本研究以氧化還原法製備石墨烯，探討三種氧化方法(Hummers法、Modified Hummers法及Tour''s Improved法)所製得氧化石墨的氧化程度及結構分析，再經由本研究所設計的三步還原法還原氧化石墨，試圖製備出低含氧基團的石墨烯，並以石墨烯作為補強材，以溶液法製備石墨烯/聚乳酸奈米複合材料，同時探討石墨烯在聚乳酸奈米複合材料中對熱性質、機械性質及電性質的補強效應。由XRD分析中發現， Hummers法製備之氧化石墨仍有原始石墨之訊號。進一步的還原石墨烯，由XPS中C1s的分峰可發現還原石墨烯中含氧基團的含量明顯降低。在石墨烯/聚乳酸奈米複合材料的熱裂解分析中可得知石墨烯/聚乳酸奈米複合材料仍屬於一級裂解，且石墨烯在聚乳酸的裂解過程中能擔任催化劑的角色。由非等溫結晶動力中可得知填加石墨烯能增加聚乳酸結晶長成的速率，但並不會影響其結晶的晶型。

In this study, the graphene was prepared by chemical oxidation and reduction reaction. The graphite oxide was prepared by Hummers, modified Hummers and Tour''s Improved methods. The degree of oxidation and structure of graphite oxide were investigated by XRD, XPS, Raman spectrum, and TGA. In reduction reaction stage, we design a synthetic strategy (triple step reaction) to prepare the graphene with low oxide content. The graphene/polylactide composites were fabricated through solvent method. The thermal and mechanical properties, nonisothermal crystallization kinetics, and the conductivity of the composites were investigated. The XRD analysis revealed that the Hummers method cannot oxidize graphite to graphite oxide completely. The C1s peak in the XPS analysis indicated that the oxide content was decreased for the graphene obtained after the triple step reaction. The thermal degradation analysis revealed that the degradation behavior of graphene/polylactide composites was first order reaction, and graphene could be the catalyst of the degradation reaction. The results of nonisothermal crystallization kinetics indicated that graphene can accelerate the crystallization rate of polylactide, but would not affect the type of crystallization.

目錄
摘要 I
Abstract II
目錄 III
圖目錄 VI
表目錄 XII
第一章緒論 1
1.1前言 1
1.2生物降解性高分子簡介 2
1.3聚乳酸之簡介 4
1.3.1聚乳酸的介紹與特性 4
1.3.2聚乳酸的製備 6
1.3.3聚乳酸之應用與生物降解性介紹 9
1.4單質碳之簡介 11
1.4.1富勒烯之簡介 12
1.4.2碳奈米管之簡介 13
1.4.3石墨烯之簡介 13
1.5石墨烯製備方法 15
1.5.1固相法 15
1.5.2液相法 16
1.5.3氣相法 20
第二章文獻回顧及研究動機 22
2.1文獻回顧 22
2.1.1石墨烯的早期研究 22
2.1.2氧化還原法製備氧化石墨 23
2.1.3氧化還原法製備還原石墨烯 26
2.1.4聚乳酸複合材料 28
2.1.5非等溫結晶動力學 34
2.1.6 Avrami方程式 34
2.2研究動機 36
第三章、實驗內容 37
3.1實驗藥品 37
3.2分析儀器 44
3.3實驗儀器 46
3.4儀器原理與測試條件 47
3.5實驗流程 52
3.5.1氧化石墨之實驗步驟 52
3.5.2還原氧化石墨之實驗步驟 54
3.5.3石墨烯/聚乳酸複合材料之製備 55
3.5.4實驗流程圖 56
第四章結果與討論 59
4.1氧化石墨性質分析 59
4. 2還原石墨烯性質分析 70
4.3聚乳酸及還原石墨烯/聚乳酸性質分析 82
4.3.1聚乳酸及還原石墨烯/聚乳酸熱性質分析 82
4.3.2還原石墨烯/聚乳酸複合材料動力學研究 89
4.4還原石墨烯/聚乳酸複合材料非等溫結晶動力學研究 101
4.5還原石墨烯/聚乳酸複合材料機械性質與導電性質分析 109
4.5還原石墨烯/聚乳酸複合材料形態學探討 112
第五章結論 114
第六章參考文獻 116

圖目錄
圖1-1.聚乳酸立體異構物示意圖 5
圖1-2.丙交酯的雙環異構物結構示意圖 5
圖1-3.聚乳酸的製備方法 7
圖1-4.工業上PLA的製備方式 8
圖1-5.碳的同素異形體 12
圖1-6.碳六邊型的蜂窩狀晶體結構 14
圖1-7.石墨烯的表面結構 15
圖1-8.氧化還原的機制 17
圖1-9.碳奈米管縱切法示意圖 18
圖1-10. 超音波分散法示意圖 19
圖1-11.有機合成法製備二維石墨烯奈米帶 20
圖2-1.石墨片在矽基材上的SEM圖 23
圖2-2. A. K. Geim及K. S. Novoselov黏貼出石墨烯之AFM圖 23
圖2-3. 石墨烯各種型態的層數分佈 24
圖2-4. (a) HGO、HGO+及IGO的XRD圖(b)氧化石墨的製備方法 25
圖2-5.石墨烯水溶液未填加PSS(左)及填加PSS(右) 26
圖2-6.以高熱還原製得石墨烯之AFM圖 27
圖2-7.(a)經硼氫化鈉還原製得之石墨烯導電度及C/O比(b) 經硼氫化鈉還原製得之石墨烯Raman光譜圖 27
圖2-8.環己醇的脫水反應 28
圖2-9.多壁奈米碳管/聚乳酸複合材料在不同填加量時之導電度 29
圖2-10. PLLA-g-GOs的合成路徑 30
圖2-11.(a)GO-TDI-OH與GO在甲苯中的分散性(b)不同GO含量的PLLA-g-GO及PLLA的導電度 31
圖2-12.聚乳酸及氧化石墨/聚乳酸奈米複材的t0.5及1/t0.5與Tc作圖 32
圖2-13.(a)GO-g-PDLA的合成路徑(b) PLA-GO奈米複合材料的製備 32
圖3-1. 微差式掃描卡計熱循環團 48
圖3-2.氧化石墨製備及分析流程圖 56
圖3-3.石墨烯製備及分析流程圖 57
圖3-4.石墨烯/聚乳酸複合材料製備及分析流程圖 58
圖4-1.(a)石墨，(b) Hummers氧化石墨，(c) Modified Hummers氧化石墨及(d) Tour''s Improved氧化石墨的XRD圖 64
圖4-2.石墨及各種氧化石墨的TGA疊圖 65
圖4-3. (a)石墨，(b) Hummers氧化石墨，(c) Modified Hummers氧化石墨及(d) Tour''s Improved氧化石墨的XPS圖 66
圖4-4.Modified Hummers法及Tour''s Improved法GO的結構推測 67
圖4-5. (a)石墨，(b) Hummers氧化石墨，(c)Modified Hummers氧化石墨及(d) Tour''s Improved氧化石墨的Raman圖 67
圖4-6.(a)石墨(放大倍率×350)，(b) Modified Hummers法氧化石墨(放大倍率×350)，(c) 石墨(放大倍率×1,000)，(d) Modified Hummers法氧化石墨(放大倍率×1,000) (e)石墨(放大倍率×5,000)及(f) Modified Hummers法氧化石墨(放大倍率×5,000)的SEM表面形態圖 68
圖4-7.(a)石墨及(b) Modified Hummers法氧化石墨在不同極性之溶劑下之分散性 69
圖4-8.製得還原石墨烯的反應路徑 74
圖4-9.(a)H r-MHGO、(b)H r-IGO、(c)HE r-MHGO、(d)HE r-IGO、(e)HET r-MHGO及(f)HET r-IGO的XRD圖 75
圖4-10.(a)H r-MHGO、(b) HE r-MHGO及(c) HET r-MHGO的XPS圖 76
圖4-11.(a)H r-MHGO、(b) HE r-MHGO及(c) HET r-MHGO的Raman圖 77
圖4-12.(a)HE r-MHGO(放大倍率×350)，(b) HET r-MHGO(放大倍率×350)，(c) HE r-MHGO (放大倍率×500)及(d) HET r-MHGO放大倍率×500)的SEM表面形態圖 78
圖4-13.(a)HE r-MHGO的AFM圖及(b) HET r-IGO的AFM圖 79
圖4-14.(a)HE r-MHGO及(b) HET r-IGO的分散性測試((1)正己烷、(2)乙酸乙酯、(3)二氯甲烷、(4)丙酮、(5)二甲基甲醯胺、(6)醋酸、(7)甲醇及(8)水) 80
圖4-15.(a)(b)為HET r-MHGO的粉體TEM圖(c)(d)為HET r-IGO的粉體TEM圖 81
圖4-16.PLA在不同升溫速率的熱重損失圖 83
圖4-17.1wt% HET r-MHGO/PLA在不同升溫速率的熱重損失圖 83
圖4-18.2wt% HET r-MHGO/PLA在不同升溫速率的熱重損失圖 84
圖4-19.3wt% HET r-MHGO/PLA在不同升溫速率的熱重損失圖 84
圖4-20.5wt% HET r-MHGO/PLA在不同升溫速率的熱重損失圖 85
圖4-21.PLA在不同升溫速率的DTG圖 85
圖4-22.1wt% HET r-MHGO/PLA在不同升溫速率的DTG圖 86
圖4-23.2 wt% HET r-MHGO/PLA在不同升溫速率的DTG圖 86
圖4-24.3 wt% HET r-MHGO/PLA在不同升溫速率的DTG圖 87
圖4-25.5 wt% HET r-MHGO/PLA在不同升溫速率的DTG圖 87
圖4-26.4-15.PLA的1/T與㏒[g(α)/T2]作圖 92
圖4-27.1wt% HET r-MHGO/PLA的1/T與㏒[g(α)/T2]作圖 92
圖4-28.2wt% HET r-MHGO/PLA的1/T與㏒[g(α)/T2]作圖 93
圖4-29.3wt% HET r-MHGO/PLA的1/T與㏒[g(α)/T2]作圖 93
圖4-30.5wt% HET r-MHGO/PLA的1/T與㏒[g(α)/T2]作圖 94
圖4-31.PLA的1/Tmax與㏑(β/Tmax2)作圖 95
圖4-32.不同含量的HET r-MHGO/PLA的1/Tmax與㏑(β/Tmax2) 95
圖4-33.不同轉化率的PLA的-1/RT與㏒β作圖 96
圖4-34.不同轉化率的1wt% HET r-MHGO/PLA的-1/RT與㏒β作圖 96
圖4-35.不同轉化率的2wt% HET r-MHGO/PLA的-1/RT與㏒β作圖 97
圖4-36.不同轉化率的3wt% HET r-MHGO/PLA的-1/RT與㏒β作圖 97
圖4-37.不同轉化率的5wt% HET r-MHGO/PLA的-1/RT與㏒β作圖 98
圖4-38.聚乳酸及不同含量的HET r-MHGO/PLA在各轉化率下的活化能 98
圖4-39.聚乳酸及不同含量的石墨/PLA在各轉化率下的活化能 99
圖4-40.PLA在不同降溫速率下的㏑t與㏑[-㏑(1-Xt)]關係圖 102
圖4-41.PLA在不同降溫速率下的t與Xt關係圖 102
圖4-42.1wt% HET r-MHGO/PLA在不同降溫速率下的㏑t與㏑[-㏑(1-Xt)]關係圖 103
圖4-43. 1wt% HET r-MHGO/PLA在不同降溫速率下的t與Xt關係圖 103
圖4-44.2wt% HET r-MHGO/PLA在不同降溫速率下的㏑t與㏑[-㏑(1-Xt)]關係圖 104
圖4-45. 2wt% HET r-MHGO/PLA在不同降溫速率下的t與Xt關係圖 104
圖4-46.3wt% HET r-MHGO/PLA在不同降溫速率下的㏑t與㏑[-㏑(1-Xt)]關係圖 106
圖4-47. 3wt% HET r-MHGO/PLA在不同降溫速率下的t與Xt關係圖 106
圖4-48.5wt% HET r-MHGO/PLA在不同降溫速率下的㏑t與㏑[-㏑(1-Xt)]關係圖 107
圖4-49. 3wt% HET r-MHGO/PLA在不同降溫速率下的t與Xt關係圖 107
圖4-50.PLA及不同含量的HET r-MHGO/PLA的儲存模數與溫度關係圖 110
圖4-51.PLA及不同含量的HET r-MHGO/PLA的損失模數與溫度關係圖 110
圖4-52.PLA及不同含量的HET r-MHGO/PLA的Tan Delta與溫度關係圖 111
圖4-53. 1wt%還原石墨烯複合材的SEM斷裂面圖((a)放大倍率800(b)放大倍率1,500)、1wt%還原石墨烯複合材的SEM斷裂面圖((c)放大倍率800(d)放大倍率1,500)及1wt%還原石墨烯複合材的SEM斷裂面圖((e)放大倍率800(f)放大倍率1,500) 113

表目錄
表1-1.PLA於各溫度及條件下之降解時間 11
表1-2.三種典型石墨烯製備方法之比較 20
表2-1.PLLA及PLLA立體錯合物奈米複合材料之DSC及WAXD分析數據 31
表4-1.石墨及各種氧化石墨的XRD分析數據 60
表4-2石墨及各種氧化石墨的TGA分析數據 61
表4-3. 石墨及各種氧化石墨C1s分峰數據 62
表4-4. 石墨及各種氧化石墨的Raman數據統整 63
表4-5.石墨及Modified Hummers法氧化石墨在不同溶劑下的分散性 65
表4-6. 還原石墨烯的XRD分析數據 70
表4-7. 各種還原石墨烯的C1s分峰數據 71
表4-8. 還原石墨烯的Raman數據統整 72
表4-9.HET r-MHGO及HET r-IGO在不同溶劑下的分散性 75
表4-10HET r-MHGO及HET r-IGO的導電度 75
表4-11.PLA/HET r-MHGO/PLA的熱性質數據統整 82
表4-12.Coats and Redfern method計算反應級數公式 83
表4-13.PLA及HET r-MHGO/PLA的Coats and Redfern method數據 88
表4-14. PLA及HET r-MHGO/PLA的Kissinger method數據 89
表4-15.PLA與不同含量的HET r-MHGO/PLA在不同轉化率的數據 93
表4-16.聚乳酸及不同含量的HET r-MHGO/PLA知數據統整 100
表4-17.聚乳酸及不同含量的HET r-MHGO/PLA的DMA數據統整 103
表4-18.聚乳酸與不同含量的HET r-MHGO/PLA之導電度 103

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