PLA/SEBS和PTT/SEBS摻混物之生物相容性、機械性質、熱性質及結晶性質研究

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研究生：	高伯爵 Bo - Jyue Kao
論文名稱：	PLA/SEBS和PTT/SEBS摻混物之生物相容性、機械性質、熱性質及結晶性質研究 Biocompatibility, Mechanical, Thermal, and Crystallization Properties of Melt-mixed PLA/SEBS and PTT/SEBS Blends
指導教授：	楊銘乾 Ming-Chien Yang
口試委員:	邱顯堂 Hsien-Tang Chiu 吳昌謀 Chang-Mou Wu 周雄 Chi-Hsiung Jou 林國賡 Gwo-Geng Lin
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：	2015
畢業學年度：	103
語文別：	中文
論文頁數：	100
中文關鍵詞：	聚乳酸(PLA) 、聚苯乙烯-聚乙烯-聚丁烯-聚苯乙烯(SEBS) 、機械性質、生物相容性/聚對苯二甲酸丙二酯(PTT) 、聚苯乙烯-聚乙烯-聚丁烯-聚苯乙烯 (SEBS) 、結晶行為、機械性質
外文關鍵詞：	Poly(lactic acid) (PLA), Styrene-ethylene-butylene-styrene (SEBS), Tensile property, Biocompatibility/Poly(trimethyleneterephthalate), Styrene–ethylene–buthylene–styrene (SEBS), Crystallization Behavior, Tensile property
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上一筆

本實驗利用有機環保高分子生物可分解聚乳酸Poly (lactic acid) ( PLA) /聚苯乙烯-聚乙烯-聚丁烯-聚苯乙烯(SEBS)由熔融混煉備製而成。以DSC,SEM和WXRD研究非恆溫結晶，熔融行為，恆溫結晶動力學，晶球型態和結晶結構。由TGA顯示隨著SEBS含量增加熱穩定性下降。形態學研究中PLA與SEBS不相容。斷裂伸長率提升，但隨著SEBS含量上升抗拉強度下降。利用小鼠成纖維細胞（mouse fibroblasts (L929)）來測定PLA、PBS/SEBS Blends和SEBS的細胞相容性。PLA的細胞相容性隨著SEBS含量上升而降低

本實驗利用聚對苯二甲酸丙二酯(PTT)/聚苯乙烯-聚乙烯-聚丁烯-聚苯乙烯(SEBS)由熔融混煉備製而成。POM觀察PTT、PTT/SEBS Blends的晶體結構。SEM觀察PTT和SEBS的相容性。TGA結果顯示熱穩定性隨著SEBS含量增加而下降。DSC研究結晶行為，Tg隨著SEBS含量增加而上升。Avrami equation用來描述等溫結晶動力學。加入SEBS使PTT的斷裂伸長率提升。

Poly(lactic acid) (PLA)/styrene-ethylene-butylene-styrene (SEBS) Blends were prepared through melt blending. Differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WXRD) were used to characterize PLA and PLA/SEBS Blends in terms of their melting behavior and crystallization. Curves from thermal gravimetric analysis (TGA) illustrated that the thermostability increased with the SEBS content. Further morphological analysis of PLA/SEBS Blends revealed that SEBS molecules were not miscible with PLA molecules in PLA/SEBS Blends.The tensile testing for PLA and PLA/SEBS Blends showed that the elongation at break was enhanced, but tensile strength decreased with increasing SEBS content. L929 fibroblasts cells were chosen to assess the cytocompatibility; the cell growth of PLA was found to decrease with increasing SEBS content. Possible reasons for these properties of PLA/SEBS Blends were proposed in this study.

Poly(trimethyleneterephthalate)(PTT)
/styrene–ethylene–buthylene–styrene (SEBS) Blends were prepared by melt compounding. Polarizing optical microscopy was used to observe the spherulitic morphology and the crystal structure of PTT and PTT/SEBS Blends. Scanning electron microscopy was used to determine the dispersion and the compatibility of fracture surfaces of PTT and SEBS. The curves of thermal gravimetric analysis illustrated that the thermo stability decreased with increasing SEBS content. Differential scanning calorimetry was used to investigate the crystallization behavior; the result showed that the glass transition temperature of the compound increased with the SEBS content. The Avrami equation described the isothermal crystallization kinetics. Stress-strain curves for PTT and PTT/SEBS Blends showed that the elongation at break was enhanced with increasing SEBS content.

中文摘要	i
英文摘要	iii
誌 謝	v
總目錄	vi
表目錄	viii
圖目錄	ix
第一章 緒論	1
1.1  前言	1
1.2  市場分析............................................................ ...........................................2
1.3  高分子摻混系統	4
1.4  材料背景	9
1.5  研究目的	19
第二章 文獻回顧	20
2.1  玻璃轉移溫度	20
2.2  Avrami equation	21
2.3  高分子結晶速率	22
2.4  晶體成長	24
2.5  區型轉移	26
2.6  多熔融峰行為	29
2.7  結晶熱力學方程式	31
2.8  X-ray繞射理論	33
    2.9  高分子機械性質..........................................................................................35
第三章 聚乳酸/聚苯乙烯-聚乙烯-聚丁烯-聚苯乙烯摻混物之生物相容性、
       機械性質、熱性質及結晶性質研究	39
3.1  實驗材料	39
3.2  實驗儀器	41
3.3  摻合物配方表..…………………………..……….………….….………..42
3.4  實驗方法……………………………………………………...…………..43
(1)試樣製作	43
(2) TGA分析	43
(3) DSC分析	44
(4) XRD分析	44
(5) SEM分析	.44
        (6) 機械性質................................................................................................45
        (7) Biocompatibility ..……………………………………………….................................45
3.5  結果與討論	46
3.5.1  TGA分析	46
3.5.2  DSC分析	49
3.5.3  XRD分析	52
    3.5.4  SEM分析.................................................................................................54
3.5.5  機械性質	56
3.5.6  Biocompatibility觀察	58
3.6  結論	60
第四章 聚對苯二甲酸丙二酯/聚苯乙烯-聚乙烯-聚丁烯-聚苯乙烯複合複材之生物
       相容性、機械性質、熱性質及結晶性質研究...………………………………….…..61
4.1  實驗材料	61
4.2  實驗儀器	63
4.3  摻合物配方表..…………………………...………….………….…….….64
4.4  實驗方法……………………………………………………...……….….65
(1)試樣製作	65
(2) TGA分析	65
(4) DSC分析	65
(5) XRD分析	65
(6) SEM分析	65
        (7) 機械性質..............………………………………………………................................67
4.5  結果與討論	68
4.5.1  TGA分析	68
4.5.2  DSC分析	71
4.5.3  XRD分析	87
4.5.4  POM觀察	90
4.5.5  SEM觀察	92
    4.5.6  機械性質..................................................................................................94
4.6  結論	96
參考文獻	97

表目錄

表2.2.1  Avrami參數與高分子結晶型態之關係……………………….…….….22
表3.3.1  PLA/SEBS複材配方表. ..........................................................................42
表3.5.1  PLA、PLA/SEBS Blends和SEBS之TGA分析表………….….........48
表3.5.2  PLA和PLA/SEBS Blends非恆溫各數值…………………….….........51
表4.3.1  PTT/SEBS複材配方表. ...........................................................................64
表4.5.1  PTT、PTT/SEBS Blends和SEBS之TGA分析表……….…...............70
表4.5.2  PTT和PTT/SEBS Blends非恆溫各數值………………………............73
表4.5.3  各結晶溫度之Avrami參數…………………………………….….…....74
表4.5.4  Hoffman–Weeks and Lauritzen-Hoffman 各數值………………..……..77



圖目錄

圖1.1   不相容或是相容性很小的體系	5
圖1.2   兩相之間過渡層λ有限的相容	5
圖1.3   UCST與LCST相圖	7
圖1.4   乳酸聚合流程圖	11
圖1.5   L(左旋)型與D(右旋)型PLA分子結構式	..13
圖1.6   芳香族聚酯的結構	.15
圖1.7   熱塑性彈性體分類....................................………………………………...17

圖2.1   晶核生成速率､晶體生長速率與過飽和度的關係	24
圖2.2   結晶速度與溫度關係圖........................................................................…..25
圖2.3   區型轉移(Regime)的示意圖	28
圖2.4   晶體成長與RegimeI、RegimeII、RegimeIII的關係圖	29
圖2.5   多熔融峰形成之示意圖	30
圖2.6   升溫速率不同造成之多熔融峰示意圖	30
圖2.7   Hoffman-Weeks線性外插法求得平衡熔點(Tm0)之示意圖	31
圖2.8   褶曲端表面自由能(σe)及鏈摺疊之板晶厚度(L)示意圖	33
圖2.9   Effect of fine crystallite size on diffraction curves	34
圖2.10  摻合體物性與組成的關係圖(A)協乘增補(B)加成律(C)出現最小值…. 35
圖2.11  應力-應變曲線示意圖................................................................................ 36
圖2.12  平緩降伏型式之應力-應變曲線示意圖.................................................... 36
圖2.13  高分子不同應力-應變曲線類型................................................................ 37

圖3.4.1  CNS 4369, K 64231號試樣之尺寸條件…………......................................45
圖3.5.1  PLA和PLA/SEBS Blends  TGA曲線圖………………..........................47
圖3.5.2  PLA和PLA/SEBS  Blends之DSC 20℃/min升溫曲線圖.....................50
圖3.5.3  PLA和PLA/SEBS  Blends之WXRD圖.................................................53
圖3.5.4  PLA、PLA/SEBS Blends和SEBS之SEM圖..........................................55
圖3.5.5  PLA和PLA/SEBS  Blends之機械性質……...........................................56
圖3.5.6  細胞成長3天(a) PLA, (b) PLA/SEBS-10, (c) PLA/SEBS-30, (d) SEBS……………...59



圖4.5.1  PTT、PTT/SEBS Blends 和SEBS之TGA曲線圖………………........ 69
圖4.5.2  PTT和PTT/SEBS  Blends之DSC 20℃/min升溫曲線圖.................... 75
圖4.5.3  PTT/SEBS-10之Avrami 作圖.................................................................. 76
圖4.5.4  PTT、PTT/SEBS-10和PTT/SEBS-30之Hoffman-Weeks 作圖........... 79
圖4.5.5  PTT、PTT/SEBS-10和PTT/SEBS-30之Lauritzen-Hoffman作圖........ 84
圖4.5.6  PTT和PTT/SEBS  Blends之WXRD圖................................................ 88
圖4.5.7  PTT、PTT/SEBS-10和PTT/SEBS-30之POM圖................................... 91
圖4.5.8  PTT、PTT/SEBS Blends和SEBS之SEM圖.......................................... 93
圖4.5.9  PTT和PTT/SEBS  Blends之機械性質……........................................... 95

                                

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