孔洞材料依據孔洞大小、排列、孔隙率和材料選擇不同而有不同應用，主要之工程限制為高孔隙率對應之機械性質弱化。自然界中有許多生物材料，如鳥喙、羽毛及骨骼等，具多階層孔洞結構且有序排列之有機/無機之複合材料，歷經數十億年的演化，往往發展出最佳化之設計。
本研究旨在研究並模仿生物材料之合成策略，以天然矽藻土為原料，透過冷凍鑄造技術(Freeze Casting)和燒結之陶瓷製程製備具微奈米多階層孔洞之孔洞材料，並探討漿料調配、燒結溫度、冷卻速率和固含量等條件對微結構與機械性質之影響，壓應力測試與正規化結果可證實此仿生策略提供了有效合成具高孔隙及高強度多孔材料之設計。藉矽藻土之高化學穩定性，進一步以溶膠-凝膠法填入二氧化矽氣凝膠(Aerogel)、高分子聚合法填入聚二甲基矽氧烷，產生功能性複合材料。此外，為避免因第二相材料填入造成孔隙率縮減，利用水溶性高分子和後交聯處理，發展出創新之單步驟合成陶瓷基有機/無機複合材料之技術，機械性質和保水力可藉由分別引入聚乙烯醇和天然海藻酸強化。
本研究合成之非等向性複合材料，提供了極佳的縱向高抗壓縮強度和徑向熱絕緣性質，能應用於綠能建材或封裝材料，此研究提出合成有機無機複合孔洞材料之創新方法，可望運用於其他材料系統，發展具多功能性之孔洞材料。

Porous materials are widely applied in various fields due to their diverse characteristics depending on the size, arrangement and shape of the pores, as well as the porosity and composition of the solid materials. The limitations are mainly due to the weak structure and mechanical property due to its high porosity. After million years of evolution, natural biological composites, such as bird beaks, feathers and bones, have developed optimal designs combining lightweight and superior mechanical strength.
Based on bioinspired strategies and using natural diatomites as raw materials, hierarchically-structured porous scaffolds were synthesized by freeze casting technique and sintering process. The effect of parameters, such as slurry preparation, sintering temperature, cooling rate and solid content, on microstructural and mechanical properties were discussed. The normalized compressive strength indicated that this bioinspired strategy provided an efficient design for scaffolds with superior strength and high porosity. Owing to the chemical stability of diatomite, silica aerogel and PDMS were successfully infiltrated into the freeze-casted diatomite, and formed functional composites. Moreover, in order to avoid the porosity reduction caused by second phase infiltration, a novel one-step synthesis of ceramic-based organic/inorganic composites was developed. The mechanical strength and water retention of composite can be enhanced by introducing PVA and alginate, respectively.
The anisotropic composites synthesized in this study, provide extraordinary axial compressive strength and radial thermal insulation properties and can be a promising materials for green building or package applications. The novel synthesis proposed in this study can be adapted to other material systems and develop multifunctional porous materials.

List of Tables VII
Figure Caption IX
Chapter 1 Introduction 1
Chapter 2 Literature Review 4
2.1 Porous Materials 4
2.1.1 Introduction 4
2.1.2 Macroporous Materials 4
2.1.3 Processing Routes for Macroporous Materials 5
2.2 Bioinspired Strategies 8
2.2.1 Characteristics of Biological Materials 8
2.2.2 Biomineralization 10
2.2.3 Structure and mechanical properties of natural materials 11
2.2.4 Fabrication of bioinspired structural materials 14
2.3 Diatomite 17
2.3.1 Introduction 17
2.3.2 Characteristics and Applications 18
2.4 Freeze Casting 20
2.4.1 Introduction 20
2.4.2 Process Procedure 20
2.4.3 Principles of Freeze Casting 23
2.4.4 Developments and Applications 25
Chapter 3 Experimental Methods 44
3.1 Synthesis of Porous Materials 44
3.1.1 Preparation of Freeze-Casted Diatomite 44
3.1.2 Synthesis of Diatomite/Silica Aerogel Composites 46
3.1.3 Synthesis of Diatomite/PDMS Composites 46
3.1.5 Synthesis of Diatomite/Alginate Composites 47
3.2 Characterizations and Measurements 48
3.2.1 Structural and Elemental Analysis 48
3.2.2 TGA and DTA Analyses 48
3.2.3 FTIR Analysis 48
3.2.4 Mechanical Property Tests 49
3.2.5 Water Absorption/Retention and Moisture Uptake 49
3.2.6 Thermal Conductivity Measurements 50
3.2.7 Density and Porosity Measurements 50
Chapter 4 Results and Discussion 53
4.1 Diatomite Scaffolds and Composites 53
4.1.1 Optimization 53
4.1.2 Evaluation of Mechanical Properties 57
4.1.3 Diatomite Scaffold-Derived Composites 58
4.2 Synthesis of Diatomite/Polymer Composites by Freeze Casting and Post-Treatments 61
4.2.1 Morphologies and Physical Properties 61
4.2.2 Mechanical Properties 63
4.2.3 Functionalities 63
4.2.4 Thermal properties 64
4.2.5 Water Absorption/Retention 66
Chapter 5 Conclusions 102
Chapter 6 Future Work 106
6.1 Fire Retardant/Resistant Materials 106
6.1.1 Introduction 106
6.1.2 Evaluation Methods 106
6.2 Sound Absorbing Materials 108
References 111

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