nanoparticles improve coating performances -...
TRANSCRIPT
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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 CoatingsPolyurethane Foams Compounds
Printing Inks Wood/Furniture Coatings Industrial CoatingsCoil CoatingsAutomotive OEM
Architectural CoatingsPVC Plastisols Ambient Curing Resins Thermoplastics Automotive Refinish
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Let´s go Nano!
This is really an innovative approachBut I‘m affraid we can‘t consider it.
It‘s never done before
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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
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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.]
SilicaAluminaZnOTiO2
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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.
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Percolation of Properties
NanoparticlesModified Properties
Properties unchanged
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NANOBYK‘s
Paint ApplicationScratch resistance in UV Clear Coatings
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W&D additiveSilicone
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 / 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
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2
3
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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 / 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
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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
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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
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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 ApplicationScratch Resistance in
Solvent Based Clear Coats
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W&D additiveCompatibilizerSilicone
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% 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
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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
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NANOBYK‘s
Paint/Plastic ApplicationUV 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
+oAbsorption Efficiency
< 370 nm< 400 nmUV-Absorption
-+Bio-activity
+oChemical Stability
-+No Photoactivity
2,42,0Refractive Index
TiO2ZnOProperty
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Nanoparticles for UV protection
250 nm
60
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Particle Size d50, nm
17NanoTek
35NanoArc
Surface Area m2/gGrade
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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
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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
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Summary