臺灣博碩士論文加值系統

聚對二甲苯（Parylene, PPXN）鍍膜為一透明、質輕、表面無針孔、保形、防潮、防蝕且絕緣之鍍膜，廣用於醫療器材、航太、軍事和電子工業。它具有之獨特性質另包括良好之生物相容性、無細胞毒性、阻水和乾式潤滑，使適用於生醫材料表面改質。短期用途如於探針或注射針頭表面增加潤滑度；長期用途如用於人工心臟、瓣膜或人工電子耳表面與組織絕緣、避免被體液腐蝕。目前商業最常用的為parylene C 和parylene N，其傳統沉積過程係始於粉末狀之對二甲苯雙體（Dimer），經約650℃高溫裂解形成氣相單體（Monomer），再於室溫下形成聚合型態的固態鍍膜。然而，這種傳統的作法有諸多缺點，包括：起始原料價格昂貴、需要高溫裂解程序造成高能源消費、沉積速率慢、鍍膜硬度差而易刮損以及真空度需求較高。本研究擬採用脈衝直流電漿聚合（Pulsed-dc plasma polymerization）的技術，以低成本之液態對二甲苯為起始原料，在常用之醫材表面被覆聚合鍍膜（Plasma polymerized para-xylene, PPX），以材料的分析檢測方法來了解鍍膜之微觀組織與特性，並以細胞培養來了解其生物相容性，期望製備出類似parylene特性之鍍膜，使可用於生醫材料表面處理。
研究結果顯示：化學氣相沉積的PPXN鍍膜為α相結晶結構，電漿聚合PPX則呈現非晶。PPXN鍍膜中呈現具有苯環及烷類烴之線性高分子結構，而PPX鍍膜分子結構在低頻高流量時傾向於生成烯類烴及烷類烴之短程結構，在高頻低氬氣流量時傾向無機結構。鍍膜的微觀形貌，PPXN鍍膜微觀組織呈現出纖維狀之組織，而PPX則為緻密推疊。PPXN的成長速率為0.16 μm/h，而PPX可從0.05 μm/h到0.48 μm /h，於高流量時的成長速率大於PPXN，表面粗度隨著頻率的上升而下降，造成在高頻率的離子轟擊下，薄膜表面平整。在機械性質表現上，鉛筆硬度達到8H之的等級，施鍍於AISI 304不�袗�之最高附著性顯示出4B的等級，展現出高於PPXN鍍膜之表面硬度和略低於PPXN鍍膜之附著性。經過電漿聚合PPX之水滴接觸角為60º~85º比PPXN水滴接觸角為86.1º更具親水性。施鍍於玻璃基材上的PPX在中、低頻以及高氬氣流量之下，高成長速率對應出較厚的鍍膜伴隨較高的薄膜內應力，而造成薄膜在細胞培養前的消毒程序中脫落。高頻、低氬氣流量所得之較薄的薄膜則附著性良好，未發生鍍膜脫落的現象，細胞生長數量高於PPXN。施鍍於軟質矽膠基材上的PPX則因鍍膜不累積內應力，因而不受細胞培養的消毒程序而脫落。於高頻率及高氬氣流量下，細胞數目高於矽膠裸材，顯示PPX具有比矽膠祼材更良好的生物相容性。此項研究說明了利用脈衝直流電漿聚合鍍膜技術，以para-xylene為原料所獲得的鍍膜具有緻密的微結構、適當的機械性質及良好的生物相容性，有機會成為parylene鍍膜的替代方案以用於醫材表面處理。

Parylene (or poly-para-xylene, PPXN) coating is known to be transparent, thin, continuous, conformal, water-proof, anticorrosive, insulating and widely used in medical, aerospace, military and electronic industries. With these unique properties, such a coating has been let to be used for biomedical material surface treatment with respect to its excellent biocompatibility, non-cytotoxicity, effective barrier and dry lubricant: short-term applications, such as probes or needles, with enhancement of lubricity; long-term applications, such as cochlear implants or cardiac assist devices with tissue isolation and inhibiting corrosive biofluids. The traditional parylene deposition process involves powdery di-para-xylene dimmer as the starting precursor, parylene C and parylene N most commonly used. Through the monomer generator operated at 650℃, the thermally decomposed monomer gas is admitted onto substrate to form solid polymerized thin film at room temperature. Drawbacks of such a process include the usage of expensive starting material, high thermal energy consumption for monomer generation, relatively low deposition rate, low film hardness and higher vacuum degree requirement.
An alternative will be proposed by using pulsed-dc plasma polymerization to deposit solid film with nature similar to parylene film. Low cost and liquid para-xylene was used as the starting material to polymerize on different substrates. A systematical study will be carried out to the optimization of deposition condition. Coatings will be instigated by using materials characterization techniques to realize film microstructure. Mechanical properties will also be studied. Cell culture will be carried out to reveal its biocompatibility. The development of such an alternative to parylene coating by using polymerization will be facilitated for biomedical material applications.
The results revealed that the crystal structure of the CVD-PPXN film is α-phase, and the plasma-polymerized PPX film is amorphous. The PPXN film is a linear polymer composed of benzene ring and alkanes. The PPX film tends to present a short-chain linear structure of alkenes and alkanes at low frequency and high gas flow rate. It tends to be inorganic structure of the deposited film when high pulse frequency and low Ar gas flow rate are employed during deposition. As for its microscopic morphology, PPXN presents with fibrous appearance, while PPX film presents dense feature. Growth rate of PPXN measures about 0.16 μm/h, and that of PPX ranges from 0.05 μm/h to 0.48 μm /h which is higher than that of PPXN at high gas glow rate. Surface roughness of PPX decreases as the frequency increases, and this should be that ionic bombardment at high frequency resulted in surface smoothness. As for its mechanical properties, a pencil hardness of 8H of PPX is higher than that of PPXN, and the ultimate film adhesion on AISI 304 stainless steel graded as 4B is slightly lower than that of PPXN. Water contact angle of PPX are 60º-85º, which is more hydrophilic than PPXN with 86.1º. PPX deposited on hard glass substrate, at low to medium frequency and high Ar gas flow rate, suffers from film spallation during sterilization prior to cell culture. This maybe caused by the high internal stress of the deposited films. For the films obtained at high frequency and low Ar flow rate reveals strong adhesion. Cell culture on PPX deposited specimens reveals a higher cell count than the PPXN deposited one. PPX deposited on soft silicone substrate, due to less internal stress built in the film, present strong film adhesion regardless of deposition conditions. Among which PPX deposited at high frequency and high Ar flow rate exhibit a higher cell count than bare silicone as revealed by the result of cell culture. These quantitative indications as revealed above implies that the pulsed-dc plasma polymerized para-xylene can possibly be an alternative to conventional parylene thin films for surface treatment of medical devices by proper control of process parameters.

總目錄

中文摘要 i
英文摘要 ..................................................................................................iii
總目錄 vi
圖目錄 viii
表目錄 xi
第一章 前言 1
第二章 文獻回顧 3
2-1 傳統聚對二甲苯鍍膜之概述 3
2-2 傳統聚對二甲苯鍍膜之製程、微觀組織與特性 7
2-3 生醫材料之表面處理及生物相容性 11
2-4 電漿聚合之原理與應用 15
2-5 電漿聚合對二甲苯薄膜替代傳統聚對二甲苯鍍膜之可行性 18
第三章 研究方法與流程 22
3-1 實驗設計與流程 22
3-2 實驗材料選擇 23
3-3 傳統聚對二甲苯鍍膜及電漿聚合對二甲苯薄膜設備與施鍍步驟 25
3-4 分析儀器及測試 32
3-4.1 薄膜晶體結構、化學結構及微觀形貌 32
3-4.2 薄膜機械性質 33
3-4.3 薄膜親水性 35
3-4.4 薄膜生物相容性 35
第四章 結果與討論 41
4-1 傳統聚對二甲苯鍍膜及對二甲苯聚合膜之結構、形貌及成長速率 41
4-1.1 薄膜晶體結構 41
4-1.2 薄膜分子結構 44
4-1.3 薄膜微觀形貌觀察 50
4-1.4 薄膜成長速率 54
4-2 傳統聚對二甲苯鍍膜及對二甲苯聚合膜之機械性質 55
4-2.1 薄膜硬度 55
4-2.2 薄膜附著性 56
4-3 傳統聚對二甲苯鍍膜及對二甲苯聚合膜之親水性 58
4-4 傳統聚對二甲苯鍍膜及對二甲苯聚合膜之生物相容性 59
第五章 結論 63
參考文獻.. 65
誌謝..........................................................................................................73

圖目錄

圖2-1 (a)起始原料di-para-xylylene雙體 (b)裂解後para-xylylene單體 (c)聚合型式之parylene薄膜結構單元 3
圖2-2 商業上常見的parylene薄膜類型(a)parylene N (b)parylene C (c)parylene D (d)parylene F 4
圖2-3 不同種類的parylene薄膜型式 4
圖2-4 PPXN製程示意圖 7
圖2-5 PPXN薄膜X光繞射圖形 8
圖2-6 PPXN紅外光譜圖 8
圖2-7 PPXN纖維微觀組織 9
圖2-8 均勻且保形的parylene薄膜示意圖 10
圖2-9 電漿聚合可能的反應機構 15
圖2-10 傳統聚合物與電漿聚合物示意圖 16
圖3-1 實驗流程圖 22
圖3-2 對二甲苯化學結構 24
圖3-3 電漿聚合系統示意圖 26
圖3-4 對二甲苯飽合瓶示意圖 26
圖3-5 雙極脈衝直流電源供應器波型圖 28
圖3-6 雙極式脈衝直流電源供應器在一個脈衝循環的工作情形 (a)在Ton時 (b)在Toff時 29
圖3-7 雙極脈衝直流電源供應器於不同電源供應器頻率及不同Toff時間之波型圖 30
圖3-8 Elcometer F107畫格器 33
圖3-9 鉛筆硬度測試儀 35
圖3-10 細胞培養流程圖 36
圖3-11 無菌生物櫃 37
圖3-12 CO2培養箱 38
圖3-13 血球計數盤 40
圖4-1 (a)未施鍍之AISI 304不�袗�原材 (b)施鍍PPXN之X光繞射圖形 41
圖4-2 固定氬氣流量為(a)10 (b)20 (c)30 (d)40 (e)50 sccm，變動脈衝頻率25~100 kHz所得之PPX X光繞射圖 42
圖4-3 PPXN紅外光譜圖，圖中s代表stretching，b代表bending 44
圖4-4 固定氬氣流量為(a)10 (b)20 (c)30 (d)40 (e)50 sccm，變動脈衝頻率25~100 kHz所得之PPX紅外光譜圖 48
圖4-5 PPXN之截面形貌(a)低倍(b)高倍 50
圖4-6 固定氬氣流量為(a)10 (b)20 (c)30 (d)40 (e)50 sccm，變動脈衝頻率25~100 kHz所得之PPX截面形貌 51
圖4-7 不同氬氣流量下變動脈衝頻率所得之PPX表面粗糙度 53
圖4-8 不同氬氣流量下變動脈衝頻率所得之PPX成長速率圖 54
圖4-9 不同氬氣流量下變動脈衝頻率所得之PPX鉛筆硬度，圖中虛線為PPXN之鉛筆硬度 55
圖4-10 (a)PPXN及(b)PPX 膠帶附著力測試之巨觀及微觀圖 56
圖4-11 不同氬氣流量變動脈衝頻率所得之PPX附著性，圖中虛線為PPXN之附著性 57
圖4-12 不同氬氣流量變動脈衝頻率所得之PPX水滴接觸角 58
圖4-13 生長於PPX上的纖維母細胞 60
圖4-14 以載玻片玻璃為基材，施鍍PPX及PPXN後進行細胞培養之細胞數目 61
圖4-15 以矽膠為基材，施鍍PPX後進行細胞培養之細胞數目 62

表目錄

表2-1 對二甲苯、叔丁基苯、甲氧苯之物理、化學性質表 17
表3-1 聚對二甲苯二聚體物理、化學性質 24
表3-2 對二甲苯物理、化學性質 24
表3-3 PPXN沉積參數 25
表3-4 雙極式脈衝直流電源供應器可設定參數之範圍 27
表3-5 前處理參數及PPX沉積參數 31
表3-6 ASTM D3359–02膠帶附著力測試結果分級表 34
表3-7 ASTM D3363–05規範由小到大之鉛筆硬度等級 35
表4-1 PPXN吸收峰位置及對應的官能基 45
表4-2 PPX吸收峰位置及對應的官能基 46
表4-3 對二甲苯原料吸收峰位置及對應的官能基 47
表4-4 以載玻片玻璃為基材，施鍍PPX及PPXN後進行細胞培養之細胞數目 60
表4-5 以矽膠為基材，施鍍PPX後進行細胞培養之細胞數目 61

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