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研究生: 郭華軒
Kuo, Hua-Hsuan
論文名稱: 碳化速率對碳/碳複合材料機械及磨潤性質影響之研究
Effect of Carbonization Rate on Mechanical and Tribological Properties of Carbon/Carbon Composites
指導教授: 朱建平
Ju, Chien-Ping
陳瑾惠
Chern Lin, Jiin-Huey
學位類別: 博士
Doctor
系所名稱: 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年: 2005
畢業學年度: 93
語文別: 中文
論文頁數: 220
中文關鍵詞: 碳/碳複合材料碳化機械性質磨潤性質
外文關鍵詞: tribological properties, mechanical properties, C/C composites, carbonization
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  •   本篇研究以PAN系碳纖維/酚醛樹脂基碳/碳複合材料為主要實驗材料,採液態含浸法進行緻密化處理,碳化處理分別以1 oC/min、100 oC/min以及 1000 oC/min之速率進行。研究目的為探討碳化速率對此類材料之密度、孔隙度、微結構以及機械性質的影響,並藉此評估以遠高於傳統製程之碳化速率製造碳/碳複合材料之可能性。實驗結果顯示,與傳統較低碳化速率製備之碳/碳複合材料相比,以較高碳化速率製備者具有更高的孔隙度、更多大尺寸的孔洞,並具有石墨化程度更高的碳結構。第二次石墨化之後,以1 oC/min和1000 oC/min製備的碳/碳複合材料具有同等的撓曲性質。以1000 oC/min製備者具有最高的破裂韌性 (fracture energy),而三組中機械性質表現最差的則為以100 oC/min製備者。
      碳/碳複合材料既已廣泛用於高性能摩擦材料,本研究中也針對以不同碳化速率製得之碳/碳複合材料進行等速(constant velocity)磨耗測試,藉由測得之摩擦係數、磨耗量以及磨耗面之觀察結果,希望得以瞭解碳化速率對碳/碳複合材料磨潤行為之影響。實驗結果顯示,不同碳化速率製備之試片(1, 100 and 1000 oC/min),各組的平均摩擦係數相當接近,約在0.40 - 0.45之間。以1000 oC/min 碳化速率製備之試片的平均重量損失約為以1 oC/min與100 oC/min 製備者的兩倍大。磨耗面觀察顯示所有試片的磨耗表面都有亮和暗的區域以不同的比例混合顯現。暗區主要由粉末狀磨屑組成,而亮區則是平滑的磨屑層。與1 oC/min或100 oC/min 碳化速率製備之試片相比,以1000 oC/min 製備者之磨耗面上可以發現到更多的磨屑以及更嚴重的結構損壞。
      本研究嘗試提出一種改進磨潤性質的方法,即在原本製程外增加一次的液態含浸與碳化、石墨化處理(稱之為「後處理」),後處理中選擇性的使用兩種不同的液態前軀體以及三種不同的碳基添加物。實驗針對經過不同後處理之碳/碳複合材料進行如前述之等速磨耗測試,藉由實驗結果評估此方法對改進碳/碳複合材料磨潤行為之潛力。結果顯示大多數試片經過後處理都呈現出密度增加以及孔隙度降低的現象。一般而言,含浸瀝青的試片在密度與孔隙度的變化大於含浸呋喃樹脂的試片。經過後處理,所有試片的摩擦係數以及磨耗量都呈現降低的現象。含浸瀝青的試片通常表現出低於含浸呋喃樹脂試片的磨耗量。含浸瀝青/碳黑和含浸瀝青/介相瀝青粉末這兩組試片的磨耗量最低(僅有以傳統慢速製程1 oC/min製備者磨耗量的一半),卻仍能維持相對上夠高的摩擦係數(接近0.4)。和未經後處理的1000 oC/min製備試片相比,大部分經過後處理試片表面的亮區都明顯佔有較大面積。含浸瀝青的試片磨耗面通常呈現出韺t浸呋喃樹脂的掑蠽韝j面積的亮區。
      為驗證前述「後處理」對其他配方之碳/碳複合材料是否也有提升磨耗表現之效果,本研究對現今飛機煞車用的主要兩大類碳/碳複合材料施以「後處理」,發現兩種材料在特定前軀體/添加物的搭配下分別可呈現出大幅穩定摩擦係數,並有效的減少近一半的磨耗量,卻又不至於對原有的摩擦係數改變太多的效果,可見此方法對改進碳/碳複合材料磨潤行為確有潛力。

      The effect of carbonization rate in a wide range (1, 100 and 1000 ℃/min) on the properties of a PAN/phenolic-based carbon/carbon (C/C) composite was studied. The results indicated that the composite processed at a higher carbonization rate had a higher porosity level, more large pores and a more graphitic structure than that processed at a lower carbonization rate. After second graphitization the bending properties of composites carbonized at 1 ℃/min and 1000 ℃/min were comparable. The composite carbonized at 1000 ℃/min had the highest fracture energy. The composite carbonized at 100 ℃/min showed the worst mechanical performance among three. The large increase in carbonization rate can be beneficial to the industry from an economic point of view.
      Since C/C composite have been widely use for frictional materials, one purpose of the present study is to evaluate the tribological behavior of a fast-carbonized (1000℃/min) C/C composite. The results indicate that average coefficient of friction (COF) values of non-post-treated composites prepared with three different carbonization rates (1, 100 and 1000 ℃/min) are similar (0.40 - 0.45). The average wear rate of samples carbonized at 1000 ℃/min is about twice as large as samples carbonized at 1 and 100 ℃/min.
      One other purpose of the study is to enhance the tribological performance of the composite by applying a post-treatment comprising re-impregnation of a carbonaceous additive-doped liquid precursor. Great majority of the samples demonstrate an increase in density and a decrease in porosity after the post-treatment. Pitch-group samples generally have larger changes in density and porosity than furan-group samples. After the post-treatment, all samples demonstrate decreases in both COF and specific wear rate coefficient. Pitch-group samples generally exhibit lower wear rate than furan-group samples. Samples post-treated with pitch/carbon black and pitch/mesophase pitch demonstrate the lowest wear rates among all samples tested (only half that of untreated samples carbonized at 1 ℃/min), while still maintaining relatively high COF values (close to 0.4). These results indicate that an appropriate post-treatment, especially a pitch treatment, may dramatically improve the tribological performance of fast-carbonized C/C composite.
      One more experiment has been carried out to verify whether this simple treatment is also capable of improving the tribological performance, especially reducing wear rate, of two other 2D C/C formulae (PAN/CVI and pitch/phenolic/CVI) which are among the most-popularly-used C/C composites for aircraft brake disk today. The results indicated that with some certain combination of C/C and precursor/additive, there will have the effect that not only largely stabilized COF, but also effectively cut down by nearly half the wear rates without changing much the COF values.

    中文摘要                             I 英文摘要                            III 誌謝                             V 總目錄                          VI 表目錄                   XI 圖目錄                   XIII 第一章 前言                   1 1-1 研究背景                   1 1-2 研究目的及重點                   4 第二章 文獻回顧                         8 2-1 碳/碳複合材料簡介                   8 2-2 碳/碳複合材料之製程及其特性                17 2-3 碳化速率對液相含浸製程製備之碳/碳複合材料之影響       24 2-4 磨潤簡介                        25 2-5 碳/碳複合材料的磨潤研究                   30 第三章 碳化過程中製程參數及材料行為之研究            61 第一部份 製程參數之影響                     61 3-1 嘗試高於傳統製程的碳化速率                  61 3-2 熱壓壓力                           64 3-3 持溫時間之影響                        65 3-4 熱壓時使用真空袋之影響                    67 第二部份 纖維與基材之影響                    69 3-5 樹脂含浸效率之比較                      69 3-6 纖維含量與碳化速率對材料之影響                70 3-7 纖維種類與碳化速率對材料之影響                73 第三部份 材料行為研究                      75 3-8 碳化過程基材中碳基面規則化行為                75 3-9 碳纖維中碳基面規則化之現象                  78 3-10 結論                             80 第四章 碳化速率對碳/碳複合材料機械性質之影響          99 第一部份 碳化速率與機械性質                   99 4-1 實驗方法                            99 4-2 實驗結果                        104 4-3 討論                             107 第二部份 快速碳化製程可行性之探討              111 4-4 製備較大尺寸碳/碳複合材料                111 4-5 升溫與降溫速率對2D編織碳/碳複材之影響         112 4-6 結論                             117 第五章 碳化速率以及調整製程對磨潤性質之影響           140 第一部份 碳化速率對碳/碳複合材料磨潤性質之影響       140 5-1 實驗方法                           140 5-2 結果與討論                          143 第二部分 改善快速碳化製備碳/碳複合材料磨潤表現之方法       145 5-3 實驗方法                           145 5-4 結果與討論                          146 第三部分 後處理對其他纖維/基材系統碳/碳複合材料之效果      149 5-5 實驗方法                           149 5-6 結果與討論                          150 5-7 結論                             153 第六章 總結論                          180 參考文獻                             182 附錄                               196 自述                               198

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