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研究生(外文):Pin-Jung Sung
論文名稱:新型類液態固體材料- 耐紫外光自癒性乳液非晶質用於三維列印支撐材
論文名稱(外文):UV-resistant Self-healing Emulsion Glass as a New Liquid-like Solid Material for 3D Printing
指導教授(外文):Heng-Kwong Tsao
外文關鍵詞:3D printingoil-in-water emulsion
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在現今科技發展中三維列印技術(3D printing)越發受到重視,對於固化時間較長的印刷油墨(printing inks)會需要支撐材(supporting mediums)輔助,而具備適當強度且易清洗的類液態固體(liquid-like solid)常被應用於此,本研究提供一種乳液系統的類液態固體作為光固化型與熱固化型3D列印的支撐材,由矽油/山梨糖醇/十二烷基硫酸鈉/水 透過低能量方式製成,設計分散的油相體積分率超過85%並施加剪應力,使微米級油滴緊密堆積於水相中形成不流動的乳液非晶質(emulsion glass),而被擠壓的油滴結構使乳液非晶質具黏彈性與自癒能力(self-healing),屬於新型的類液態固體材料。而研究發現隨著油黏度與油含量上升,降伏強度(yield stress)也隨之上升,此性質可用於搭配不同黏性與強度的印刷油墨,同時,這種乳液非晶質在光固化與熱固化過程後仍可重複回收使用達6次,在未來可望有更多發展應用。

延續第一部份關於乳液非晶質的探討,此章節改變了乳液製備方法和調整油/水/界面活性劑之間比例,來獲得熱力學穩定的類固體(solid-like) 微乳液,表現出類固體的性質,也成功應用於3D列印支撐材。此研究的乳液系統是以癸烷為油相,硫琥辛酯鈉與山梨醇酯80/山梨醇酐酯80為界面活性劑,以相轉換方法(Phase-inversion method)形成水包油微乳液(O/W microemulsion),實驗中發現在持續添加水的相轉換過程中,水含量達一範圍值時乳液會呈現類固態性質,乳液會呈現類固態性質,其中,以山梨醇酯80/山梨醇酐酯80組合作為界面活性劑的乳液系統,在不同製備方法和長時間觀察下皆可量測出相似特性,表現熱力學穩定性,且透過加裝偏光片的光學顯微鏡觀察到類晶體的結構。接著我們透過調整界面活性劑親酯親水性(Hydrophilic-lipophilic balance)和油/水比例得到不同降伏強度的類固體微乳液,並實際作為3D列印的支撐材。
Chapter 1
UV-resistant Self-healing Emulsion Glass as a New Liquid-like Solid Material for 3D Printing.
Directly writing 3D structures into supporting mediums is a relatively new developing technology in additive manufacturing. In this work, durable and recyclable liquid-like solid (LLS) materials are developed as supporting mediums that are stable for both UV- and thermal-solidification. Our LLS material is comprised of densely packed oil droplets in a continuous aqueous medium, known as emulsion glass. Its elastic nature emerges from the jammed structure of oil droplets, which offers this LLS material rapidly self-healing ability. Moreover, the yield stress of the glass is relatively low and can be tuned by the viscosity and weight percentage of oil. The capability of the emulsion glass as supporting mediums is successfully demonstrated by directly writing and then curing designed structures. The emulsion glass has been repeatedly used at least 6 times upon exposure to UV irradiation and heat, implying it can expand the applications of supporting medium to the writing process involving UV- and thermal-curable inks simultaneously.

Chapter 2
In the second part, we changed the preparing procedures and the ratio of oil/water/surfactant in emulsions. Two emulsion systems formed by low-energy phase inversion methods are studied. The oil phase is decane while the surfactant is Tween 80 and Span 80 for system 1 and Dioctyl sulfosuccinate sodium salt (AOT) for system 2.
With increasing the water content, the sample transited from liquid-like water-in-oil (W/O) emulsion to solid-like oil-in-water (O/W) emulsion. Eventually, liquid-like O/W emulsion was obtained as the amount of water is higher than 60wt%. The thermodynamic stability of solid-like O/W emulsion were confirmed by different preparation methods and long-term observation, it can be classified to be microemulsions. We also found that the viscoelastic property of the solid-like emulsions can be tuned by varying hydrophilic-lipophilic balance (HLB) and water content.
Abstract I
摘要 III
致謝 V
Contents VI
List of Figures VIII
List of Tables XI
Chapter 1 UV-resistant Self-healing Emulsion Glass as a New Liquid-like Solid Material for 3D Printing 1
1-1 Introduction 1
1-2 Experiment Section 4
1-2-1 Material 4
1-2-2 Apparatus 4
Particle size measurements 4
Viscoelasticity measurement 5
Three dimension writing instrument 5
UV oven curing box 5
1-2-3 Methods 6
Preparation of the stable silicone oil-in-water emulsion glass 6
Preparation of the thermal-curing inks 6
Solidification of the written inks 7
1-3 Results and Discussion 8
1-4 Conclusions 21
1-5 Reference 22

Chapter 2
2-1 Introduction 25
2-2 Experiment Section 27
2-2-1 Material 27
2-2-2 Apparatus 27
Particle size measurements 27
Viscoelasticity measurement 28
2-2-3 Methods 28
Phase-inversion method 28
Calculation of HLB value 28
2-3 Result and Discussion 29
Phase inversion process 29
Solid-like behavior in certain water amount range 32
Thermodynamic stability 34
Influence of surfactant fractions (HLB) 36
Application: 3D printing supporting medium 40
2-4 Conclulsions 42
2-5 Reference 43
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