核能級石墨因具等向性、高熱導率、低熱膨脹係數和較佳的中子特性，故被擇為超高溫氣冷式反應器(Very High Temperature Gas-Cooled Reactor, VHTR)的緩速劑和爐心結構材料。世界各國同時針對傳統和新型的核能石墨測試，探討其應用於超高溫氣冷式反應器不同運轉環境下的變化。其中最嚴重的反應器運轉事故之一為進氣事故(Air-ingress Accident)，當高溫氣冷式反應器破管，爐心溫度可能達到1600 ℃，爐心石墨石墨暴露在含氧環境下並發生嚴重氧化，進而影響石墨機械性質，造成爐心崩塌和輻射物質外洩等事故。因此，完整的測試和研究核能石墨在高溫下於不同氣體環境的氧化機制，對於可靠的預測核能石墨運用於高溫氣冷式反應器至關重要。
本論文討論核能級石墨在超高溫度區間下氧化行為的變化，並基於量測結果比較氧化抗性較佳的核能級石墨的抗氧化性。實驗選擇八種核能級石墨進行氧化測試，包含IG 110，IG-430，MA，MB，ATR-2E，PGA，G347A和G458A，並使用三區加熱爐管架設動態氧化測試系統，量測核能級石墨在超高溫度區間(700-1600 ℃)於不同氣體環境下質量損失，以此計算氧化速率和活化能。本實驗結果提供詳盡的氧化數據以供事故模擬使用。
研究亦發現石墨在超高溫度的氧化趨勢推翻過去文獻預測，文獻推斷氧化速率在1100 ℃後達到飽和，但本實驗結果顯示在溫度高於1200 ℃後，氧化速率再度顯著上升，而此趨勢直到溫度達1500 oC後才趨緩。八種核能級石墨的氧化測試結果證實此發現，不同核能級石墨雖氧化趨勢相近但氧化速率仍具差異，只細晶粒級別的石墨之間在900 ℃以上氧化速率的差異較小。
本研究亦針對不同溫度下氧化的石墨進行表徵研究，進一步探討石墨在不同溫度區間的氧化機制。氧化前後的試片以場發射掃描式電子顯微鏡(FEG-SEM)觀察表面形貌，以水銀測孔儀(Mercury Porosimetry)和氦氣密度分析儀(Helium Pycnometry)分析孔洞分佈，Ｘ光繞設儀(XRD)和拉曼光譜儀(Raman Spectrometry)分析材料晶體常數，化學分析電子能譜儀(XPS)和霍氏轉換紅外光譜儀(FTIR)測量表面或界面的電子結構，以瞭解原子的鍵結狀態。在溫度高於1200 ℃觀察到石墨材料中填充物(Filler Particles)的表面型態和微晶結構的變化，其變化與氧化速率呈正相關。
本論文亦在不同溫度區間下討論石墨組成性質和抗氧化性的關係，以及可能影響氧化行為的內在因子，此外單獨針對溫度影響造成的石墨微結構變化做深入探討。

Graphite is used in the gas-cooled nuclear reactors as both a neutron moderator and structural components, while both traditional and novel graphite materials are being studied worldwide for applications in Generation IV reactors. One of several accident scenarios for VHTRs is caused by a depressurisation accident, also known as an air ingress accident. These can occur during an air ingress accident when the fuel temperature is likely to reach 1600 ℃ when atmospheric air may ingress into the reactor core and the graphite components are predicted to be severely oxidised thereby changing their mechanical properties. Therefore, a comprehensive investigation of the oxidation mechanisms of graphite in various gaseous environments at elevated temperatures is essential for the reliable prediction of the behaviour of graphite under such conditions.
This research study investigated of graphite oxidation behaviour under conditions where air ingresses accidentally at very high temperatures. The aim, therefore, was to investigate the oxidation behaviour of proposed graphite grades for VHTRs and to recommend the appropriate form for use in VHTRs based on levels of oxidation resistance. In addition, related characterisation examinations for graphite oxidised at different temperatures were conducted, in order to understand the detailed mechanisms of graphite oxidation corresponding to the simulation of actual graphite components.
The materials selected were nuclear graphite grade IG-110, IG430, MA, MB, ATR-2E, PGA, G347A, and G458A. A dynamic oxidation system was constructed with a 3-zone furnace. The oxidation characteristics of graphite pellets in both air-rich environments and helium-containing environments at temperatures ranging from 700 to 1600 ℃ were investigated. The oxidation rates and activation energies were determined based on mass loss measurements in a series of oxidation tests. Although the thermal oxidation mechanism was previously considered to be the same for all temperatures higher than 1000 ℃, the significant increases in oxidation rates observed at very high temperatures suggest that the oxidation behaviour of the selected graphite materials at temperatures higher than 1200 ℃ is different. In addition, it was discovered that, at temperatures above 900 ℃, the difference in oxidation behaviour between fine grain graphite grades was less.
The surface microstructure of each graphite pellet sample was characterized by Scanning Electron Microscopy, Mercury Porosimetry, Helium Pycnometry, Raman Spectroscopy, X-ray Diffraction, Fourier Transform Infrared Spectroscopy and X-ray Photoelectron Spectroscopy, before and after oxidation. An overall comparison of surface morphology, pore structure, crystallite structure, and surface functional group was revealed. The changes in surface morphology and crystallite structure of the filler particles in the graphite materials were observed at temperatures above 1200 ℃.
This study also demonstrates the relationship between graphite properties and oxidation resistance, and possible intrinsic factors that contribute to oxidation at different temperature ranges, and these are discussed taking into account the dominant role played by temperature.

摘要 i
Abstract iii
Acknowledgements v
Table of Contents vii
List of Tables xii
List of Figures xiii
1 Introduction 1
1.1. Background 1
1.2 The Aims and Objectives of the Study 3
2 Literature Review 4
2.1 Very High-Temperature Gas-Cooled Reactors 4
2.1.1 History 5
2.1.2 Core Design of VHTRs 6
2.1.3 Reactor Structural Design 8
2.1.4 Coolant Properties 9
2.1.5 Reactor Safety Design 11
2.2 Air Ingress Accident 11
2.3 Nuclear Graphite 15
2.3.1 Basic Structure and Properties 16
2.3.2 Manufacturing Process 18
2.4 The Theory of Graphite Oxidation 24
2.5 Thermal Oxidation Behaviour of Nuclear Graphite 26
2.5.1 Oxidation on Atomic-scale 27
2.5.2 Oxidation on the Micro-scale 29
2.5.3 Oxidation on Macro-scale 31
2.6 Past Graphite Oxidation Studies at High Temperatures 34
2.7 Summary 38
3 Methods and Materials 39
3.1 Materials 39
3.1.1 Introduction 39
3.1.2 Specimen Preparation 41
3.2 Oxidation Test System 42
3.2.1 Oxidation System Setup 42
3.2.2 Experimental Procedures 44
3.3 Oxidation Behaviour Analyses 48
3.3.1 Determination of Oxidation Rate 48
3.3.2 Determination of Activation Energy 48
3.3.3 Bulk Density Profile 49
3.4 Characterisation Techniques 51
3.4.1 Scanning Electron Microscopy (SEM) 53
3.4.2 Optical Microscopy 57
3.4.3 Mercury Porosimetry 60
3.4.4 Helium Pycnometry 62
3.4.5 X-Ray Diffraction (XRD) 62
3.4.6 Raman Spectroscopy 65
3.4.7 X-ray Photoelectron Spectrometry (XPS) 68
3.4.8 Fourier Transform Infrared Spectroscopy (FTIR) 69
4 Thermal Oxidation Behaviour 73
4.1 Oxidation Rate 73
4.1.1 The Effect of Temperature 76
4.1.2 Discussion of the Reliability of the Oxidation Test 79
4.1.3 The Effect of Various Inert-Gas Environments 83
4.2. Activation Energy 89
4.3 Bulk Density Profile 92
4.4 Summary 97
5 Surface Morphologies of Oxidised Graphite 99
5.1 Optical Microscopy (OM) 99
5.2 Scanning Electron Microscopy (SEM) 104
5.2.1 IG-110 and IG-430 104
5.2.2 MA and MB 110
5.2.3 PGA and ATR-2E 117
5.3 Analysis 121
5.3.1 Roughness 121
5.3.2 Volume Reduction of Filler Particles 122
5.4 Summary 128
6 Characterisation of Pore Structure 129
6.1 Mercury Porosimetry 129
6.2 Surface porosity 133
6.3 Helium Pycnometry 140
6.4 Summary 142
7 Characterisation of Crystal Structure 143
7.1 X-Ray Diffraction (XRD) 144
7.2 Raman Spectroscopy 150
7.2.1 Preliminary Measurements 150
7.2.2 Mapping Measurements 156
7.2.2.1 IG-430 Specimens Oxidised in Dry Air 156
7.2.2.2 IG-430 Specimens Oxidised in 10%O2 164
7.2.3 Specific Measurements 165
7.3 Summary 175
8 Characterisation of Surface Chemical Compositions 176
8.1 Energy Dispersive Spectroscopy (EDS) 176
8.2 X-ray Photoelectron Spectrometry (XPS) 178
8.2.1 Qualitative and Quantitative Analysis 180
8.2.2 Chemical-state Analysis 182
8.2.3 Catalytic effect of Aluminium 185
8.3 Fourier Transform Infrared Spectroscopy (FTIR) 187
8.4 Summary 195
9 General Discussions 197
9.1 Oxidation Mechanism at Very High Temperatures 197
9.1.1 Microscopic Scale 200
9.1.2 Crystallite Scale 203
9.2 Intrinsic and Extrinsic Factors for Thermal Bulk Oxidation 207
9.3 Graphite Oxidation occurring in an Air Ingress Accident 211
10 Conclusions and Future Work 216
10.1 Conclusions 216
10.2 Future Work 218
References 221

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