1. © The Lubrizol Corporation 2014, all rights reserved Formulating High Performance Coatings with Novel Adhesion Test Methods Dr. Yutao Yang NW Coatings Fest 2014 October 9th, 2014 Hood River, Oregon

2. © The Lubrizol Corporation 2014, all rights reserved 2 Outlines Introduction - Molecular Adhesion - Adhesion Mechanisms - Adhesion Test Methods Results & Discussion - Case Study 1: Contact angle and surface free energy - Case Study 2: Effect of coalescent solvents - Case Study 3: Effect of particle size and special monomer - Case Study 4: Effect of elasticity - Case Study 5: Polymer composition effect - Case Study 6: Adhesion between a top coat and primers on paper Summary

3. © The Lubrizol Corporation 2014, all rights reserved 3 Introduction: Cohesion Work of Cohesion: W = 2 γ 1 Bulk properties: => Cohesion => Density Hardness Melting point 1 1 1

4. © The Lubrizol Corporation 2014, all rights reserved 4 Introduction: Adhesion Work of Adhesion W = γ 1 + γ 2 - γ 12 Interfacial behavior: => Adhesion => Adsorption Corrosion Friction Wear 1 1 2 2

5. © The Lubrizol Corporation 2014, all rights reserved 5 Introduction: Molecular Adhesion Van der Waals Forces

6. © The Lubrizol Corporation 2014, all rights reserved 6 Introduction: Adhesion Mechanisms Molecular Adhesion Contamination Brownian motion Roughness effect Cracking mechanism Elastic deformation Non-elastic deformation Plasticity of surfaces Non-equilibrium adhesion Chemical Bonding Covalent (C-O, C-N) Ionic (M-X) Hydrogen (X-H…Y) Acid-base Interaction

7. © The Lubrizol Corporation 2014, all rights reserved 7 Evolution of Adhesion Test Methodology Traditional Standard Test MethodsOutputs ASTM D3359 Tape TestQualitative Classifications ASTM D4541 Pull-off TestBreaking Stress ASTM D3330 Peel TestPeel Adhesion Strength References: [1] Dickinson, Materials Today, 12, 2009, 46. [2] Dhinojwala, Rev. of Scien. Instru. 73, 2002, 2321. Introduction: Test Method Development Nano / Molecular Test MethodsOutputs Nano Indentation with AFM [1] Forces between nano-domains Sum Frequency Generation Spectrum [2] Molecular interfacial interactions Practical Novel Test MethodsOutputs Micro-Macro scale at interfaceInterfacial force or energy

8. © The Lubrizol Corporation 2014, all rights reserved 8 Results & Discussion Case Study 1 Contact angle and surface free energy for floor panels

9. © The Lubrizol Corporation 2014, all rights reserved 9 Results & Discussion Case Study 2 Effect of coalescent solvents on adhesion Formulation 1 Formulation 2 Formulation 3 Substrate A Crosshatch Cut (ASTM D3359) 1B 5B Surface Tension (mN/m) 53 51 40 Coalescent Solvents DPM/TPM = 7:3 DPM/TPM = 1:1 DPM/TPM = 3:7 *Coalescent Solvent key: DPM = Dipropylene Glycol Methyl Ether TPM = Tripropylene Glycol Methyl Ether

10. © The Lubrizol Corporation 2014, all rights reserved 10 Results & Discussion Case Study 3 Effect of particle size and special monomer on adhesion performance Polymer Contact Angle on Glass (degree) Adhesion Energy (mJ/m 2 ) Breaking Stress (N/m 2 )Crosshatch Cut P1 28 ± 1475 ± 273327 ± 12753B P2 24 ± 1641 ± 364688 ± 20683B P3 31 ± 1 187 ± 152896 ± 11032B P4 26 ± 1283 ± 194509 ± 19343B (New test method)(ASTM D4541)(ASTM D3359)

11. © The Lubrizol Corporation 2014, all rights reserved 11 Results & Discussion Case Study 3 Effect of particle size and special monomer on adhesion performance & Comparison of adhesion test methods

12. © The Lubrizol Corporation 2014, all rights reserved 12 Results & Discussion Case Study 4 Effect of elasticity on adhesion for PUD coatings: strong positive correlation

13. © The Lubrizol Corporation 2014, all rights reserved 13 Results & Discussion Case Study 5 Polymer composition effect on paint adhesion performance

14. © The Lubrizol Corporation 2014, all rights reserved 14 Results & Discussion Case Study 5 Polymer composition effect on paint adhesion performance Adhesion performance is measured and differentiated with the novel method!

15. © The Lubrizol Corporation 2014, all rights reserved 15 Results & Discussion Case Study 6 Adhesion between a top coat and primers on paper substrate Substrate ~ 100 μm Primer ~ 25 μm Top coat ~ 25 μm Crosshatch cut test is hard to apply!

16. © The Lubrizol Corporation 2014, all rights reserved 16 Results & Discussion Case Study 6 Adhesion between a top coat and primers on paper substrate Adhesion performance is measured and differentiated with the novel method!

17. © The Lubrizol Corporation 2014, all rights reserved 17 Summary Newly developed adhesion test methods have been applied to coating systems: - Surface free energy of substrates - Surface tension of coating liquids - Adhesion energy of dry coating films on substrates - Elastic modulus of dry coating films on substrates - Adhesion forces between top coats and primers Newly developed adhesion test methods demonstrate higher resolution and precision than conventional ASTM methods: - Enhance the understanding of polymer structure effects on adhesion - Improve the formulations by detecting the composition effects - Accelerate the development of polymers and coating formulations

18. © The Lubrizol Corporation 2014, all rights reserved 18 Acknowledgements The Lubrizol Corporation Larry Schnieders Lee Young Mary Solomon Thank you! Questions?