論文提要(中)

本論文是以穿透式電子顯微鏡(TEM)、掃瞄式電子顯微鏡(SEM)配合X光繞射分析(X-ray diffraction)，來研究在Ni1-xO-Co1-xO-ZrO2系統中，成分與固溶比例不同的三種二元固溶燒結體，在高溫時由相互擴散所引發的奈米孔洞(nanopores)、布朗運動(Brownian motion)、解理與癒合(cleaving and healing)、缺陷聚集(defect clusters)以及複合材微觀組織之演化。此三種二元固溶燒結體分別為:莫耳比1:2的Ni1-xO/Co1-xO (N1C2)系統;莫耳比1:99的ZrO2/Co1-xO (Z1C99)系統;以及莫耳比1:9的ZrO2/Ni1-xO (Z1N9)系統。

在N1C2系統中，Ni1-xO與Co1-xO粉末於1000oC反應燒結可得單相均質之岩鹽結構(rock salt-type structure)固溶體(Ni0.33Co0.67)1-dO，而後續720oC的退火則使得尖晶石(spinel)顆粒析出在差排和晶界上，形成(NimCo1-m)1-δO之岩鹽相與含鎳之Co3-δO4尖晶石相複合材。由於燒結時緻密化的不完全，次微米的孔洞散佈在岩鹽結構基材之晶界上與晶粒內;而退火時因尖晶石顆粒的析出需要快速排出鎳離子，使得大量奈米孔洞藉由Kirkendall效應在尖晶石相中析出。這些細長且成列的中孔徑孔洞(mesopores)具有{100}之晶面，其形成得利於尖晶石相具有相對較低的平衡空孔濃度(equilibrium vacancy concentration)，以及在垂直岩鹽相與尖晶石相界面之拉伸應力影響下，快速之淨空孔流量。此類非計量過度金屬氧化物中成列之中孔徑孔洞，在熱障塗層(thermal barrier bond coating)與非均質觸媒(mass-transport limited heterogeneous catalysis)等領域極具潛力。

而在Z1C99與Z1N9系統中，對稱性較低的非立方晶(non-cubic) ZrO2顆粒在高溫(1650oC)燒結時於高對稱性的立方晶(cubic) Ni1-xO/Co1-xO岩鹽結構晶粒內，可發生晶向轉動與形狀改變，進而達成晶向關係。由TEM的觀察，可發現次微米級的正方晶/斜方晶(tetragonal/monoclinic) ZrO2顆粒與Ni1-xO/Co1-xO達成三種不同的晶向關係:(1)平行磊晶(parallel topotaxy);(2)共晶式磊晶(eutectic topotaxy):[100]Z//[111]C,N, [010]Z//[0 1]C,N;(3)偶發式磊晶(occasional topotaxy):[100]Z//[111]C,N, [01 ]Z//[0 1]C,N。其中，平行磊晶之ZrO2顆粒可與基材形成低能量的{100}Z/C,N與{111}Z/C,N界面，而ZrO2顆粒由偶發式磊晶調整晶向至更低能量的共晶式磊晶，可藉由特定之(100)Z/(111)C,N界面來達成。此種在高溫時，由兩相間特定晶向關係下之低能量界面來趨動顆粒轉動，進而與基材達成晶向關係的現象，可以布朗運動(Brownian-type rotation)來描述之。而岩鹽相晶界之通過(bypassing)與脫離(detachment)，亦可使沿晶(intergranular)之ZrO2顆粒發生轉動與形狀變化。

再者，利用高解析的穿透式電子顯微鏡，可研究在Z1C99系統中，因ZrO2之多形性(polymorphism)所引發Co1-xO基地之解理、自發性癒合及析出的現象。實驗結果顯示，試片冷卻時Co1-xO基材沿{100}與{110}晶面發生解理，且隨即由平行磊晶之ZrO2和Co3−δO4尖晶石顆粒自我癒合。由於尺寸效應(size effect)與基材約束(matrix constraint)，於解理面析出之奈米尺寸(nanometer-size) ZrO2顆粒得以在室溫維持正方晶結構。

本研究同時觀察，當Zr4+離子於高溫(1650oC)時溶入Ni1-xO/Co1-xO之多晶燒結體，可增加Z1C99與Z1N9試片內部之缺陷濃度，進而造成缺陷集合的順晶排列(paracrystalline array)。此外，當試片自高溫爐冷至900oC以下時，析出溶入Zr4+的Co3-δO4尖晶石顆粒中亦可觀察到依順晶排列的缺陷集合，這些含有順晶(paracrystal)的尖晶石相主要是析出在ZrO2與Co1-xO之界面，以及Co1-xO基材之解理面與差排處。本實驗中順晶的形成是由電荷補償(charge-compensating)與體積補償(volume-compensating)效應，使得四個八面體位置空孔(octahedral vacant site)環繞一個佔據四面體間隙位置(tetrahedral interstitial site)的Co3+離子，形成4:1的缺陷集合，並由此為單位形成規則聚集而稱之。其中，溶入Zr4+的Ni1-xO、Co1-xO及Co3-δO4內部順晶分佈的間距分別為其晶格常數之3.3、2.9與4.9倍，而Zr4+的溶入可使得Co3-δO4中之缺陷集合間距縮小為不含Zr4+時的0.98倍，若與母相Co1-xO相較，則溶入Zr4+的Co3-δO4順晶分佈間距為母相的3.4倍。

Abstract
This research is designed to investigate the occurrence of interdiffusion-induced mesopores, Brownian motion, cleaving and healing and defect clusters in three binary composites, i.e. Ni1-xO/Co1-xO, Ni1-xO/ZrO2 and Co1-xO/ZrO2 of the Ni1-xO-Co1-xO-ZrO2 system.

Firstly, the (NimCo1-m)1-δO/Ni-doped Co3-dO4 composites prepared by reactive sintering Ni1-xO and Co1-xO powders (1:2 molar ratio, denoted as N1C2) at 1000oC with or without further annealing at 720oC in air were studied by X-ray diffraction and electron microscopy to clarify the formation mechanism of mesoporous spinel precipitates. Submicron-sized inter- and intragranular pores, due to incomplete sintering and grain boundary detachment, prevails in (Ni0.33Co0.67)1-δO protoxide with rock salt structure; whereas nanosize pores due to Kirkendall effect were restricted to the spinel precipitates having Ni component progressively expelled upon annealing. A rapid net vacancy flux and a tensile misfit stress perpendicular to the protoxide/spinel interface caused the formation of elongated and aligned {100}-faceted mesopores in the spinel precipitates with a relatively low equilibrium vacancy concentration. Aligned mesopores in diffusion zone of nonstoichiometric metal oxides have potential applications on thermal barrier bond coating and mass-transport limited heterogeneous catalysis.

Also, this thesis deals with the reorientation and shape change of low-crystal-symmetry (non-cubic) ZrO2 within the high-crystal-symmetry grains of Co1-xO/Ni1-xO cubic rock salt-type structure. ZrO2/Co1-xO composites 1:99 and ZrO2/Ni1-xO composites 1:9 in molar ratio were sintered and then annealed at 1650oC for 24 and 100 h in air to induce reorientation of the embedded particles. Transmission electron microscopic observations in both systems indicated that the submicron tetragonal/monoclinic (t/m) ZrO2 particles fell into three topotaxial relationships with respect to the host Co1-xO/Ni1-xO grain: (1) parallel topotaxy, (2) “eutectic” topotaxy i.e. [100]Z//[111]C,N, [010]Z//[0 1]C,N and (3) “occasional” topotaxy [100]Z//[111]C,N, [01 ]Z//[0 1]C,N. The parallel topotaxy has a beneficial low energy for the family of {100}Z/C,N and {111}Z/C,N interfaces. The change from the occasional topotaxy to an energetically more favorable eutectic topotaxy was likely achieved by a rotation of the ZrO2 particles over a specific (100)Z/(111)C,N interface. Brownian-type rotation is probable for the embedded t-ZrO2 particles in terms of anchorage release at the interphase interface with the Co1-xO/Ni1-xO host. Detachment or bypassing of rock salt type grain boundaries could also cause orientation as well as shape changes of intergranular ZrO2 particles.

Zirconia-polymorphism-induced cleaving and spontaneous healing by precipitation was studied in Co1-xO polycrystals containing a dispersion of ZrO2 particles. Conventional, analytical, and high-resolution transmission electron microscopy indicated that the Co1-xO matrix cleaves parallel to {100} and {110} planes and heals itself by co-precipitation of parallel-topotaxial ZrO2/Co3-δO4 particles upon cooling. Due to size effect and matrix constraint, nanometer-size ZrO2 precipitates at cleavages were able to retain tetragonality upon further cooling to room temperature.

Paracrystalline array of defect cluster was shown to form in Zr-doped Ni1-xO and Co1-xO polycrystals while prepared by sintering at relative high temperature, i.e., 1650oC to increase the defect concentration. Paracrystalline array of defect clusters in Co3-δO4 spinel structure also occurred when doped with Zr4+ at high temperature or cooled below 900oC to activate oxy-precipitation of Co3-dO4 at dislocations. transmission electron microscopic observations indicated the spinel precipitate and its paracrystal predominantly formed at the ZrO2/Co1-xO interface and the cleavages/dislocations of the Co1-xO host. Defect chemistry consideration suggests the paracrystal is due to the assembly of charge- and volume-compensating defects of the 4:1 type with four octahedral vacant sites surrounding one Co3+-filled tetrahedral interstitial site. The spacing of paracrystalline distribution is 3.3, 2.9 and 4.9 times the lattice parameter for Zr-doped Ni1-xO, Zr-doped Co1-xO and Zr-doped Co3-dO4. This spacing between defect clusters is about 0.98 times that of the previously studied undoped Co3-dO4. There is much larger (3.4 times difference) paracrystalline spacing for Zr-doped Co3-δO4 than its parent phase of Zr-doped Co1-xO.

Contents
誌謝 I
論文提要(中) II
Abstract V
Contents VIII
List of Figures XI
Chapter 1. Introduction
1.1. Mesoporous materials 1
1.2. The Kirkendall effect 3
1.3. Nonstoichiometry and defect clusters of rock salt-type structure 5
1.3.1. Fe1-xO
1.3.2. Ni1-xO
1.3.3. Co1-xO and Co3-dO4
1.4. Transformation toughening of ceramics 10
1.5. Shape of rock-salt type and fluorite-type oxides 11
1.5.1 Co1-xO, Ni1-xO and ZrO2 and their interfaces
1.5.2. Shape change of intragranular ZrO2 particles in ZDC
1.6. Scope of this research 15

Chapter 2. On the Mesoporous Spinel Precipitation in (Ni0.33Co0.67)1-dO Protoxide: Implications for Interdiffusion/Oxyexsolution-Induced Mesopores
2.1. Introduction 16
2.2. Experimental 18
2.3. Results 19
2.3.1. XRD
2.3.2. TEM
2.4. Discussion 22
2.4.1. Sintering relic pores in protoxide
2.4.2. Uneven Ni/Co/O flux for local NiO/CoO diffusion couple
2.4.3. Nanosized Kirkendall pores in the spinel
2.4.4. Specific diffusion path at 1000oC vs. 720oC in the Ni-Co-O ternary system in air
2.4.5. Controlled vacancy relaxation at pore surface
2.5. Concluding remarks 28
Figures 29

Chapter 3. Interface-Specific Reorientation and Shape Change of Embedded Tetragonal ZrO2 Particles within Rock Salt-type Co1-xO/Ni1-xO Grains
3.1. Introduction 42
3.2. Experimental 44
3.3. Results 45
3.3.1. XRD and SEM
3.3.2. TEM
3.4. Discussion 50
3.4.1. Phase transformation of embedded ZrO2 particles
3.4.2. Size-dependent orientation change of intragranular particles
3.4.3. Energy cusps specification for embedded particles
3.4.4. Orientation change of intergranular t-ZrO2 particles
3.5. Conclusions 57
Figures 58

Chapter 4. Transformation-Enabled Cleaving and Healing in Zirconia Dispersed Co1-xO
4.1. Introduction 87
4.2. Experimental 88
4.3. Results 89
4.3.1. SEM observations of chemically etched specimens
4.3.2. TEM observations
4.4. Discussion 92
4.4.1. Cleaving-healing of Co1-xO with embedded ZrO2 particles
4.4.2. t→m transformation of ZrO2 precipitates at healing cleavages
4.4.3. Implications to thermal-cycling behavior of ZDC
4.5. Conclusions 96
Figures 98

Chapter 5. Defect cluster of Zr4+ Dissolved Ni1-xO, Co1-xO and Co3-dO4 Spinel
5.1. Introduction 106
5.2. Experimental 108
5.3. Results 109
5.3.1. SEM and XRD
5.3.2. TEM
5.4. Discussion 113
5.4.1. Defect chemistry of Ni1-xO polycrystals
5.4.2 Defect chemistry of Co1-xO polycrystals
5.4.3. Heterogeneous nucleation of Zr-doped paracrystals
5.4.4. Spacing between defect clusters
5.5. Conclusions 121
Figures 123

References 131
Appendix I XXII
Appendix II XXII

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