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論文名稱(中文) 三種鉻酸鹽(MCrO4, M:Ba,Pb,Sr)之高壓X光繞射與拉曼光譜研究
論文名稱(英文) High-Pressure X-ray Diffraction and Raman Spectroscopy Studies of Three Chromates(MCrO4, M:Ba,Pb,Sr)
校院名稱 成功大學
系所名稱(中) 地球科學系碩博士班
系所名稱(英) Department of Earth Sciences
學年度 99
學期 1
出版年 100
研究生(中文) 黃慶祥
研究生(英文) Ching-Hsiang Huang
學號 L4891104
學位類別 博士
語文別 中文
論文頁數 96頁
口試委員 指導教授-龔慧貞
口試委員-余樹楨
口試委員-黃怡禎
口試委員-林志明
口試委員-李建興
中文關鍵字 鉻酸鹽  鑽石高壓砧  X光繞射  高壓  相變 
英文關鍵字 chromate  diamond anvil cell  X-ray diffraction  high pressure  phase transition 
學科別分類
中文摘要 利用鑽石高壓砧進行鉻酸鋇(重晶石結構)、鉻酸鉛(鉻鉛礦,獨居石結構)與鉻酸鍶(獨居石結構)等三種鉻酸鹽的高壓實驗,結果與前人研究進行比較並討論兩種體彈模量經驗公式的適用性。實驗首先是利用拉曼光譜儀測量樣本在高壓下的晶格振動模的變化,並以同步輻射X光粉末繞射方法探討樣本在高壓下的結構變化並定出其晶格參數。本研究將以三個樣本的實驗結果,來探討鉻酸鹽化合物在高壓下體彈模量、相變壓力與高壓相結構的系統性行為。
實驗的最高壓力為25 GPa,在此範圍內,X光繞射的實驗結果顯示三種鉻酸鹽都有發生結構相轉變(相變),其中鉻酸鍶的相變壓力最低,鉻酸鋇的相變壓力最高;三種樣本都有高、低壓相共存的過渡現象。其中鉻酸鋇的高壓相空間群判定為P21/m,在相變時,高低壓相的體積相差9%,鉻酸鋇的相變為一階可逆相變。在加壓過程中,三種鉻酸鹽的三軸壓縮均呈現不等量變化,其共同點是最難被壓縮的軸都在多面體與多面體共邊的方向上。鉻酸鋇、鉻酸鉛、鉻酸鍶三者的體彈模量分別定為53 (1) GPa、62(1) GPa及60(2) GPa。
拉曼光譜的實驗結果顯示鉻酸鋇的拉曼振動模變化趨勢在相變發生的9 GPa附近有不連續的現象,與鉻酸鋇的相變壓力相同。鉻酸鋇振動模的格留乃森參數平均數值為0.87。鉻酸鍶的拉曼振動模變化趨勢在9.5 GPa以及15 GPa呈現兩次的不連續性,其振動模的格留乃森參數平均數值為0.84。
本研究結果中,鉻酸鋇之相變行為與過去學者提出之相變趨勢理論吻合,而壓縮實驗結果並不支持過去學者所提出之體彈模量經驗公式,顯示這些經驗公式是否適用於本研究的鉻酸鹽類或是其他化合物,仍有待進一步的驗證或修正。
英文摘要 High-pressure Raman spectroscopic and X-ray diffraction experiments of three chromates were carried out in a diamond anvil cell up to 25 GPa. The goal is to determine the equation of states of the phases in this study. In addition, the mechanism of the phase transition is also inferred.
On the basis of the changes in the X-ray diffraction patterns and the variation of the lattice parameters with pressure, it is inferred that three chromates undergo reversible phase transition. The phase transition pressure of barium chromate is the highest of three chromates and strontium chromate is the lowest. The low pressure phase and high pressure phase of three chromates coexisted after phase transition. The phase transition of barium chromate is first-order transformation, the volume decreases 9% after phase transition. The phase transition of barium chromate is reflected by the splitting in the CrO4 vibration modes and the discontinuity in the slope of mode frequency verse pressure in the Raman observation. Strontium chromate has two discontinuities in the slope of mode frequency verse pressure at 9.5 GPa and 15 GPa, respectively. The mean Grüneisen parameter for barium chromate is 0.87. The mean Grüneisen parameter for strontium chromate is 0.84.
The three chromates show anisotropic compressibility along three crystallographic axes. In barium chromate, a axis is the most uncompressible axis, which corresponding to the direction with edge share between Cr-O tetrahedral and Ba-O polyhedral. In lead chromate and strontium chromate, c axis is the most uncompressible axis which corresponding to the direction with edge share between Cr-O tetrahedral and Pb-O(Sr-O) polyhedral.
The bulk modulus (K) of barium chromate is 53(1) GPa, the K value of lead chromate and strontium chromate is 62(1) GPa and 60(2) GPa, respectively.
論文目次 中文摘要 I
Abstract II
誌謝 III
第一章 前言 1
1-1 緒論 1
1-2 研究動機與目的 1
第二章 前人研究 4
2-1 ABO4化合物 4
2-2 鉻酸鋇結構與鉻酸鍶結構 4
2-2-1 鉻酸鋇結構 4
2-2-2鉻酸鍶結構 5
2-3 拉曼光譜應用在B陽離子配位數上的計算 7
2-4 ABO4化合物之高壓相變 7
2-5 ABO4化合物之體彈模量經驗公式 9
第三章 實驗方法、原理、儀器與數據分析軟體 11
3-1 實驗流程 11
3-2 樣本合成與分析 12
3-3 鑽石高壓砧 12
3-4 實驗原理與儀器 13
3-4-1 拉曼光譜原理與儀器 13
3-4-2 X光繞射原理與儀器 14
3-4-3 角度分散分析法(Angle-dispersive X-ray diffraction) 16
3-4-4 壓力測量 16
3-5 X光繞射數據處理流程 18
3-5-1 Peakfit 19
3-5-2 CHEKCELL 19
3-5-3 GSAS 19
3-5-4 EOSFIT 5.2 21
3-6 X光粉末繞射實驗條件 21
第四章 實驗結果 22
4-1 X光粉末繞射 22
4-1-1 鉻酸鋇 22
4-1-2 鉻酸鍶 29
4-1-3 鉻酸鉛 34
4-2 拉曼光譜研究 37
4-2-1 鉻酸鋇 38
4-2-2 鉻酸鍶 45
第五章 討論 53
5-1相變途徑與相變壓力 53
5-1-1 鉻酸鋇高壓相變 54
5-1-2 鉻酸鍶高壓相變 56
5-1-3鉻酸鉛高壓相變 57
5-1-4 四種鉻酸鹽的相變壓力比較 57
5-2 體彈模量經驗公式 58
第六章 結論 62
參考文獻 63
附錄 A 68
附錄 B 92
附錄 C 93
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