製備可調控孔洞大小之陽極氧化鋁模板與探討結合3D列印與模板法之高分子表面性質

Abstract

近年來，高分子奈米材料之相關研究蓬勃發展，其中，陽極氧化鋁模板是製備一維奈米材料的熱門選項之一，因其具有自組裝之特性，可排列成規則的奈米孔洞陣列。然而，陽極氧化鋁模板所製備出的奈米材料受限於一般實驗條件製備出的筆直孔道，往往只能呈現奈米柱或奈米管等基本形狀。本研究使用之溫度調控劇烈陽極氧化法（Temperature modulation hard anodization, TMHA）可透過電解液熱對流程度，改變鋁片電流密度，進而實現陽極氧化鋁孔徑大小變化的準確控制。不同於以往TMHA法獲得似雙節棍般的奈米結構，本實驗獲得波浪狀的奈米孔道。進一步以磷酸擴孔後發現「Nanoholes in nanopores」結構，此立體網狀構型被認為具有特殊光學性質。此外，以熔融退火法將PS-b-PDMS導入此陽極氧化鋁模板後，透過SEM及TEM皆可觀察到高分子結構。 在本論文之序論中，首先介紹陽極氧化鋁形成原理、製備方法以及影響孔洞大小的因素。接著，在第二章介紹本研究中使用到的藥品以及儀器。本研究之實驗結果主要分為兩個部分。第一部分（第三章）探討以TMHA法製備具波浪狀奈米孔道的陽極氧化鋁之最佳條件，之後利用磷酸進行長時間擴孔，觀察孔徑較大處彼此相通後形成「Nanoholes in nanopores」結構。在第二部分（第四章）結合3D列印與陽極氧化鋁模板，利用熱退火效應將高流動性高分子導入陽極氧化鋁模板，透過3D列印機噴頭加熱高分子可獲得奈米半球陣列，而以高溫烘箱進行熱退火可獲得奈米柱陣列。同時，探討以不同方式移除陽極氧化鋁模板後對高分子奈米陣列的形貌影響。

Anodic aluminum oxide（AAO） is one of the most commonly used templates to prepare 1-D polymer nanomaterials. According to the derivative work of Raoufi et al., the fabrication of AAO templates with controlled pore diameters is achieved by temperature modulation hard anodization （TMHA）. By decreasing the convection of the electrolyte, the current density could be increased from 35 to 700 mA cm−2, and hence, the pore diameter increased. Nanopores with modulated pore diameters were obtained. On the basis of these ideas, we fabricate wavelike nanostructures by TMHA method. With further pore widening process, we obtain “nanoholes in nanopores” nanostructures. We believe that these 3D network-like structures have special properties of photonics and can be used in various nanotechnology applications. We also combined AAO with a hot topic in academia and in industry – 3D printing. 3D printing touted as a replacement for traditional manufacturing and a potential to change the way we design or produce all kinds of products. We develop a novel approach to fabricate hierarchical structures by combining 3D printing and template wetting. We directly use 3D printer to print ABS on AAO templates and place samples into an oven for further thermal annealing. Nanospheres were obtained without thermal annealing while nanorod were obtained with 200 °C thermal annealing. Hierarchical structures with hydrophobicity were fabricated successfully.