對於設計和製造機械變材料，特別是在納米尺度上，越來越感興趣，主要是因為它們具有卓越的機械性能，例如高模數、強度和能量耗散能力，同時又輕巧，這是受自然界啟發的有意結構，例如螳螂蝦抗衝擊表面、多刺海星柔韌的骨架結構，以及海膽棘刺的高強度。請注意，自然材料由陶瓷基材和有機基材結構精心設計，具有卓越的機械性能。受自然啟發，這項研究旨在通過使用自組裝的嵌段共聚物作為模板（自下而上的方法）來製造有序的納米網結構材料作為機械變材料。通過利用自組裝的層狀形成的嵌段共聚物，特別是聚苯乙烯-聚二甲基矽氧烷（PS-b-PDMS），可以通過選擇性溶劑對PS進行溶液鑄造來獲得鑽石結構。隨後，通過使用氫氟酸（HF）蝕刻PDMS可以獲得帶有明確納米通道的納米多孔PS，然後將其用作模板進行模板合。受到螳螂蝦的啟發，這項工作旨在製造有序的納米網狀羥基磷灰石（HAp）以展示結構設計對能量吸收能力的影響。通過將PS模板背填充以硝酸鈣四水合物和三乙基磷酸酯的前體，進行模板溶膠反應，然後在焙燒後可以去除PS模板，製造有序的納米網狀羥基磷灰（HAp）。通過納米壓痕和單軸微壓縮測試的證據，製造的納米網狀HAp能夠吸收比固有對應物更多的機械能量，這是由於拓撲效應，使得等向性納米尺度支撐上的載荷應力均勻分布，可以防止可能導致災難性損壞的微裂紋傳播。
使用相似的方法，受到多刺海星柔韌骨架的啟發，可以通過模板結晶反應製造鑽石結構的方解石單晶（CSC），以研究納米尺度對機械性能的影響。與自上而下的方法相比，自下而上的方法超越了納米尺度製造的限制，使得檢驗“小而強大”的概念成為可能。像多刺海星一樣，鑽石結構的CSC由於網絡紋理的效應，呈現出脆弱到韌性的轉變。最有趣的是，所製造的鑽石結構CSC由於網絡結構的納米尺度效應，表現出優越的能量吸收和強度，優於多刺海星和自上而下方法的人造對應物。
製造結構材料的目標是獲得具有出色機械性能的材料，包括高模量、高強度和高韌性，但對於這種網絡材料仍然存在挑戰。請注意，有序的納米網絡增強了能量吸收效率，但由於多孔性而犧牲了模量和強度。瓢蟲採用了一種卓越的策略來克服這個問題，即將HAp與幾丁質和/或蛋白質混合。因此，通過使用製造的納米網絡HAp作為模板對甲基丙烯酸甲酯（PMMA）進行模板聚合，可以解決機械性能上的多孔性問題。通過3-(三甲氧基矽烷)丙基甲基丙烯酸酯（γ-MPS）嫁接到納米網絡HAp上，可以完全填充PMMA前驅體以進行聚合，同時增強了混合物的界面強度。通過納米壓痕和微壓縮測試的證據表明，製造的雙連續PMMA/HAp納米混合物具有高彈性模量和壓縮強度的卓越組合，還具有卓越的韌性。因此，將硬HAp作為高模量和強度的網絡與軟PMMA基體相結合，以實現形狀、尺寸和強界面強度的聯合效應，實現高能量吸收。
與瓢蟲相比，仍然有一個謎團，即瓢蟲受到衝擊後的彈性恢復。換句話說，如何承受並恢復應力，而不會遭受重大損害，應該是下一個目標。目前有幾種情景，例如在分子級別上製造有序的納米網絡混合物和具有礦化幾丁質的特定基質，就像瓢蟲一樣。最有趣的是製造具有管狀框架而不是實心支柱的網絡材料。將有序的納米網絡材料製造成管狀網絡結構，將是結構材料的最終目標。

The increased interest in designing and fabricating mechanical metamaterials, especially at the nanoscale, is driven by their remarkable mechanical properties such as high modulus, strength, and energy dissipation capabilities with lightweight due to the deliberate structuring inspired by nature such as the impact-resistant surface of mantis shrimp, the flexible skeleton structure of knobby starfish, and the high strength of sea urchin spines. Note that natural materials are composed of ceramic-based and organic-based materials with deliberate structuring, giving superior mechanical properties. Inspired by nature, this study aims to fabricate well-ordered nanonetwork materials as mechanical metamaterials by templated synthesis using a self-assembled block copolymer as a template (bottom-up approach). By utilizing self-assembled lamellae-forming BCP, specifically polystyrene-b-polydimethylsiloxane (PS-b-PDMS), a diamond structure can be obtained through solution casting using a selective solvent for PS. Subsequently, by etching the PDMS with hydrofluoric acid (HF), nanoporous PS with well-defined nanochannels can be obtained and then utilized as a template for templated syntheses.
Inspired by mantis shrimp, this work aims to fabricate well-ordered nanonetwork hydroxyapatite (HAp) for demonstration of the effect of deliberate structuring on energy absorption capability. By back-filling the PS template with precursors of calcium nitrate tetrahydrate and triethyl phosphite for templated sol-gel reaction, well-ordered nanonetwork hydroxyapatite (HAp) can be fabricated after removal of the PS template through calcination. As evidenced by the nanoindentation and uniaxial micro-compression tests, the nanonetwork HAp fabricated can absorb a large amount of mechanical energy as compared to the intrinsic counterpart due to the topological effect, giving a homogeneous distribution of loading stress along the isotropic nanosized struts, which can prevent the microcracks propagation that might cause catastrophic failure.
With a similar methodology, inspired by the flexible skeleton of knobby starfish, diamond-structured calcite single-crystal (CSC) can be fabricated by templated crystallization reaction to investigate the nanosized effect on mechanical performance. In contrast to the top-down approach, the bottom-up approach surpasses the limitation of nanoscale fabrication, giving the feasibility to examine the concept of “smaller is stronger and tougher”. Like the mechanical behaviors of knobby starfish, the diamond-structured CSC gives a brittle to ductile transition due to the effect of network texture. Most interestingly, the diamond-structured CSC fabricated exhibits exceptional energy absorption and strength superior to knobby starfish and artificial counterparts from a top-down approach due to the nanosized effect of network structure.
The goal for the fabrication of structural materials is to attain materials with outstanding mechanical properties including high modulus, high strength, and high toughness, yet remaining challenge for such network materials. Note that the well-ordered nanonetwork enhances energy absorption efficiency but with a sacrifice in modulus and strength due to porosity. Mantis shrimp adopts a superior strategy to overcome this problem by hybridization of the HAp with chitin and/or protein. Accordingly, by templated polymerization of poly(methyl methacrylate) (PMMA) using the fabricated nanonetwork HAp as a template, it is possible to solve the porosity problem on mechanical performance. With the nanonetwork HAp grafted by 3-(trimethoxysilyl)propyl methacrylate (γ-MPS), it is possible to completely pore-fill the MMA precursors for polymerization and also strengthen the interfacial strength of the hybrids. As evidenced by nanoindentation and micro-compression tests, the bicontinuous PMMA/HAp nanohybrids fabricated exhibit an outstanding combination of high elastic modulus and compression strength in addition to superior toughness. As a result, it is feasible to combine the hard HAp as a network for high modulus and strength in the soft PMMA matrix to have high energy absorption resulting from the combined effects of shape, size, and hybridization with strong interfacial strength.
In contrast to the mantis shrimp, there is still a mystery; the resilience after the impact of the mantis shrimp. Namely, how to withstand and recover from applied stress without experiencing significant damage should be the next goal. Currently, there are a couple of scenarios such as fabricating well-ordered nanonetwork hybrids at the molecular level and specific substrates like the mantis shrimp with mineralized chitin. The most interesting one is to fabricate network materials with tubular frames instead of solid struts. It will be promising to fabricate well-ordered nanonetwork materials with tubular network texture as the ultimate goal for structural materials.

Abstract I
Acknowledgements VI
Contents XI
List of Figures XIII
List of Tables XXVI
Abbreviations XXVII
Chapter 1 1
Introduction 1
1.1. Cellular Materials in Nature 1
1.1.1. Impact Surface for Dactyl Club of Mantis Shrimp 2
1.1.2. Skeleton of Knobby Starfish 2
1.1.3. Spines of Sea Urchins 4
1.2. Mechanical Metamaterials 5
1.2.1. Topological Design 6
1.2.2. Size Effect in Micro/Nanolattice 8
1.2.3. Mechanical Metamaterials with Bicontinuous Hybrids 12
1.2.4. Mechanical Metamaterials with Resilience Properties 18
1.3. Self-assembly of Block Copolymers 23
1.3.1. Self-assembly of Silicon-containing BCPs. 25
1.3.2. Nanoporous Templates from Degradable Block Copolymers 31
1.4. Block Copolymer Templated Synthesis 35
1.4.1. Templated Sol-Gel Reaction 38
1.4.2. Templated Polymerization 40
Chapter 2 46
Objectives 46
Chapter 3 49
Experimental Section 49
3.1. Materials and Methods 49
3.1.1. Materials 49
3.1.2. Fabrication of PS-b-PDMS 49
3.1.3. Solution Casting of PS-b-PDMS 50
3.1.4. Self-assembly of PS-b-PDMS Thin-film with Diamond Structure 51
3.1.5. Fabrication of Nanoporous PS with Diamond Structure 52
3.1.6. Templated Sol-Gel Synthesis of Nanonetwork HAp 52
3.1.7. Fabrication of Diamond-Structured CSC 54
3.1.8. Fabrication of Bicontinuous PMMA/HAp Nanohybrids 55
3.2. Characterization and Instrumentation 56
3.2.1. Transmission Electron Microscopy (TEM) 56
3.2.2. Field-Emission Scanning Electron Microscopy (FESEM) 56
3.2.3. Energy-dispersive X-ray Spectroscopy (EDS) 56
3.2.4. Small-angle X-ray Scattering (SAXS) 57
3.2.5. Wide-angle X-ray Diffraction (WAXD) 57
3.2.6. Thermogravimetric Analysis (TGA) 57
3.2.7. Nanoindentation Test 58
3.2.8. Focused Ion Beam (FIB) 58
3.2.9. Uniaxial Micro-Compression Test 58
3.2.10. Finite Element Analysis (FEA) 59
Chapter 4 60
Results and Discussion 60
4.1. Bioinspired Nanonetwork HAp from Templated Sol-Gel Reaction 60
4.1.1. Design and Fabrication Strategy 60
4.1.2. Effect of PVP on the Templated Sol-Gel Reaction of HAp 64
4.1.3. Effect of Thermal Treatment on Diamond Morphology 67
4.1.4. Characterization of Nanonetwork HAp 72
4.1.5. Mechanical Performance of Nanonetwork HAp 77
4.1.6. Investigation of Energy Dissipation Mechanism 85
4.2. Starfish-Inspired Diamond-Structured Calcite Single Crystal from Templated Crystallization Reaction 87
4.2.1. Hierarchical Structure of Knobby Starfish 88
4.2.2. Fabrication of Diamond-Structured CSC 89
4.2.3. Effect of Deliberate Structuring on the Mechanical Properties 99
4.2.5. Finite Elemental Analysis 111
4.3. Bioinspired Well-Ordered PMMA/HAp nanohybrids for Mechanical Metamaterials 115
4.3.1. Fabrication of PMMA/HAp Nanohybrids 116
4.3.2. Characterization of HAp/PMMA Nanohybrids 118
4.3.3. Mechanical Performance of PMMA/HAp Fabricated 123
Chapter 5 139
Conclusions and Perspective 139
Chapter 6 144
References 144
Publications 161

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