http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/40 Mon, 05 Oct 2026 04:11:30 GMT 2026-10-05T04:11:30Z http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/57878 標題: 黏土插層/脫層機制之策略性研究與黏土/磷難燃性奈米複合材料之應用; Intercalation Strategies of Synthesizing Clay/Polymer Hybrids and Clay/Phosphazene Nanocomposites for Fire-Retarding and the Synergistic Effect 作者: Jau-Yu Chiou; 邱昭諭 摘要: 本論文探討黏土插層/脫層機制形成“黏土/高分子混成材料”之策略性研究與黏土含磷之難燃性衍生奈米複合材料與應用，研究內容主要分敘如下。 黏土插層/脫層機制形成黏土/高分子混成材料之策略性研究，係藉由聚醚胺(polyoxyalkylene-amines) 插層劑之親/疏水性質與末端基差異性，探討對層狀黏土有機化改質機制之影響。研究中發現在相同分子量之線性疏水鏈段聚醚胺 (polyoxypropylene-amines, POP-amines)，一端末端基為甲基之 POP-M-amines，與雙端皆為胺基之 POP-D-amines 相比具有最大層間距擴張。由動態實驗發現，POP-M-amines進行黏土插層具有特殊之第二步插層現象，有別於一般插層劑經離子交換進入黏土層間(第一步插層)所觀察到有機量關鍵性插層 (critical intercalation)；第二步插層，黏土之層間距與插層劑量成正比。此階段式插層現象，除了可達到天然黏土脫層型態外，進一步地，可利用此特殊插層機制，將有機化黏土做為奈米容器，把材料儲存於黏土層間之奈米空間，如原油吸附與回收、藥物釋放及相變化 (PCM) 材料 (如paraffin wax) 之包覆等。 高分子/黏土 (Polymer layered silicate, PLS) 奈米複合材具有優秀的機械性質、熱穩定性質與生物相容性質。關鍵技術在於親水性之黏土與疏水性高分子間之相容性。本研究，黏土含磷之難燃性衍生奈米複合材料與應用，係以合成 Phosphazene-poly(oxypropylene)-amines (HCP-D400) 為始，並依三種改質方式製得 HCP-D400/NSP、HCP-D400/MMT及HCP-D400/Na+-MMT 有機化黏土，並具有 lower critical aggregate temperature (LCAT) 之特殊性質。經由SEM-EDX、XRD 及 TEM 分析，發現 HCP-D400 與脫層之奈米矽片(NSP) 以物理摻混方式製備之 HCP-D400/NSP 於環氧樹酯中分散效果最佳。更進一步分析複合材料之熱穩定性，當添加 10wt% HCP-D400/NSP 於環氧樹酯，T¬¬10wt% 由 350 oC 增加至 447 oC，T¬¬10wt% 由 500 oC 增加至757 oC ，有效提升環氧樹酯熱裂解溫度 127 oC (T10wt%)與 257 oC (T¬¬80wt%)。限氧指數 (limit oxygen index, LOI) 則提升 7% 至 27%。研究中發現HCP-D400不僅可使奈米矽片均勻分散於環氧樹酯中，進一步的與奈米矽片產生協同作用 (synergistic effect)，提升高分子材料之熱穩定性質。; Layered silicate clays are natural crystallites and are well recognized for their organic intercalation for nanocomposite applications. In this study, a new mechanism is revealed by selection of hydrophobic polyetheramines with a poly(oxypropylene) (POP) backbone and a methyl terminus as the intercalation agent. Specifically, the monoamine with a molecular weight of 2000 g/mol widened the basal spacing of the layered sodium montmorillonite up to 74 A and further expansion to 84 A, 96 A, and 100 A by a second intercalation different from the ionic exchange reaction. Kinetic studies indicated that the first stage of intercalation occurred after a critical concentration of a monoamine, while the second stage had no critical concentration behavior. This two-step method shows the potentials for synthesizing suitable organoclay nanostructures for encapsulating phase change materials (PCM) and oil recovery from the spilt ocean. The exploration of the in-depth understanding of clay confinement chemistry leads the strategic design of new materials and oil recovery process. We further synthesized the phosphazene-amine adduct of hexachlorocyclophosphazene (HCP) and poly(oxypropylene)-diamines of 400 g/mol molecular weight (D400) by amine/chloride substitution and triethylamine removal of HCl. Subsequently, the adduct HCP-D400 was physically mixed with exfoliated silicate platelets (SP) to prepare the HCP-D400/silicate hybrids (HCP-D400/SP). The HCP-D400/MMT (HCP-D400 intercalated Na+-MMT) and HCP-D400/Na+-MMT (HCP-D400 physically mixed with Na+-MMT) were also prepared for comparison with HCP-D400/SP. A more homogeneous silicate distribution HCP-D400/SP than the HCP-D400/MMT counterparts in epoxy nanocomposites was revealed by SEM-EDX, XRD, and TEM analyses. The epoxy nanocomposite with 10 wt% of HCP-D400/SP, HCP-D400/MMT, and HCP-D400 had a degradation temperature at 80 % weight loss (T80 wt%) of 757 oC, 712 oC, and 519 oC, respectively, in comparison with the 500 oC of the pristine epoxy system. Anti-flame test confirmed that the HCP-D400/SP epoxy nanocomposite had a higher limit oxygen index (LOI) of 27.0 % than the HCP-D400/MMT counterpart (24.0 %). The degree of exfoliating the layered clay into random silicate platelets is the predominant factor for the thermal stability enhancement. It is also demonstrated that the co-presence of phosphazene-amines and silicate platelets has a synergistic effect in improving the thermal behavior of the nanocomposites. Wed, 01 Jan 2014 00:00:00 GMT http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/57878 2014-01-01T00:00:00Z http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/54312 標題: 黏土之溶膠-凝膠反應與複合材料應用; Clay Sol-Gel Reaction for Molecular Composite 作者: Jenny Jauhari; 仇寶雁 摘要: Nanosilicate platelets (NSP) 是由層狀蒙托土 (Na+-MMT) 脫層而得。利用 sol-gel反應將 3-aminopropyltriethoxysilane (APTES) 與NSP邊緣 ≡Si—OH連接形成共價鍵之NSP-amine。另外，NSP-amine 與 Glycidyl methacrylate (GMA) 可藉由開環反應得 NSP-acrylate。定性分析方面利用 29Si 固態核磁共振光譜儀確定 APTES 接上 NSP。NSP-amine 及 NSP-acrylate 定量分析（接枝量和接枝率）由熱重分析儀 (TGA) 分析計算而得。進一步將 NSP、NSP-amine 和 NSP-acrylate 導入紫外線固化系統進行光交聯成膜。亦可將 NSP 和 NSP-amine 導入環氧樹脂藉由熱交聯硬化成膜。並以鉛筆硬度測試硬度差異。利用紫外線固化技術，導入0.5 及 1.0 wt% NSP-acrylate，硬度從4H（未添加黏土）提升至7H及8H。於環氧樹脂系統中，導入0.5 至5wt% NSP-amine，膜之硬度從HB（未添加黏土）提升至 2H、3H 和 4H。另外，未改質之 NSP 導入丙烯樹脂，膜之硬度提升至 6H。而 NSP/環氧樹脂膜提升至 2H。; Nanoscale silicate platelets (NSP) were previously prepared from the newly developed exfoliation of sodium silicate clays (Na+-MMT) by ionic exchange reaction. We further designed the molecular composites by covalently functionalized NSP through its edged ≡Si—OH groups with 3-aminopropyltriethoxysilane (APTES) for amine-functionalized NSP. The consecutive reaction allowed the conversion of NSP-amines to NSP-acrylates through the reaction with Glycidyl methacrylate (GMA). NSP-amine was structurally characterized by 29Si solid-state NMR and thermogravimetric analysis (TGA), while NSP-acrylate only by thermogravimetric analysis (TGA). The NSP-acrylate was applied to the UV-cured resins through the acrylate polymerization in forming molecular composites exhibiting an highly enhanced hardness up to 6H and 8H from the pristine 4H (without clay) by 0.5 and 1.0 wt% NSP loadings, respectively. In epoxies, the NSP-amines promoted the hardness from HB to 2H, 3H, and 4H depending on the NSP loadings from 0.5% to 5% by weight. By comparison, the nanocomposites of dispersing NSP without the covalent bonding amine or acrylate functionalities only achieve the property of hardness in moderate degree, such as 6H and 3H for UV and epoxy systems, respectively. The significances of the silicate platelets in covalently bonding with organic polymer matrices as the molecular composites was realized by comparing with the analogous nanocomposites. Thu, 01 Jan 2015 00:00:00 GMT http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/54312 2015-01-01T00:00:00Z http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/48679 標題: 黏土、奈米碳管及奈米銀粒子之混成材料及其導電性探討; Synthesis of Nanohybrids Involving Silicate Clays, Carbon Nanotubes and Silver Nanoparticles, and their Conductivity Studies 作者: Rui-Xuan Dong; 董睿軒 摘要: 製造具自我排列特性的奈米材料，其分散技術為製程中之關鍵。於此，我們利用離子交換反應以及非共價鍵方式製造奈米混摻材料，如：將奈米銀粒子修飾在矽酸鹽黏土與奈米碳管上。這篇論文將分成三部份，分別探討奈米材料之分散性、粒徑大小、粒徑分佈及其電性探討。 第一部分 此部分是探討利用無機矽酸鹽黏土噹分散劑，可合成窄小尺寸分佈及具低熔點之奈米銀粒子。由於天然黏土是片狀幾何形狀，可提供其高表面積固定奈米銀粒子，使其尺寸維持在粒徑大小17−88 nm的範圍。當銀離子/黏土的離子交換當量比為1/1時，可透過掃描式電子顯微鏡及可見光吸收觀察生成之銀粒子具窄小分佈的尺寸(polydispersity of Dw/Dn = 1.2 at 26 nm)及波長為420nm時，有一特徵吸收峰。在無有機分散劑存在下，膠狀之黏土仍可和銀離子嵌合並穩定生成之銀粒子。由於那層間距離僅微小的擴張 (12.0 A versus 13.9 A)，銀粒子是穩定生成在黏土之表面。在經過80 的乾燥並再分散回水中後，銀粒子仍穩定且例子大小均一；更進一步藉由掃描式電子顯微鏡觀察得知，那黏土表面上之奈米銀粒子具有一低熔點 (110)性質。這類銀奈米粒子在低溫下製造銀導線及導管是有其潛在之應用性。 第二部分 經由將銀離子溶於DMF/water溶劑中，並以poly(oxyethylene)-imide (POE-imide)當為分散劑可將銀粒子修飾於碳管表面，而此高分子(POE-imide)可使碳管及銀粒子不會聚集於溶液之中並可將銀離子還原為銀粒子。由此法製備而成的奈米銀粒子其粒徑分佈為8−30nm並且經由TEM觀察可看到有部分的銀粒子會貼附於碳管表面之上。 若無此高分子幫助穩定及還原銀離子，硝酸銀藉由DMF還原過程中，產生銀鏡現象且附著在反應容器之壁上。可以利用紫外光/可見光光譜儀於波長為550nm及420nm分別觀察碳管及奈米銀粒子的特徵吸收峰變化情形。經由水洗將分散劑與自由奈米銀粒子去除後可得奈米銀粒子(20-30nm)之單一多壁奈米碳管。從未經修飾之多壁奈米碳管，此有機分散劑的合成提供了簡單的方法來製備Ag/MWNT奈米混掺材料。 第三部分 我們呈現一種直接合成poly(oxyethylene)-imide (POE-imide)複合奈米銀粒子/多壁奈米碳管方式，並利用加熱方法探討其混成薄膜之電性。藉由簡單塗層Ag/MWNT/POE-imide混合液於聚醯亞胺基材上並加熱至160 oC，奈米銀粒子遷移至表面且聚集成直徑為100−150 nm，當溫度增加至170 oC時，那複合薄膜外觀轉變成呈現乳白色，其片電阻值也大幅降低為2.2 x 10-1 Ohm/sq，當溫度持續加熱至350 oC時，此時複合膜顯示為白色之表面且具有最佳之片電阻值(2.7 x 10-2 Ohm/sq)。電性之提升是由於奈米銀粒子催化高分子降解並進而熔融，此機制可由掃描式電子顯微鏡(FE-SEM)、熱重分析儀(TGA)及廣角X-ray繞射(WAXRD)等儀器鑑定得知。就我們所知，於此低溫度下所測量之Ag/MWNT薄膜片電阻值是最低的且目前文獻上沒有報導。; “Dispersion technology” is considered as the key step in Bottom-Up process, for self-assemblies and fabricating nanomaterial devices. Herein, nanohybrid materials, including silver nanoparticles decorated on the silicate clay and carbon nanotube, were fabricated by ionic excharge reaction and non-covalent method. These materials were investigated on dispersing ability, particle size and distribution, and electrical behavior. The thesis is divided into three parts: Part 1. Silver nanoparticles (AgNPs) of narrow size distribution and low melting point were synthesized from the reduction of silver nitrate in the presence of inorganic silicate clays. The natural clays with a lamellar geometric shape provided a high surface area for immobilizing AgNPs with nanometer diameter in the range of 17-88 nm. At a 1/1 equivalent ratio of Ag+ to clay counter ions, the generated particles had a narrow size distribution (polydispersity of Dw/Dn = 1.2 at 26 nm Dn by SEM) and a UV absorption at 420 cm-1. Without organic dispersants, the colloidal clays could complex with Ag+ in the initial stage of mixing and subsequently stabilized the generated Ag0 particles. It seems that the high surface area stabilizes the clay rather than the Ag metal intercalation into the layered structure since the basal spacing was only slightly enlarged (12.0 A versus 13.9 A by XRD). The resulting AgNPs were highly stable and maintained their particle size after several cycles of drying at 80 oC and re-dispersion in water. Moreover, the AgNPs on the clay surface melted at a low temperature (110 oC), observed by SEM. Such AgNPs may have potential applications for fabricating silver arrays or conductors at low temperature. Part 2. Nanohybrids of silver nanoparticles (AgNPs) decorated on the surface of multiwalled carbon nanotubes (Ag/MWNT) were synthesized via the in situ reduction of AgNO3 in N,N-dimethylformamide (DMF) and water mixtrues. The process required the presence of a poly(oxyethylene)-backboned oligoimide (POE-imide), which stabilized the dispersion of MWNTs and AgNO3 initially, and subsequently the reduced Ag0 nanoparticles. AgNPs in the range of 8–30 nm diameter were generated and some of these were directly attached to the MWNT surfaces, as observed by transmission electron microscopy (TEM). Without the presence of POE-imide, AgNO3 can only be reduced into Ag0 mirror by DMF slowly and deposits on the side of the reactor wall. The kinetic formation of these nanohybrids was characterized by UV-visible (UV-vis) absorption for MWNTs at 550 nm and AgNPs at 420 nm. The single MWNT tubes of decorated with AgNPs (20–30 nm) were isolated by washing off the dispersant and free AgNPs. The synthesis involving an organic dispersant provides a convenient and facile method for preparing Ag/MWNT nanohybrids from the unmodified MWNTs. Part 3. We fabricate a flexible and surface conductive films by hybridizing silver nanoparticles on multi-walled carbon nanotubes (Ag/CNT) via an in situ silver nitrate reduction in poly(oxyethylene)-imide (POE-imide) dispersion. The POE-imide copolymers provided dual functions for homogenizing CNT dispersion in DMF/H2O mixture and subsequently stabilizing the Ag/CNT nanohybrids during the solvent evaporation into films. By simple coating on polyimide substrate and heating to 160 oC, the generated silver nanoparticles (AgNPs) migrated to surface and aggregated to larger size of 100−150 nm. Continuing heating at 170 oC and 350 oC, the film surface appeared to have color changes from golden to milky-white with lower sheet resistance of 2.2 x 10-1 Ohm/sq and 2.7 x 10-2 Ohm/sq, respectively. The enhancement of surface electrical conductivity was attributed to the AgNPs migration through CNT network and melt into silver granule connection while simultaneously annealing at the preferable temperature of 350 oC. The mechanistic aspects were elucidated by surface observation on a scanning electronic microscope, measurement of organic degradable temperature by thermal gravimetric analyzer and silver characterization by wide-angle X-ray diffraction. The synthesis is viable for making flexible polyimide film exhibiting an unprecedented high conductivity that easily lighting a light-emitting diode lamps. Fri, 01 Jan 2010 00:00:00 GMT http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/48679 2010-01-01T00:00:00Z http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/103210 標題: 鹼誘導異靛藍化合物轉化為2-胺基苯甲酸; Base-Induced Transformation of Isoindigos into 2-Aminobenzoic Acids 作者: 張襄柔; Hsiang-Jou Chang 摘要: 異靛藍因具有優異的光電特性與化學穩定性，已廣泛應用於有機電子材料領域。然而，目前相關研究多聚焦於材料設計與元件應用，對於材料使用後的再造與降解機制仍缺乏探討。先前研究發現，異靛藍可於三乙胺、水及氧氣存在下發生骨架重組反應，轉化為3,3’-(ethane-1,2-diylidene)bis(indolin-2-one)。此結果顯示異靛藍骨架具有進一步發生結構轉換與材料再造之潛力。接續先前的研究，本研究以異靛藍衍生物為模型系統，探討其於鹼性條件下之化學轉化行為。研究結果顯示，異靛藍能在鹼、水及氧氣共同作用下發生骨架裂解，並形成2-胺基苯甲酸衍生物。透過光譜分析、質譜分析、單晶結構鑑定以及反應氣體分析，確認反應過程伴隨骨架裂解與脫羰基現象。進一步結合反應中間體偵測與理論計算結果，提出異靛藍經由靛紅與羥吲哚中間體逐步轉化為2-胺基苯甲酸之反應途徑。此研究結果提供了一種新的異靛藍降解與再造策略。此外，本研究亦初步觀察到聚異靛藍在相似條件下產生結構變化，顯示此轉化策略具有延伸至共軛高分子系統之潛力。; Isoindigo is widely used in organic electronics because of its excellent optoe-lectronic properties and outstanding chemical stability. However, studies have pri-marily focused on material design and device performance, whereas the degradation and recycling of isoindigo-based materials remain largely unexplored. Our previous work shows that isoindigo undergoes skeletal rearrangement in the presence of tri-ethylamine, water, and oxygen to afford 3,3’-(ethane-1,2-diylidene)bis(indolin-2-one), highlighting the potential of the isoin-digo framework for chemical transformation and material recycling. Building upon this finding, the present study systematically investigates the chemical transfor-mation of isoindigo derivatives under alkaline conditions. The results reveal that isoindigo undergoes skeletal cleavage in the presence of base, water, and oxygen, leading to the formation of 2-aminobenzoic acid derivatives. Spectroscopic charac-terization, mass spectrometry, single-crystal X-ray diffraction, and gas analysis con-firm that the transformation involves skeletal cleavage and decarbonylation. Fur-thermore, mechanistic studies and theoretical calculations suggest a stepwise path-way proceeding through isatin and oxindole intermediates to yield 2-aminobenzoic acid derivatives. These results establish a new strategy for the degradation and recy-cling of isoindigo-based materials. In addition, preliminary results indicate that poly(isoindigo) also undergoes structural transformation under similar conditions, suggesting that this strategy can be extended to conjugated polymer systems. Thu, 01 Jan 2026 00:00:00 GMT http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/103210 2026-01-01T00:00:00Z