• 學位論文

基於流形學習與局部信息於非線性製程監測與故障診斷

本研究以流形學習（Manifold Learning）和局部信息之概念對非線性製程變數進行監測、分析以及診斷。在無故障訊息的情況下，傳統上使用的非線性製程監測方法為Kernel Principal Component Analysis (KPCA)，而流形學習方法最大方差展開（Maximum Variance Unfolding, MVU）利用保持局部信息的特性建立一全局模型，改善了KPCA無法很好保持潛在流形的特性，但MVU有個缺陷是模型只適用於訓練樣本，因此本文以非線性投影方法Gaussian Process Regression (GPR)逼近MVU之輸入以及輸出空間，發展出一種擴展的最大方差展開方法（Extended Maximum Variance Unfolding, EMVU），GPR的另個優點是其參數能自動學習，而KPCA的核參數選擇問題卻仍未有一個較明確的解決方案，在線上監測中，EMVU不只以傳統的T2和SPE指標監測模型之距離及擬合度，並加入輸出預測變異量作為一新指標，能夠更大的顯示輸入空間中測試樣本與訓練樣本的差異性。在有故障數據的情形下，常用分類方法建立模型，其中，支持向量機是近年來最被廣泛使用的一種分類方法。本研究基於局部模型可能趨向線性或模型非線性複雜度較全局模型低的概念，以即時學習（Just In Time Learning, JITL）的方式，在新樣本採集時即時以鄰近點建立局部多分類支持向量機（Multiclass Support Vector Machines, MSVM）模型、即時監測，因此將之命名為JITL-MSVM，而每個模型建立時皆採用快速的留一交叉驗證法（Fast Leave One Out, FLOO）自動選擇模型參數，以符合”即時”的目的。本研究最後使用田納西伊士曼程序（Tennessee Eastman process process）模擬一連續非線性製程進行分析並與傳統方法比較。

• 學位論文

Thermo- and photo-driven crystalline molecular switches comprising pseudorotaxanes

This thesis describes the thermo- and photo-driven molecular switches comprising ferrocene-containing pseudorotaxanes in the solid state. Chapter 1 presents an overview of supermolecular chemistry as well as the purpose of this project. Chapter 2 describes the reversible mechanical deformations of the single crystals of the pseudorotaxanes caused by a combination of temperature control and light-irradiation. Laser irradiation to the ferrocenyl group of the pseudorotaxane induces molecular structural changes in the crystals: it triggers a crystal-to-crystal thermal phase transition deforming the crystal shape at 124 ºC; it causes rapid and reversible expansion of the crystal at room temperature. In addition, the local laser irradiation to a part of the single crystal enables selective transport of micro-particles. Chapter 3 describes the preparation and morphological studies of the thermally responsive pseudorotaxane films. The thin films of the pseudorotaxane molecule can be prepared on a glass or SiO2 substrates by a solution casting method, which affords the polycrystalline films without dissociation of the pseudorotaxane molecule. Obtained films are characterized by X-ray diffraction, differential scanning calorimetry (DSC), polarized optical microscopy, and grazing incident wide-angle X-ray scattering (GIWAXS) measurement with temperature control. The pseudorotaxane film on the substrate exhibits the reorganization of the molecule to give a large crystal face with 50-100 μm on heating, followed by the reversible solid-to-solid thermal phase transition on heating and cooling. GIWAXS analysis can conduce to the molecular alignment of the pseudorotaxane in the film; the pseudorotaxane adopts edge-on orientation, in which one-side of oligo-ethylene glycol group -(CH2CH2O)n- of the dibenzocrown ether molecule in the pseudorotaxane lies on the substrate, probably due to the molecule-surface interaction and formation of the bulky interlocked structure. Chapter 4 described the synthesis and characterization of a new pseudorotaxane composed of 4,4’,5,5’-tetrabromodibenzo[24]crown-8 ether as a ring molecule and ferrocene-containing ammonium cation as an axle molecules. The optical properties of the pseudorotaxane are observed and related to the molecular alignment in the single crystal state. Chapter 5 presents the conclusions of the project and gives forecast of this research. Finally chapter 6 presents the experimental conditions.

• 學位論文

Synthesis of poly(2,6-dimethyl-1,4-phenylene oxide) derivatives in water using water-soluble copper complex catalyst with natural ligands

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) was synthesized by oxidative polymerization of 2,6-dimethylphenol (DMP) using a water-soluble copper complex catalyst under oxygen and with natural ligands in alkaline water. Arginine, guanine, adenine, cytosine, histidine, and folic acid were used as ligands for the copper complex. Arginine performed the best, with a yield of 72%, a number average molecular weight (Mn) of 4400, and a molecular weight distribution (Mw/Mn) of 1.7. It was then used to optimize the reaction conditions. Surfactants, temperature, catalyst and sodium hydroxide concentration were varied in copolymerization of DMP and 2-allyl-6-methylphenol (AMP) to produce allyl-containing PPO with 77% yield (Mn = 4500, Mw/Mn = 1.8). The optimum conditions were also applied to copolymerization of DMP, AMP, and bisphenol A, as well as vinylbenzyl terminated copolymerization of DMP and diallyl bisphenol A, leading these PPO derivatives analogs containing thermally cross-linkable allyl and vinyl groups. The thermal properties of these thermosetting PPOs were studied by differential scanning calorimeter, thermogravimetric analysis, and Fourier-transform infrared spectroscopy.

• 學位論文

基於混和判別監測進行多模態連續製程及多階段批式製程的故障檢測、診斷及判定

為了更有效的利用製程故障的數據，監督式學習法(Supervised learning techniques)近年來已被廣泛的研究且應用於製程監測(Process monitoring)上，然而，要良好的使用現有的監督式學習法監測製程，在訓練數據庫中需要包含製程正常操作數據以及所有的製程故障數據。對於真實的工業製程，這個條件通常是很嚴苛的，因為有一些故障並不是時常發生，要收集到此類故障數據較為困難，而且隨著產線設備使用時間增加，機器不免會有老化現象，會出現從沒發生過的未知故障，當這些故障發生時，數據庫中沒有這些故障訊息，導致現存方法無法良好的監測出未知故障。另外，現有監督式學習法用於製程監測上大部分都含有一個強烈的假設，其假設每類別需符合高斯分佈(Gaussian distribution)，而在真實工業生產中，製程數據往往無法符合此項假設，導致無法很好的處理非高斯分佈數據。 本文結合混和判別分析法(Mixture discriminant analysis, MDA)及統計製程控制(Statistical process control, SPC)的概念，發展出一套混和判別監測法(Mixture discriminant monitoring, MDM)，對於批式製程獨有的三維數據特性亦發展出自適應批式混和判別監測法(Adaptive batch MDM, ABMDM)，同時解決上述兩個問題，於多模態連續製程及多階段批式製程中的製程監測更凸顯其適性。針對監測出已知故障，藉由工程師或操作員對製程的了解可及時的做出故障診斷(Diagnosis)，若是監測出未知故障，使用重構方法(Reconstruction-based)來進行故障判定(Isolation)的工作，進而找出故障發生的原因最有可能是由哪一個製程變數造成。 最後，以田納西伊士曼製程(Tennessee Eastman process)及塑膠射出成型製程的監測為例，驗證此方法的有效性。

• 學位論文

利用耗散粒子動力學模擬帶電荷三嵌段共聚物於水溶液中之自組裝行為

帶電嵌段共聚物之應用層面非常廣泛，但在目前的文獻當中對於其奈米微結構仍非全然了解。因此本論文利用耗散粒子動力學模擬方法，來研究中性三嵌段共聚物與帶電三嵌段共聚物於水溶液中之自組裝行為，並探討在該系統下靜電作用力對於形態變化所造成的影響。同時藉由改變三嵌段共聚物之嵌段比例以及水溶液中之共聚物濃度，來觀察其形態變化。 研究結果顯示，藉由調整嵌段比例以及共聚物濃度，能夠有效地控制其形態變化，有微胞、層板、柱狀、網狀等基本結構，而且在帶電系統中之共聚物確實能夠利用靜電作用力來誘導其形態轉變。不過在低濃度下之中性嵌段共聚物與帶電嵌段共聚物系統，一律都是以微胞結構呈現，但由於受靜電作用之影響，其微胞之聚集方式與大小會有所不同，因此可利用此方法來製備出尺寸更小之奈米微胞，藉以應用於藥物釋放、仿生材料等相關領域。

• 學位論文

Synthesis and characterization of cyclopentadithiophene (CPDT)-naphthalene (NDI) push-pull ABA-type oligomers and copolymers

This thesis presents the synthesis, characterization, and device performance of a series of cyclopentadithiophene (CPDT)-naphthalene (NDI) donor-acceptor (D-A) ABA-type oligomers and copolymers. These oligomers composed of CPDT-NDI-CPDT unit with various alkyl chains are successfully synthesized via direct arylation using palladium complex catalyst. The corresponding copolymers are synthesized by oxidative polymerization using FeCl3. All of oligomers and copolymers are systematically characterized and analyzed by gel permeation chromatography (GPC), 1H NMR and UV-vis-NIR absorption spectroscopies, cyclic voltammetry (CV), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). GPC measurement shows that these polymers are of relatively high molecular weight, Mn = 21800-76000. These copolymers show deep-red absorption including near-infrared region (up to 1100 nm) due to their quite narrow bandgap. Impressively, the electrochemical property of the resulting copolymers exhibits lowest unoccupied molecular orbital (LUMO) at about - 3.7 eV, which has been considered as the favorable level as n-type materials for use in organic photovoltaic devices (OPVs). These copolymers exhibit only n-type property giving the highest electron mobility of 3.7 x 10-4 cm2 V-1 s-1 in organic field-effect transistor because of its strong intermolecular interaction. On the other hand, the copolymer with highly soluble branched alkyl chain shows the highest power conversion efficiency of 0.25% in organic photovoltaic device. To investigate the versatile reactivity of C-H direct arylation, the copolymers composed of above unit with benzothiadiazole, thiophene, or bithiophene are also II synthesized by direct arylation polymerization. All polymers have higher molecular weight (Mn = 18000-52000) than the alternative polymers of dibromo-NDI and CPDT obtained from similar reaction condition. The optical and electrochemical properties of these polymers are measured by UV-vis-NIR spectra, 1H-NMR, GPC and CVs.

• 學位論文

利用耗散粒子動力學模擬π形接枝共聚物在平衡與非平衡系統下之相態衍變

本論文使用耗散粒子動力學模擬π形接枝共聚物在平衡與非平衡系統下改變接枝粒子數與分子濃度。此π形接枝共聚物是由親水性，疏水性，強疏水性的三種高分子所組成。其結果發現在平衡系統下，當濃度低時，產生球狀和圓柱狀；當濃度高時，產生層板或網狀結構，在濃度100%時產生了應用性相當廣泛的孔洞結構。當加入流場後，發現流場影響了最終形態與形態的方向。其中分子622模擬出的條狀特殊結構，我們相信這結構在奈米科技上有廣泛的應用。最後將所有形態整理成相圖，使實驗人員透過調整濃度與接枝數目能得到所需要的形態。接著探討黏度與濃度的關係，其趨勢是隨著濃度增加，黏度也跟著增加，不過有些因為受到形態及分子間作用力的影響，導致黏度大小產生非預期的變化。最後我們期許這些結果在未來能用來解決在光電、生物、醫藥或奈米科技上的問題。

• 學位論文

PEO-b-P4VP及其錯合物之低臨界有序化現象研究

我們利用小角度X光散射實驗解析各種分子量與組成的嵌段共聚物poly(ethylene oxide)-block-poly (4-vinylpyridine) (PEO-b-P4VP)以及參混界面活性劑dodecylbenzene sulfonic acid(DBSA)的相轉換行為。結果發現，PEO-b-P4VP共聚物可以呈現一種極不尋常的「低臨界有序化」(lower critical orderingtransition，LCOT)行為，即在低溫時PEO與P4VP鏈段互容，但當加熱至一臨界溫度時，兩鏈段發生微相分離，呈現一種「無序到有序態的轉化」(disorder-to-order transition，DOT)。奈米結構的形態乃是受控於兩鏈段的分離強度(χN)和體積分率，在多組不同分子量的PEO-b-P4VP中，我們發現兩相中較不對稱比例和較小的分子量，會導致無序到有序態之轉化溫度的上升。除了以實驗建構相圖之外，我們亦將運用文獻上的理論模型定量計算PEO-b-PVP系統的相圖，藉由與實驗相圖的擬和，揭露共聚物呈現LCOT相行為的機制與驅動力。根據P4VP以及其異構物P2VP，一個給定的組成和分子量，PEO-b-P4VP共聚物的無序到有序態之轉化溫度低於PEO-b-P2VP，這是由於P4VP和P2VP的溶解度參數之間的差距。另外，當PEO-b-P4VP(DBSA)中的DBSA增量時，會導致無序到有序態之轉化溫度上升，由於產生不對稱的組成和兩相之間的χ參數的改變。

• 學位論文

以精密塗佈技術製作高分子微針

本研究之目的為研發適當的配方，並利用精密塗佈技術製作出品質良好的微針結構，並且結合藥物，提供一種新穎的給藥方式，以提升人類的醫療品質。 　　本研究一共分成三個部分，分別是結構配方設計、製程和藥物結合。在結構配方設計部分，首先要先設計微針的長度、直徑和規格等等，製作出微針模仁，之後再搭配不同材料的嘗試，找出最適當的配方，有利後續微針的製作。製程部分，則是關係到整體微針結構的完整性及良率，避免因塗佈不均勻或是真空乾燥過程中的參數調整不恰當，而造成一些氣泡或皺褶等等的缺陷出現。最後製作出的良好微針成品將會進行下列幾項測試：(1) 微針表面結構觀察 (2) 微針機械強度分析 (3) 微針染料點觀察 (4) 微針穿刺深度觀察，藉由這些測試來分析評估成品的好壞與否。最後才設計如何將微針與藥物作結合，使藥物分佈於微針當中。 　　目前微針成品經過上述實驗證實，其品質皆有一定的水準，並且已能夠成功的與染料和藥物作結合，使其分佈在不同需求的位置。未來可依照藥物不同的特性和需求，來搭配不同的分佈位置及濃度含量，進而達到新穎給藥之目標。

• 學位論文

含高比例顆粒磷光材料懸浮液塗佈特性之研究

因申請專利緣故，資料延後公開