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博碩士論文 etd-0726112-123843 詳細資訊
Title page for etd-0726112-123843
論文名稱
Title
脈衝雷射於水中與氯化鈉水溶液中碎化氧化鈮粉末的效應及變化
PLAL fragmentation of Nb2O5 powders in water with optional NaCl addition
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
52
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2012-06-12
繳交日期
Date of Submission
2012-07-26
關鍵字
Keywords
脈衝雷射剝熔蝕碎化、相變化、氧化鈮粉末、顯微結構光學性質
PLAL, optical property, powder fragmentation, Nb2O5, microstructure, phase
統計
Statistics
本論文已被瀏覽 5781 次,被下載 302
The thesis/dissertation has been browsed 5781 times, has been downloaded 302 times.
中文摘要
本實驗將粒徑約為次微米與微米級具有單斜結構及(101)滑移面的氧化鈮Nb2O5(H-type)粉末溶於去離子水與飽和食鹽水中,經波長532nm、能量400mJ、雷射停留時間16ns的Nd-YAG脈衝雷射碎化,研究所造成的顆粒細化以及結晶構造、形狀、光學性質等的變化。
藉由X光與電子繞射發現H-Nb2O5粉末溶於水中剝熔蝕之後產生高壓穩定的斜方T-Nb2O5相、擬六方TT-Nb2O5相以及非計量成份的非結晶相,三者或共存於單一顆粒或各自形成奈米顆粒,與細化之H-Nb2O5顆粒同時受氫化影響其缺陷化學,以致於影響拉曼光譜及膠體溶液之顏色與UV-Visible吸收光譜,使最小能隙值調降為3.0±0.1eV 以及 2.5±0.1eV。
依此製程將Nb2O5顆粒細化的極限約5nm,顆粒小於10nm時可觀察到特定晶面的出現,隨著顆粒粒徑的增加則由於表面吸附原子團以及減少表面暴露的效應使得形狀趨於球形。於飽和食鹽水中進行H-Nb2O5粉末之剝蝕碎化所得的結果與去離子水中者相似,顯示鈉離子與氯離子未明顯參與反應。
Abstract
The H-type Nb2O5 powders (monoclinic structure with (101) crystallographic shear plane) submicron to micrometers in size were subjected to pulsed laser ablation fragmentation in water (PLAL) with optional NaCl addition in order to study the structure change of the resultant Nb2O5 nanoparticles by x-ray diffraction and electron microscopy. The Nb2O5 nanoparticles via such a dynamic PLAL fragmentation process turned out to be H-type relic and newly formed T-type (an orthorhombic high-pressure phase), TT-type (a pseudohexagonal high-pressure phase) and a nonstoichiometric amorphous phase which coexist within a faceted nanoparticle (down to ca. 5 nm) or coalesced with each other. The composite Nb2O5 nanoparticles were protonated and imposed with a considerable internal compressive stress to modify the structure units and band structure as indicated by vibrational (Raman and FTIR) spectra and uv-visible absorption spectrum of the darkened colloidal solution indicating a stepwise minimum band gap lowering down to stepwise 3.0±0.1 eV and 2.5±0.1eV. NaCl spiking in water did not cause appreciable change on the phase behavior of Nb2O5 powders upon PLAL.
目次 Table of Contents
論文審定書 i
誌謝 ii
摘要 iii
Abstract iv
目錄 v
表目錄 vii
圖目錄 vii
一、前言 1
二、實驗步驟與方法 3
2-1. 脈衝雷射碎化 3
2-2. X光繞射儀觀察 3
2-3. UV-Visible 吸收光譜 3
2-4. 拉曼光譜分析 3
2-5. 霍式轉換紅外光譜儀 4
2-6. 偏光顯微鏡 4
2-7. 場發式掃描式電子顯微鏡 4
2-8. 解析型穿透式電子顯微鏡(AEM)觀察與試片製作 4
三、實驗結果 6
3-1. X光繞射分析 6
3-2. UV-Visible 吸收光譜 6
3-3. 拉曼光譜與霍式轉換紅外光譜 7
3-4. 偏光顯微鏡 8
3-5. 電子顯微鏡 9
四、討論 10
4-1. 經由PLAL所造成之Nb2O5相選擇 10
4-2. 食鹽水對於Nb2O5剝熔蝕結構單位的影響 11
4-3. Nb2O5膠體溶液顏色或吸收光譜變化的原因與潛在應用 12
五、結論 13
六、參考文獻 14
附錄 34
參考文獻 References
Aleshina, L.A., Malinenko, V.P., Phouphanov, A.D., Jakovleva, N.M. “The short-range order of anodic amorphous oxide films of Ta and Nb,” J. Non-Cryst. Solids 87 (1986) 350-360.
Arsova, I., Arsov, L., Hebestreit, N., Anders, A., Plieth, W. “Electrochemical formation of anodic oxide films on Nb surfaces: ellipsometric and raman spectroscopical studies,” J. Solid State Electrochem. 11 (2007) 209-214.
Bhide, V., Husson, E., Gasperin, M. “Etude de niobates de structure GTB par absorption infra-rouge et diffusion raman,” Mater. Res. Bull. 15 (1980) 1339-1344.
Brauer, G. “Die oxyde des niobs,” Z. Anorg. Allg. Chem. 248 (1941) 1-31.
Cvelbar, U., Ostrikov, K., Drenik, A., Mozetic, M. “Nanowire sensor response to reactive gas environment,” Appl. Phys. Lett. 92 (2008) 133505.
Elliott, S.R. “Physics of amorphous materials,” 2nd ed. Longman Scientific & Technical, Essex, 1990 p. 24-25.
Filonenko, V.P., Zibrov, I.P. “High-pressure phase transitions of M2O5 (M= V, Nb, Ta) and thermal stability of new polymorphs,” Inorg. Mater. 37 (2001) 953-959.
Frevel, L.K., Rinn, H.W. “Powder diffraction standards for niobium pentoxide and tantalum pentoxide,” Anal. Chem. 27 (1955) 1329-1330.
Fu, Z.W., Kong, J.J., Qin, Q.Z. “Electrochemical and electrochromic properties of niobium oxide thin films fabricated by pulsed laser deposition,” J. Electrochem. Soc. 146 (1999) 3914-3918.
Gatehouse, B.M., Wadsley, A.D. “The crystal structure of the high temperature form of niobium pentoxide ,” Acta Cryst. 17 (1964) 1545-1554.
George, P.P., Pol, V.G., Gedanken, A. “Synthesis and characterization of Nb2O5@C core-shell nanorods and Nb2O5 nanorods by reacting Nb(OEt)5 via RAPET (reaction under autogenic pressure at elevated temperatures) technique,” Nanoscale Res. Lett. 2 (2007) 17-23.
Holland TJB, Redfern SAT (1997a) UNITCELL: a nonlinear least-squares program for cell-parameter refinement and implementing regression and deletion diagnostics. J Appl Cryst 30: 84.
Holland TJB, Redfern SAT (1997b) Unit cell refinement from powder diffraction data: the use of regression diagnostics. Mineralogical Magazine 61 65-77.
Huang, Y., Zhang, Y., Hu, X. “Structural, morphological and electrochromic properties of Nb2O5 films deposited by reactive sputtering,” Sol. Energy Mater. Sol. Cells 77 (2003) 155-162.
Ikeya, T., Senna, M. “Amorphization and phase transformation of niobium pentoxide by fine grinding,” J. Mater. Sci. 22 (1987) 2497-2502.
Ikeya, T., Senna, M. “Change in the structure of niobium pentoxide due to mechanical and thermal treatments,” J. Non-Cryst. Solids 105 (1988) 243-250.
Jehng, J.M., Wachs, I.E. “Structural chemistry and raman spectra of niobium oxides,” Chem. Mater. 3 (1991) 100-107.
Kato, K., Tamura, S. “Die kristallstruktur von T-Nb2O5,” Acta Cryst. B 31 (1975) 673-677.
Kikuchi, M., Kusaba, K., Bannai, E., Fukuoka, K., Syono, Y., Hiraga, K. “Observation of shock-induced phases of Nb2O5 single crystal under high-resolution electron microscopy,” Jap. J. Appl. Phys. 24 (1985) 1600-1606.
Lin, Z., Guo, Z., Sun, C. Fast Ionic Conductor—Fundamental, Materials and Applications, Shanghai Sciences and Technology Press, China, 1983 (in Chinese).
Liu, I.L. “Coarsening/coalescence and phase change of Al2O3 nanoparticles by PLA in air, vacuum and aqueous solutions with/without NaOH,” Ph.D. Thesis, National Sun Yat-sen University, 2010.
Liu, I.L., Lin, B.C., Chen, S.Y., Shen, P. “NaAlO2 and γ–Al2O3 nanoparticles by pulsed laser ablation in aqueous solution,” J. Phys. Chem. C 115 (2011) 4994-5002.
McConnell, A.A., Anderson, J.S., Rao, C.N.R. “Raman spectra of niobium oxides,” Spectrochimica Acta A 32 (1976) 1067-1076.
Orel, B., Maček, M., Grdadolnik, J., Meden, A. “In situ uv-vis and ex situ ir spectroelectrochemical investigations of amorphous and crystalline electrochromic Nb2O5 films in charged/discharged states,” J. Solid State Electrochem. 2 (1998) 221-236.
Ozer, N., Chen, D.G., Lampert, C.M. “Preparation and properties of spin-coated Nb2O5 films by the sol-gel process for electrochromic applications,” Thin Solid Films 277 (1996) 162-168.
Rodrigues, L.A., da Silva, M.L.C.P. “An investigation of phosphate adsorption from aqueous solution onto hydrous niobium oxide prepared by co-precipitation method,” Colloids Surf. A 334 (2009) 191-196.
Rosario, A.V., Pereira, E.C. “Influence of the crystallinity on the Li+ intercalation process in Nb2O5 films,” J. Solid State Electrochem. 9 (2005) 665-673.
Schafer, H., Breil, G. “Uber das system Nb2O5-Ta2O5-NbO2-TaO2-H2O-H2,” Z. Anorg. Allg. Chem. 267 (1952) 265-276.
Schafer, H., Schulte, F., Gruehn, R. “New modifications of Nb2O5,” Angew. Chem. Internat. Edit. 3 (1964) 511.
Schafer, H., Gruehn, R., Schulte, F. “The modifications of niobium pentoxide,” Angew. Chem. Internat. Edit. 5 (1966) 1-52.
Tamura, S. “High-pressure phase research on Nb2O5,” J. Mater. Sci. 7 (1972) 298-302.
Tanabe, K. “Catalytic application of niobium compounds,” Catal. Today 78 (2003) 65-77.
Varghese, B., Haur, S.C., Lim, C.T. “Nb2O5 nanowires as efficient electron field emitters,” J. Phys. Chem. C 112 (2008) 10008-10012.
Wachs, I.E., Chen, Y., Jehng, J.M., Briand, L.E., Tanaka, T. “Molecular structure and reactivity of the group V metal oxides,” Catal. Today 78 (2003) 13-24.
Waring, J.L., Roth, R.S., Parker, H.S. “Temperature-pressure phase relationships in niobium pentoxide,” J. Res. Nat. Bur. Stand. Sec. A Phys. Chem. 77 (1973) 705-711.
Wu, J., Li, J., Lu, X., Zhang, L., Yao, J., Zhang, F., Huang, F., Xu, F. “A one-pot method to grow pyrochlore H4Nb2O7-octahedron-based photocatalyst,” J. Mater. Chem. 20 (2010) 1942-1946.
Yan, C., Xue, D. “Formation of Nb2O5 nanotube arrays through phase transformation,” Adv. Mater. 20 (2008) 1055-1058.
Yang, Z.J., Li, Y.F., Wu, Q.B., Ren, N., Zhang, Y.H., Liu, Z.P., Tang, Y. “Layered niobic acid with self-exfoliatable nanosheets and adjustable acidity for catalytic hydration of ethylene oxide,” J. Catal. 280 (2011) 247-254.
Zhou, Y., Oiu, Z., Lu, M., Zhang, A., Ma, Q. “Preparation and spectroscopic properties of Nb2O5 nanorods,” J. Luminescence 128 (2008) 1369-1372.
張恩旗 “脈衝雷射剝熔蝕鈦箔及碎化TiO2粉末的效應及變化,” 國立中山大學99學年度碩士論文。
陳咨伶 “非晶質不含或含鋅矽石粉末之初期燒結與水中脈衝雷射碎化,” 國立中山大學99學年度碩士論文。
呂蕙荻 “錫石奈米顆粒之早期燒結及次微米粉末於水中的雷射碎化,” 國立中山大學99學年度碩士論文。
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