MgO-Fe2O3二元成分系統於大氣及水中脈衝雷射剝熔蝕之相行為

Phase behavior of MgO-Fe2O3 binary by PLA in air v.s. water

林宗義

水中脈衝雷射 ； 大氣脈衝雷射 ； 相變化 ； 特殊晶界 ； 奈米凝聚物 ； 層狀結構 ； 超晶格 ； 順晶 ； 電子顯微鏡 ； (MgXFe1-X)O ； 光譜 ； MgFe2+XO4 ； electron microscopy ； PLA ； absorption spectrum ； nanocondensates ； phase transformation ； PLAL ； MgFe2+XO4 ； paracrystal ； (MgXFe1-X)O ； special grain boundary ； lamellae

中山大學材料與光電科學學系研究所學位論文

2014年

碩士

沈博彥

繁體中文

本實驗利用特定之Nd-YAG脈衝雷射參數於大氣及水中對MgO-α-Fe2O3二元成分系統(摩爾比9:1為主, 1:1, 1:9為輔)固溶粉末與固溶燒結圓碇靶材進行轟擊，並且使用X光繞射、電子顯微鏡與振動/吸收光譜，觀察在此動態高溫高壓以及急熱急冷實驗條件下的產物，尤其著重於比較不同環境情況下鎂方鐵礦，亦即(MgXFe1-X)O及鎂鐵礦(MgFe2+XO4)結晶凝聚物之相對穩定性、形狀、壓縮內應力、與缺陷微觀組織。 結果發現於大氣中，而且脈衝雷射功率1.5x107 W/cm2的條件下轟擊9:1成份圓碇靶材的時候，具有岩鹽結構(簡稱R)內含順晶缺陷的鎂方鐵礦為相對穩定，其奈米凝聚物大致以立方體呈現，具有發達的{100}、{110}表面，以及次要的{111}表面與階檻，藉以聚簇成鍊狀，並且貼合形成[110]A//[100]B的(11 ̅1 ̅)A//(001)B異質晶界以及與少量尖晶石(S)顆粒聚簇形成(100)R/(310)S的異質晶界使(01 ̅1)R//(001)S。此外，經由急速凝固而形成的鎂方鐵礦則為球狀，其粒徑較大。根據吸收光譜量測，這些綜合奈米凝聚物以及次微米凝固顆粒物質之最小能隙值約為~3 eV。至於在雷射較高功率1.67x1011 W/cm2的條件下，針對MgO-α-Fe2O3=9:1之圓碇靶材進行轟擊，奈米鎂方鐵礦凝聚物更是穩定，以具有發達的{100}、{110}表面以及極性{111}階檻的立方體呈現，而且均勻散佈，奈米顆粒間易形成雙晶具有整合{111}或非整合異質界面，甚或{110}70.5°扭轉晶界，內部除了有壓縮內應力(高達2.5 GPa)之外，也出現點缺陷集合的波浪狀順晶排列，其週期約為2nm，根據吸收光譜，其最小能隙值亦約為~3eV。至於1:1或1:9成份圓碇靶材經脈衝雷射FR-1064nm-1100mJ-240μs剝熔蝕的時候，具有鎂鐵礦尖晶石結構的MgFe2+XO4則相對穩定，最小能隙值約為2.5 至3eV。 而MgO:Fe2O3=9:1反應固溶為 (MgXFe1-X)O及MgFe2+XO4之粉末於水中進行脈衝雷射模式為Q1064-600mJ-16ns (功率1.25x1011 W/cm2)的轟擊，則形成球狀奈米鎂方鐵礦及含鎂之α-Fe2O3，以及水合非晶態層狀物，或聚簇形成球狀核殼奈米結構，其中核為(MgX Fe1-X)O與MgFe2+XO4尖晶石平行磊晶共存，周圍環繞的層狀殼為雙氫氧化物(lamellar layer double hydroxide)。這些岩鹽與尖晶石結構共生的凝聚物常常聚簇成具有高角度彎曲晶界的多晶球狀顆粒。

This research is about Nd-YAG pulsed laser ablation (PLA) of MgO-Fe2O3 (M9F1, i.e. molar ratio 9:1 and additional M1F1, M1F9 for comparison) solid solution powder in water vs. sintered disk in air in order to fabricate alloyed condensates and particulates of rock salt- (i.e. magnesiowüstite,(MgXFe1-X)O) and/or spinel- type (i.e. magnesioferrite, MgFe2+xO4) for X-ray diffraction, electron microscopy and vibration/absorption spectroscopy characterizations. The product by PLA of the sintered M9F1 disk in air turned out to be predominant magnesiowüstite in the form of solidified spherical particulate and condensed nanoparticles with significant internal compressive stress, paracrystalline distribution of defect clusters, and well- developed {100}, {110} faces and {111} facets for (hkl)-specific coalescence as single crystal or twinned bicrystal with coherent {111} interface, incoherent ledge and/or {110} 70.5o twist boundary and A/B bicrystal with (11 ̅1 ̅)A/(001)B interface having [110]A//[100]B. By contrast, PLA of M9F1 solid solution powder in water caused mainly the formation of turbostratic LDH (layer double hydroxide)-encapsulated spherical polycrystals with intimate intergrowth of parallel epitaxial magnesiowüstite and magnesioferrite in domains separated by high-angle grain boundary. The additional attempt on PLA of M1F1 and M1F9 in air or water caused rather complicated phase assemblage, i.e. predominant MgFe2+XO4,minor (MgXFe1-X)O derivatives and α-Fe2O3.The nanoparticles as-formed by PLA under a dynamical high-temperature high-pressure condition in air have a minimum band gap around 3 eV, which can be tailored lower by decreasing MgO content for potential opto-electronic catalytic applications.

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