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研究生:廖巍博
研究生(外文):Wei-Po Liao
論文名稱:以小角度散射法決定高分子微結構
論文名稱(外文):Determination of Polymeric Microstructure by Small-Angle Scattering
指導教授:王紀
指導教授(外文):Chi Wang
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系碩博士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:158
中文關鍵詞:小角度X光散射對排聚苯乙烯小角度光散射
外文關鍵詞:sPSSALSSAXS
相關次數:
  • 被引用被引用:4
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本論文主要分為三個部分,第一個部分是以小角度X光散射儀(SAXS)分析不同比例對排聚苯乙烯(sPS)/亂排聚苯乙烯(aPS)的混摻,以及不同比例metallocene-聚乙烯(mPE1)/聚丙烯(PP)的混摻的微結構,並對數據處理的方法作一整理。第二個部分探討則是以小角度光散射法(SALS)觀察sPS/aPS混摻在等溫結晶時的Hv pattern變化,判斷其內部的晶體結構。第三個部分是以電荷耦合感光元件(CCD)搭配偏光顯微鏡(POM),量測sPS及sPS/aPS混摻晶體成長及熔化時光強度的改變,求得結晶動力學的分析,並觀察正負球晶的熔化情形。
在以SAXS研究混摻的微結構方面,均發現有zero angle scattering的發生。而sPS/aPS的混摻中,aPS添加量的增加並未對長週期尺寸發生影響,表示aPS並未能達到interlamellar級的分散;mPE1/PP混摻中則並未發現有兩種長週期厚度的分佈。
以SALS判斷sPS系統晶體的實驗中,發現並未觀察到明顯的四片葉子,而其強度的分佈也是隨q(散射向量)的增加而decay,可判斷表現出來的Hv pattern較接近球晶與軸晶的混合,另一方面發現隨時間的增加以及結晶溫度的升高,散射圖形皆有漸小的趨勢。
利用CCD搭配POM的部分中,發現sPS正、負球晶具有相同的熔化機制,而所求得的熔點和示差掃瞄熱卡計(DSC)所得相當接近。由CCD搭配POM所求得的平衡熔點為286oC,和DSC所得的292oC略有差異,其中的差異可能在於與DSC的樣品量的多寡所造成熱傳的不同。等溫結晶之Avrami參數之n值接近3。
The research is separated into three parts. In the first part, small-angle X-ray scattering (SAXS) is used to analyze the microstructure of syndio tactic polystyrene (sPS)/atatic polystyrene (aPS) and metallocene polyethylene (mPE1)/polypropylene (PP) blends in different ratios. A procedure in dealing with the raw data is established. In the second part, the internal crystal structures of sPS/aPS blends were carried out by observing the changes of Hv patterns obtained from small-angle light scattering (SALS). In the final part, charged coupled device (CCD) and a polarized optical microscope (POM) were used to measure the change of light intensities in the growth or melting of the sPS/aPS blends. The melting process of positive or negative spherulites can also be observed.
In the study of microstructure, zero-angle scattering can be detected by SAXS in sPS/aPS and mPE1/PP blends. The values of long period remain constant with increasing aPS in sPS/aPS blends, implying that the addition of aPS can’t reach the level of interlamellar segregation. Only single distribution of the long period can be found in mPE1/PP blends.
Apparent cloverleaf patterns can’t be observed by small-angle light scattering (SALS) in the sPS system. The scattering intensity decays with q (scattering vector). According to this, we can conclude that the Hv patterns obtained are from the contribution of both spherulites and axilites. On the other hand, the longer time or higher crystallization temperature, the smaller scattering patterns.
The same melting behavior is found in positive and negative spherulites of sPS by CCD and POM. Melting points computed from POM experiment are close to the differential scanning calorimeter (DSC) results. The melting points obtained from DSC and POM are 292oC and 286oC, respectively. The difference may result from different heat transfer mechanism.
中文摘要 i
英文摘要 ii
誌謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
附錄目錄 xii
一、前言 1
二、簡介 2
2.1 SAXS部分 2
2.2 SALS部分 4
2.3 CCD+POM部分 5
三、文獻回顧 7
3.1 SAXS部分 7
3.2 SALS部分 8
3.3 CCD+POM部分 9
四、理論 11
4.1 SAXS理論模型 11
4.2 SALS理論與公式 14
4.3 Avrami 方程式 17
4.4 平衡熔點(Tmo) 20
五、實驗部分 21
5.1 實驗樣品 21
5.2 實驗儀器 21
5.3 實驗步驟 23
5.3.1 樣品製備 23
5.3.2 SAXS操作步驟 25
5.3.3 SALS操作步驟 31
5.3.4 CCD+POM使用步驟 35
5.3.5 CCD軟體使用步驟 36
5.3.6 DSC操作步驟 41
六、結果與討論 42
6.1 SAXS部分 42
6.1.1 sPS/aPS微結構分析 42
6.1.2 mPE1/PP微結構分析 44
6.2 SALS部分 47
6.2.1 L的校正 47
6.2.2 radius average 47
6.2.3 LDPE等溫結晶 48
6.2.4 sPS系統微結構分析 49
6.3 CCD+POM部分 51
6.3.1 純sPS及摻合系統晶體熔化行為 51
6.3.2 Avrami方程式 52
6.3.3 平衡熔點 52
6.3.4 球晶成長速率 52
七、結論 53
八、參考文獻 54
表 59
圖 66
附錄 137
1.G. H. Meeten, “Optical Properties of Polymers”, Elsevier Applied Science Publishers, London and New York.
2.P. Debye, A. M. Bueche, “Scattering by an Inhomogeneous Solid”, J. Appl. Phys., 20, 518 (1949).
3.M. Goldstein, E. R. Michalik, J. Appl. Phys., 26, 1450 (1955).
4.J. A. Prins, W. Prins, Physica, 22, 567 (1956).
5.S. Clough, M. B. Rhodes, R. S. Stein, “Theory of Light Scattering from Oriented and Fiber Structures” J. Polym. Sci. C, 18, 1 (1967).
6.R. S. Stein, C. Picot, “The Effect of Interference between Anisotropic Scattering Entities on the Light Scattering from Polymer Films. I. Case of NO Impingement”, J. Polym. Sci. A-2, 8, 1955 (1970).
7.R. S. Stein, “Rheo-Optical Studies of the Deformation of Crystalline Polymers”, J. Polym. Sci. C, 15, 185 (1966).
8.F. H. Norris, R. S. Stein, “The Scattering of Light Thin Polymer Films Ⅳ. Scattering from Oriented Polymers” J. Polym. Sci., 17, 87 (1958).
9.R. E. Prud’Homme, R. S. Stein, “Scattering from Truncated Spherulites”, J. Polym. Sci., Polym. Phys. Ed., 13, 1683 (1973).
10.M. Gruwe, “High Speed Multiplexed Pipelined Optoelectronic Devied: CCDs and EBCCDs”, Nuclear Instruments and Methods in Physics Research, A, 387, 282 (1997).
11.M. Avella, E. Martuscelli, “Poly-D(-)(3-Hydroxybutyrate) Poly(Ethylene Oxide) Blends - Phase-Diagram, Thermal and Crystallization Behavior”, Polymer, 29, 1731 (1998).
12.H. L. Chen, S. F. Wang, T. L. Lin, “Morphological Structure of Crystalline Polymer Blend Involving Hydrogen-Bonding - Polycaprolactone/Poly(4-Vinylphenol) System”, Macromolecules, 31, 8924 (1998).
13.H. J. Chiu, H. L. Chen, T. L. Lin, J. S. Lin, “Phase-Structure of Poly(3-Hydroxy Butyrate)/Poly(Vinyl Acetate) Blends Probed by Small-Angle X-Ray-Scattering”, Macromolecules, 32, 4969 (1999).
14.H. L. Chen, M. S. Hsiao, “Morphological Structure Induced by Combined Crystallization and Liquid-Liquid Demixing in Poly(Ethylene-Terephthalate) Poly(Ether Imide) Blends” Macromolecules, 31, 6579 (1998).
15.W. Wenig, F. Z. Karasz, W. J. Macknight, J. W.“Structure and Properties of the System:Poly(2,6-dimethyl-phenylene oxide) Isotactic Polystyrene. Small-Angle X-ray Studies” J. Appl. Phys., 46, 4194 (1975).
16.F. B. Khambatta, F. Warner, T. P. Rusell, R. S. Stein, “Small-Angle X-Ray and Light Scattering Studies of the Morphology of Blends of Poly(��-caprolactone) with Poly(vinyl chloride)” J. Polym. Sci., Polym. Phys. Ed. 14, 1391 (1976).
17.T. P. Russell, R. S. Stein, “An Investigation of the Compatibility and Morphology of Semicrystalline Poly(��-caprolactone)-Poly(vinyl chloride) Blends” J. Polym. Sci., Polym. Phys. Ed. 21, 999 (1983).
18.S. Talibuddin, L. Wu, J. P. Runt, J. S. Lin, “Microstructure of Melt-Miscible, Semicrystalline Polymer Blends” Macromolecules, 29, 7527 (1996).
19.H. L. Chen, L. J. Li, T. L. Lin, “Formation of Segregation Morphology in Crystalline/Amorphous Polymer Blends - Molecular-Weight Effect” Macromolecules, 31, 2255 (1998).
20.H. L. Chen, H. H. Liu, J. S. Lin, “Microstructure of Semicrystalline Poly(L-lactide)/Poly(4-vinylphenol) Blends Evaluated from SAXS Absolute Intensity Measurement” Macromolecules, 33, 4856 (2000).
21.H. L. Chen, M. S. Hsiao, “Morphology Structure Induced by Combined Crystallization and Liquid-Liquid Demixing in Poly(ethylene terephthalate)/Poly(ether imide) Blends”, Macromolecules, 31, 6579 (1998).
22.F. P. Warner, W. J. Macknight, R. S. stein, “Small-Angle X-Ray Scattering Study of Blends of Isotactic and Atactic Polystyrene” J. Polym. Sci., Polym. Phys. Ed., 15, 2113 (1977).
23.J. D. Barnes, G. B. Mckenna, B. G. Landes, R. A. Bubeck, D. Bank, “Morphology of Syndiotactic Polystyrene as Examined by Small-Angle X-Ray-Scattering” Polym. Eng. Sci., 37, 1480 (1997).
24.J. D. Barnes, R. Kolb, K. Barnes, A.I. Nakatani, B. Hammouda, “Microstructure Analysis Using Temperature-induced Contrast Variation in Small-Angle Scattering” J. Appl. Cryst., 33, 758 (2000)
25.S. M. Hong, S. H. Choi, C. H. Lee, S. S. Hwang, K. U. Kim, I. Cho, “Crystalline Morphology and Melting Behavior of 100% Syndiotactic Polystyrene and 70/30 Blend of Syndiotactic Polystyrene and Poly(2,6-dimethyl-1, 4-phenylenoxide)” Polymer journal, 32, 187 (2000).
26.J. M. Schulz, “Rapid Small-Angle and Wide-Angle X-Ray Studies of Crystallization Behavior in Polymers”J. Polym. Sci., Polym. Phys. Ed., 14, 2291 (1976).
27.R. S. Stein, M. B. Rhodes, “Photographic Light Scattering by Polyethylene Films”, J. Appl. Phys., 31, 1873 (1960).
28.R. J. Tabar, P Leite-James, R. S. Stein, “Quantitative Small-Angle Light-Scattering Studies of the Melting Poly(ethylene terephthalate)”, J. Polym. Sci., Polym. Phys. Ed., 23, 2085 (1985).
29.M. Okamoto, H. Kubo, T. Kotaka, “Elongational Flow-Induced Higher-Order Structure Development in a Supercooled Liquid of a Metallocene-Catalyzed Syndiotactic Polystyrene”, Macromolecules, 32, 6206 (1999).
30. M. Okamoto, H. Kubo, T. Kotaka, “Elongational Flow-Induced Crystallization and Structure Development in Supercooled Poly(Ethylene Naphthalate)” Macromolecules, 31, 4223 (1998).
31.K. Tashiro, M. Izuchi, M. Kobayashi, R. S. Stein, “Cocrystallization and Phase Segregation of Polyethylene Blends Between the D and H Species .3. Blend Content Dependence of the Crystallization Behavior”, Macromolecules, 27, 1234 (1994).
32.許耀中, “對排聚苯乙烯結晶動力學研究”, 元智大學化學工程所碩士論文 (1999).
33.羅俊峰, “對排聚苯乙烯及對排/亂排聚苯乙烯摻合體熔融結晶與晶體成長研究”, 元智大學化學工程所碩士論文 (2000).
34.張世昌, “對排/亂排聚苯乙烯混摻晶體成長研究”, 成功大學化學工程所碩士論文 (2001).
35.J. H. Magill, “A new Method for Following Rapid Rates of Crystallization I. Poly(hexamethylene adipamide)”, Polymer, 2, 221 (1961).
36. J. H. Magill, “A new Technique for Following Rapid Rates of Crystallization Ⅱ.Isotactic Polypropylene”, Polymer, 3, 85 (1962).
37.F. J. Binsbergn, “Heterogeneous Nucleation in the Crystallization of Polyolefins: Part2. Kinetics of Crystallization of Nucleated Polypropylene”, polymer, 11, 309 (1970).
38.Y. C. Kim, C. Y. Kim, S. C. Kim, “Crystallization Characteristics of Isotactic Polypropylene with and without Nucleating-Agents”, Polym. Eng. Sci., 31, 1009 (1991).
39. C. F. Pratt, S. Y. Hobbs, “Comparative Study of Crystallization Rates by DSC and Depolarization Microscopy”, polym., 17, 12 (1976).
40.Z. Ding, J. E. Spruizll, “An Experimental Method for Studying Nonisothermal Crystallization of Polymers at Very High Cooling Rates”, J. Polym. Sci., Polym. Phys. Ed., 34, 2783 (1996).
41.L. A. Feigin, D. I. Svergun, “Structure Analysis by Small-Angle X-Ray and Neutron Scattering”, Plenum Press, New York and London (1989).
42.A. Guinier, G. Fourent, “Small-Angle Scattering of X-rays”, New York (1955).
43.O. Glatter, O. Kratky, “Small-Angle X-ray Scattering”, Academic Press, New York (1982).
44. 倪子傑, “mPE/LDPE與mPE/PP摻合物之結晶動力學研究”, 元智大學化學工程所碩士論文 (1998).
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