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 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 2 1
Applications / End-Uses of BYK Chemie Automotive OEM Printing Inks Coil Coatings Wood/Furniture Coatings Industrial Coatings Polyurethane Foams Pigment Concentrates Powder Coatings Compounds Can Coatings PVC Plastisols Ambient Curing Resins Architectural Coatings Thermoplastics Automotive Refinish 3 Let s go Nano! This is really an innovative approach But I m affraid we can t consider it. It s never done before 4 2
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 Energie Increase in specific surface area Reactivity Surface energy Shape Anisotropy of properties Surface Atoms [%] 100% 80% 60% 40% 20% 0% 0 1 2 3 4 5 6 7 8 9 10 Diameter [nm] 5 Nanoparticles Basic Processes Top-Down Grinding Bottom-up Gas Phase Synthesis Chemical precipitation Sol-Gel-Chemistry Emulsion techniques Plasma-spraying Spray drying Hydrothermal synthesis... 6 3
Nanoparticles PVS Al 2 O 3 Precipitated Al 2 O 3 Flame Synthesis Al 2 O 3 7 Nanoparticles Material Property Silica Hardness Alumina Hardness Zirkonia Hardness Diamond Hardness Silicone carbide Hardness Layered Silicates Barrier / Flame retardant Zinc oide UV/bactericide Titania UV Ceria UV Iron oide Magnetism Cupper oide /Silver oide Bactericide Metals Conductivity ITO/ATO Conductivity / IR-Absorption Carbon nanotubes Conductivity / Mechanical prop. Silsesquioane Mechanical prop. Dendrimers Mechanical prop. Capsules Carrier 8 4
Nanoparticles Effect of Material and Particle Size on Transparency Silica 40 nm 20 nm 10 nm Alumina ZnO TiO2 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 Magnitude of Rayleigh Scattering [a.u.] 9 Nanoparticles Effect of Material and Film Thickness on Transparency 25 µm / 0,2% Silica Alumina ZnO TiO2 100 µm / 0,2% 25 µm / 2% 100 µm / 2% 1,00E-03 1,00E-02 1,00E-01 1,00E+00 1,00E+01 1,00E+02 1,00E+03 1,00E+04 Magnitude of Rayleigh Scattering [a.u.] 10 5
Nanoparticles Nanoparticle Core Mechanical Prop. Chemical Prop. Electronic Prop. Biological Prop. Nanoparticle Shell Solubility Reactivity Compatibility Nanoparticle Core Determines mechanical, chemical, electronical and biological properties Nanoparticle Shell Determines solubility, reactivity, and compatibility Interface Region in the Matri Glass Transition Temperature Conductivity E-Modulus Cross-linking density. 11 Nanoparticles Modified Properties Properties unchanged Percolation of Properties 12 6
NANOBYK s Paint Application Scratch resistance in UV Clear Coatings 13 Nanoadditives for UV-curable coatings Al 2 O 3 W&D additive Silicone 14 7
Nanoadditives for UV-curable coatings Grades, abrasion scrub tester, 1000 cycles, eight different resin systems 6 5 4 3 2 1 1. aromatic Epoy acrylate / EA 2. aromatic Epoy 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 0 Control 1,5% 40 nm Alumina 0 = no scratches; 6 = many scratches 15 Nanoadditives for UV-curable coatings Grades, abrasion scrub tester, 1000 cycles, eight different resin systems 6 5 4 3 2 1 1. aromatic Epoy acrylate / EA 2. aromatic Epoy 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 0 Control 0 = no scratches; 6 = many scratches 1,5% 40 nm Alumina + 0.1% Silicone polyether 16 8
Nanoadditives for UV-curable coatings Microscopic images after 500 cycles of abrasion scrub tester Control 2% 40 nm Alumina 0,1% silicone polyether 17 Nanoadditives for UV-curable coatings Al 2 O 3 W&D additive Silicone 18 9
Nanoadditives for UV-curable coatings Gloss 20 [%], dry abrasion scrub tester, 1000 cycles 100 100 Gloss [20 ] 95 90 85 80 75 70 89 89 80 88 Gloss [85 ] 95 90 85 80 75 70 65 60 82 73 73 71 65 55 60 Control 0,25% 20 nm Alumina (with Silicone Coating) + 0,1% Silicone polyether 50 Control 0,25% 20 nm Alumina (with Silicone Coating) 19 Nanoadditives for UV-curable coatings Observation: Synergistic effects with Organosiloanes Hypothesis: different kinds of particle-additive-matri interactions (1) surface interaction between nanoparticle surface and polar modified polysiloane unit (formation of core-shell-particle) (2) surface interaction between polar modified polysiloane unit and coating matri (3) long-distance interaction between the core shell nanoparticles in the coating matri 20 10
Nanoadditives for UV-curable coatings matri nanoparticle polar modified polysiloane 21 Nanoadditives for UV-curable coatings functions: polar modified polysiloane (1) compatibility between matri and nanoparticle (2) stabilization of nanoparticles against agglomeration (3) effect on phase boundary properties 22 11
NANOBYK s Paint Application Scratch Resistance in Solvent Based Clear Coats 23 Nanoadditives for Solvent-Born clear coatings SiO 2 W&D additive Compatibilizer Silicone 24 12
Nanoadditives for Solvent-Born clear coatings TEM pictures (50 000 times enlargement) 500nm 200nm System: 2 Pack Acrylate / NCO 25 Nanoadditives for Solvent-Born clear coatings Difference of silicone addition versus silicone modification System: 2 Pack Acrylate / NCO Control 2% Nanosilica + silicone 2% silicone-modified Nanosilica 26 13
Nanoadditives for Solvent-Born clear coatings 27 Nanoadditives for Solvent-Born clear coatings Dosage* Crockmeter gloss retention (10 cycles) 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 28 14
Nanoadditives for Solvent-Born clear coatings Mineraloil-based air drying PU-wood coating (Reichhold UROTUF-F77M60) Microscopic images after 100 cycles of abrasion scrub tester Reference with 0,1% Silicone 0,60% 20 nm Alumina with 0,1% Silicone Gloss retention: 25% Gloss retention: 82% 29 NANOBYK s Paint Application Dielectric Properties 30 15
Nanoparticles to improve Dielectric Strength Bond Strength, 25 C, lbs. Bond Strength, 150 C, lbs. Dielectric Strength, vpm Pulse Endurance, minutes Standard 21 6 3300 4 Standard with 30% Filler 23 4 4200 > 6000 Standard with 1% Nanomaterial 18 4 3500 4 Standard with 3% Nanomaterial 20 4 4300 > 6000 The P.D. George Company 31 NANOBYK s Paint/Plastic Application UV Protection 32 16
Nanoparticles for UV protection Active ingredient Chemistry Activity Cost of goods Refractive Inde Zn Oide moderate low 2,0 Zn Doped oide moderate low 2,0 Ti Coated Oide high moderate 2,4 Ce Oide moderate moderate 2,2 33 Nanoparticles for UV protection 34 17
Nanoparticles for UV protection Property ZnO TiO 2 Refractive Inde 2,0 2,4 No Photoactivity + - Chemical Stability o + Bio-activity UV-Absorption Absorption Efficiency + < 400 nm o - < 370 nm + 35 Nanoparticles for UV protection 250 nm Grade NanoArc NanoTek Particle Size d 50, nm 30 60 Surface Area m 2 /g 35 17 36 18
Nanoparticles for UV protection QUV Test Plastic Application 2,1 4,9 6,9 2,5% NANO ZnO 1% NANO ZnO 10,2 0,5% NANO ZnO 1 9,1 1,0% OA-2 0,5% OA-2 7,9 9,1 1,0% OA-1 0,5% OA-1 9,6 Control 0,00 1,00 2,00 3,00 4,00 5,00 6,00 7,00 8,00 9,00 10,00 11,00 b after 2000h UV-A eposure 37 Currently available nanomaterials and their properties Property Material Aluminumoide Zinc Oide Indium Tin Oide Antimony Tin Oide Silica Scratch resistance Mechanical properties UV-stability Conductivity () () Anti-static IR-absorption Barrier Coating 38 19
Nanoadditives overview Trade name Material Particle Size Active content Medium Property NANOBYK-3600 Alumina 40 nm 50% Water Scratch resistance in aqueous UV coatings NANOBYK-3601 Alumina 40 nm 30% TPGDA Scratch resistance in non-aqueous UV coatings NANOBYK-3602 Alumina 40 nm 30% HDDA Scratch resistance in non-aqueous UV coatings NANOBYK-3610 Alumina 20 nm 30% PMA Scratch resistance in non-aqueous coatings NANOBYK-3650 Silica 20 nm 25% PMA Scratch resistance in non-aqueous coatings LP-Products Zinc Oide 30 nm / 60 nm 30-50% Various UV-Protection 39 Conclusions Transparency is the key driver for nanotechnology in paint application Synthesis, material and particle size determine Nanomaterials performance Low refractive inde 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 40 20
Summary 41 21