臺灣博碩士論文加值系統

本論文是以四種不同熱處理溫度之補強材纖維---氧化纖維、600、1000及1800℃碳纖維補強酚醛樹脂，接著經230℃穩定化後，再熱處理至600、1000、1800及2400℃，製成碳/碳複合材料。本研究最主要是探討這些碳/碳複合材料及酚醛樹脂在碳化過程中結構、物性及顯微結構之變化。
碳/碳複合材料經光學偏光顯微鏡(OM)得知，補強材為高溫纖維之碳/碳複合材料其基材會受到纖維之影響，使得纖維附近之基材會沿著纖維表面形成光學異向性結構，這是由於界面伴隨一應力，致使界面附近之基材應力石墨化所致。另外在空孔附近之基材也有此一現象存在。
由穿透式電子顯微鏡(TEM)得知，若纖維和基材之間的結合度很高的話，其碳層平面並不會沿著纖維表面高度順向排列，而是穿過界面混亂排列，顯示界面有強鍵結，此種情況即使是熱處理到石墨化溫度依舊不會改變。接下來若界面強度稍弱，則會在界面處沿著纖維表面形成較大且非常整齊之碳層平面堆疊，纖維與基材鍵結愈弱此一情況愈明顯。另外不管是纖維、基材或界面中存
在之空孔，熱處理至高溫，碳層平面都會沿著這些空孔表面高度順向排列，顯示這些碳層平面的堆疊不是沿著纖維，而是沿著界面或空孔所伴隨之應力集中區整齊地排列。在氧化纖維之碳/碳複合材料中，其纖維之中心區域和skin區域之間存在一排空孔，為此碳/碳複合材料特有之現象，此結構會由低溫一直維持至石墨化溫度。另外發現原本就存在酚醛樹脂中之氣泡，酚醛樹脂熱處理至高溫時，其氣泡之內部會長出一石墨化程度很高之碳結構物。
由X光繞射分析儀(XRD)得知，補強材為熱處理溫度愈高之纖維，其碳/碳複合材料會受到纖維之影響，導致其在石墨化溫度時其石墨化程度會大幅提昇。但由拉曼光譜(Raman)發現此高溫纖維之碳/碳複合材料，會因熱裂現象產生許多的缺陷，致使量測之石墨化程度較低。

The stabilized fiber felt was carbonized up to 600, 1000, 1800℃, respectively. The carbon/carbon composites were made by the stabilized PAN fiber felt, carbonized fiber felts and resol-type phenol-formaldehyde resin. After stabilized, the carbon/carbon composites were carbonized 600, 1000, 1800 and 2400℃, respectively. The manufacture, physical and microstructure of these composites and phenolic resin were investigated.
The matrix of carbon/carbon composites, which were developed from high temperature carbonized felt, showed an optical antisotropy structure near the fibers and pores.
If the fiber and matrix has high degree of combination, the carbon stacking plane do not grow along with fiber''s surface, it will through the interface randomly by high-resolution electron microsope(TEM). This is indicated that the interface has a strong bonding. This phenomenon will still leave in the interface at graphite temperature. But, if the interface bonding was weaker, there are bigger and very order carbon stacking plane along with carbon fiber. This phenomenon will be clearer if the interface bonding is weaker. Besides, the carbon stacking plane also will be grow along with pores in heat treatment. It can be seen that the carbon stacking plane does not stack along with carbon fiber surface, it stacks along with stress region in the interface or pores. At the same time, this study also found the original bubbles in phenolic resin, it will be grow a graphite like substance in the bubbles at high heat-treated temperature under the study of high resolution electron microsope.
The graphitic degree is higher under the study X-ray diffraction spectroscopy(XRD) if the carbon/carbon composites were developed from high temperature fiber. The graphitic degree is lower under the study of raman spectroscopy, because the composites have too many defects.

第一章 前言…………………………………………………………………….…..1
1.1 碳/碳複合材料……………………………………………………………….…..1
1.2 酚醛樹脂…………………………………………………………………………2
第二章 研究目的與主題…………………………………………………………...4
第三章 理論依據與文獻回顧……………………………………………………...5
3.1 碳化、石墨化…………………………………………………………………….5
3.2 碳材料的結構…………………………………………………………………....6
3.3 碳纖維…………………………………………………………………………....7
3.3.1 碳纖維的構造與特性…………………………………………………….7
3.3.2 聚丙烯月青（PAN）系碳纖維……………………………………………9
3.4 酚醛樹脂………………………………………………………………………..15
3.4.1 酚醛樹脂在初期碳化階段的化學變化………………………………...15
3.4.2 酚醛樹脂之結構模型…………………………………………………...17
3.4.3 升溫速率及其試片厚度對酚醛樹脂碳化過程的影響………………...19
第四章 實驗……………………………………………………………………….20
4.1 實驗流程………………………………………………………………………..20
4.2 實驗材料………………………………………………………………………..21
4.3 實驗設備………………………………………………………………………..21
4.4 實驗方法………………………………………………………………………..21
4.4.1 纖維、碳/碳複合材料………………………………………………..…21
4.4.2 酚醛樹脂………………………………………………………………...25
4.5 實驗測試………………………………………………………………………..25
第五章 結果與討論…………………………………………………………….…31
第一部份：碳/碳複合材料………………………………………………………….31
5.1.1 重量損失……………………………………………………………………...31
5.1.2 收縮率………………………………………………………………………...32
5.1.3 開放性空孔含量……………………………………………………………...34
5.1.4 密度…………………………………………………………………………...35
5.1.5 元素分析……………………………………………………………………...37
5.1.6 熱分析………………………………………………………………………...41
5.1.7 光學偏光顯微鏡分析………………………………………………………...43
5.1.8 紅外線光譜分析…………………………………………………………...…49
5.1.9 X光繞射分析………………………………………………………………....52
5.1.10 拉曼光譜…………………………………………………………………….59
5.1.11 碳/碳複合材料之撓曲測試分析及其斷面掃瞄式電子顯微鏡分析………70
1. 補強材纖維為1800℃以下之碳/碳複合材料……….…………………..70
2. 補強材為2400℃石墨纖維之碳/碳複合材料…………………………..84
5.1.12 碳/碳複合材料之穿透式電子顯微鏡分析………………………………....86
1. 氧化纖維所製成之碳/碳複合材料，熱處理至1000℃………………..86
2. 氧化纖維所製成之碳/碳複合材料，熱處理至1800℃………………..97
3. 氧化纖維所製成之碳/碳複合材料，熱處理至2400℃……………….104
4. 600℃碳纖維所製成之碳/碳複合材料，熱處理至2400℃………….…112
5. 1000℃碳纖維所製成之碳/碳複合材料，熱處理至2400℃….………..120
6. 1800℃碳纖維所製成之碳/碳複合材料，熱處理至2400℃….………..125
7. 熱處理至2400℃之石墨纖維…….…………………………………….130
第二部分：未穩定化及經32小時穩定化之酚醛樹脂………………………….133
5.2.1 重量損失…………………………………………………………………….133
5.2.2 收縮率…………………………………………………………………….....134
5.2.3 密度……………………………………………………………………..…...134
5.2.4 元素分析……………………………………………………………...……..136
5.2.5 熱分析…………………………………………………………………...…..139
5.2.6 紅外線光譜分析………………………………………………………….…140
5.2.7 X光繞射分析…………………………………………………………….......143
5.2.8 拉曼光譜…………………………………………………………………….147
5.2.9 熱處理至2400℃酚醛樹脂之穿透式電子顯微鏡分析………………….…154
第六章 結論………………………………………………………………...……162
參考文獻……………………………………………………………………...……163
誌謝……………………………………………………………………………...…165
附錄……………………………………………………………………………...…167

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