第四章 結論與未來工作
4.2 未來工作
第四章 結論與未來工作
4.1 結論
目前初步結果，成形 honeycomb pattern 必須要有高濕度的環境，由濕度溫 度和空氣氣流量的參數來說，而目前在濕度溫度為 30℃和空氣氣流量 7slm 之下 honeycomb pattern 的變因甚多，目前初步結果 PLA 產品的特性，如分子量等，
和溶劑與溶質之間混合的均勻度，改變孔洞的尺寸為較大的相關性；控制空氣氣 可調控的濕度環境下成形 honeycomb pattern 的狀況。
調控與計算出適當的溶劑揮發速度，了解 honeycomb pattern 形成孔洞 尺寸與溶劑揮發之間關係。
在溶液裡加入微量比例的水與介面活性劑的運用搭配，使得孔洞的尺寸 是可有調整性與均勻性。
利用 SEM 來看成形 honeycomb pattern 的平面和縱軸的結構。
表面改質上，使用低溫常壓電漿作為 honeycomb pattern 表面處理的主 要設備，下列提出了，幾項目標。
利用 XPS 以及傅立葉轉變衰減全反射紅外光譜儀(ATR-FTIR)來探討，
經過電漿處理過後官能基植入 honeycomb pattern 表面的狀況。
利用細胞培養技術來探討 honeycomb pattern 材料經過低溫常壓電漿表 面改質的前後，對於細胞貼附性質與生物行為的探討。
在不同孔洞尺寸的 honeycomb pattern 培養特定的細胞，找出孔洞的尺 寸最有利於特定的細胞的生長。
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表1透過不同混合氣體之電漿處理材料表面後使用水滴接觸角量測儀測得水與帶入公式計算表面能[46]
表2試片在氨氣電漿處理前後使用XPS來分析表面化學元素，可植入NH 和C-N 的官能基[46]
表3 SpecLine軟體分析親水電漿光譜，NO-γ區域的光子能量
表4 試片經由電漿處理表面後由XPS來做表面分析，看出表面上經由電漿處理過後植入胺基(primary amine group) 和氧相關的官能基，N/C提19.1 %，O/C由原本的3.8%提高到61% [48]
圖1.1 聚乳酸結構式，全名為 Poly Lactic Acid 或 Polylacide (以下簡稱 PLA)。
[3]
圖1.2 PLA 分子結構，左邊為左旋體 (l-isome)的 PLA (L-(+)Lactic acid) 和右 邊為右旋體 (d-isomer) 的 PLA (D-(-)Lactic acid)。[3]
圖1.3 XuJun Wu 等人，使用 PLGA (poly(lactic-co-glycolic acid)混合不同的比 例，如 PLGA50:50、PLGA75:25 和 PLGA85:15，配置在不同的溶劑，
如氯仿、THF(四氫呋喃)、乙酸乙酯(C4H8O2)，在濕度的環境下所成形 的結果。[23]
圖1.4 Martina H. Stenzel 等人，測試等多種溶質(聚合物，圖 a 到 g)，在濕度 的環境下，使用高揮發性二硫化碳(CS2)為主要溶劑，搭配不同的溶質。
[24]
圖1.5 聚乳酸溶液在濕度的環境下發揮成形 honeycomb pattern 的過程圖，圖 (a)為配製的聚乳酸溶液放置在具有濕度氣流的環境底下，圖(b)為當溶 劑揮發產生吸熱反應凝結附近水滴，而容易內部產生對流現象，水滴 將往下移動，圖(c)為當水滴往下移動將以最低能量形態排列而成，圖(d) 為水滴凝結而聚乳酸將產生張力包圍水滴，形成三相共存的現象 [24,28]。
Humidified Flow
圖1.6 根據多篇文獻整理出 11 種不同的細胞，培養在不同孔洞尺寸
honeycomb pattern 上；MC3T3-E1 纖維母細胞，目前找到最多相關的 文獻將細胞培養在 3 ~ 10 m 的孔洞，Cardiac myocytes，目前只有找到 相關文獻將細胞培養在 4、6、8 m 的研究。[5][30][32-42]
圖1.7 3T3 細胞培養在 PDLLA 表面，氨氣電漿處理前後與塗佈膠原蛋白之比 較，圖(A)為對照組，圖(B)經過氨氣電漿處理過，圖(C)塗佈膠原蛋白，
圖(D)在塗佈膠原蛋白後再以氨氣電漿處理過。[34]
圖1.8 試片經由兩道電漿(two-step plasma treatment)處理表面後由 AFM 來做 表面分析，看出表面粗糙度由未處理 0.88 nm 提高到 73.22 nm。[48]
圖1.9 試片表面經由 ATR-FTIR 分析，氮的官能基(-NH-、-NH2 -)從未經過電 漿處理前的沒有訊號，再經過兩道電漿處理過後有明顯訊號上升。[48]
圖2.1 成形 honeycomb-pattern 的設備圖(圖上標示為組件 1 到 7)，分為蒸氣系 統和加熱系統。
蒸氣系統：組件 4 為壓縮空氣與 L 型玻璃彎管、組件 5 為錐形燒杯、
組件 6 為不鏽鋼圓管、組件 7 錐形不鏽鋼濕度罩。
加熱控溫系統：組件 2 為包覆組件 6 的加熱帶加熱系統、組件 3 為加 熱錐形燒杯內 Di-water 之加熱器。
圖2.2 Sine wave 電漿設備圖，主要由幾個部分組成: 平行板介電質大氣電漿 束、電源供應器( DC quasi pulsed )、氣體管路系統與實驗腔體及其他相 關之實驗量測設備。
圖2.3 平行板 DBD 電漿設備，產生電漿區域局部放大設計圖和電漿出口 X-Y-Z 三維定義。
Y
Z
圖2.4 Sine wave DC pulse 電源供應器由電源供應器、脈衝電源控制器 (SPIK2000A)和高壓脈衝變壓器(HV-1500-03)頻率操作範圍 15 到 35 kHz(由上而下。)
圖2.5 常壓電漿之實驗腔體
圖2.6 單向移動平台
圖2.7 五位數的精密電子秤，型號為 Mettler Toledo XP 105 DR。
圖2.8 濕度量測器是 Thermo Recorder 型號為 TR-77Ui 靜電電容式的感測器。
圖2.9 光譜儀(Optical Emission Spectroscopy,OES) ，型號為 PI Acton SP 2500。
圖2.10 水滴接觸角量測系統(CA)。
圖2.11 場發射掃描電子顯微鏡(SEM)，使用的型號為 Hitachi S-4700I，操作電 壓為 0.5kV~30kV，解析度為 15Ao。
圖3.1 聚乳酸 719935-Poly(D,L-lactide), Mw 10,000-18,000, 0.16-0.24 dL/g, 0.1% (w/v) in chloroform(25 °C, Ubbelohde), 以下簡稱 719935 PLA。
圖3.2 719935-Poly(D,L-lactide)濃度為 120 mg/ml，氣流量為 1 slm 在濕度罩下 所成形之 honeycomb pattern。
圖3.3 719935-Poly(D,L-lactide)濃度為 120 mg/ml，氣流量為 3 slm 在濕度罩下 所成形之 honeycomb pattern。
圖3.4 719935-Poly(D,L-lactide)濃度為 120 mg/ml，氣流量為 5 slm 在濕度罩下 所成形之 honeycomb pattern。
圖3.5 719935-Poly(D,L-lactide)濃度為 120 mg/ml，氣流量為 7 slm 在濕度罩下 所成形之 honeycomb pattern。
圖3.6 719935-Poly(D,L-lactide)濃度為 120 mg/ml，氣流量為 9 slm 在濕度罩下 所成形之 honeycomb pattern。
圖3.7 719935-Poly(D,L-lactide)濃度為 120 mg/ml，氣流量為 11 slm 在濕度罩 下所成形之 honeycomb pattern。
圖3.8 濕度溫度為 25℃和 30℃ 時在濕度氣流為 1~11 slm，在蒸氣罩下 15 分 鐘所成形 honeycomb pattern 孔洞尺寸。
9 slm – 11 slm
圖3.9 在濕度氣流量為 9 (左圖) 和 11 slm (右圖) 時所成形的 honeycomb pattern 情形，黑色框起來區域為未成形 honeycomb pattern 的區域。
圖3.10 719935-Poly(D,L-lactide)之溶液濃度為 70 mg/ml。
圖3.11 719935-Poly(D,L-lactide)之溶液濃度為 100 mg/ml。
圖3.12 719935-Poly(D,L-lactide)之溶液濃度為 120 mg/ml。
圖3.13 719935-Poly(D,L-lactide)之溶液濃度為 150 mg/ml。
圖3.14 719935 PLA 濃度 120 mg/ml、空氣流量 7 slm、濕度溫度 30℃、濕度 罩下等待 15 分鐘。
圖3.15 719951 PLA 濃度 120 mg/ml、空氣流量 7 slm、濕度溫度 30℃、濕度 罩下等待 15 分鐘。
圖3.16 P1691 PLA 濃度 120 mg/ml、空氣流量 7 slm、濕度溫度 30℃、濕度罩 等待 15 分鐘。
圖3.17 P1566 PLA 濃度 80 mg/ml、空氣流量 7 slm、濕度溫度 30℃、濕度罩 下等待 15 分鐘。
圖3.18 4 種 PLA 在最試當可成形 honeycomb pattern 的濃度，蒸氣罩下等待 15 分鐘後 honeycomb pattern 孔洞尺寸機率分布範圍。
圖3.19 DBD 電漿電性圖，由 sine wave DC 電源供應器輸入 64V 和頻率 15kHz。
圖3.20 DBD 電漿電性圖，由 sine wave DC 電源供應器輸入 64V 和頻率 20kHz。
DBD 電漿電性圖，由 sine wave DC 電源供應器輸入 64V 和頻率 25kHz。
圖3.21 DBD 電漿電性圖，由 sine wave DC 電源供應器輸入 64V 和頻率 30kHz。
圖3.22 DBD 電漿電性圖，由 sine wave DC 電源供應器輸入 64V 和頻率 35kHz。
圖3.23 水銀溫度量測 sine wave 電漿出口下方 1 mm 電漿焰溫度。
圖3.24 Sine wave 電源供應器，不同頻率所產生的電漿焰溫度。
圖3.25 Sine wave 電漿光譜量測系統架構，收光頭位在電漿出口下方 1 mm。
圖3.26 頻率為 30 kHz，Sine wave 電漿光譜量測之訊號強度，波長 200 到 280 為 NO-γ 區域，放光的機制為 N2(A) + NO(X) → NO(A) + N2 、NO(A) → NO(X) + hv-，波長 300 到 380 為 NO-β，放光的機制為 N + O + N2 → NO(B) + N2、NO(B) → NO(X) + hvβ，波長 337.3 為 N2 2nd positive，放 光的機制為 2N2(A) → N2(C) + N2、N2(C) → N2(B) + hSPS。
圖3.27 在各頻率下，Sine wave 電漿光譜量測之訊號強度，波長 200 到 280 為 NO-γ 區域，放光的機制為 N2(A) + NO(X) → NO(A) + N2 、NO(A) → NO(X) + h-。
圖3.28 在各頻率下，Sine wave 電漿光譜量測之訊號強度，波長 300 到 380 為 NO-β，放光的機制為 N + O + N2 → NO(B) + N2、NO(B) → NO(X) + hβ。
圖3.29 在各頻率下，Sine wave 電漿光譜量測 N2 2nd positive 之訊號強度，波長 337.3 為 N2 2nd positive，放光的機制為 2N2(A) → N2(C) + N2、N2(C) → N2(B) + hSPS。
圖3.30 電漿設備和 Honeycomb 試片放在距離電漿出口 1 mm 的處理位置，試 片平均受到電漿處理時間算法，電漿束(plasma jet)到達材料表面時的有
圖3.30 電漿設備和 Honeycomb 試片放在距離電漿出口 1 mm 的處理位置，試 片平均受到電漿處理時間算法，電漿束(plasma jet)到達材料表面時的有