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3D Printing of Shape Memory Polymers Via Stereolithography Process This document is downloaded from DR‑NTU (https://dr.ntu.edu.sg) Nanyang Technological University, Singapore. 3D printing of shape memory polymers via stereolithography process Choong, Yu Ying Clarrisa 2018 Choong, Y. Y. C. (2018). 3D printing of shape memory polymers via stereolithography process. Doctoral thesis, Nanyang Technological University, Singapore. http://hdl.handle.net/10356/75861 https://doi.org/10.32657/10356/75861 This work is licensed under a Creative Commons Attribution‑NonCommercial 4.0 International License (CC BY‑NC 4.0). Downloaded on 07 Oct 2021 14:49:07 SGT 8 1 0 2 OF SHAPEOF MEMORY POLYMERS VIA CHOONG YU YING CLARRISA YING YU CHOONG STEREOLITHOGRAPHY PROCESS 3D PRINTING SCHOOL OF MECHANICAL AND AEROSPACE ENGINEERING AEROSPACE AND MECHANICAL OF SCHOOL 3D PRINTING OF SHAPE MEMORY POLYMERS VIA STEREOLITHOGRAPHY PROCESS CHOONG Y.Y.C. 2018 3D PRINTING OF SHAPE MEMORY POLYMERS VIA STEREOLITHOGRAPHY PROCESS CHOONG YU YING CLARRISA SCHOOL OF MECHANICAL AND AEROSPACE ENGINEERING A thesis submitted to Nanyang Technological University in partial fulfilment of the requirement for the degree of Doctor of Philosophy 2018 II ABSTRACT Additive manufacturing (AM), also known as 3D printing, with the innovative combination of smart responsive materials such as shape memory polymers (SMPs) has brought about 4D printing as an emerging technology for creation of more dynamic devices. However, its applications have been impeded by the limited printable materials and inferior properties in terms of curing speed, mechanical strength and thermomechanical shape memory properties of currently available 4D printing materials. In recognition of these drawbacks, the motivation of this work is to develop photo- curable thermoset SMP resins that exhibit enhanced shape memory properties with rapid curing characteristics. A tight coupling exists between material development and process development, hence the interaction between material properties of the developed SMPs and process parameters of the stereolithography (SLA) process was examined. While the SLA process can be divided into two major categories – projection and scanning type, the SMPs fabricated via these two systems were compared and found to have distinct curing characteristics. Theoretical calculations on critical energy density and threshold penetration depth were derived for the developed SMPs to enable the material to be successfully printable in any types of UV based 3D printing systems. Following which, characterizations and analysis of tailoring shape memory properties were carried out and the durability of the 4D printed structures was also evaluated. By tuning the material compositions, the flexibility of the developed SMPs allows tailorable thermomechanical properties including glass transition temperatures (from 54.9 ˚C to 74.1 ˚C), high shape recovery (from 90 to 100%) and prolonged shape memory durability (up to 22 cycles). The ability to freely tune the thermomechanical properties of 4D printed parts presents III a huge advancement for 4D printing technology to broaden the selection of suitable materials. The robustness of the developed SMPs also addresses the issue of thermomechanical durability of the materials to perform as engineering materials for wide industry adoption. Moreover, for AM to be viable in mass production, print speeds must increase by at least an order of magnitude while maintaining excellent part accuracy. A shape memory polymer composite (SMPC) using nanosilica particles was developed to enhance the speed and performance of 4D printed parts. The nanosilica particles were discovered to promote remarkably fast curing due to nucleation enhancing activity. The curing time of each layer was reduced to 0.7s which effectively shorten the total printing time. The presence of nanosilica particles with high specific surface area promotes stress transfer, hence improving the tensile strength in the rubbery state by 2.4 - 3.6 times higher and the elongation in rubbery state reaches 85.2%. In particular, the shape memory durability was enhanced which offers a promising material for more robust applications. By comprehensively analysing and discussing the approach of process optimization and material evaluation, this work has enabled the use of the stereolithography technology to fabricate high performance responsive SMP components. IV ACKNOWLEDGEMENT I would like to express my utmost gratitude to all the people here who have given me support throughout my PhD study: ▪ My supervisor, Prof Su Pei-Chen (NTU), and co-supervisor, Dr Maleksaeedi Saeed (SIMTech) for their generous support and valuable insights gained under their supervision. ▪ My project team from A*STAR SIMTech and IMRE: Eng Hengky, Dr. Wei Jun, Dr. Florencia Wiria Edith, Dr. Yu Suzhu, Dr. Wang Fuke and Dr. Wang Fei for their valuable time and effort in rendering help and advices in the experimental work. ▪ My research group mates: Tan Hong Yi Kenneth, Liu Kang-Yu, Lee Tsung-Han, Xie Hanlin, Li Yong and Baek Jong Dae for their constructive suggestions and advices on improving my research work. ▪ Technical staffs from NTU School of Mechanical and Aerospace Engineering and Singapore Centre for 3D Printing: Mr Chia Yak Khoong, Mr Wee Tiew Teck Tony, Mr Soh Beng Choon, Mdm Chia Hwee Lang, Mr Lee Siew Chuan, Mr Lim Yong Seng, Mr Wong Cher Kong Mack, Mr Wong Hang Kit and Ms Yong Mei Yoke for training and usage of equipment. ▪ Research staff from SIMTech: Ms Ma Cho Cho Khin, Ms Liu Yuchan, Mr Goh King Liang Jeffrey and Mr Goh Min Hao for their guidance and training. ▪ Family and friends whom I have made during my PhD and have given me the most support and encouragement over the 4 years: Yap Yee Ling, Tan Wen See, Tan Hong Wei, Chua Kok Hong Gregory, Chua Zhong Yang, Cheung See Lin, Ratima Suntornnond, Tan Yong Sheng Edgar, Lee Jia Min and Tan Hong Yi Kenneth and more to be listed. V This project is funded by the Science and Engineering Research Council of Singapore Agency of Science Technology and Research (A*STAR)-IAP (NTU Grant No. M4070219). TABLE OF CONTENTS ABSTRACT .................................................................................................................. III ACKNOWLEDGEMENT ............................................................................................. V TABLE OF CONTENTS .............................................................................................. VI TABLE OF FIGURES ................................................................................................... X LIST OF TABLES ...................................................................................................... XV ABBREVIATIONS AND SYMBOLS ...................................................................... XVI CHAPTER 1. INTRODUCTION ................................................................................... 1 1.1 Background ........................................................................................................... 1 1.2 Technology Gaps and Research Needs ................................................................. 4 1.3 Motivation ............................................................................................................. 8 1.4 Objectives ........................................................................................................... 10 1.5 Scope ................................................................................................................... 11 1.6 Outline of Report ................................................................................................ 12 CHAPTER 2. LITERATURE REVIEW ...................................................................... 13 2.1 General Aspects of SMPs ................................................................................... 13 2.1.1 Classifications .............................................................................................. 13 2.1.2 Basic Molecular Requirements and Working Mechanism .......................... 16 2.1.3 Types of Shape Memory Polymers .............................................................. 18 2.1.4 Characterizing Shape Memory Effects ........................................................ 21 2.1.5. Mechanical Properties ................................................................................. 27 VI 2.1.6 Conventional Fabrication Technologies for SMPs ...................................... 28 2.2 Additive Manufacturing ...................................................................................... 31 2.2.1 Introduction on AM or 3D Printing ............................................................. 31 2.2.2 Polymer Based AM ...................................................................................... 33 2.2.3 4D Printing ................................................................................................... 36 2.2.4 Single Thermoplastic Material ..................................................................... 37 2.2.5 Multi-Thermoset Materials .......................................................................... 38 2.3 Shape Memory Polymer Composites ................................................................. 40 2.3.1 Traditionally Fabricated SMPCs ................................................................. 41 2.3.2 3D Printing of SMPCs ................................................................................. 43 2.4 Applications .......................................................................................................
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