第五章 結論與未來展望
5.1 未來展望
在基材中添加石墨烯除了提升奈米複合材料整體之楊氏係數、玻璃轉 換溫度與熱膨脹係數等性質外，石墨烯本身具有良好的導電性與導熱性。
因此本研究未來將討論高分子的幾何與排列對於奈米複合材料導電性與導 熱性之影響。
50
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56
附 表
表 1 原子代號與原子質量[36]
原子種類 原子代號與狀態描述 原子質量
碳(Carbon)
C_2 :與氧以雙鍵連結
12.011 C_R :構成苯環之碳
氫(Hydrogen) H_ :接於碳上的氫 1.008
氧(Oxygen)
O_2 :與碳以雙鍵連結
15.994 O_3 :與碳以單鍵連結
氮(Nitrogen) N_3 :與碳以單鍵連結 14.0067
57
表 2 凡得瓦勢能參數表[36]
原子種類
(Kcal/mol) (Å)
碳(C_R、C_2) 碳(C_R、C_2) 0.0951 3.4730 氫(H_) 氫(H_) 0.0152 2.8464 氧(O_2、O_3) 氧(O_2、O_3) 0.0957 3.0332 氮(N_3) 氮(N_3) 0.0774 3.2626 碳(C_R、C_2) 氫(H_) 0.0380 3.1597 碳(C_R、C_2) 氧(O_2、O_3) 0.0954 3.2531 碳(C_R、C_2) 氮(N_3) 0.0858 3.3678 氫(H_) 氧(O_2、O_3) 0.0381 2.9398 氫(H_) 氮(N_3) 0.0343 3.0545 氧(O_2、O_3) 氮(N_3) 0.0816 3.1479
58
表 3 延展鍵結勢能參數表[36]
Kr (Kcal/mol-Å2) r0 (Å)
N_3－C_R 700 1.362
N_3－C_2 700 1.392
C_R－C_2 1050 1.360
C_R－C_R 1050 1.390
C_R－O_3 700 1.350
C_2－O_2 1400 1.220
H_－C_R 700 1.020
H_－N_3 700 1.022
表 4 角度勢能參數表[36]
Kθ (Kcal/mol) θ0 (degree)
XX－N_3－XX 109.000862 106.70 XX－C_R－XX 133.333333 120.00 XX－C_2－XX 133.333333 120.00 XX－O_2－XX 106.697940 104.51 XX－O_3－XX 106.697940 104.51
59
表 5 扭轉勢能參數表[36]
Aτ (Kcal/mol-rad2) δ(degree) m
XX－N_3－C_R－XX 0.125 -180 6
XX－N_3－C_2－XX 0.125 -180 6
XX－C_R－C_R－XX 1.25 180 2
XX－C_R－C_2－XX 1.25 180 2
XX－O_3－C_R－XX 0.25 -180 6
表 6 聚酰亞胺與三種不同石墨烯奈米複合材料機械與熱性質之比較
PI (Exp.)
PI (Simulation)
Nanocomposites
Graphene flakes Intercalated graphene
Intercalated graphene oxide
E (GPa) 3.52[58] 3.60 4.93 5.41 6.03
Tg (K) 539[59] 550 560 570 570 Volumetric
CTE (10-6/K) 240[60] 245.8 226.1 216.3 215.0 Linear CTE
(10-6/K) 80[60] 81.9 75.4 72.1 71.7
60
表 7 聚酰亞胺/石墨烯與聚酰亞胺/表面改質石墨烯互動能量與剪切應力之比較 PI/Graphene PI/Graphene oxide
Shear stress
(MPa) 43.69 54.24
Interaction energy
(Kcal/mol) -1322.42 -1646.94
表 8 樹脂與三種不同石墨烯奈米複合材料機械與熱性質之比較
Epoxy (Exp.)
Epoxy (Simulation)
Nanocomposites
Graphene flakes Intercalated graphene
Intercalated graphene oxide
E (GPa) 3.24[63] 3.16 5.48 5.63 6.36
Tg (K) 377[64] 380 390 400 400 Volumetric
CTE (10-6/K) 366[65] 346.8 290.7 275.9 272.7 Linear CTE
(10-6/K) 122[65] 123.7 103.1 96.6 94.8
61
表 9 樹脂/石墨烯與樹脂/表面改質石墨烯間互動能量與剪切應力之比較
Epoxy/Graphene Epoxy/Graphene oxide Shear stress
(MPa) 50.43 67.86
Interaction energy
(Kcal/mol) -340.25 -460.47
表 10 樹脂與石墨烯奈米複合材料機械性質之實驗文獻
Epoxy Epoxy nanocomposites
E (GPa) Tg (K) CTE ref (10-6/˚C)
Graphene concentration
(wt %) E (GPa) Tg (K) CTE (10-6/˚C)
2.85 - - 0.1 3.74 - - [17]
2 - - 0.5 3.1 - - [66]
- 409.2 82.0 1.0 - 413.0 72.0 [18]
- 428 - 1.5 - 468 - [67]
- 425 - 1.0 - 446 - [68]
圖2 bond
2. 1 鍵結能 d)及(c)扭
能示意圖：
扭轉鍵結勢
圖
：(a)延展鍵 勢能(torsion
圖 2. 2 主
62
附
鍵結勢能(
n bond)、
主胞室與映
圖
stretch bo (d)反向勢
映像胞室示
ond)、(b)角 勢能(inver
示意圖
角度鍵結勢 rsion bond
勢能(angle d)
e
圖 3 石墨
3.2 建構石 墨烯前視圖
(b) 石墨烯示意 圖)
圖3
意圖 ((a)石
63
3. 1 聚酰亞
(
石墨烯上
亞胺單體
(a)
上視圖 (b)群
(c) 群聚石墨
) 墨烯前視圖
圖 (c)分散散
圖3 石墨
3.3 (a)氫氧 墨烯中之原
氧基(-OH) 原子結構模
(a)
(b)環氧基 模型
64
(c) 基(-O-) (c)
)氫氧基與 (b)
與環氧基以以10%的比比例植入
圖3 墨烯
3. 4 模型 I 烯 (b)分散
(b I：石墨烯/
散石墨烯 (
b) /聚酰亞胺 (c)表面改
65
(a)
胺奈米複合 改質分散石
合材料平衡 石墨烯)
(c 衡結構分子
c) 子模型 ((
(a)群聚石石
圖3
圖3. 7 聚
圖3
聚酰亞胺單
3. 8 參考向
單體上碳
向量Z 軸與
67
碳原子與氮
與C-N 代
氮原子所連
代表向量所
連結之代表
所夾角度之
表向量示意
之示意圖 意圖
圖
圖3. 9 平
Density(g/cc)
300 1.05
1.1 1.15 1.2 1.25
平衡結構
圖3. 1
400
68
構施予模擬
0 溫度與
Temperatu 500
擬室單方向
密度示意
ure (K) 600 Tg
向應變示意
意圖
700
意圖
圖3
(a 3. 12 (a)單
圖3. 11 石
a) 單獨石墨烯
69
石墨烯抽出
烯分子模型
出分子模
型圖 (b)高
模型圖
(b) 高分子基材
) 材模型圖
圖3
圖
3. 14 EPO
圖 3. 13 (a
ON862以
a)硬化劑 T
以及TETA
70
(a)
(b) TETA (b
A構成交叉 結構
b)樹脂 EP
叉鍵結樹脂 構
ON862化
脂(Cross-l
化學式
linked epooxy)代表
圖3 烯 (
3. 15 模型 (b)分散石
(b)
型I：石墨烯 石墨烯 (c)表
烯/樹脂奈 表面改質
71
(a)
奈米複合材 質分散石墨
材料平衡結 墨烯)
(c)
結構分子模模型 ((a)群群聚石墨墨
圖3. 16 交叉鍵結結樹脂上碳
72
碳原子與碳碳原子所連連結之代表表向量示意意圖
73
圖 4. 1 聚酰亞胺高分子溫度與密度之關係圖
圖 4. 2 聚酰亞胺高分子在群聚石墨烯複合材料中密度分布
Temperature (K)
Density(g/cc)
400 500 600 700
1.05 1.1 1.15 1.2 1.25
Tg=550K
Z position (Å)
Density(g/cc)
-60 -40 -20 0 20 40 60
0.8 1 1.2 1.4 1.6 1.8 2 2.2
74
圖 4. 3 聚酰亞胺高分子在分散石墨烯複合材料中密度分布
圖 4. 4 聚酰亞胺高分子在分散表面改質石墨烯複合材料中密度分布
Z position (Å)
Density(g/cc)
-20 -10 0 10 20
0.8 1 1.2 1.4 1.6 1.8 2 2.2
Z position (Å)
Density(g/cc)
-20 -10 0 10 20
0.8 1 1.2 1.4 1.6 1.8 2 2.2
75
圖 4. 5 聚酰亞胺高分子在群聚石墨烯複合材料中秩序分布
圖 4. 6 聚酰亞胺高分子在分散石墨烯複合材料中秩序分布
Z position (Å)
Orderparameter
-60 -40 -20 0 20 40 60
-0.5 -0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3
Z position (Å)
Orderparameter
-20 -10 0 10 20
-0.5 -0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3
76
圖 4. 7 聚酰亞胺高分子在分散表面改質石墨烯複合材料中秩序分布
Z position (Å)
Orderparameter
-20 -10 0 10 20
-0.5 -0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3
77
(a)
(b) (c)
圖4. 8 聚酰亞胺複材溫度與密度之關係圖((a)群聚石墨烯 (b)分散石墨烯 (c) 分散表面改質石墨烯)
Temperature (K)
Density(g/cc)
400 500 600 700
1.15
400 500 600 700
1.15
Temperature (K)
Density(g/cc)
400 500 600 700
1.15
78
圖4. 9 不同抽出距離石墨烯與聚酰亞胺高分子間的互動能量
Displacement (Å)
Interactionenergy(Kcal/mol)
0 10 20 30 40 50 60 70
-2000 -1500 -1000 -500 0 500
Graphene Graphene oxide
79
圖4. 10 樹脂高分子溫度與密度之關係圖
圖4. 11 樹脂在群聚石墨烯複合材料中密度分布
Temperature (K)
Density(g/cc)
200 300 400 500 600
0.9 0.95 1 1.05 1.1 1.15 1.2
Tg=380K
Z position (Å)
Density(g/cc)
-60 -40 -20 0 20 40 60
0.8 1 1.2 1.4 1.6 1.8 2 2.2
80
圖4. 12 樹脂在分散石墨烯複合材料中密度分布
圖4. 13 樹脂在分散表面改質石墨烯複合材料中密度分布
Z position (Å)
Density(g/cc)
-20 -10 0 10 20
0.8 1 1.2 1.4 1.6 1.8 2 2.2
Z position (Å)
Density(g/cc)
-20 -10 0 10 20
0.8 1 1.2 1.4 1.6 1.8 2 2.2
81
圖4. 14 樹脂在群聚石墨烯複合材料中秩序分布
圖4. 15 樹脂在分散石墨烯複合材料中秩序分布
Z position (Å)
Orderparameter
Z position (Å)
Orderparameter
82
圖4. 16 樹脂在分散表面改質石墨烯複合材料中秩序分布
Z position (Å)
Orderparameter
-20 -10 0 10 20
-0.5 -0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5
83
(a)
(b) (c)
圖4. 17 樹脂複材溫度與密度之關係圖((a)群聚石墨烯(b)分散石墨烯 (c)分 散表面改質)
Temperature (K)
Density(g/cc)
200 300 400 500 600
1.1
Temperature (K)
Density(g/cc)
200 300 400 500 600
1.1
Temperature (K)
Density(g/cc)
200 300 400 500 600
1.1
84
圖 4. 18 不同抽出距離石墨烯與樹脂間的互動能量
Displacement (Å)
Interactionenergy(Kcal/mol)
0 5 10 15 20 25 30 35
-600 -500 -400 -300 -200 -100 0 100 200
Graphene Graphene oxide