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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 鄧茂華(Mao-Hua Teng) | |
dc.contributor.author | Yu-Shan Liu | en |
dc.contributor.author | 劉羽珊 | zh_TW |
dc.date.accessioned | 2021-06-17T06:19:54Z | - |
dc.date.available | 2018-08-21 | |
dc.date.copyright | 2018-08-21 | |
dc.date.issued | 2018 | |
dc.date.submitted | 2018-08-19 | |
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Sun, (1999) “Thermal decomposition and reconstitution of hydroxyapatite in air atmosphere.” Biomaterials, 20(19), p.1807-1813. [9] 郭迦豪 (2015) “利用熱膨脹儀探討氫氧基磷灰石之熱分解反應與反應動力學”,台灣大學碩士論文。 [10] E. Nery, R. LeGeros, K. Lynch, and K. Lee, (1992) “Tissue response to biphasic calcium phosphate ceramic with different ratios of HA/beta TCP in periodontal osseous defects.” Journal of Periodontal, 63(9), p.729-735. [11] E. Champion, (2013) “Sintering of calcium phosphate bioceramics.” Acta Biomaterialia, 9(4), p.5855-5875. [12] B. Dickens, W. E. Brown, G. J. Kruger, and J. M. Stewart, (1973) “Ca4(PO4)2O, tetracalcium diphosphate monoxide, crystal structures and relationships to Ca5(PO4)3OH and K3Na(SO4)2.” Acta Crystallogr, Sect B, 29, p.2046–2056. [13] H. Aoki, (1994) “Medical application of hydroxyapatite.” Ishiyaku EuroAmerica, St. Louis. [14] M. Yashima and A. 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Assollant, P. Thomas, (2002) “Calcium phosphate apatites with variable Ca/P atomic ratio I. Synthesis, characterisation and thermal stability of powders.” Biomaterials, 23, p.1065-1072. [28] T. Kijima and M. Tsutsumi, (1979) “Preparation and thermal properties of dense polycrystalline oxhydroxyapatite.” J. Am. Ceram. Soc., 62 (9/10), p.455-460. [29] J. Zhou, X. Zhang, J. Chen, S. Zeng, and K. DE Groot, (1993) “High temperature characteristics of synthetic hydroxyapatite.” J. Mater. Sci. Mater. Med., 4, p.83-85. [30] T. Wang and A. Dorner-Reisel, (2004) “Thermo-analytical investigations of the decomposition of oxyhydroxyapatite.” Materials Letters, 58, p.3025-3028. [31] A. Rapacz-Kmita, A. Slosarczyk, Z. Paszkiewicz, and C. Paluszkiewicz, (2005) “FTIR and XRD investigations on the thermal stability of hydroxyapatite during hot pressing and pressureless sintering processes” J. Mol. Struct., p.744-747, p.653-656. [32] Y. Liu and Z. Shen, (2012) “Dehydroxylation of hydroxyapatite in dense bulk ceramics sintered by spark plasma sintering.” Journal of the European Ceramic Society, 32, p.2691–2696. [33] 王紹宇 (2011) “主導動力學曲線與三種不同動力學模型之比較研究”,台灣大學碩士論文。 [34] 梁家豪 (2003) “三種分析反應動力學及燒結資料的新方法”,台灣大學碩士論文。 [35] 陳孟霞(2004) “主導曲線模型運用在奈米氧化鋁和奈米二氧化鈦陶瓷粉末燒結之研究”,台灣大學碩士論文。 [36] 林書弘 (2007) “蒸發岩礦物熱分解反應動力學之研究方法與應用探討”,台灣大學碩士論文。 [37] 吳尚庭(2012) “藍晶石熱分解反應微結構變化與動力學探討”,台灣大學地質科學系碩士論文。 [38] J. D. Hansen, R. P. Rusin, M. H. Teng, and D. L. Johnson, (1992) “Combined-Stage Sintering Model.” Journal of the American Ceramic Society, 75(5), p.1129-1135. [39] H. Su and D. L. Johnson, (1996) “Master Sintering Curve: a Practical Approach to Sintering.” Journal of the American Ceramic Society, 79(12), p.3211-3217. [40] 連維帆 (2010) “銳鈦礦-金紅石與霰石-方解石相變反應之主導動力學曲線研究”,台灣大學碩士論文。 [41] C. B. DiAntonio and K. G. Ewsuk, (2005) “Controlled and Predicted Ceramic Sintering Through Master Sintering Curve Theory.” Ceramic Transactions, 157, p.15–23. [42] W. L. Huang and G. A. Otten, (1998) “Oil Generation Kinetics Determined by DAC-FS/IR Pyrolysis: Technique Development and Prelimary Results.” Organic Geochemistry, 29(5-7), p.1119-1137. [43] P. Garg, S. J. Park, R. M. German, (2007) “Effect of die compaction pressure on densification behavior of molybdenum powders.” International Journal of Refractory Metals and Hard Materials, 25(1), p.16-24. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/72030 | - |
dc.description.abstract | 氫氧基磷灰石(Hydroxyapatite, Ca10(PO4)6(OH)2, HA)是人體骨骼、牙齒琺瑯質和象牙質中的主要無機組成,可以用來製備生醫材料,過程中常需要經過加熱處理。氫氧基磷灰石隨著溫度的上升會發生三種反應,分別是熱分解、燒結與相變,而其中的相變往往會使由氫氧基磷灰石粉末製備的生醫陶瓷材料的機械性能降低,所以很多學者針對氫氧基磷灰石的相變反應進行溫度範圍研究,然結果皆不一致。
前人多利用X光粉末繞射、傅立葉轉換紅外光譜、拉曼光譜、熱重與差熱分析研究晶格、分子與晶相的定性和定量分析、質量隨溫度的變化以及特定溫度條件下的能量變化情形。本研究利用熱膨脹儀來進行氫氧基磷灰石坯體在升溫過程中隨時及連續的長度變化,換算成體積變化,發現隨著溫度的上升,有兩個主要的收縮反應(熱分解、燒結),再配合數值模擬方法分離出一個膨脹反應(相變),但這三種體積變化反應有相當大的溫度重疊範圍。所以,本研究希望藉由兩階段燒結法使燒結反應提前完成,在較低溫將坯體燒結到緻密,以期之後繼續升溫時能測得單獨的相變反應體積變化。 本研究設計以兩階段燒結歷程嘗試解決數據重疊問題,希望能將燒結反應與相變反應之溫度重合部分加以分離。實驗結果為利用升溫速率30℃/min升溫至1170℃持溫5分鐘,再以50℃/min降溫至1120℃持溫6小時,測得坯體之相對密度達99%,並由XRD結果確定在1200℃以下可得到未相變之緻密樣品,後續再利用此方法進行高溫相變反應的實驗。接續上述實驗步驟獲得緻密坯體後,以每分鐘20℃和30℃升溫至1500℃持溫1小時的過程中,測得此緻密坯體有再收縮反應,推測與殘餘孔隙的移除、氫氧基的再結合或是高升溫速率造成的儀器偵測延遲有關。而1400℃後才發生膨脹反應也許是因為緻密坯體要發生相變需要克服坯體中的應力,導致坯體由外向內發生多期次的小規模膨脹。目前比較升溫至1200℃之傳統燒結與兩階段燒結實驗的主導動力學曲線(Master Kinetics Curve, MKC)擬合結果,其視活化能值分別為870.6 kJ/mol及1615 kJ/mol,具有較高初始壓坯密度的兩階段燒結實驗樣本,除了具有較高的視活化能值,LogΘ值也向較小的方向平移,意味著可以較快地達到緻密化。 | zh_TW |
dc.description.abstract | Hydroxyapatite (Ca10(PO4)6(OH)2, HA) under increasing temperature involves two shrinkage reactions, i.e., dehydroxylation and sintering, and one expansion reaction due to phase transformation. The temperature range of the above three reactions, though obviously overlapping, were found contradictory in literature. In this study, we use a dilatometer, which can detect the length variations of a sample in-situ with increasing temperature continuously, to identify the temperature ranges of the three reactions of HA. Among the three reactions, the volume change of sintering, which occurs between the other two reactions, is particularly difficult to separate out.
Here we use a two-step sintering (TSS) technique and try to solve above problem. In the TSS process, the HA samples were fully dense with relative densities over 99% and with no phase transformation before 1200℃. The obtained samples with phase transformation reactions after 1400℃. Furthermore, the Master Kinetics Curve (MKC) results for thermal decomposition reactions (from 700℃ to 1200℃) using conventional sintering (CS) and two-step sintering (TSS) technique, show the apparent activation energy of 870.6 kJ/mol and 1615 kJ/mol, respectively. In TSS Master Kinetics Curve (MKC) results, the curve is shifted to the left relative to CS, which means less sintering time to complete densification with high green density. Several expansion reaction maybe the densification of samples are too much over, which cause residual stress had to be variant from outside to inside and the phase change also occur, and the other reason is due to the fast heating rate cause the delay of instrument detection. | en |
dc.description.provenance | Made available in DSpace on 2021-06-17T06:19:54Z (GMT). No. of bitstreams: 1 ntu-107-R03224110-1.pdf: 3062199 bytes, checksum: baf4b6e61ad5cada1aa998619c5da247 (MD5) Previous issue date: 2018 | en |
dc.description.tableofcontents | 誌謝……………………………………….......................................................... i
中文摘要.............................................................................................................. ii Abstract….…………………………………………….…………………….... iv 目錄……………………………………………………………………..….……v 圖目錄……………………………………………………..…………………...vii 表目錄………………………………………………………..…………..........viii 縮寫對照表……………………………………………………..……………... ix 第一章 緒論……................................................................................................ 1 1.1 研究動機與目的…….…………………………………..............….... 1 第二章 文獻回顧………………………………………………………...…..... 3 2.1 關於氫氧基磷灰石升溫過程中的反應……………………….…….. 3 2.1.1 脫氫氧基反應與相變反應………….………………..…......... 3 2.1.2 燒結反應…………………………….………………..…......... 5 2.1.3 氫氧基磷灰石升溫過程中三種反應.…………………........... 8 2.2 主導動力學曲線模型………………………………………....…..…. 9 2.2.1主導燒結曲線模型……………………………………............. 9 2.2.2主導動力學曲線模型………………........................................ 11 第三章 實驗方法............................................................................................... 15 3.1 利用熱膨脹儀測量氫氧基磷灰石熱分解之實驗步驟….................. 15 3.1.1 粉末購置和分析....................................................................... 15 3.1.2 圓錠製備………….…………………………………...…....... 15 3.2 傳統燒結與兩階段燒結不同升溫歷程之實驗設計…………......… 16 3.2.1 氫氧基磷灰石的傳統燒結 ..................................................... 16 3.2.2 氫氧基磷灰石的兩階段燒結 ................................................. 18 3.3 實驗分析儀器……………………………………………………….. 18 3.3.1 X光粉末繞射儀……………………………….…….…..….... 18 3.3.2 比表面積分析儀…………....................................................... 19 3.3.3 熱膨脹儀………………………............................................... 20 3.3.4 密度測量…………………………………............................... 23 第四章 實驗結果與討論....................................................................................24 4.1 原始粉末分析結果…………….....………………………….…..….. 24 4.2 熱膨脹儀分析結果與討論…….....……………………….…....…… 25 4.2.1 傳統燒結實驗結果…..……..................................................... 25 4.2.2 兩階段燒結實驗結果............................................................... 28 4.2.3 討論XRD分析結果……………………….………….…..…. 30 4.3 利用主導動力學曲線模型擬合熱分解反應的結果與討論….......... 32 4.3.1 利用收縮長度作為換算反應百分比擬合的結果與討論…... 32 4.3.2 期望藉由熱膨脹儀兩階段燒結法所解決的問題…............... 35 第五章 結論與建議………............................................................................... 37 參考文獻……………......................................................................................... 38 附錄A 符號表……………............................................................................... 43 附錄B 實驗數據……………........................................................................... 44 | |
dc.language.iso | zh-TW | |
dc.title | 利用熱膨脹儀與兩階段燒結法探討氫氧基磷灰石相變溫度範圍及反應動力學 | zh_TW |
dc.title | Study on the temperature range and reaction kinetics of phase transformation of hydroxyapatite using a dilatometer and two-step sintering technique | en |
dc.type | Thesis | |
dc.date.schoolyear | 106-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 劉雅瑄(Ya-Hsuan Liou),林中魁(Chung-Kwei Lin),吳樂群(Leh-chyun Wu) | |
dc.subject.keyword | 氫氧基磷灰石,熱膨脹儀,兩階段燒結法,主導動力學曲線, | zh_TW |
dc.subject.keyword | hydroxyapatite,dilatometer,two-step sintering,Master Kinetics Curve, | en |
dc.relation.page | 46 | |
dc.identifier.doi | 10.6342/NTU201804023 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2018-08-20 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 地質科學研究所 | zh_TW |
顯示於系所單位: | 地質科學系 |
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