本研究結合time-stamped force-bias Monte Carlo (tfMC)方法與模擬退火過程，預測活性碳材料微觀結構的流程。透過該流程，本研究分別各建立三種密度為0.5、0.7、1.3 g/cm3的活性碳物理模型以及0.7、0.9、1.3 g/cm3的球型活性碳物理模型。其退火速率為每30及6,000個tfMC步階下降5K。並且個別分析其孔隙率、比表面積與孔徑分布。另外，我們對活性碳模型進行模擬拉伸，探討不同密度及不同退火速率活性碳之楊氏模數、極限抗拉強度，並探討其微觀結構破裂情形以及環數變化。對於球型活性碳進行模擬壓縮，探討其結構破壞的過程。其結構研究結果顯示活性碳和球型活性碳之比表面積會與密度成正比。然而孔隙率以及孔徑大小會與密度成反比值。隨著退火速率變慢其比表面積會變大，孔隙率會下降。在活性碳拉伸模擬中，其環數變化會由六碳環轉變成五碳環及四碳環，且由區域應變顯示其破裂地方會集中於碳壁的邊緣，並且會隨應變增加並朝垂直拉伸方向沿伸。在球型活性碳壓縮模擬中，由應力應變圖可發現球型活性碳內部結構，影響其在鬆弛階段的應變區間大小，當密度越小、退火速率越快其內部結構會越鬆散。透過本研究之模擬方法不僅提供了預測活性碳以及球型活性碳結構的方法，同時也探討其內部結構特性與機械性質，其結果對未來開發功能性活性碳提供一些有用的資訊。

Combining the time-stamped force-bias Monte Carlo and simulated-annealing methods, a structural prediction procedure for activated carbon (AC) and bead shape activated carbon (BAC) of different densities and quench rates were constructed. AC models were constructed, corresponding to densities of 0.5, 0.7, and 1.3 g/cm3 and BAC models were constructed, corresponding to densities of 0.7, 0.9, and 1.1 g/cm3. The quench rates were 5 K per 30 tfMC steps and 5 K per 6,000 tfMC steps, respectively. The structural properties of these models were examined, including porosity, specific surface area and pore distribution. In addition, the tensile and compress simulations were systematically applied to those AC and BAC models. In tensile simulation, the Young's modulus and the fracture of microstructures were also investigated. The specific surface area and Young's modulus are proportional to the density of AC, but the porosity and the main distribution of pore size are inversely related. The probability distribution of the ring size shows that six-atom rings translate to four- and five- atom ring during tensile simulation. The local shear strain analysis indicates that the fractures appear adjacent to the edge of the carbon wall frame in AC and will expand vertically along the tensile axis. In compress simulation, it found that in the low density and fast quench rate of BAC, there has sufficient space to relax the stress during the the compression and exhibit wide range of strain in relax region. This study not only constructs a structural prediction procedure of AC and BAC but also provides several detailed information of internal structure and mechanical property. The results can provide useful information on the development of functional activated carbon in the future.

目 錄
論文審定書. i
論文公開授權書. ii
致謝.....iii
中文摘要............... iv
Abstract ................. v
目 錄.................... vi
圖目錄........ viii
表目錄..... x
第一章 緒論.......... 1
1.1 研究動機與目的......................................... 1
1.2 活性碳(activated carbon)介紹................. 3
1.2.1 活性碳的結構.................................. 3
1.2.2 活性碳的吸附特性............ 5
1.2.3 活性碳的製備............... 6
1.3 活性碳的相關研究與應用之文獻回顧......... 8
1.4 本文架構....................... 12
第二章 模擬方法與理論介紹................. 13
2.1 分子力學方法 (molecular mechanics) ...... 13
2.1.1 共軛梯度法 (conjugate gradient method ) ...................... 13
2.2 tfMC (time-stamped force-bias Monte Carl) .................................. 15
2.3 勢能函數..................................................... 16
2.3.1 REBO 勢能 ......................................................................................... 16
2.3.2 AIREBO 勢能 ..................................................................................... 17
2.3.3 非鍵結三體勢能(Nonbonding 3-body harmonic potential) ............. 17
2.3.4 虛擬壁面............................................................................................ 18
第三章 數值模擬方法................................................................................................ 20
3.1 週期性邊界................................................................................................... 20
3.2 鄰近原子表列法........................................................................................... 21
3.2.1 截斷半徑法........................................................................................ 21
3.2.2 維理表列法........................................................................................ 22
3.2.3 巢室表列法........................................................................................ 23
3.2.4 維理表列法結合巢室表列法............................................................ 24
3.3 分子力學流程圖........................................................................................... 25
3.4 統計之參數計算........................................................................................... 26
3.4.1 分子表面網格 (Surface mesh)的建構 ............................................. 26
3.4.2 孔徑大小分佈.................................................................................... 27
vii
3.4.3 區域應變(Local shear strain)與von Mises stress 分析 .................... 28
3.4.4 原子級應力計算理論........................................................................ 29
第四章 結果分析與討論............................................................................................ 33
4.1 活性碳之物理模型....................................................................................... 33
4.1.1 活性碳物理模型................................................................................ 33
4.1.2 球型活性碳物理模型........................................................................ 37
4.2 活性碳之結構性質分析............................................................................... 41
4.3 拉伸及壓縮試驗與機械性質探討............................................................... 46
4.3.1 拉伸模型建立.................................................................................... 46
4.3.2 壓縮模型建立.................................................................................... 47
4.3.3 活性碳拉伸應力應變圖.................................................................... 48
4.3.4 球型活性碳壓縮應力應變圖............................................................ 50
4.3.4 活性碳結構於拉伸時的環數變化.................................................... 54
4.3.5 球型活性碳結構於模擬壓縮時的環數變化.................................... 57
4.3.6 活性碳結構於模擬拉伸時的區域應變及von Mises stress 分析 ... 60
第五張 結論與未來展望............................................................................................ 64
5.1 結論............................................................................................................... 64
5.2 未來展望....................................................................................................... 66
參考文獻...................................................................................................................... 6758

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