臺灣博碩士論文加值系統

本研究旨在利用熱塑性高分子(聚氧乙烯(polyethylene oxide，PEO))改質novolac type酚醛樹脂，作為碳/碳複合材料中碳基材之前軀體（precursor）。利用熱塑性樹脂的加入，期望能對酚醛樹樹脂在形成碳基材過程中之微結構變化與纖維間之界面有所改進，並改善加工製程等，最重要目標在於增進碳/碳複合材料之機械性質(抗曲強度、層間剪切強度(Interlaminar shear strength，ILSS等))、物理性質（增韌行為、內應力減少等）及動力學參數（活化能、碰撞因數）等之探討。實驗成果顯示，由SEM觀察碳纖維與加入PEO改質的酚醛樹脂在交聯硬化後，碳纖維與基材之界面鍵結力，明顯隨著PEO的增加而提昇，即樹脂與碳纖維之含浸效果較佳。在PEO/酚醛樹脂系統中，經穩定化處理後之碳/碳複合材料前軀體，因PEO的加入對其密度與孔隙度之影響不大，但含5 phr之PEO卻可對三點抗曲強度有明顯的增加效果，其強度上升約10﹪。經碳化處理後之碳/碳複合材料，PEO含量的增加雖會造成其密度下降、孔隙度提高，但卻可降低材料內部內應力的形成，而提高材料之抗曲強度，在含量10 phr PEO下，其抗曲強度約上升40％。在PEO/酚醛樹脂系統中，經穩定化處理後之碳/碳複合材料前軀體，PEO之加入提供基材與纖維之鍵結力，使得層間剪切強度大都比原樹脂之ILSS還高，尤其以加入10 phr之PEO上升約40﹪。在經碳化處理後之碳/碳複合材料，因為材料經高溫裂解碳化後熱塑性高分子樹脂完全被裂解完，所以對碳化後ILSS之影響不大，但在碳化前因10 phr之PEO鍵結力較好，所以其碳化後之ILSS強度比原樹脂上升10%。在液態樹脂重複含浸過程中，碳/碳複合材料之三點抗曲強度、密度均隨著含浸次數的增加而增加。在純酚醛樹脂時，經四次重複含浸後，其三點抗曲強度比未做重複含浸前之三點抗曲強度約提升90﹪。在含10 phr PEO/純酚醛樹脂系統中，經四次重複含浸後，其三點抗曲強度比未做重複含浸前之三點抗曲強度約提升18%。在PEO/酚醛樹脂熱裂解之動力方面，熱塑性高分子能夠使得酚醛樹脂的最大裂解溫度隨著PEO的含量增加而下降，其最大裂解損失量也隨著PEO的含量增加而增加。

The objectives of this study are utilizing thermoplastic polymer (poly(ethylene oxide, PEO)) to modify Novolac type phenolic resin and to prepare carbon/carbon composites.Different ratios of PEO were added to the Novolac type phenolic resin to fabricate carbon/carbon composites and to investigate the microstructure of carbon matrix of phenolic resin and the interface between resin matrix and carbon fiber. The mechanical properties (density, porosity, flexural strength and interlaminar shear strength), physical properties (toughness behavior, internal pressure build up) and degradation kinetic parameter (activation energy, frequency factor) of the composites before and after carbonization were studied.The wet-out between the carbon fiber and the matrix of the PEO modified novolac type phenolic resin after SEM photographs investigated curing. Apparently, the interfacial bonding between carbon fiber and resin matrix was improved significantly with the increasing of PEO content.The flexural strength of carbon/carbon composites precursor with 5 phr ( part per hundred parts of resin) PEO is 10﹪higher than that of specimen of neat phenolic resin. However, the density and the porosity do not change significantly. The flexural strength of carbon/carbon composites with 10 phr PEO is 40﹪ higher than that of specimen of neat phenolic resin. Although the density was decreased，the porosity was increased for carbon/carbon composites containing PEO. The existence of PEO will help to reduce the internal stress build-up and to enhance the flexural strength of the fabricated carbon/carbon composites.The interlaminar shear strength (ILSS) of carbon/carbon composites precursor with 10 phr PEO is 40﹪ higher than that of specimen of neat phenolic resin. PEO was added to improve the interfacial bonding between the matrix and the fiber. The interlaminar shear strength of carbon/carbon composites with 10 phr PEO is 10﹪higher than that of specimen of neat phenolic resin.The flexural strength and the density of the 2-D carbon/carbon composites densified via liquid resin reimpregnation process were increased with reimpregnation times. The flexural strength of carbon/carbon composites through four times densification process is 90﹪ higher than that of the undensified neat phenolic resin . The flexural strength of carbon/carbon composites with four times densification process is 18﹪higher than the undensified 10 phr PEO/phenolic resin system.For degradation kinetic parameter of PEO/phenolic resin system, thermoplastic polymer can reduce the maximum degradation temperature of phenolic resin with the increasing PEO content. The maximum weight loss by degradation also was increased with PEO content.

中文摘要I英文摘要III謝誌VI目錄VII圖目錄IX表目錄XVI第一章 緒論1第二章 研究目的與內容2-1. 研究目的32-2. 研究內容5第三章 理論基礎與文獻回顧3-1. 碳材料之製程及性質之簡介73.1.1 碳材料的結晶構造及性質73.1.2 含顆粒狀碳材料的製程及性質93.1.3 碳纖維的種類、製程及性質123-2 酚醛樹脂製備與性質之研究183.2.1 Novolac type酚醛樹脂之製備與特性193.2.2 Resol type酚醛樹脂之製備與特性233.2.3 與酚醛樹脂之改質相關的研究263-3 PEO，PEG熱塑性樹脂之製備與特性333.3.1 聚醚樹脂(PEO)、聚醇樹脂(PEG)相關文獻 343-4 碳/碳複合材料的簡介及發展413-5 碳/碳複合材料之製程433.5.1 化學氣相沈積法453.5.2 液態樹脂含浸法473-6 酚醛樹脂熱裂解行為及裂解動力之探討483.6.1 酚醛樹脂之熱裂解機構483.6.2 熱裂解動力學理論分析553-7 碳/碳複合材料之相關文獻59第四章 研究方法654-1 實驗材料654-2 實驗設備及儀器674-3 實驗流程694.3.1 實驗流程圖694.3.2 實驗步驟72 第五章 結果與討論775-1 PEO/Phenolic resin之摻混系統775.1.1 密度775.1.2 孔隙度775.1.3 三點式抗曲強度785.1.4 2D碳/碳複合材料之增韌型態分析875.1.5 層間剪切強度925.1.6 2D碳/碳複合材料之破壞型態分析955.1.7 液態樹脂重覆含浸之物性及機械性質關係985.1.7 (a)重複含浸次數與密度之關係995.1.7 (b)重複含浸次數與空孔率之關係1025.1.7 (c)重複含浸次數與機械性質之關係1055.1.7 (d)重複含浸次數與型態學之關係1115.1.8 酚醛樹脂之熱裂解分析1205.1.9 PEO摻混酚醛樹脂之熱裂解分析125第六章 結論141第七章 參考文獻144

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