表面场诱导线性三嵌段共聚物薄膜的微结构及其转变规律
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摘要
采用实空间自洽场理论研究了ABC对称线性三嵌段共聚物薄膜的自组装结构及其转变规律.选取具有特定聚合物参数的对称线性三嵌段共聚物,对无修饰条纹和有修饰条纹的两类薄膜受限表面情况,通过调节其薄膜表面场强度和薄膜厚度,获得了一系列新颖的聚合物薄膜微结构.研究结果表明,在无修饰条纹的单一薄膜受限情况下,共聚物趋向于形成规整有序的层状或穿孔层状结构;而在有条纹修饰情况下,共聚物在相应的条纹修饰区域下发生微相分离并趋于形成水平柱状结构.
The real space self-consistent field theory was applied to investigate microstructures and transformation of linear triblock copolymer films induced by surface field. We choose symmetric composition of copolymers fA∶ fB∶ fC= 0. 2∶ 0. 6∶ 0. 2 and the incompatibility degrees of copolymers are set as χAB= χAC= χBC=30. The thickness of films is set to be 4. 5Rgor 9Rgin our simulation. In order to obtain a series of novel microstructures under the above two different thicknesses of films,we study two kinds of thin films with nonmodified stripes and modified stripes. And in the process of simulation,we can adjust the surface field strength of the thin films regularly. The strongest surface field strength is set equal to the interaction between copolymers( χi WN = 30,i∈A,B,C). The surface interaction is increased from the weakest surface interaction( χi WN = 5)in turn to the strongest surface field strength,and the gap of adjacent two kinds surface field strength is set asΔχi WN = 5. Depending on changing these parameters of simulation,we have obtained a wealth of microstructures. The microstructures show that the copolymers tend to form a regular and ordered lamellar or perforated layer confined thin films with non-modified stripes,while in the case of films with modified stripes,the copolymers tends to self assemble into horizontal structures in their respective modified stripe areas.
The real space self-consistent field theory was applied to investigate microstructures and transformation of linear triblock copolymer films induced by surface field. We choose symmetric composition of copolymers fA∶ fB∶ fC= 0. 2∶ 0. 6∶ 0. 2 and the incompatibility degrees of copolymers are set as χAB= χAC= χBC=30. The thickness of films is set to be 4. 5Rgor 9Rgin our simulation. In order to obtain a series of novel microstructures under the above two different thicknesses of films,we study two kinds of thin films with nonmodified stripes and modified stripes. And in the process of simulation,we can adjust the surface field strength of the thin films regularly. The strongest surface field strength is set equal to the interaction between copolymers( χi WN = 30,i∈A,B,C). The surface interaction is increased from the weakest surface interaction( χi WN = 5)in turn to the strongest surface field strength,and the gap of adjacent two kinds surface field strength is set asΔχi WN = 5. Depending on changing these parameters of simulation,we have obtained a wealth of microstructures. The microstructures show that the copolymers tend to form a regular and ordered lamellar or perforated layer confined thin films with non-modified stripes,while in the case of films with modified stripes,the copolymers tends to self assemble into horizontal structures in their respective modified stripe areas.
引文
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29 Fredrickson D,Fredrickson G.Phys Rev Lett,1999,83(21):4317-4320
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34 Jiang Z B,Wang R,Xue G.Chinese J Polym Sci,2009,27(4):583-592
35 Ramírez H,Liu G,Nealey P.Macromolecules,2012,45(5):2588-2596
2 Tsoyi K,Jang H,Kim Y,Lee Y,Kim H,Seo H,Lee J,Chang K C.Br J Pharmacol,2011,162(7):1498-508
3 Alexander V,Elena V,Valery Y.J Control Release,2002,82:189-212
4 Tian Ye(田野),Tang Lidan(唐丽丹),Liu Jianping(刘建平),Ge Liang(葛亮).Prog Pharm Sci(药学进展),2014,07:1-5
5 Breuer M,Drossel B.Macromolecules,2008,41(20):7679-7686
6 Horvat A,Lyakhova K,Sevink G,Zvelindovsky A,Magerle R.J Chem Phys,2004,120(2):1117-1126
7 Alejandro S,Ezquerra T,Rebeca H,Michael S,Aurora N.J Chem Phys,2015,142(6):1091-1094
8 Takahashi H,Laachi N,Delaney K T,Hur S,Weinheimer C.Macromolecules,2012,45(15):6253-6265
9 Yang Y,Jeon Y,Kim J,Cho J.Eur Phys J.E,2012,35(9):1-10
10 Wang Q,Nath S K,Graham M,Nealey P F,Pablo J.J Chem Phys,2000,112(22):9996-10010
11 Wang Q.Macromol Theor Simul,2005,14(2):96-108
12 Ye X,Edwards B J,Khomami B.Macromolecules,2010,43(23):9594-9597
13 Zhang Hongdong(张红东),Yang Qiutang(杨邱唐).Sci China(中国科学),2006,49:21-43
14 Lin C Y,Schick M,Andelman D.Macromolecules,2005,38(13):5766-5773
15 Xiao X,Huang Y,Liu H,Hu Y.Macromol Theor Simul,2007,16(2):166-177
16 He X,Huang L,Liang H,Pan C.J Chem Phys,2003,118(21):9861-9863
17 Chen P,Liang H J.J Phys Chem B,2006,110(37):18212-18224
18 Fan Juanjuan(樊娟娟),Han Yuanyuan(韩媛媛),Jiang Wei(姜伟).Acta Chim Sinica(化学学报),2011,19(19):2341-2346
19 Cui J,Jiang W.Langmuir,2010,26(16):13672-13656
20 Qiu W,He L,Ji Y,Wang X,Li S B.Polymer,2012,53(15):3392-3402
21 Tan H,Song Q G,Yang X H,Deng Y.Open Journal of Applied Sciences,2012,02(3):163-167
22 Lin B,Zhang H D,Qiu F,Yang Y L.Langmuir,2010,26(24):19033-19044
23 Joona B S,Eric D,Matthew J,Hawker T.J Am Chem Soc,2006,128(23):7622-7629
24 Jiang Z B,Qiu Y,Wang X,Zhou D S,Xue G.Nanoscale Res Lett,2014,9:359-69
25 Huinink HP,Brokken J,Dijk M,Sevink G.J Chem Phys,2000,112(5):2452-2462
26 Khanna V,Hexemer A,Stein G,Fredrickson G,Kramer XL,Wang J,Hahn S.Macromolecules,2006,39(26):9346-9356
27 Han W,Li X,Qiu F,Zhang H D,Yang Y.J Phys Chem B,2008,112(44):13738-13748
28 Edward S.Proceedings of the Physical Society,1965,85(4):613-624
29 Fredrickson D,Fredrickson G.Phys Rev Lett,1999,83(21):4317-4320
30 Nagpal U,Detcheverry F,Nealey P,Pablo J.Macromolecules.2011;44(13):5490-5497
31 Xia J F,Qiu F,Zhang H D,Yang Y L.Macromolecules,2005,38(22):9324-9332
32 Shi A C,Li B H.Soft Matter,2013,9(5):1398-1413
33 Li W H,Liu M J,Qiu F.J Phys Chem B,2013,117(17):5280-5288
34 Jiang Z B,Wang R,Xue G.Chinese J Polym Sci,2009,27(4):583-592
35 Ramírez H,Liu G,Nealey P.Macromolecules,2012,45(5):2588-2596