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研究生:盧明憲
研究生(外文):MingShane Lu
論文名稱:低溫下以四氯化鈦製備高濃度二氧化鈦結晶覆膜液
論文名稱(外文):Synthesis of Nanosized TiO2 Coating Solution from Titanium Tetrachloride
指導教授:陳郁文陳郁文引用關係
指導教授(外文):YuWen Chen
學位類別:碩士
校院名稱:國立中央大學
系所名稱:化學工程研究所
學門:工程學門
學類:化學工程學類
論文出版年:2001
畢業學年度:89
語文別:中文
論文頁數:71
中文關鍵詞:二氧化鈦光催化銳鈦礦四氯化鈦超親水性介電材料
外文關鍵詞:TiO2catalystanataseTiCl4super-hydrophilicitydielectric material
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二氧化鈦薄膜是一具有高折射率、高介電常數、在可見光及近紅外光區不吸收、化學性質穩定、硬度高耐磨等優良特性的薄膜材質,其可以廣泛應用在光催化、及其他導電性介電材料的批覆。本論文係應用無機鹽類製備出高濃度二氧化鈦微結晶粒子覆膜液,並批覆在不具親水性的基體上,使其具有高度的親水性,而達到去漬、自潔的功用。首先將系統控制在5℃,配製0.5M的TiCl4 水溶液,再將NaOH溶液,滴入TiCl4 水溶液中調整pH值範圍,經過老化、水洗過濾,再加入不同濃度或莫耳比[H+]/[Ti]的HCl,經過24~48小時的酸解解膠,可以得到穩定的TiO2懸浮液。再將所得的TiO2懸浮液以一定比例加入HPC (150-400 cps)當作粒子分散劑,我們可以得到10 %的TiO2懸浮液。
由XRD、DLS、TEM、氮吸附觀察得知,結晶粒子屬於anatase晶形,而其一次粒子為長軸20 nm,短軸5 nm的菱形粒子;且其具有高表面積141 cm3/g的微孔結構。最後測量批覆7 %TiO2薄膜的玻片基材的接觸角,證明本實驗所製備出的TiO2微結晶懸浮液僅需三次鍍膜便可完整批覆在基材表面,並使基材達到超親水性的性質。

TiO2 has been used as a coating material because of its excellent UV light-scattering effect, high refractive index, and chemical stability, even in acidic or basic environment. TiO2 in anatase phase for applications in optical or electronic devices has generally been adopted in the form of a thin film. The aim of this study was to prepare suspended titanium dioxide solution with high concentration. Titanium tetrachloride was used as a precursor. It was slowly added to the distilled water at 5 ℃. Aqueous solution of sodium hydroxide was added to adjust the pH of the system to 8-12. After aging for a period of time, the peptizate sol was filtered and sufficiently washed. The filtered cake was repulped in water. Hydrochloric acid was slowly added to the solution with stirring. After condensation reaction and crystallization, a transparent suspended TiO2 solution was formed. XRD results show that the crystalline phase was anatase. The suspended TiO2 particles were rhombus primary particles with the major axis ca. 20 nm and the minor axis ca. 5 nm. The sample prepared at pH 8 has the largest surface area of 141 cm3/g, and it was microporous. The compositions of the solution which has the smallest suspended TiO2 particles are TiO2: HCl (35 % HCl)= 1: 1 (molar ratio), concentration of TiO2 = 10 % and HPC with viscosity of 150-400 cps was added as a surfactant. The transparent thin film substrates could be obtained through dip-coating the glass in TiO2 coating solution. The dip-coating on glass can be less than three times to have one monolayer TiO2. The transparent TiO2 thin film has super-hydrophilicity after being illuminated by UV light.

Abstracti
List of contentsiii
List of tablesvi
List of figuresvii
Chapter 1 Introduction1
1.1 The prorperties of titanium dioxide1
1.2 Application of titanium dioxide5
Chapter 2 Literature review9
2.1 Synthesis method9
2.2 Literature review11
2.2.1 Inorganic salt as a precursor11
2.1.2 Alkoxide as a precursor14
Chapter 3 Experiment17
3.1 Chemicals17
3.2 Synthesis17
3.3 Characterization19
3.3.1 X-ray diffraction (XRD) 19
3.3.2 N2 sorption 19
3.3.3 Thermogravimetric analysis (TGA)20
3.3.4 Differential scanning calorimetery (DSC) 20
3.3.5 Transmission electron microscopy (TEM) 21
3.3.6 Scanning electron microscopy (SEM)21
3.3.7 Dynamic light scattering (DLS)21
3.3.8 Ultravillet /visible absorption (UV-vis)22
3.3.9 Contact anglemeter22
Chapter 4 Results and Discussion23
4.1 Particle size distribution23
4.1.1 Effects of pH value23
4.1.2 Effects of [H+]/[Ti] ratio24
4.1.3 Effects of HCl concentration29
4.1.4 Effects of stored temperature on particle diameter33
4.2 Stability of suspension36
4.2.1 Effects of condensation reaction36
4.2.2 Effects of HCl concentration39
4.2.3 Effects of stored temperature39
4.2.4 Effects of residual ions39
4.3 Degree of crystallization41
4.3.1 Effects of pH41
4.3.2 Effects of [H+]/[Ti] ratio and HCl Concentration45
4.4 TiO2 solid content 45
4.4.1 Combination of all factors for best condition45
4.4.2 Effects of HPC surfactant47
4.4.3 Other factors48
4.5 Thermal analysis51
4.5.1 TGA51
4.5.2 DSC51
4.6 N2 sorption52
4.7 Best preparing method58
4.8 Ultraviolet / Visible adsorption (UV-vis)60
4.9 Contact angle60
Chapter 5 Conclusion65
Reference67
Appendix71
List of tables
Table 1. X-ray data of TiO23
Table 2. Mean diameter of TiO2 crystallite from XRD results24
Table 3. The particles size distribution of TiO224
Table 4. The results of Wang (2000)38
Table 5. The pH value in the solution38
Table 6. Effects of HCl Concentration45
Table 7. Effects of [H+]/[Ti] ratio47
Table 8. TiO2 Solid Content49
Table 9. Weight loss of TiO2 prepared at different pH value51
Table 10. Summary results59
Table 11. Particles size of the samples59
Table 12. 5 % TiO2 coating solution64
Table 13. 7 % TiO2 coating solution64
List of figures
Figure 1. (A) structure of Rutile; (B) structure of Anatase4
Figure 2. Schematic representation of the possible application
of transparent TiO2 thin film photocatalysts in the
environment8
Figure3. Flow chart illustrating the preparation of transparent
suspended TiO218
Figure 4. XRD spectra of TiO2 prepared at different pH values25
Figure 5. XRD spectra of standard anatase type TiO2 prepared at
pH=8, [H+]/[Ti] = 1, HCl=1M26
Figure 6. SEM image of aggregated TiO2, but still could see
some disperse particle <100 nm 27
Figure 7. TEM image of TiO2 with rhombus form27
Figure 8. TEM image of TiO2 prepared at different pH values (A) pH
=8; (B) pH=9; (C) pH=10; (D) pH=11. (Store temperature
=30℃)28
Figure 9. XRD spectra of TiO2 prepared at different [H+]/[Ti] ratios30
Figure 10.TEM image of TiO2 prepared at pH=8 and [H+]/[Ti] = 131
Figure 11.TEM image of TiO2 prepared at pH=8 and [H+]/[Ti] = 1.532
Figure 12.XRD spectra of TiO2 prepared at different concentration
of HCl (pH =9; [H+]/[Ti] = 1)………………………………34
Figure 13. TEM image of TiO2 prepared at different HCl
Concentration. (A) pH =8, 1M HCl ; (B) pH=8, 2M HCl35
Figure 14. TEM image of TiO2 at different stored temperature. (A)
pH =8, 5℃; (B) pH=8, 30℃37
Figure 15. XRD spectra of TiO2. The crystal type was converted
into rutile crystal phase at different pH value……………..42
Figure 16. XRD 3D graph of TiO2 (A) suspended TiO2 only
has anatase crystal phase; (B) In precipitate
TiO2, anatase crystalline converted into rutile crystalline43
Figure 17. TEM image of TiO2 (A) Opacity; (B) precipitate (C)
The way of TiO2 aggregation was head to head44
Figure 18. TEM image of TiO2 (A) pH= 8 (A1) TEM SAD pattern;
(B) pH= 12 (B1) TEM SAD pattern46
Figure 19. TEM image of TiO2 at different concentration (A) pH
=8, 10%; (B) pH=10, 7 %; (C) pH=10, 10 %50
Figure 20. TGA spectra of TiO2 prepared at pH= 853
Figure 21. TGA spectra of TiO2 prepared at different pH values53
Figure 22. DSC spectra of TiO2 prepared at pH= 8 and pH=1254
Figure 23. (A) TiO2 was calcined at temperature 450℃, pH=8 1M
HCl, [H+/Ti]=1. (B) TiO2 was calcined at temperature
650℃, pH=8 1M HCl, [H+/Ti]=155
Figure 24. N2 sorption isotherm of TiO2 at pH=856
Figure 25. N2 sorption isotherms of TiO2 after calcinations at
various temperature57
Figure 26. The best preparation method58
Figure 27. UV-visible spectra of TiO2 (not calcined) 61
Figure 28. UV-visible spectra of TiO2 ( calcined at 150℃) 61
Figure 29. UV-visible spectra of Degussa P-25 TiO262

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