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Pattern Transfer and Characterization of Biomimetic Micro-Structured Surfaces for Hydrophobic and Icephobic Applications

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Pattern Transfer and Characterization of Biomimetic Micro-Structured Surfaces for Hydrophobic and Icephobic Applications Pattern Transfer and Characterization of Biomimetic Micro-Structured Surfaces for Hydrophobic and Icephobic Applications by Brendan McDonald A thesis presented to the University of Waterloo in fulfillment of the thesis requirement for the degree of Master of Applied Science in Chemical Engineering - Nanotechnology Waterloo, Ontario, Canada, 2013 © Brendan McDonald 2013 Author’s Declaration I hereby declare that I am the sole author of this thesis. This is a true copy of the thesis, including any required final revisions, as accepted by my examiners. I understand that my thesis may be made electronically available to the public. ii Abstract Using both artificial and natural templates, biomimetic micro-structures are fabricated on conventional coating materials (epoxy and silicone elastomers) to mimic both artificial and natural templates through effective pattern transfer processes. The pattern transfer processes use a soft-polymer negative stamp, where the flexibility of the stamp allows for easy conformation to both flat and curved surfaces. Patterns have been successfully transferred as a rigid epoxy to complex surfaces or as a soft elastomer replica of a hydrophobic Trembling Aspen leaf. The hydrophobicity and friction behaviour of the resulting micro-patterned surfaces are systematically investigated, showing that surface patterning can be used as an effective way to improve hydrophobicity while reducing the surface adhesion and friction without a loss of the structural integrity or rigidity typical of epoxy coatings. The relative strength of the micro-pattern was determined through indentation testing in order to support the claim of a robust pattern on the micro-scale that is able to withstand the harsh environment of industrial application or weather exposure. With the well characterized patterned epoxy material fabricated and able to be transferred to many different surfaces, the potential for the patterned surface to act as an icephobic coating was pursued. The robustness of the epoxy material with the unique ability to coat surfaces that are typically unable to possess a micro-structure makes this coating an ideal candidate for large-scale icephobic application. The potential use of a micro-patterned epoxy coating is investigated against comparable surface coatings within an innovative experimental set-up to measure the relative ice-adhesion strength of different substrates. In characterizing the relative shear-force required to remove frozen water droplets from the coating surface at the interface, several variables and factors were explored. The addition of a surface pattern was found to impact the icephobic ability of several materials, where different materials with the same pattern were compared to identify that the surface energy of the substrate influences the icephobic nature of a surface. Moreover, previous studies that relate the water contact angle or hysteresis to ice- adhesion strength are questioned through a preliminary qualitative analysis of ice adhesion strength data. This work demonstrates a potential process for the utilization of biomimetic epoxy micro-patterns as an enhanced hydrophobic and icephobic option for large scale protective coatings. iii Acknowledgements I would like to express my thanks and gratitude to all of those who have helped me shape and develop my work to its current state with the hope that it shall be continued and those following will be able to build upon this foundation. To my research supervisor, Professor Boxin Zhao, I would express my appreciation for providing a solid footing and an open approach in allowing me to explore the field of biomimetics, and learn at the forefront of this research. All of my family and friends have provided constant support both by contributing their time and by continually providing an extra push or challenge to help me through and over all obstacles. I would like to thank my lab-mates and all of those who have helped me in training, and in thinking of the many solutions that were found over my time as part of this research group. All of these people have made sure that I was able to keep a light-hearted approach to my work, while maintaining the focus required. More specifically, I would like to acknowledge the contributions of several individuals who have directly aided me in my work. Owen Crookston, an undergraduate research assistant played a large role in refining the friction testing of the epoxy surfaces and collecting a complete data set. Poonam Patel has offered much of her time as a volunteer to offer her knowledge from a biological perspective and help shape the direction of the biological mimicry work while also with sample fabrication and characterization. Both Aleksander Cholewinski and Josh Trinidad, fellow graduates of the University of Waterloo Nantechnology Engineering program have spent a great deal of time developing an alternate coating process within our lab that was trialed as part of the icephobic research proposed, as well as collecting data for that work. Current PhD candidate Hamed Shahsavan provided much insight and direction for the friction characterization of the epoxy pillar system, and was recognized with the second authorship of that paper. Additionally, there have been countless others who have played a large role in my training, understanding, and development as a student, to all of whom I am grateful. iv Table of Contents Author’s Declaration ........................................................................................................................ ii Abstract ........................................................................................................................................... iii Acknowledgements ......................................................................................................................... iv Table of Contents ............................................................................................................................. v List of Figures ................................................................................................................................ vii List of Tables .................................................................................................................................. xi Chapter 1 Introduction ..................................................................................................................... 1 Research Objective and Development ......................................................................................... 1 Superhydrophobicity .................................................................................................................... 3 Icephobicity ................................................................................................................................. 5 Biomimetic Pattern Transfer and Surface Coatings ..................................................................... 6 Chapter 2 Literature Review ............................................................................................................ 7 Intermolecular Forces .................................................................................................................. 7 Thermodynamic Principles of Wetting ........................................................................................ 8 Hydrophobicity - Wetting Interaction at the Solid Interface ..................................................... 10 Solid-Liquid Contact .............................................................................................................. 11 Equilibrium Wetting Conditions - Young’s Law ................................................................... 13 Enhancing Wetting Properties - Physical Modification ......................................................... 16 Solid-Solid Contact and Interaction - Tribology ........................................................................ 18 Hertz Non-Adhesive Elastic Contact ..................................................................................... 19 Adhesive and Anti-Adhesive Mechanisms ............................................................................ 20 Dry-Friction Behaviour and Mechanism ............................................................................... 21 Current Icephobic Research ....................................................................................................... 22 Superhydrophobic Surfaces as an Icephobic Approach ......................................................... 23 The Mechanism of Freezing .................................................................................................. 24 v Mechanical Properties of Ice ................................................................................................. 25 Chapter 3 Pattern Transfer of Biomimetic and Natural Structured Surfaces ................................. 27 Soft Lithography ........................................................................................................................ 27 Transfer to Epoxy Substrate ....................................................................................................... 28 Material Information .............................................................................................................. 29 Epoxy Dual-Pattern Transfer Process .................................................................................... 30 Replication of Trembling Aspen Leaves ..................................................................................
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