研究生: |
陳心傑 Hsin-Chieh Chen |
---|---|
論文名稱: |
混摻對聚偏二氟乙烯奈米纖維物性與生物相容性之影響 Characterization and Biocompatibility of Electrospun PVDF Blending Mats |
指導教授: |
楊銘乾
Ming-Chien Yang |
口試委員: |
李振綱
none 于大光 none 蘇清淵 none 楊禎明 none |
學位類別: |
博士 Doctor |
系所名稱: |
工程學院 - 材料科學與工程系 Department of Materials Science and Engineering |
論文出版年: | 2010 |
畢業學年度: | 98 |
語文別: | 中文 |
論文頁數: | 98 |
中文關鍵詞: | 靜電紡絲(電紡) 、聚乳酸 、聚偏二氟乙烯 、Pluronic F127 、共溶劑 、生物相容性 、延伸性 、細胞增生 |
外文關鍵詞: | Electrospinning, Poly(vinylidene fluoride) (PVDF), Polylactide (PLA), Pluronic F127, Co-solvent, Biocompatibility, Elongation, Cell proliferation |
相關次數: | 點閱:322 下載:4 |
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本研究目的在於藉由靜電紡絲(電紡, Electrospinning)技術探討聚偏二氟乙烯(Polyvinylidene fluoride, PVDF)及混掺聚乳酸(Polylactide, PLA)、Pluronic F127 混合奈米纖維膜其最佳成型參數、表面特性、機械特性、熱穩定性與生物相容性。期望能藉由掺合電紡改良PVDF的延伸性、親水性與生物相容性,開發出具奈米尺寸之混掺PVDF纖維薄膜,此一材料未來將可應用在多方面,如生物組織基材、過濾膜材、或電池隔離膜。
第一部分首先探討單溶劑二甲基甲醯胺(N,N-dimethylformamide, DMF)與共溶劑系統DMF/丙酮(acetone)作為溶劑時,不同比例條件下對PVDF電紡製程的影響,藉由SEM觀察纖維尺寸與分佈情況並以變異係數(coefficient of variation, CV)評估奈米纖維膜均勻度,結果顯示溶劑在重量百分比例為90:10條件下所得的電紡纖維膜均勻度最高(184nm, CV=0.40),並且利用此一最佳比例進行下一階段試驗。
第二部分探討製程條件對混摻電紡PVDF/PLA的影響。從SEM發現PVDF與PLA具有不同纖維直徑分佈;10%PVDF/5%PLA奈米纖維薄膜可以得到最佳奈米纖維膜平均尺寸為215nm,CV=0.27。從FTIR與DSC分析可知,相較於塗佈法所得之非極性α相PVDF/PLA奈米纖維膜,以電紡法製備的PVDF/PLA奈米纖維膜屬於具有極性之β相;雖然混摻PLA會降低整體結晶度,但是對熱穩定性並無影響。在接觸角分析方面,電紡製程所產生的奈米纖維膜會使PLA的接觸角提高,有類似蓮花效應的疏水效果。在生物相容性評估方面,電紡PVDF/PLA奈米纖維膜所造成的表面孔洞小於純PVDF與PLA所形成的奈米纖維膜,也小於血小板尺寸(1~5μm),此一微小孔洞所造成的介面效應導致血小板吸附量少,,也抑制凝血酵素的活性達到抗凝血效果。除此之外,纖維母細胞(L929)培養也顯示PVDF/PLA混摻奈米纖維膜是良好的細胞增生基材。
在第三部分延伸研究方面,為了改變PVDF奈米纖維膜的疏水特性,利用混掺Pluronic F127改善電紡PVDF奈米纖維膜的疏水性,探討最佳參數條件下製成PVDF/F127親水奈米纖維膜。從SEM-EDX及FTIR的結果顯示F127成功地分佈於PVDF奈米纖維膜上,5% F127混掺即可使純電紡PVDF的接觸角從125°大幅降低至54.7°,雖然奈米纖維膜的平均纖維直徑增加為372nm,另一方面F127亦扮演連結電紡PVDF奈米纖維的角色,其抗拉強度與斷裂延伸率都因此上升。在生物相容性評估方面,F127的PPO觸手效應使得血小板不易吸附,而產生抗凝血作用;同時纖維母細胞L929在PVDF/F127電紡纖維膜的細胞增生表現優於純PVDF與PVDF/PLA,顯示此一混摻奈米結構可應用在生物支架與組織修復領域。
The objectives of this study are to optimize the parameters of electrospinning (ES) poly(vinylidene fluoride) (PVDF) using a co-solvent system of N,N-dimethylformamide(DMF) and acetone, and to blend with polylactide (PLA) and Pluronic F127 to spin into nanoscale nonwoven mats which may improve the elongation, hydrophilicity, and biocompatibility of PVDF for applying in biomatrix, filter, or battery seperation.
The physical properties of the resulting mats were subjected to characterization including scanning electron microscope (SEM), Fourier transform infrared spectrometer (FTIR), wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), capillary flow porometer, contact angle, tensile test, and the biocompatibility based on blood coagulation time (APTT&PT) and cell proliferation of L929 fibroblast.
In the first section, using a co-solvent system of DMF/acetone at a ratio of 90:10, the average fiber diameter of PVDF mat achieved 184 nm without beads and CV=0.40. Thus these parameters were applied to the following sections.
In the second section, PLA was mixed with PVDF and spun into nonwoven mats via electrospinning technique using DMF/acetone as the co-solvent. The viscosity of the solution was measured, and the average fiber diameter achievable without beads for PLA, PVDF/PLA, and PVDF mats were 191 nm, 215 nm, and 184 nm, respectively. Infrared (IR) spectra showed that electrospinning can induce β phase crystallization of PVDF. From the results of DSC, the PVDF/PLA mats exhibited higher melting temperature but lower crystallinity than both PLA and PVDF. The tensile strength of PVDF/PLA was lower than those of PLA and PVDF. By stretching during eletrospinning, the ratio of strength in machine direction (MD) to that in cross direction (CD) was increased to 2. In addition, electrospun PVDF/PLA mats exhibited higher cell proliferation for L929 fibroblasts than both PLA and PVDF mats.
In the final section, PVDF was blended with Pluronic F127 and spun into nanofibers via electrospinning (ES) process using a co-solvent of DMF and acetone with a ratio of 90/10. The average diameters of the resulting PVDF/F127 nanofibers ranged from 300 to 500nm (avg. dia=372nm, CV=0.30). The embedding of F127 in PVDF matrix was evidenced by EDX, IR spectra. The blending of F127 not only improved the hydrophilicity of PVDF nanofiber (contact angle was decreased from 125° to 54.7°) but also reduced the pore size. In addition, F127 can serve as the binding agent for the electrospun nanofibers to improve its tensile strength and breaking elongation. Furthermore, L929 fibroblasts proliferated on the electrospun PVDF/F127 mats. These results indicate that the electrospun PVDF/F127 nanofiber is a potential substrate for tissue engineering scaffolds.
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