奈米幾丁聚醣之製備及應用研究 施詔銘、?耀國

奈米幾丁聚醣之製備及應用研究 施詔銘、?耀國

E-mail: 211269@mail.dyu.edu.tw

摘 要

本研究分為兩部分主題進行論述，第一部份係以噴霧乾燥法製備幾丁聚醣奈米粉末，第二部份則是以幾丁聚醣懸浮液製備 金奈米粉末。第一部份以1% (w/v) 幾丁聚醣懸浮液進行噴霧乾燥製備後可獲得幾丁聚醣奈米粉末。在壓力4 kg/cm2與樣品 流量30 mL/min條件下，由噴霧角度與霧氣外觀比較，超音波霧化器產生之液滴更加微細，且經噴霧乾燥製得產物顆粒粒 徑亦較二流體式霧化器者微小。由於旋風收集器處僅能收集微米級顆粒，此處先以靜電棉證實次微米級顆粒存在後，再以 實驗型靜電集塵器加以收集。以超音波霧化器進行噴霧乾燥，當高壓空氣條件上升時產率隨之增加(2.6%、5.7%、15.5%)

、含水率隨之降低(9.1%、8.3%、6.8%)、顆粒表面漸趨平滑，能提供商業化生產奈米粉末另一選擇。第二部份金/幾丁聚 醣奈米顆粒可藉由鹼性幾丁聚醣懸浮液來製備，幾丁聚醣同時扮演分散劑與還原劑角色。金奈米顆粒與奈米粉末可藉由簡 單之熱裂解與酸水解方法製得，經熱裂解可獲得黑色的奈米金粉末。FESEM證明金奈米粉末粒徑範圍約介於50~200 nm。

酸水解是另一個快速降解幾丁聚醣的方法，本研究採用醋酸來進行酸水解。由AEM證明，紫紅色金懸浮液中金奈米顆粒粒 徑均小於40 nm，其分散性佳。幾丁聚醣懸浮液可製備極佳之奈米金粉末與奈米金顆粒，其製程不需使用毒性物質。

關鍵詞 : 奈米粉末、奈米顆粒、超音波霧化器、靜電集塵器、熱裂解、酸水解、幾丁聚醣、奈米粉末、奈米顆粒、超音波 霧化器、靜電集塵器

目錄

封面內頁 簽名頁 授權書 iii 中文摘要 iv 英文摘要 v 誌謝 vii 目錄 viii 圖目錄 xi 表目錄 xv 1. 緒言 1 2. 文獻回顧 2 2.1 幾丁質與 幾丁聚醣 2 2.1.1 幾丁質與幾丁聚醣的化學結構 3 2.1.2 幾丁質與幾丁聚醣的製備與分析 3 2.1.3 幾丁聚醣的應用 13 2.2 奈米 科技 15 2.2.1 物質尺度定義 16 2.2.2 奈米化技術 19 3. 以噴霧乾燥法製備幾丁聚醣奈米粉末 22 3.1 文獻回顧 22 3.1.1 噴霧乾 燥 22 3.1.2 霧化器種類 22 3.1.3 產品收集方式 29 3.1.4 噴霧乾燥的相關研究 34 3.2 研究目的 36 3.3 材料與儀器設備 38 3.3.1 材料 38 3.3.2 儀器設備 39 3.4 研究方法 40 3.4.1 幾丁聚醣懸浮液之製備 40 3.4.2 噴霧乾燥設備之安裝 40 3.4.3 奈米粉末之收 集 47 3.4.4 噴霧乾燥設備操作條件 49 3.4.5 產品分析 50 3.5 結果與討論 51 3.5.1 幾丁聚醣懸浮液之製備 51 3.5.2 霧化器效果 54 3.5.3 以旋風分離器收集產品 57 3.5.4 以靜電吸引力收集樣品 60 3.6 結論 66 4. 以幾丁聚醣懸浮液製備金奈米粉末 67 4.1 文獻回顧 67 4.1.1 金 67 4.1.2 金的奈米化 69 4.1.3 金奈米顆粒的應用 71 4.1.4 幾丁聚醣對金屬離子之吸附機制 71 4.2 研究目 的 75 4.3 材料與儀器設備 76 4.3.1 材料 76 4.3.2 儀器設備 77 4.4 研究方法 78 4.4.1 幾丁聚醣懸浮液之製備 78 4.4.2 幾丁聚 醣/金複合物懸浮液之製備 78 4.4.3 金奈米粉末之製備 79 4.4.3.1 熱裂解法 79 4.4.3.2 酸水解法 79 4.4.4 樣品分析 80 4.5 結果 與討論 81 4.5.1 金離子的還原 81 4.5.2 金/幾丁聚醣複合物奈米顆粒 86 4.5.3 以熱裂解法製備金奈米顆粒 93 4.5.4 以酸水解 法製備金奈米顆粒 98 4.6 結論 107 5. 總結 108 參考文獻 110 附錄 126 圖附錄 139 圖目錄 圖2.1.1 纖維素、幾丁質及幾丁聚 醣之化學結構 4 圖2.1.2 幾丁質之α形態結晶結構A為鏈結朝上者B為鏈結朝下者 5 圖2.1.3 幾丁質之β形態結晶結構A為鏈 結朝上者B為鏈結朝下者 6 圖2.1.4 竽螺外殼破裂面之交錯層結構 8 圖3.1.1 (A)壓力式、(B)旋轉式與(C)二流體式霧化器內部 結構 24 圖3.1.2 旋轉式霧化器之噴霧影像圖 26 圖3.1.3 壓力式霧化器之噴霧影像圖 27 圖3.1.4 超音波霧化器 28 圖3.1.5 旋風 分離器中氣流流動示意圖 30 圖3.1.6 旋風分離器中氣流流動模擬圖 31 圖3.1.7 一階式靜電集塵器之結構示意圖 32 圖3.1.8 二 階式靜電集塵器之結構示意圖 33 圖3.4.1 實驗型設備簡圖 42 圖3.4.2 自行設計之氣體儲槽 43 圖3.4.3 噴霧乾燥時氣體壓力變 化示意圖 44 圖3.4.4 自行設計之脈衝破壞器 45 圖3.4.5 噴霧乾燥時樣品進料量變化示意圖 46 圖3.4.6 二階式靜電集塵器原型 機之俯視示意圖 48 圖3.5.1 中性幾丁聚醣懸浮液之AEM影像圖 52 圖3.5.2 中性幾丁聚醣懸浮液之粒徑分佈圖 53 圖3.5.3 二 流體式霧化器之噴霧影像圖(進料速率為30 mL/min、高壓空氣壓力為4kgf/cm2) 55 圖3.5.4 超音波霧化器之噴霧影像圖(進料 速率為30 mL/min、高壓空氣壓力為4kgf/cm2) 56 圖3.5.5 以旋風收集器收集之幾丁聚醣粉末FESEM影像圖:使用二流體式霧 化器(進料速率為30 mL/min、高壓空氣壓力為4 kgf/cm2) 58 圖3.5.6 以旋風收集器收集之幾丁聚醣粉末FESEM影像圖:使用 超音波霧化器(進料速率為30 mL/min、高壓空氣壓力為4 kgf/cm2) 59 圖3.5.7 以靜電集塵棉收集之幾丁聚醣粉末FESEM影 像圖：放大100倍(使用超音波霧化器、進料速率為30 mL/min、高壓空氣壓力為4 kgf/cm2) 62 圖3.5.8 以靜電集塵棉收集之 幾丁聚醣粉末FESEM影像圖：放大1000倍(使用超音波霧化器、進料速率為30 mL/min、高壓空氣壓力為4 kgf/cm2) 63 圖3.5.9 以ESP原型機收集之幾丁聚醣粉末FESEM影像圖：操作時之噴霧壓力2 kgf/cm2(使用超音波霧化器、進料速率為30 mL/min) 64 圖3.5.10 以ESP原型機收集之幾丁聚醣粉末FESEM影像圖：操作時之噴霧壓力4 kgf/cm2(使用超音波霧化器、

進料速率為30 mL/min) 65 圖4.1 幾丁聚醣與金屬離子螯合情形：(A)分子內(B)分子間 74 圖4.5.1 鹼性金/幾丁聚醣懸浮液C1 之光譜圖 83 圖4.5.2 鹼性金/幾丁聚醣懸浮液C3之光譜圖 84 圖4.5.3 鹼性金/幾丁聚醣懸浮液C1、C2與C3經反應16小時後

之光譜圖 85 圖4.5.4 中性金/幾丁聚醣懸浮液C1之AEM影像圖 87 圖4.5.5 中性金/幾丁聚醣懸浮液C2之AEM影像圖 88 圖4.5.6 中性金/幾丁聚醣懸浮液C3之AEM影像圖 89 圖4.5.7 中性金/幾丁聚醣懸浮液C1之SAED圖 90 圖4.5.8 中性金/幾丁 聚醣懸浮液C2之SAED圖 91 圖4.5.9 中性金/幾丁聚醣懸浮液C3之SAED圖 92 圖4.5.10 C1/600銀片上樣本經熱裂解後製得 奈米金結構之FESEM影像圖與局部放大圖 94 圖4.5.11 C1/800銀片上樣本經熱裂解後製得奈米金結構之FESEM影像圖與局 部放大圖 95 圖4.5.12 C3/600銀片上樣本經熱裂解後製得奈米金結構之FESEM影像圖與局部放大圖 96 圖4.5.13 C3/800銀片 上樣本經熱裂解後製得奈米金結構之FESEM影像圖與局部放大圖 97 圖4.5.14 C1H1金奈米顆粒之AEM影像圖 99 圖4.5.15 C2H1金奈米顆粒之AEM影像圖 100 圖4.5.16 C3H1金奈米顆粒之AEM影像圖 101 圖4.5.17 C1H2金奈米顆粒之FESEM影像 圖 102 圖4.5.18 C2H2金奈米顆粒之FESEM影像圖 103 圖4.5.19 C3H2金奈米顆粒之FESEM影像圖 104 圖4.5.20 C3H2金顆 粒之FESEM影像(由選取區域spectrum 3進行EDS分析) 105 圖4.5.21 C3H2金顆粒之EDS分析圖 106 表目錄 表2.1 幾丁聚醣的 應用 14 表2.2.1 1940-1980年間顆粒尺度之定義 17 表2.2.2 德國國家標準對顆粒尺度之定義 18 表3.1 各種形式霧化器之比較 25 表3.2 噴霧乾燥在醫藥領域之相關研究 35 表3.3 幾丁聚醣顆粒製備方式 37 表4.1 金的物理性質 68 表4.2 金的奈米化方法 70 表4.3 金奈米顆粒的應用 73

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