臺灣博碩士論文加值系統

磷酸鈣材料已經被廣泛應用在牙齒、骨骼等外科材料。文獻記載，藉著磷酸鈣材料在人體內的生物降解速率不同，調整磷酸三鈣(β–TCP)和磷灰石(HA)之間的比例已應用在骨骼替代材料。一般來說β–TCP的形成是由其它磷酸鈣分解而來，像是在HA加熱到高溫800 ℃時會產生β–TCP相。如何標定β–TCP和HA的含量仍是極具有挑戰性。近年來，參考強度比時常被用在比較這兩者定量上，但是此法需要一外標準品做為標定，且並未考慮到峰的半高寬影響。Rietveld結構精算在多重相定量已被廣泛使用多年，此法可在定量上調整參數影響如消光性、排列取向，比以往的定量方法可再確認晶格常數、化學組成、修正取向、微米級吸收影響，因此本篇論文主要利用X光粉末繞射之Rietveld結構精算來鑑定BCP(二相磷酸鈣)並且對此二相含量做定量分析，Raman光譜、紅外光光譜輔次。
在HA、β–TCP(磷酸三鈣-燒結)、β–TCP’(磷酸三鈣-未燒結)的純相研究中，從拉曼光譜我們可以看到磷酸根在968 cm-1附近的對稱振動(?1)，可用以分辨β–TCP和β–TCP’，X光粉末繞射分析可以幫助我們區分HA和β–TCP，而IR光譜在磷酸根1026 cm-1附近則沒有明顯的不同。HA和β–TCP定量上，最好的方式是藉由Rietveld結構精算法分析高解析度的X光粉末繞射數據。為了因應產業界快速應用，則可使用β–TCP繞射峰(2 0 -10)、HA繞射峰(1 2 1)，的繞射峰面積比例，可求得相對成分的大略比值。 

Calcium phosphates have been extensively used for dental and orthopedic surgical applications due to the biodegradability in human being. It was found that a suitable mixing ratio between β–TCP (β-tricalcium phosphate, Ca3(PO4)3) and HA (hydroxyapatite, Ca5(PO4)3(OH)) is important for the biodegradable bone replacement. In general, β–TCP is synthesized by the decomposition of other calcium phosphate phases such as HA at temperature higher than 800 ℃. Consequently, how to determine the ratio between β–TCP and HA is an important issue on characterization methods. Recently, reference intensity ratio (RIR) method is used for quantification under the comparison with standard reference, but it ignores the peak broadening effect. Rietveld refinement has been widely used in multiphase quantification for many years due to less susceptible on primary extinction effects and minor amounts of preferred orientation. In addition, the advantages of this technique over traditional quantitative analysis methods include the determination of precise cell constants, the approximation of chemical compositions, the potential for the correction of preferred orientation, and microabsorption effects. Therefore, the characterizations of these structures and their quantities by x-ray diffraction (XRD), Raman spectroscopy, Infrared spectroscopy (IR), and Rietveld refinement in such biphasic calcium phosphate (BCP) system are the major work in this study.
In the single phase study of HA, β–TCP(sintered), and β–TCP’(unsintered), the Raman spectroscopy can be used to distinguished between β–TCP and β–TCP’ based on the symmetric stretching frequency (?1) of PO4 around 968 cm-1, and XRD can be used to differentiate between HA and β–TCP. However, there are no significant differences on the vibrational frequency of PO4 around 1026 cm-1 in IR spectra. In the quantification of mixing ratio between HA and β–TCP, the best strategy is to apply Rietveld refinement on high resolution powder XRD data. However, for the convenience on the application of industry, the area ratio between reflection (2 0 -10) of β–TCP and reflection (1 2 1) of HA could be used to get the rough results.

中文摘要 I
ABSTRACT III
誌 謝 V
LISTS OF TABLES VI
LISTS OF FIGURES VIII
CONTENTS XI
Chapter 1 INTRODUCTION 1
1.1 Calcium phosphate 1
1.2 Motivation 5
Chapter 2 EXPERIMENT 6
2.1 Sample preparation 6
2.2 Total reflection x-ray fluorescence 7
2.3 Raman spectroscopy 8
2.4 Attenuated total reflectance – Infrared spectroscopy 9
2.5 X-ray diffraction 10
2.5.1 Introduction 10
2.5.2 Brentano radiation geometry 13
2.5.3 Synchrotron radiation 15
2.6 Rietveld refinement 18
2.6.1 Introduction 18
2.6.2 Phase quantification by Rietveld refinement 21
2.7 Reference intensity ratios 23
Chapter 3 RESULTS AND DISCUSSION 26
3.1 Pure phase characterization 26
3.1.1 XRD 26
3.1.2 Raman 27
3.1.3 IR 29
3.1.4 TXRF 30
3.2 BCP weight quantification 32
3.2.1 Pure samples HA and b-TCP study 32
3.2.2 Quantification study by different methods 38
3.2.3 Rietveld discussion 45
3.2.4 BCP weight percentage 45
3.2.5 Calibration results 53
Chapter 4 CONCLUSION 55
REFFERENCE 56
APPENDIX 59

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