臺灣博碩士論文加值系統

本實驗利用恆溫流動式的結晶槽並利用顯微照相系統來探討蔗糖晶體的成長動力學，可以從實驗中觀察到晶體間存在成長速率分佈(GRD)及晶體的成長速率與晶體大小無關(size-independent)。這些結果顯示此結晶系統CCG model是成立的。在此提出一修改過的雙重阻力模式(two-step model)來解釋我們所觀察到的現象。本實驗中，若增加槽內溶液的流速則由於質傳擴散造成的晶體成長阻力可以忽略，所以整個成長過程可視為表面反應控制且能僅對表面晶格排入晶體的反應研究。我們在此探討晶體過飽和度、溫度、流速對成長速率的影響來找出質傳擴散係數，晶面整合反應係數等參數並分析其成長機制。
基於在恆溫流動式的結晶槽實驗得到的平均成長速率，可以得到蔗糖晶體的表面反應活化能為14.9Kcal/mol。比較個別晶體在表面反應控制時的平均成長速率，我們發現晶體表面的螺旋生長點密度分佈為平均差排密度的50%至150%之間。
在此亦研究以果糖當雜質對蔗糖晶體成長的影響。由於蔗糖為一分子果糖和一分子葡萄糖構成，因此當果糖加入時，可能會吸附於蔗糖晶體表面而形成新的成長基，而加速晶體的成長。

The growth kinetics of sucrose crystals from aqueous solutions is studied using a photomicroscopic technique in an isothermal, continuous-flow chamber. The phenomena of size-independent growth and growth rate dispersion are observed in the experiments. These results indicate that the constant crystal growth model is applicable in the studied crystallization system. A modified two-step model is proposed to account for the observed growth phenomena. In this work, the resistance to crystal growth due to the volume diffusion is eliminated by increasing the solution flow rate through the growth chamber. Thus the crystal growth process becomes surface reaction-controlled and the effects of the sole surface reaction step on the growth kinetics can be investigated. The effects of supersaturation, temperature and solution velocity on the growth rates are investigated in these experiments to recover the mass transfer coefficient and the surface reaction constant.
Based on the mean growth rate data in the isothermal, continuous-flow experiments, the activation energy of 14.9 Kcal/mol is obtained for the surface reaction process in sucrose crystal growth. By comparing the growth rate of each individual crystal with the mean growth rate in a purely surface reaction-controlled growth process, it is found that the distribution of the dislocation activity among crystals mainly falls within the range of 50% to 150% of the average dislocation density.
The effects of fructose on the growth kinetics of sucrose crystals are also investigated. As one sucrose molecule consists of one fructose and one glucose, the adsorption of fructose on the sucrose crystal surface might cause the formation of new growth sites, resulting in the faster growth rate on the sucrose surface.

指導教授推薦書
口試委員審定書
授權書 iii
誌謝 v
中文摘要 vi
英文摘要 vii
目錄 ix
圖表目錄 xi
第一章 序論……………………………………………………... 1
第二章 文獻回顧………………………………………………... 3
2-1 結晶理論………………………………………………... 3
2-2-1 過飽和度產生……………………………………. 3
2-2-2 成核現象…………………………………………. 5
2-2-3 晶體成長現象……………………………………. 10
2-2-4 凝聚現象…………………………………………. 13
2-2 雜質對結晶過程的影響………………………………... 14
2-2-1 雜質進入晶體的機構與現象……………………. 16
2-2-2 雜質對成核速率的影響…………………………. 19
2-2-3 雜質對成長速率的影響…………………………. 20
2-3 蔗糖的性質……………………………………………... 23
2-4 蔗糖晶體的成長………………………………………... 25
2-5 雜質對蔗糖晶體成長的影響…………………………... 27
第三章 原理……………………………………………………... 44
3-1 雙重阻力模式…………………………………………... 44
3-2 雙重阻力模式中影響參數變因的探討………………... 45
第四章 實驗裝置與步驟………………………………………... 55
4-1 實驗藥品………………………………………………... 56
4-2 分析儀器………………………………………………... 56
4-3 實驗步驟………………………………………………... 56
第五章 結果與討論………………………………………... 60
5-1 晶體大小與成長速率的關係…………………………... 60
5-2 過飽和度對成長速率的影響…………………………... 60
5-3 溫度影響參數之探討…………………………………... 61
5-4 流速影響參數之探討…………………………………... 64
5-5 BCF模式探討參數的影響……………………………... 67
5-6 雜質影響之探討………………………………………... 67
5-7 其他影響成長速率因素之探討………………………... 68
第六章 結論……………………………………………………... 95
參考文獻…………………………………………………………... 97
符號說明…………………………………………………………... 103
附錄………………………………………………………………... 104

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