Nanoparticles Improve Coating Performances presented by Dr. Thomas - - PDF document

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Nanoparticles Improve Coating Performances presented by Dr. Thomas - - PDF document

Feb 25, 2024 296 likes •524 views

Nanoparticles Improve Coating Performances presented by Dr. Thomas Sawitowski, Manager Nanotechnology The use of Nanoadditives in plastic and coating composites ICNT, San Francisco 2005 1 Out-line Definition of Nanotechnology

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presented by

Nanoparticles Improve Coating Performances

  • Dr. Thomas Sawitowski,

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

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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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Applications / End-Uses of BYK Chemie

Pigment Concentrates Powder Coatings Can Coatings Polyurethane Foams Compounds Printing Inks Wood/Furniture Coatings Industrial Coatings Coil Coatings Automotive OEM Architectural Coatings PVC Plastisols Ambient Curing Resins Thermoplastics Automotive Refinish

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Let´s go Nano!

This is really an innovative approach But I‘m affraid we can‘t consider it. It‘s never done before

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Energie

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% 1 2 3 4 5 6 7 8 9 10 Diameter [nm] Surface Atoms [%]

  • Increase in specific surface area
  • Reactivity
  • Surface energy
  • Shape
  • Anisotropy of properties

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Nanoparticles

  • Basic Processes

Top-Down

  • Grinding

Bottom-up

  • Gas Phase Synthesis
  • Chemical precipitation
  • Sol-Gel-Chemistry
  • Emulsion techniques
  • Plasma-spraying
  • Spray drying
  • Hydrothermal synthesis
  • ...
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PVS Al2O3 Flame Synthesis Al2O3 Precipitated Al2O3

Nanoparticles

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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

  • ……
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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

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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.]

Silica Alumina ZnO TiO2

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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 Shell

Solubility Reactivity Compatibility

  • Nanoparticle Shell
  • Determines solubility, reactivity, and

compatibility

Nanoparticle Core

Mechanical Prop. Chemical Prop. Electronic Prop. Biological Prop. 12

Percolation of Properties

Nanoparticles

Modified Properties Properties unchanged

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NANOBYK‘s

Paint Application

Scratch resistance in UV Clear Coatings

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W&D additive Silicone

Al2O3

Nanoadditives for UV-curable coatings

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Nanoadditives for UV-curable coatings

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

  • 1. aromatic Epoxy acrylate / EA
  • 2. aromatic Epoxy acrylate / EA
  • 3. Polyester acrylate / PE
  • 4. Polyester acrylate / PE
  • 5. aliphatic Urethane acrylate / UA
  • 6. aromatic Urethane acrylate / UA
  • 7. Polyether acrylate / PO
  • 8. amine modified Oligoether acrylate /POA

1 2 3 4 5 6

Control 1,5% 40 nm Alumina

0 = no scratches; 6 = many scratches

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Nanoadditives for UV-curable coatings

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

  • 1. aromatic Epoxy acrylate / EA
  • 2. aromatic Epoxy acrylate / EA
  • 3. Polyester acrylate / PE
  • 4. Polyester acrylate / PE
  • 5. aliphatic Urethane acrylate / UA
  • 6. aromatic Urethane acrylate / UA
  • 7. Polyether acrylate / PO
  • 8. amine modified Oligoether acrylate /POA

1 2 3 4 5 6

Control + 0.1% Silicone polyether 1,5% 40 nm Alumina

0 = no scratches; 6 = many scratches

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Microscopic images after 500 cycles of abrasion scrub tester

Control 2% 40 nm Alumina 0,1% silicone polyether

Nanoadditives for UV-curable coatings

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Al2O3

W&D additive Silicone

Nanoadditives for UV-curable coatings

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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 Gloss [20°] 73 73 82 71 50 55 60 65 70 75 80 85 90 95 100 Control Gloss [85°] 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

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Nanoadditives for UV-curable coatings

polar modified polysiloxane nanoparticle matrix

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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

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NANOBYK‘s

Paint Application

Scratch Resistance in Solvent Based Clear Coats

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W&D additive Compatibilizer Silicone

SiO2

Nanoadditives for Solvent-Born clear coatings

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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

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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

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Nanoadditives for Solvent-Born clear coatings

Reference with 0,1% Silicone 0,60% 20 nm Alumina with 0,1% Silicone Gloss 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 Application

Dielectric Properties

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Nanoparticles to improve Dielectric Strength

4300 3500 4200 3300 Dielectric Strength, vpm > 6000 4 > 6000 4 Pulse Endurance, minutes 4 4 4 6 Bond Strength, 150°C, lbs. 20 18 23 21 Bond Strength, 25°C, lbs. Standard with 3% Nanomaterial Standard with 1% Nanomaterial Standard with 30% Filler Standard

The P.D. George Company 32

NANOBYK‘s

Paint/Plastic Application

UV Protection

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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

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Nanoparticles for UV protection

+

  • Absorption Efficiency

< 370 nm < 400 nm UV-Absorption

  • +

Bio-activity +

  • Chemical Stability
  • +

No Photoactivity 2,4 2,0 Refractive Index TiO2 ZnO Property

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Nanoparticles for UV protection

250 nm 60 30 Particle Size d50, nm 17 NanoTek 35 NanoArc Surface Area m2/g Grade

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Nanoparticles for UV protection

QUV 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

x

Barrier Coating

x x

Aluminum-

  • xide

x x

IR-absorption

x x

Anti-static

(x) (x)

Conductivity

x

UV-stability

x x

Mechanical properties

x

Scratch resistance Silica Antimony Tin Oxide Indium Tin Oxide Zinc Oxide Property Material

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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 coatings PMA Alumina NANOBYK-3610 Scratch resistance in non-aqueous UV coatings HDDA Alumina NANOBYK-3602 Scratch resistance in non-aqueous UV coatings TPGDA Alumina NANOBYK-3601 LP-Products NANOBYK-3650 NANOBYK-3600 Trade name Scratch resistance in aqueous UV coatings Water Alumina Scratch resistance in non-aqueous coatings PMA Silica UV-Protection Various Zinc Oxide Property Medium Material

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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

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Summary