SAXS研究四臂聚氧化乙烯片晶的增厚
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摘要
使用小角X光散射(SAXS)方法研究了每臂分子量为5000的四臂聚氧化乙烯在从熔点以上的温度淬火到室温后,在室温到熔点前的温度区域里片晶的增厚过程.采用一维相关函数分析方法分析了SAXS数据,获得了样品的长周期、线性结晶度、结晶层和无定形层厚度随温度的变化.按照这些参数在升温过程中的演变规律,确定了3个特征区域.Ⅰ区约在26~45℃内,存在着3种不同厚度的片晶,最厚的片晶层厚度为9.3 nm,线性结晶度、长周期、结晶层和无定形层厚度等参数基本不变,称为不变区.Ⅱ区约在45~52℃之间,这些参数都发生变化,SAXS的主峰分化为两个主要的峰,长周期、结晶层和无定形层厚度开始增加,但是,线性结晶度升高后又降低,称为转变区.Ⅲ区约在52~60℃之间,体系中只有单一厚度的片晶,其厚度不断增厚,到60℃结晶层厚度达15.8 nm,称为增厚区.从分子运动和片晶亚稳定本质分析,可以解释实验上观察到的3个区域发生变化的本质:在不变区里,主要的分子运动几乎被冻结,不可能发生可检测到的片晶结构变化.在转变区里,分子运动开始起作用,未结晶的分子开始结晶.同时,薄片晶会熔融,尔后又重新结晶.在增厚区里,线性结晶度和结晶层厚度增加,也意味着熔融-重结晶过程还在继续,直至达到这个样品可能形成的最厚片晶的熔点.实验观察到的熔融-重结晶过程的本质是聚合物片晶的亚稳态特性,稳定性低的薄片晶向稳定性高的厚片晶转变,即一个典型的奥斯瓦尔德熟化(Ostwald ripening).
Studies on the lamellar thickening of a 4-arm poly( ethylene oxide) with Mn= 5000 for each arm are reported. The samples were prepared by quenching from 70 ℃ to 10 ℃. Small-angle X-ray scattering( SAXS) was used to track the variation of lamellar structure during heating process. Then the SAXS data were further analyzed using one-dimensional correlation function. The following parameters,such as long period, linear crystallinity,crystalline layer thickness and amorphous layer thickness,were determined. Their changes with increasing temperature suggest three temperature regions. Region Ⅰ is in 26 ~ 45 ℃. There are three broad scattering peaks with low scattering intensity. They correspond to lamellae with different thicknesses. The crystalline layer thickness of the dominated lamella is about 9. 3 nm. Importantly,the parameters mentioned above remain unchanged in Region Ⅰ. Region Ⅱ within 45 ~ 52 ℃ is a transition one. The main peak of the SAXS curves turns into two. The long period,linear crystallinity,crystalline layer thickness and amorphous layer thickness began to increase. Region Ⅲ( 52 ~ 60 ℃) is a thickening region within which the crystalline layer thickness clearly increased with increasing temperature. At 60 ℃ its value is 15. 8 nm. These observed results found in the three regions were further explained based on the role of metastable states of polymer lamellae. Within region Ⅰ macromolecules were in a frozen state,thus it was impossible to detect any change related to the lamellar structure. Within region Ⅱ,the temperature is higher enough to let some thin crystalline layers melt and then the melted macromolecules would recrystallize around the thicker ones. In region Ⅲ the continuous melting-recrystallization process proceeds until the melting point of the sample. The observed melting-recrystallization process reflects the metastability of polymer lamellae: Thinner lamellae are in a metastable state with a lower stability,thus will melt to recrystallize to form thicker lamellae with a higher stability. Acctually,the continuous melting-recrystallization process is a typical Ostwald ripening of polymer lamellae.
Studies on the lamellar thickening of a 4-arm poly( ethylene oxide) with Mn= 5000 for each arm are reported. The samples were prepared by quenching from 70 ℃ to 10 ℃. Small-angle X-ray scattering( SAXS) was used to track the variation of lamellar structure during heating process. Then the SAXS data were further analyzed using one-dimensional correlation function. The following parameters,such as long period, linear crystallinity,crystalline layer thickness and amorphous layer thickness,were determined. Their changes with increasing temperature suggest three temperature regions. Region Ⅰ is in 26 ~ 45 ℃. There are three broad scattering peaks with low scattering intensity. They correspond to lamellae with different thicknesses. The crystalline layer thickness of the dominated lamella is about 9. 3 nm. Importantly,the parameters mentioned above remain unchanged in Region Ⅰ. Region Ⅱ within 45 ~ 52 ℃ is a transition one. The main peak of the SAXS curves turns into two. The long period,linear crystallinity,crystalline layer thickness and amorphous layer thickness began to increase. Region Ⅲ( 52 ~ 60 ℃) is a thickening region within which the crystalline layer thickness clearly increased with increasing temperature. At 60 ℃ its value is 15. 8 nm. These observed results found in the three regions were further explained based on the role of metastable states of polymer lamellae. Within region Ⅰ macromolecules were in a frozen state,thus it was impossible to detect any change related to the lamellar structure. Within region Ⅱ,the temperature is higher enough to let some thin crystalline layers melt and then the melted macromolecules would recrystallize around the thicker ones. In region Ⅲ the continuous melting-recrystallization process proceeds until the melting point of the sample. The observed melting-recrystallization process reflects the metastability of polymer lamellae: Thinner lamellae are in a metastable state with a lower stability,thus will melt to recrystallize to form thicker lamellae with a higher stability. Acctually,the continuous melting-recrystallization process is a typical Ostwald ripening of polymer lamellae.
引文
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41 Ma Z P,Zhang G L,Zhai X M,Jin L X,Tang X F,Yang M,Zheng P,Wang W.Polymer,2008,49:1629~1634
42 Zhang G L,Jin L X,Ma Z P,Zhai X M,Yang M,Zheng P,Wang W,Wegner G.J Chem Phys,2008,129:224708
43 Jin L X,Zhang G L,Zhai X M,Ma Z P,Zheng P,Wang W.Polymer,2009,50:6157~6157
44 Zhang G L,Jin L X,Zheng P,Shi A C,Wang W.Polymer,2010,51:554~562
45 Zhang G L,Cao Y,Jin L X,Zheng P,van Horn R M,Lotz B,Cheng S Z D,Wang W.Polymer,2011,52:1133~1140
46 Zhang G L,Zhai X M,Ma Z P,Jin L X,Zheng P,Wang W,Cheng S Z D,Lotz B.ACS Macro Lett,2012,1:217~221
47 Zhang G L,Jin L X,Zheng P,Wang W,Wen X J.Chinese J Polym Sci,2013,31(5):798~808
48 Zhang Guoliang(张国梁),Wen Xiaojing(温笑菁),Zhai Xuemei(翟雪梅),Wang Wei(王维).Acta Polymerica Sinica(高分子学报),2013,(3):398~405
49 Chen E Q,Lee S W,Zhang A,Moon B S,Harris F W,Cheng S Z D,Hsiao B S,Yeh F,Merrewell E V,Grubb D T.Macromolecules 1999,32:4784~493
50 Strobl G R,Schneider M.J Polym Sci Part B Polym Phys B,1980,18:1343~1359
51 Stribeck N,X-ray Scattering of Soft Matters.Berlin:Springer,2007.145
2 Ratke L,Voorhees P W.Growth and Coarsening-ostwald Ripening in Material Processing.Berlin:Springer,2002
3 Bassett B C.Principles of Polymer Morphology.Cambridge:Cambridge University Press,1981
4 Wunderlich B.Macromolecular Physics.New York:Ed.Academic Press,1973
5 Armistead K,Goldbeck-Wood G.Adv Polym Sci,1992,100:221~312
6 Strobl G.The physics of polymers,2nd Ed.Berlin,Heidelberg,New York:Springer,1997
7 Keller A,Cheng S Z D.Polymer,1998,39:4461~4487
8 Ungar G,Zeng X B.Chem Rev,2001,101:4157~4188
9 Cheng SZD,Phase Transitions in Polymers:The role of Metastable States.Berlin:Elsevier Science,2008
10 O’Leary K,Geil P H.J Macromol Sci-Phys,1967,B1:147~160
11 Mandelkern L,Sharma R K,Jackson J F.Macromolecules,1969,2:644~656
12 Fischer E W.Pure Appl Chem,1971,26:385~422
13 Ichida T,Tsuji M,Murakami S,Kawaguchi A,Katayama K.Colloid&Polym Sci,1985,263:293~300
14 Cho M H,Kyu T,Lin J S,Saijo K,Hashimoto T.Polymer,1992,33:4152~4157
15 Matsuda H,Aoike T,Uehara H,Yamanobe T.Komoto T.Polymer,2001,42:5013~5021
16 Zhai X M,Wang W,Ma Z P,Wen X J,Yuan F,Tang X F,He B L.Macromolecules,2005,38:1717~1722
17 Tang X F,Wen X J,Zhai X M,Xia N,Wang W.Macromolecules,2007,40:4386~4388
18 Xia Nan(夏楠),Tang Xiongfeng(唐雄峰),Wen Xiaojing(温笑菁),Zhang Guoliang(张国梁),Zhai Xuemei(翟雪梅),Wang Wei(王维).Acta Polymerica Sinica(高分子学报),2011,(9):1040~1052
19 Ikeda Y,Nagasaki Y.Adv Polym Sci,2012,247:115~140
20 Ohya Y,Takahashi A,Nagahama K.Adv Polym Sci,2012,247:65~114
21 Stephan A M.Eur Polym J,2006,42:21~42
22 Kovacs A J,Gonthier A,Straupe C.J Polym Sci Polym Symp,1975,50:283~325
23 Kovacs A J,Straupe C,Gonthier A.J Polym Sci Polym Symp,1977,59:31~54
24 Kovacs A J,Straupe C.J Cryst Growth,1980,48:210~226
25 Hoffman J D.Macromolecules,1986,19:1124~128
26 Arlie P,Spegt P A,Skoulios A.Makomol Chem,1966,99:160~174
27 Arlie P,Spegt P A,Skoulios A.Makomol Chem,1967,104:212~229
28 Mandelkern L,Sharma R K,Jackson J F.Macromolecules,1969,2:644~656
29 Spegt P.Makromol Chem,1970,139:139~152
30 Dreyfuss P,Keller A J.J Macromol Sci-Phys,1970,B4:811~836
31 Pope D P,Keller A J.J Polym Sci:Polym Phys Ed,1976,14:821~831
32 Takhashi Y,Tadokoro H.Macromolecules 1973,6:672~675
33 Thierry A,Skoulios A E.Eur Polym J,1977,13:169~170
34 Cheng S Z D,Zhang A Q,Barley J S,Chen J H,Habenschuss A,Zschack P R.Macromolecules,1991,24:3937~3944
35 Cheng S Z D,Chen J H,Zhang A Q,Barley J S,Habenschuss A,Zschack P R.Macromolecules,1992,25:1453~1460
36 Cheng S Z D,Wu S S,Chen J H,Zhuo Q,Quirk R P,von Meerwall E D,Hsiao B S,Habenschuss A,Zschack P R.Macromolecules,1993,26:5105~5117
37 Zhu D S,Liu Y X,Shi A C,Chen E Q.Polymer,2006,47:5239~5242
38 Liu Y X,Li J F,Zhu D S,Chen E Q,Zhang H D.Macromolecules,2009,42:2886~2890
39 Zhai X M,Wang W,Zhang G L,He B L.Macromolecules,2006,39:324~329
40 Zhai X M,Zhang G L,Ma Z P,Tang X F,Wang W.Macromol Chem Phys,2007,208:651~656
41 Ma Z P,Zhang G L,Zhai X M,Jin L X,Tang X F,Yang M,Zheng P,Wang W.Polymer,2008,49:1629~1634
42 Zhang G L,Jin L X,Ma Z P,Zhai X M,Yang M,Zheng P,Wang W,Wegner G.J Chem Phys,2008,129:224708
43 Jin L X,Zhang G L,Zhai X M,Ma Z P,Zheng P,Wang W.Polymer,2009,50:6157~6157
44 Zhang G L,Jin L X,Zheng P,Shi A C,Wang W.Polymer,2010,51:554~562
45 Zhang G L,Cao Y,Jin L X,Zheng P,van Horn R M,Lotz B,Cheng S Z D,Wang W.Polymer,2011,52:1133~1140
46 Zhang G L,Zhai X M,Ma Z P,Jin L X,Zheng P,Wang W,Cheng S Z D,Lotz B.ACS Macro Lett,2012,1:217~221
47 Zhang G L,Jin L X,Zheng P,Wang W,Wen X J.Chinese J Polym Sci,2013,31(5):798~808
48 Zhang Guoliang(张国梁),Wen Xiaojing(温笑菁),Zhai Xuemei(翟雪梅),Wang Wei(王维).Acta Polymerica Sinica(高分子学报),2013,(3):398~405
49 Chen E Q,Lee S W,Zhang A,Moon B S,Harris F W,Cheng S Z D,Hsiao B S,Yeh F,Merrewell E V,Grubb D T.Macromolecules 1999,32:4784~493
50 Strobl G R,Schneider M.J Polym Sci Part B Polym Phys B,1980,18:1343~1359
51 Stribeck N,X-ray Scattering of Soft Matters.Berlin:Springer,2007.145