奈米纖維 (nanofibers) 為直徑小於 100 nm 的纖維，而奈米纖維獨特的微小特性、表面效應，具有不同於一般纖維的力學、光學、熱學、磁學及生物活性等性能，故奈米纖維賦予紡織產品具有新功能。因此，在能源與電子、環境工程與生物科技、防禦與安全、生醫工程、加工及特性等相關研究，奈米纖維皆佔有一席之地。而靜電紡絲 (electrospinning) 技術是現今製備奈米纖維的核心技術之ㄧ，其透過帶有靜電場的黏彈性射流不斷地延伸及薄化，最終固化形成奈米纖維。然而，直至目前為止，利用傳統的靜電紡絲技術仍舊無法同時提昇奈米纖維的單軸向排列、鏈段構形、分子位向性、結晶度、硬度與彈性模數等。為了改善這些問題，本實驗室將外加離心場 (1,800 rpm) 導入傳統的靜電紡絲技術中，有效地將離心場 (centrifugal field) 與靜電場 (electrostatic field) 結合，不僅能移除紡絲過程中射流所產生的彎曲不穩定性，更能進ㄧ步提昇奈米纖維的單軸向排列、鏈段構形、分子位向性、結晶度、硬度與彈性模數等。此外，目前大多數的文獻皆著重於系統、操作與環境變數的調整來改變奈米纖維的形態或直徑，僅有極少數的文獻深入地去探討溶液構形、射流行為與纖維構形。
本文首先以聚碳酸酯 (PC) 溶液來進行電紡絲實驗，並研究溶液構形對 PC 奈米纖維性質之影響。由 NMR 可以發現 PC 溶解在 THF-d8 氘代溶液中的作用時間 (τc = 9.3 ns (methyl) / 15.3, 15.8 ns (phenyl ring)) 高於 CH2Cl2-d2 (τc = 8.5 ns (methyl) / 13.1, 13.4 ns (phenyl ring)) 及 CHCl3-d1 (τc = 7.8 ns (methyl) / 10.2, 10.7 ns (phenyl ring)) 氘代溶液。實驗結果證實當 PC 溶解在 THF-d8 氘代溶液中，甲基 (碳) 與苯環 (碳) 水平翻轉的速度是最緩慢的。藉由 DLS 可以證實 PC/THF (Rh = 1.5 nm) 溶液中，高分子與溶劑間的作用力較弱，分子鏈段較偏向緊密的構形；相反的，在 PC/CH2Cl2 (Rh = 9.2 Å) 及 PC/CHCl3 (Rh = 7.9 Å) 溶液中，高分子與溶劑間的作用力較強，分子鏈段較偏向鬆散的構形。由此可以得知當溶劑急速揮發的時候，緊密的構形會形成鏈摺疊或鏈聚集，這種現象便能誘導結晶的形成。對於聚乳酸 (PLA) 的溶液構形，也如同上述結果，可成功地誘導 PLA 產生結晶。
另一方面，傳統的靜電紡絲技術僅具有軸向的拉伸應力，而新式的靜電紡絲技術多了切線方向的拉伸應力，可提昇射流的瞬時速度 (υ = r × ω = 15.08 m/s) 及切線加速度 (ac = √(ax2 + ay2) = r × ω2 = 2.84×103 m/s2)。故藉由 Re 與 We numbers 可以得知慣性力/黏彈力與慣性力/表面張力的比值，及其對射流曲率半徑的影響；另藉由 Pe 與 ε numbers 可以得知電對流/電傳導與靜電力/慣性力的比值，對射流長度的影響；最後，由 Oh 與 Π1 numbers 可以得知黏彈力/表面張力與靜電力/黏彈力的比值，推得 Taylor cone 的形態變化。本文研究結果顯示，當 Re＞6.57×10－2、We＞4.74、Pe＞2.20×10－2、ε＞3.03×10－3、Π1＞4.39×10－6、Oh＞33.14，聚碳酸酯射流具有較強的慣性力 (曲率半徑較大)、電對流 (射流長度較長) 與黏彈力 (Taylor cone 較穩定)，進而提昇射流的拉伸應力與延伸速度。同時，對於聚乳酸與聚丙烯腈奈米纖維的射流行為，也有相似的結果。
本研究在外加離心場 (1,800 rpm) 的存在下，藉由最佳的操作條件 (η = 48.1 cp at 14 wt% PC/THF, FR = 0.25 mL/hr, WD = 20 cm, EF = 25 kV, and T = 25°C)，可以大幅提昇其鏈段構形 (67%) 與結晶度 (6.5%)，進而製備出高硬度 (0.52 GPa) 與高強度 (7.11 / 5.13 GPa) 之聚碳酸酯奈米纖維。其次，藉由最佳的操作條件 (η = 35.5 cp at 6.67 wt% PLA/CHCl3/THF, FR = 0.25 mL/hr, WD = 20 cm, and EF = 30 kV)，可以大幅提昇其鏈段構形 (57%)、分子位向性 (D = 1.89) 與結晶度 (37%)，進而製備出高硬度 (0.26 GPa) 與高強度 (2.64 / 3.30 GPa) 之聚乳酸奈米纖維。另藉由最佳的操作條件 (η = 229 cp at 12 wt% PAN/DMF, FR = 0.25 mL/hr, WD = 20 cm, and EF = 30 kV)，可以大幅提昇其分子位向性 (D = 0.78; f = 0.21) 與比結晶度 (34%)，進而製備出高硬度 (0.43 GPa) 與高強度 (6.29 / 4.55 GPa) 之聚丙烯腈奈米纖維。

Nanofibers are referred to the fibers with diameters less than 100 nm. Because it’s small features and surface effects, particular properties of mechanical, optical, thermal, magnetic, and biological activity, nanofibers can give the textile products with the novelty performance. Thus, nanofibers are widely applied into the energy and electronics, environmental engineering and biotechnology, defense and security, bioengineering, processing and characterization. Electrospinning is still the cone technology for fabricating the nanofibers now; however, the conventional electrospinning technique can not simultaneously enhance the uniaxially alignment, conformation, molecular orientation, crystallinity, hardness, and elastic modulus of nanofibers. To solve above problems, an additional centrifugal field (1,800 rpm) was applied in the conventional electrospinning technique in our laboratory. The combination of centrifugal field and electrostatic field not only can remove the bending instability, but also can simultaneously enhance the uniaxially alignment, conformation, molecular orientation, crystallinity, hardness, and elastic modulus of nanofibers. Furthermore, to change the morphology and diameter of nanofibers, most of the literatures are still focused on the system, operational, and environmental variables; only a fewer literatures are deeply investigated the solution conformation, jet behavior, and nanofiber conformation.
First, this study was used the polycarbonate (PC) solution to perform the electrospinning experiments, and investigate the solution conformation for the effects of polycarbonate nanofibers. Nuclear magnetic resonance (NMR T1) showed that the correlation time (τc = 9.3 ns (methyl) / 15.3, 15.8 ns (phenyl ring)) when the PC dissolved in THF-d8 solution was higher than the CH2Cl2-d2 (τc = 8.5 ns (methyl) / 13.1, 13.4 ns (phenyl ring)) and CHCl3-d1 (τc = 7.8 ns (methyl) / 10.2, 10.7 ns (phenyl ring)) solutions. This result demonstrates that the velocity of the horizontal flip of the methyl and benzene ring when PC in THF-d8 was the slowest. Dynamic light scattering (DLS) showed that the polymer solvent interaction between PC and THF (Rh = 1.5 nm) was weaker than in the case of CH2Cl2 (Rh = 9.2 Å) and CHCl3 (Rh = 7.9 Å). The PC chains probably adopted a more densely worm-like conformation (or a more compact internal structure) in the THF case. By contrast, the PC chains preferentially adopted a more extended worm-like conformation in CH2Cl2 and CHCl3. Chain collapse and aggregation were probably occurred when the PC/THF solution became more concentrated, and the collapse and aggregation from a more densely worm-like conformation may have induced crystallization. The solution conformation of polylactic acid (PLA) is also similar to the above result; the particular solvent can successfully induce the formations of PLA crystal.
On the other hand, the conventional electrospinning technique only has the stretching force with axial direction, and the novel electrospinning technique has the stretching force with axial and tangent directions. The instantaneous velocity (υ = r × ω = 15.08 m/s) and tangent acceleration (ac = √(ax2 + ay2) = r × ω2 = 2.84×103 m/s2) can be simultaneously enhanced for a viscoelastic jet under the driven of an additional centrifugal field. The changes of curvature radius can be obtained through Re (inertial stress / viscous stress) and We (inertial stress / surface stress) numbers. Subsequently, the changes of jet length can be obtained through Pe (charge convection / charge conduction) and ε (electrostatic stress / inertial stress) numbers. Finally, the changes of Taylor cone can be obtained through Π1 (electrostatic stress / viscous stress) and Oh (viscous stress / surface stress) numbers. The polycarbonate jet has stronger inertial stress, charge convection, and viscous stress when Re > 6.57 × 10－2, We > 4.74, Pe > 2.20 × 10－2, ε > 3.03 × 10－3, Π1 > 4.39 × 10－6, and Oh > 33.14. The stretching force and extension speed will be substantially promoted under the driven of stronger inertial stress, charge convection, and viscous stress. Simultaneously, the jet behavior of polylactic acid and polyacrylonitrile are also similar to the above result.
In the presence of an additional centrifugal field, the polycarbonate nanofibers with the superior conformation (67%), crystallinity (6.5%), hardness (0.52 GPa), and elastic modulus (7.11 / 5.13 GPa) can be achieved by the optimal operational conditions (η = 48.1 cp at 14 wt% PC/THF, FR = 0.25 mL/hr, WD = 20 cm, EF = 25 kV, and T = 25°C). Subsequently, the polylactic acid nanofibers with the superior conformation (57%), molecular orientation (D = 1.89), crystallinity (37%), hardness (0.26 GPa), and elastic modulus (2.64 / 3.30 GPa) by the optimal operational conditions (η = 35.5 cp at 6.67 wt% PLA/CHCl3/THF, FR = 0.25 mL/hr, WD = 20 cm, and EF = 30 kV). Finally, the polyacrylonitrile nanofibers with the superior molecular orientation (D = 0.78; f = 0.21), specific crystallinity (34%), hardness (0.43 GPa), and elastic modulus (6.29 / 4.55 GPa) by the optimal operational conditions (η = 229 cp at 12 wt% PAN/DMF, FR = 0.25 mL/hr, WD = 20 cm, and EF = 30 kV).

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