臺灣博碩士論文加值系統

改良式的水熱法被用來合成磷酸鹽的粉末及鍍層.這種由我們實驗室自行設計的水熱合成法,和傳統的水熱法比較起來,在反應槽內,改良式的水熱法有較大的溫度差.因此兩種方式的水熱法的反應機制也有相當大的差異.
在此系統中,粉末合成的適當條件是在300℃持溫24小時.主要的成份相包括CaHPO4,Ca(OH )2,Ca2P2O7,和Ca10(PO4)6(OH)2.在較高的處理溫度及較長的持溫時間下,反應的進行較為完全.
當起始成份的鈣磷比(Ca/P)較低時,可以得到Ca2P2O7.當Ca/P比值逐漸增加,主要的成份相變為CaHPO4.Hydroxyapatite在Ca/P繼續增加後可以產生出來.但是當Ca/P的比值持續再增加,Hydroxyapatite的波峰在XRD圖形中的強度並不會繼續增強,只有Ca(OH)2的波峰強度會增強.在反應物內加入較多的磷酸,也就是降低系統的pH值,Hydroxyapatite可以較容易獲得.
在不鏽鋼基板的表面上合成磷酸鹽陶瓷鍍層的過程中,主要是被表面反應物的濃度以及表面的溫度差所影響.整個製程主要可以分為幾個階段來進行:首先,基板的表面會被磷酸所改質,然後部份粉末隨著氣相被輸送到基板處並附著在基板上.經過一段時間後,這些附著在基板上的粉末逐漸變成晶格中的一部份,經過成核長晶的過程後,最後就可以在基板上得到鍍層以及一些晶體.
鍍層的主要成份是綠色的磷酸鐵氫氧化物(Fex(PO4)y(OH)z).在實驗中得到的晶體主要是包括JCPDS #44-762 Ca2P2O7.H2O,JCPDS #9-348
Ca3(PO4)2 以及JCPDS #9-80 CaHPO4

A modified hydrothermal method was used to synthesize calcium phosphate powders and coatings. This modified hydrothermal method, that designed by our laboratory, have larger thermal gradient (△T ) in the reaction chamber than the traditional autoclave, and the reactive mechanisms are quite different between these two methods.
The suitable condition for the powder synthesis is at 300℃ for 24hr, and the phases of the calcium phosphate powders synthesized by the hydrothermal method mainly include CaHPO4,
Ca(OH )2, Ca2P2O7, and Ca10(PO4)6(OH)2. With higher temperature and longer heating time, the reaction becomes more completed.
When the Ca/P ratios of the raw materials are low, Ca2P2O7 can be obtained. As the Ca/P ratio increases, CaHPO4 gradually becomes the major phase of the powders. Hydroxyapatite can be produced with more quantity of calcium oxide. However, as the quantity of the calcium oxide powder continues increasing, the peaks of the hydroxyapatite phase does not become stronger; only the peaks of the Ca(OH )2 greatly increase. Adding more phosphoric acid into the system, that is, decreasing the pH value in this system, hydroxyapatite phase could be easier observed.
When synthesize calcium phosphate coatings onto 304 stainless steel substrate, the surface processes of the ceramic coating growth are regarded as function of the concentration of the reactants and the temperature difference immediately at the surface. The process is mainly assumed to occur in some stages: First, the surface of the substrate would be modified by the phosphoric acid; then the powders coming along with the vapor condense into the substrate. Those adsorbed powders are gradually built into the lattice. After the nucleation and growth processes, finally the coating and some crystal could be attained.
The major composition of the coating is iron phosphate hydroxide (Fex(PO4)y(OH)z), and the color of it is green. The crystals obtained in this experiment include calcium pyrophosphate (JCPDS #44-762 Ca2P2O7.H2O), tricalcium phosphate (JCPDS #9-348 Ca3(PO4)2), and monetite (JCPDS #9-80 CaHPO4).

Chapter1 Introduction
1.1 Paper review
1.2 Inorganic phosphate
1.2.1 Hydroxyapatite
1.2.2 Calcium orthophosphates
1.3 304 stainless steel
1.4 The goal of this experiment
Chapter 2 Basic theories
2.1 Hydrothermal reaction
2.2 Pressure in the autoclave
2.3 The effects of process parameters
2.4 Mechanism for the crystal growth from solution
2.4.1 Nucleation of crystal
2.4.2 Growth of crystal
2.5 Phosphating
2.6 Metallic substrate coated with calcium phosphate ceramics
Chapter 3 Experiment
3.1 Experimental apparatus
3.2 Experiment procedure
3.2.1 Hydrothermally synthesis calcium phosphate powder
3.2.2 Substrate preparation
3.2.3 Stainless steel substrate coated with calcium phosphate
by hydrothermal method
3.2.4 Products analysis
Chapter 4 Results and Discussions
4.1 Hydrothermal synthesis of calcium phosphate powders
4.2 Hydrothermal Growth the calcium phosphate coating onto the
304 stainless steel substrate
4.2.1 Introduction
4.2.2 The coating mechanism
4.2.3 The model for the ceramic coating
4.2.4 The results of the calcium phosphate coating onto the
304 stainless steel substrate
4.3 The influence with the volume change of the crucible
Chapter 5 Conclusion
Chapter 6 Reference

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