Spray drying• Hydrothermal synthesis• ...

Page 4: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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PVS Al2O3

Flame Synthesis Al2O3

Precipitated Al2O3

Nanoparticles

8

Nanoparticles

Material Property

• Silica Hardness• Alumina Hardness• Zirkonia Hardness• Diamond Hardness• Silicone carbide Hardness• Layered Silicates Barrier / Flame retardant• Zinc oxide UV/bactericide• Titania UV• Ceria UV• Iron oxide Magnetism• Cupper oxide /Silver oxide Bactericide• Metals Conductivity• ITO/ATO Conductivity / IR-Absorption• Carbon nanotubes Conductivity / Mechanical prop.• Silsesquioxane Mechanical prop.• Dendrimers Mechanical prop.• Capsules Carrier• ……

Page 5: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Nanoparticles

Effect of Material and Particle Size on Transparency

1,E+00 1,E+01 1,E+02 1,E+03 1,E+04 1,E+05 1,E+06 1,E+07 1,E+08 1,E+09 1,E+10

TiO2

ZnO

Alumina

Silica

Magnitude of Rayleigh Scattering [a.u.]

40 nm 20 nm 10 nm

10

Nanoparticles

Effect of Material and Film Thickness on Transparency

1,00E-03 1,00E-02 1,00E-01 1,00E+00 1,00E+01 1,00E+02 1,00E+03 1,00E+04

100 µm / 2%

25 µm / 2%

100 µm / 0,2%

25 µm / 0,2%

Magnitude of Rayleigh Scattering [a.u.]

SilicaAluminaZnOTiO2

Page 6: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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• Interface Region in the Matrix• Glass Transition Temperature• Conductivity• E-Modulus• Cross-linking density• ….

Nanoparticles

• Nanoparticle Core• Determines mechanical, chemical,

electronical and biological properties

Nanoparticle ShellSolubilityReactivity

Compatibility

• Nanoparticle Shell• Determines solubility, reactivity, and

compatibilityNanoparticle CoreMechanical Prop.Chemical Prop.Electronic Prop.Biological Prop.

12

Percolation of Properties

NanoparticlesModified Properties

Properties unchanged

Page 7: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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NANOBYK‘s

Paint ApplicationScratch resistance in UV Clear Coatings

14

W&D additiveSilicone

Al2O3

Nanoadditives for UV-curable coatings

Page 8: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Nanoadditives for UV-curable coatings

Grades, abrasion scrub tester, 1000 cycles, eight different resin systems

1. aromatic Epoxy acrylate / EA2. aromatic Epoxy acrylate / EA3. Polyester acrylate / PE4. Polyester acrylate / PE5. aliphatic Urethane acrylate / UA6. aromatic Urethane acrylate / UA7. Polyether acrylate / PO8. amine modified Oligoether acrylate /POA

0

1

2

3

4

5

6

Control 1,5% 40 nm Alumina

0 = no scratches; 6 = many scratches

16

Nanoadditives for UV-curable coatings

Grades, abrasion scrub tester, 1000 cycles, eight different resin systems

1. aromatic Epoxy acrylate / EA2. aromatic Epoxy acrylate / EA3. Polyester acrylate / PE4. Polyester acrylate / PE5. aliphatic Urethane acrylate / UA6. aromatic Urethane acrylate / UA7. Polyether acrylate / PO8. amine modified Oligoether acrylate /POA

0

1

2

3

4

5

6

Control+ 0.1% Silicone polyether

1,5% 40 nm Alumina

0 = no scratches; 6 = many scratches

Page 9: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Microscopic images after 500 cycles of abrasion scrub tester

Control 2% 40 nm Alumina0,1% silicone polyether

Nanoadditives for UV-curable coatings

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Al2O3

W&D additiveSilicone

Nanoadditives for UV-curable coatings

Page 10: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Nanoadditives for UV-curable coatings

Gloss 20 ° [%], dry abrasion scrub tester, 1000 cycles

89 89

80

88

60

65

70

75

80

85

90

95

100

Control 0,25% 20 nm Alumina(with Silicone Coating)

+ 0,1% Silicone polyether

Glo

ss[2

0°]

73 73

82

71

50

55

60

65

70

75

80

85

90

95

100

Control

Glo

ss[8

5°]

0,25% 20 nm Alumina(with Silicone Coating)

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Nanoadditives for UV-curable coatings

Observation: Synergistic effects with Organosiloxanes

Hypothesis:

different kinds of particle-additive-matrix interactions

(1) surface interaction between nanoparticle surface and polar modified polysiloxane unit (formation of core-shell-particle)

(2) surface interaction between polar modified polysiloxane unit and coating matrix

(3) long-distance interaction between the core shell nanoparticles in the coating matrix

Page 11: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Nanoadditives for UV-curable coatings

polar modified polysiloxane

nanoparticle

matrix

22

Nanoadditives for UV-curable coatings

functions:(1) compatibility between matrix and nanoparticle(2) stabilization of nanoparticles against agglomeration(3) effect on phase boundary properties

polar modified polysiloxane

Page 12: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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NANOBYK‘s

Paint ApplicationScratch Resistance in

Solvent Based Clear Coats

24

W&D additiveCompatibilizerSilicone

SiO2

Nanoadditives for Solvent-Born clear coatings

Page 13: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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TEM–pictures (50 000 times enlargement)

500nm 200nm

System: 2 Pack Acrylate / NCO

Nanoadditives for Solvent-Born clear coatings

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Control 2% Nanosilica + silicone 2% silicone-modified Nanosilica

System: 2 Pack Acrylate / NCO

Difference of silicone addition versus silicone modification

Nanoadditives for Solvent-Born clear coatings

Page 14: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Nanoadditives for Solvent-Born clear coatings

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Acrylic / NCO Polyester / NCO Acrylate / Melamine

Control 33 19 28

0.5% 82 60 79

1.0% 86 72 86

1.5% 91 69 90

2.0% 90 81 91

5.0% 94 84

* % Nanoparticles on solid resin

Dosage* Crockmeter gloss retention (10 cycles)

Nanoadditives for Solvent-Born clear coatings

Page 15: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Nanoadditives for Solvent-Born clear coatings

Reference with 0,1% Silicone 0,60% 20 nm Alumina with 0,1% SiliconeGloss retention: 25% Gloss retention: 82%

Microscopic images after 100 cycles of abrasion scrub tester

Mineraloil-based air drying PU-wood coating(Reichhold UROTUF-F77M60)

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NANOBYK‘s

Paint ApplicationDielectric Properties

Page 16: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Nanoparticles to improve Dielectric Strength

4300350042003300Dielectric Strength,vpm

> 60004> 60004Pulse Endurance, minutes

4446Bond Strength, 150°C, lbs.

20182321Bond Strength,25°C, lbs.

Standardwith 3%

Nanomaterial

Standardwith 1%

Nanomaterial

Standardwith 30%

Filler

Standard

The P.D. George Company

32

NANOBYK‘s

Paint/Plastic ApplicationUV Protection

Page 17: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Nanoparticles for UV protection

Active ingredient Chemistry Activity Cost of goods Refractive Index

Zn Oxide moderate low 2,0

Zn Doped oxide moderate low 2,0

Ti Coated Oxide high moderate 2,4

Ce Oxide moderate moderate 2,2

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Nanoparticles for UV protection

Page 18: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Nanoparticles for UV protection

+oAbsorption Efficiency

< 370 nm< 400 nmUV-Absorption

-+Bio-activity

+oChemical Stability

-+No Photoactivity

2,42,0Refractive Index

TiO2ZnOProperty

36

Nanoparticles for UV protection

250 nm

60

30

Particle Size d50, nm

17NanoTek

35NanoArc

Surface Area m2/gGrade

Page 19: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Nanoparticles for UV protectionQUV Test – Plastic Application

9,6

7,9

9,1

9,1

10,2

6,9

4,9

2,1

0,00 1,00 2,00 3,00 4,00 5,00 6,00 7,00 8,00 9,00 10,00 11,00

1

∆b after 2000h UV-A exposure

2,5% NANO ZnO

1% NANO ZnO

0,5% NANO ZnO

1,0% OA-2

0,5% OA-2

1,0% OA-1

0,5% OA-1

Control

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Currently available nanomaterials and their properties

xBarrier Coating

x

x

Aluminum-

oxide

xxIR-absorption

xxAnti-static

(x)(x)Conductivity

xUV-stability

xxMechanical properties

xScratch resistance

SilicaAntimony Tin

Oxide

Indium Tin

Oxide

Zinc

OxidePropertyMaterial

Page 20: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Nanoadditives overview

30 nm / 60 nm

20 nm

20 nm

40 nm

40 nm

40 nm

Particle Size

30-50%

25%

30%

30%

30%

50%

Active content

Scratch resistance in non-aqueous coatingsPMAAluminaNANOBYK-3610

Scratch resistance in non-aqueous UV coatingsHDDAAluminaNANOBYK-3602

Scratch resistance in non-aqueous UV coatingsTPGDAAluminaNANOBYK-3601

LP-Products

NANOBYK-3650

NANOBYK-3600

Trade name

Scratch resistance in aqueous UV coatingsWaterAlumina

Scratch resistance in non-aqueous coatingsPMASilica

UV-ProtectionVariousZinc Oxide

PropertyMediumMaterial

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Conclusions

• Transparency is the key driver for nanotechnology in paint application• Synthesis, material and particle size determine Nanomaterials performance• Low refractive index and high efficiency are key in nanotechnology for paint application.

• Nanoparticles improve• Scratch resistance of high gloss high transparent coatings

• UV Coatings: 0,3 – 1,0% Nanoparticles• 2K Coatings: 1,0 – 2,0% Nanoparticles• Air-Drying solvent based coatings: 0,3 – 1,0% Nanoparticles

• Long-term UV stability of polymer composites• All coatings 1,0 – 4,0% Nanoparticles

• Dielectric Properties• Unsaturated Polyesters 1,0 – 3,0% Nanoparticles

• Impact resistance of thermoplastics• PP 1,0 - 2,0% Nanoparticles

Page 21: Nanoparticles Improve Coating Performances - ianano.orgianano.org/Presentation-ICNT2005/Sawitowski-ICNT BYK Nano.pdf · 2 3 Applications / End-Uses of BYK Chemie Polyurethane Foams

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Summary