我們可以利用固態有機金屬的前驅物，經由一個從未報導過的"
微波電漿" 法製備出良好石墨層包覆的金屬碳奈米顆粒，並且沒有碳
管副產物的出現。微波電漿的產生可藉由在聚焦式微波爐中，矽碎片
或金屬絲的吸收微波。石墨層包覆的鐵奈米顆粒的特徵性質可由不同
的光譜所測量而得。石墨層包覆的鐵奈米顆粒的順磁性可由超導量子
干涉儀所測得，並顯示有大約115 高斯的矯頑力。我們可以進一步將
這些磁性奈米顆粒進行表面官能基化，使其帶上酸根或胺根，其水中
溶解度可達每升五百毫克，並且在水中不失去其磁性。我們從電子顯
微鏡中得知，這些磁性奈米顆粒表面上寡聚合物的分佈並不均勻，而
是應力較大的區域比較平緩的區域會有較多的接枝。除了鐵以外，鎳
和鈷金屬亦可由類似的方是被包覆在石墨層中。

We have demonstrated that the well graphitized core-shell
iron/carbon nanoparticles (Fe@CNPs) were produced via an
unprecedented "microwave arcing" process from solid metallocene precursors without co-formation of carbon nanotubes. Microwave arcing was generated by microwave absorption of and subsequent discharging between small silicon pieces or short metal wires in a focused microwave oven. Fe@CNPs were well-characterized by various spectroscopic measurements. Saturation magnetization measurement shows that the as-produced core-shell Fe@CNPs are ferromagnetic in nature with a coercivity value of ~ 115 Gauss. The Fe@CNPs were surface functionalized to have either carboxylate or amine functionalities with a water solubility of ~ 500 mg/L and without losing the magnetic
properties. The distribution of surface grafted oligomers indicates that the chemical reactivity of the outmost graphene shell is not the same at different locations, with highly strained regions having higher reactivity than less curved regions. Core-shell Ni/ or Co/carbon nanoparticles can also be prepared in a similar way.

Chapter 1 Introduction and Background...1
1.1 Carbon nanotubes...1
1.2 Structure of carbon nanotubes...3
1.3 Production of the carbon nanotube...4
1.3.1 Arc discharge...4
1.3.2 Laser ablation...5
1.3.3 Chemical vapor deposition (CVD)...6
1.4 Functionalization of carbon nanotubes...9
1.5 Carbon nanoparticles...10
1.5.1 Carbon nanocapsule and carbon onion...10
1.5.2 Graphite encapsulated metal nanoparticle...10
1.6 References...13
1.8 Figure caption...17
Chapter 2 Solid State Microwave Arcing Induced Formation and Surface Functionalization of Core-Shell Metal/Carbon Nanoparticles...25
2.1 Introduction...25
2.2 Experiment...28
2.2.1 Microwave arcing process...28
2.2.2 Surface functionalization...29
2.2.3 Synthesis of Cobalt nanoparticles...30
2.2.4 Preparation of graphite encapsulated cobalt nanoparticles...30
2.2.5 In situ XRD measurement...31
2.3 Materials and characterization...31
2.3.1 Materials...31
2.3.2 Charcterization methods...32
2.4 Results and discussion...33
2.4.1 Characterization of graphite encapsulated iron nanoparticles prepared from solid state focused microwave arcing process...33
2.4.2 Surface functionalization of core-shell iron/carbon
nanoparticles...35
2.4.3 Graphite encapsulated cobalt nanoparticles...39
2.4.4 Growth mechanism...42
2.5 Conclusion...43
2.6 Reference...43
2.7 Figure caption...49
Chapter 3 In-situ observation of graphite Layers generation and boundary Retraction of metal nanoparticles during Formation of Carbon Nanocapsules...60
3.1 Introduction...60
3.2 Experiment...63
3.2.1 Synthesis of Nickel nanoparticles...63
3.2.2 Synthesis of iron nanoparticles...64
3.2.3 Fe or Ni Nanoparticles +C60/70 mixture...65
3.2.4 Synthesis of iron encapsulated carbon nanoparticles...65
3.3 Materials and characterization...66
3.3.1 Materials...66
3.3.2 Characterization methods...66
3.4 Results and discussion...67
3.4.1 Growth of graphene layers from a Fe3C nanoparticle (Fe3C NP)...67
3.4.2 Growth of graphene layers from FeNPs-C60/70system...75
3.4.3 Growth of graphene layers from NiNPs-C60/70system...77
3.4.4 Retraction of disordered surface metal atoms ...79
3.4.6 Internal catalysis & Retraction of surface boundary atoms...79
3.4.5 "Surface melting-internal graphene layer" growth model...80
35 Conclusion...84
3.6 References...85
3.7 Figure caption...89
Chapter 4 Heteroatom Effect of Solid State Microwave Arcing Process...99
4.1 Introduction...99
4.2 Experiment...102
4.2.1 Synthesis of heteroatom doped carbon nanotubes...102
4.3 Materials and characterization...103
4.3.1 Materials...103
4.3.2 Characterization methods...103
4.4 Results and discussion...105
4.4.1 Characterization of boron doped MWCNTs produced from
triphenylborine...105
4.4.2 Characterization of boron doped MWCNTs produced from
boron oxide (B2O3)...109
4.4.3 Characterization of phosphorus doped MWCNTs produced
from triphenylphosphine...111
4.4.4 Electrical resistance measurement of boron and
phosphorus-doped MWCNTs...116
4.4.5 The morphology of the product was incorporated by
Sulfur...117
4.5 Conclusion...119
4.6 References...121
4.8 Figure caption...126
Chapter 5 Growth Mechanism of vertically aligned carbon nanotube arrays...149
5.1 Introduction...149
5.2 Experiment...153
5.3 Materials and characterization...154
5.3.1 Materials...154
5.3.2 Characterization methods...154
5.4 Results and discussion...155
5.4.1 Growth of Vertically Aligned Carbon Nanofiber Array :
Temperature Effect & Residual Gas Effect...155
5.4.2 Growth of Vertically Aligned Carbon Nanofiber Array :
Substrate Effect...160
5.4.3 Growth Mechanism of Vertically Aligned Carbon Nanofiber
Array...164
5.5 Conclusion...167
5.6 References...168
5.7 Figure caption...174

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