刚-柔嵌段共聚物在有序排列的微米圆盘表面自组装构筑多级结构
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摘要
在材料表面构筑聚合物多级结构可以显著提升其性能并赋予新的性能,但是目前已有的制备方法较为繁琐,需要开发简单易行的新方法。结合聚苯乙烯(PS)的可控蒸发组装和聚(γ-苄基-L-谷氨酸酯)-聚乙二醇(PBLG-b-PEG)刚-柔嵌段共聚物溶液自组装方法,在硅片表面构建了梯度排列且表面具有纳米条纹的微米圆盘多级结构。采用光学显微镜、原子力显微镜(AFM)和接触角测量仪等对微结构形貌及硅片的表面润湿性进行了表征。PS溶液经可控蒸发自组装在硅片表面形成梯度变化的微米圆点图案,经热处理及溶剂清洗后,得到微米圆盘。通过溶液自组装方法,PBLG-b-PEG在PS微米圆盘表面形成有序排列的周期性纳米条纹。材料的接触角随着图案表面微结构从半球状圆点到表面平整的圆盘再到表面带有纳米条纹的圆盘的变化持续降低。
Hierarchical structures on the surface of materials can enhance their physical-chemical properties and enable extra functions.However,current fabrication method usually involves complex procedures and special treatments.A facile method towards the formation of hierarchical structures on the surface of materials is highly desired.In this work,orderly arrayed PS micro-disks were firstly prepared through controlled evaporating self-assembly of PS solutions on the silicon substrate followed by heating treatment and rinsing with solvent.Subsequently,hierarchical structures on the silicon substrate were prepared through self-assembly of poly(γ-benzyl-L-glutamate)-block-poly(ethylene glycol)(PBLG-b-PEG)rod-coil block copolymers on the obtained orderly arrayed PS micro-disks.The surface morphology of the microdisks was observed by optical microscope and atom force microscope,and the wettability of the patterned surface was characterized by contact angle meter.PS hemispherical micro-dots were formed by the controlled evaporating self-assembly of PS solutions on the silicon substrate,and the micro-dots well organized in gradient arrays.After thermal annealing and extensive rinsing with solvent,the PS segments were irreversibly adsorbed on the silicon substrate,leading to ultrathin PS micro-disks.The surface of the micro-disks is smooth and the thickness of the disks is approximately 11 nm.These PS micro-disks are immersed in the THF/DMF solution of PBLG-b-PEG block copolymers.With the addition of water,the block copolymers self-assembled on the surface of the micro-disks,giving rise to periodic nano-sized stripes.The height,pitch,and width of the nano-sized stripes are approximately 5,50 nm,and 22 nm,respectively.Interestingly,the surface wettability of the substrates presents dependence on the microstructures.As the microstructures transformed from the PS micro-dots to the PS micro-disks and then to the stripe-patterned disks,the contact angle decreases gradually,indicating the increase in wettability.This work provides an effective approach to construct hierarchical structures on the surface of materials,and the stripe-patterned disks obtained in this work will have potential applications in bionics,biosensors,and nanotechnology.
Hierarchical structures on the surface of materials can enhance their physical-chemical properties and enable extra functions.However,current fabrication method usually involves complex procedures and special treatments.A facile method towards the formation of hierarchical structures on the surface of materials is highly desired.In this work,orderly arrayed PS micro-disks were firstly prepared through controlled evaporating self-assembly of PS solutions on the silicon substrate followed by heating treatment and rinsing with solvent.Subsequently,hierarchical structures on the silicon substrate were prepared through self-assembly of poly(γ-benzyl-L-glutamate)-block-poly(ethylene glycol)(PBLG-b-PEG)rod-coil block copolymers on the obtained orderly arrayed PS micro-disks.The surface morphology of the microdisks was observed by optical microscope and atom force microscope,and the wettability of the patterned surface was characterized by contact angle meter.PS hemispherical micro-dots were formed by the controlled evaporating self-assembly of PS solutions on the silicon substrate,and the micro-dots well organized in gradient arrays.After thermal annealing and extensive rinsing with solvent,the PS segments were irreversibly adsorbed on the silicon substrate,leading to ultrathin PS micro-disks.The surface of the micro-disks is smooth and the thickness of the disks is approximately 11 nm.These PS micro-disks are immersed in the THF/DMF solution of PBLG-b-PEG block copolymers.With the addition of water,the block copolymers self-assembled on the surface of the micro-disks,giving rise to periodic nano-sized stripes.The height,pitch,and width of the nano-sized stripes are approximately 5,50 nm,and 22 nm,respectively.Interestingly,the surface wettability of the substrates presents dependence on the microstructures.As the microstructures transformed from the PS micro-dots to the PS micro-disks and then to the stripe-patterned disks,the contact angle decreases gradually,indicating the increase in wettability.This work provides an effective approach to construct hierarchical structures on the surface of materials,and the stripe-patterned disks obtained in this work will have potential applications in bionics,biosensors,and nanotechnology.
引文
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[21]张朔,蔡春华,黄琦婧,等.分子间相互作用对聚肽共聚物/聚苯乙烯衍生物共混体系自组装形貌影响的研究[J].高分子学报,2018(1):109-118.
[22]周永丰.聚肽嵌段共聚物/均聚物共混自组装:一种构筑仿病毒粒子的方法[J].功能高分子学报,2018,31(2):95-97.
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[24] CAI C,LI Y,LIN J,et al.Simulation-assisted self-assembly of multicomponent polymers into hierarchical assemblies with varied morphologies[J].Angew Chem Int Ed,2013,52(30):7732-7736
[25] ZHANG S,CAI C,GUAN Z,et al.Fabrication of virus-like particles with strip-pattern surface:A two-step selfassembly approach[J].Chin Chem Lett,2017,28(4):839-844
[26]杜振飞,许占文,林嘉平.多嵌段共聚物/纳米粒子杂化多级结构的光学性能[J].功能高分子学报,2017,30(3):249-258.
[27] YU Q,GUAN P,DONG Q,et al.Inverted size-dependence of surface-enhanced Raman scattering on gold nanohole and nanodisk arrays[J].Nano Lett,2008,8(7):1923-1928.
[28]赵子鑫,阿孜古丽·木尔赛力木,阿比旦·阿布都乃则尔,等.以聚乙二醇-b-聚四乙烯基吡啶为模板制备聚联苯胺微/纳米颗粒及其电容特性[J].功能高分子学报,2017,30(3):306-313.
[29]任伟,蒋晓菡,俞强.聚丙烯-聚乙二醇嵌段共聚物的制备及其对聚丙烯薄膜的表面改性[J].功能高分子学报,2015,28(4):386-392.
[30] CAI C,ZHU W,CHEN T,et al.Synthesis and self-assembly behavior of amphiphilic polypeptide-based brush-coil block copolymers[J].J Polym Sci Part A:Polym Chem,2009,47(22):5967-5978.
[31] XU J,XIA J,HONG S W,et al.Self-assembly of gradient concentric rings via solvent evaporation from a capillary bridge[J].Phys Rev Lett,2006,96(6):066104.
[32] YABU H,SHIMOMURA M.Preparation of self-organized mesoscale polymer patterns on a solid substrate:Continuous pattern formation from a receding meniscus[J].Adv Funct Mater,2005,15(4):575-581.
[33] JIANG N,SHANG J,DI X,et al.Formation mechanism of high-density,flattened polymer nano layers adsorbed on planar solids[J].Macromolecules,2014,47(8):2682-2689.
[34] CAI C,WANG L,LIN J,ZHANG X.Morphology transformation of hybrid micelles self-assembled from rod-coil block copolymer and nanoparticles[J].Langmuir,2012,28(9):4515-4524
[35] ZHU X,GUAN Z,LIN J,et al.Strip-pattern-spheres self-assembled from polypeptide-based polymer mixtures:Structure and defect features[J].Sci Rep,2016,6:29796.
[36]孔雪丽,王小凡,陈健壮,等.偶氮苯聚合物的光控图案化[J].功能高分子学报,2017,30(3):259-264.
[2] ZHANG L,ZHANG X,DAI Z,et al.Micro-nano hierarchically structured nylon 6,6surfaces with unique wettability[J].J Colloid Interface Sci,2010,345(1):116-119.
[3] WANG G,SHEN Y,TAO J,et al.Fabrication of a superhydrophobic surface with a hierarchical nanoflake-micropit structure and its anti-icing properties[J].RSC Adv,2017,7(16):9981-9988.
[4] YUAN Z,WANG X,BIN J,et al.A novel fabrication of a superhydrophobic surface with highly similar hierarchical structure of the lotus leaf on a copper sheet[J].Appl Surf Sci,2013,285(1):205-210.
[5] LEE W S,PARK Y S,CHO Y K.Hierarchically structured suspended TiO2 nanofibers for use in UV and pH sensor devices[J].ACS Appl Mater Interfaces,2014,6(15):12189-12195.
[6] CUMMINS C,GANGNAIK A,KELLY R A,et al.Aligned silicon nanofins via the directed self-assembly of PS-b-P4VP block copolymer and metal oxide enhanced pattern transfer[J].Nanoscale,2015,7(15):6712-6721.
[7] WU G,LIU X,CHEN X,et al.Directed self-assembly of hierarchical supramolecular block copolymer thin films on chemical patterns[J].Adv Mater Interfaces,2016,3(13):1600048.
[8] ZHANG J,LU Z Y,SUN Z Y.Self-assembly structures of amphiphilic multiblock copolymer in dilute solution[J].Soft Matter,2013,9(6):1947-1954.
[9] WANG L,LIN J,ZHANG X.Hierarchical microstructures self-assembled from polymer systems[J].Polymer,2013,54(14):3427-3442.
[10]崔宝宝,潘俊星,张进军,等.纳米粒子驱动受限环境下两嵌段共聚物/均聚物混合体系的自组装行为[J].高分子学报,2017(6):959-966.
[11]张连斌,王珂,朱锦涛.中国嵌段共聚物受限自组装的研究进展[J].高分子学报,2017(8):1261-1276.
[12] KIM E,AHN H,PARK S,et al.Directed assembly of high molecular weight block copolymers:Highly ordered line patterns of perpendicularly oriented lamellae with large periods[J].ACS Nano,2013,7(3):1952-1960.
[13] JEONG S J,JI E K,MOON H S,et al.Soft graphoepitaxy of block copolymer assembly with disposable photoresist confinement[J].Nano Lett,2009,9(6):2300-2305.
[14] CHOI H K,CHANG J B,HANNON A F,et al.Nanoscale spirals by directed self-assembly[J].Nano Futures,2017,1(1):015001.
[15] ZIEGLER J I,JR H R.Plasmonic response of nanoscale spirals[J].Nano Lett,2010,10(8):3013-3018.
[16] TRITSCHLER U,PEARCE S,GWYTHER J,et al.50th Anniversary perspective:Functional nanoparticles from the solution self-assembly of block copolymers[J].Macromolecules,2017,50(9):3439-3463.
[17] JANES D W,THODE C J,WILLSON C G,et al.Light-activated replication of block copolymer fingerprint patterns[J].Macromolecules,2013,46(11):4510-4519.
[18] SUN W,YANG K,YANG F.Formation of self-organized surface structures on poly(methyl methacrylate)films:Effect of two contacting metallic wires[J].J Polym Res,2015,22(5):90.
[19] BYUN M,HAN W,LI B,et al.An unconventional route to hierarchically ordered block copolymers on a gradient patterned surface through controlled evaporative self-assembly[J].Angew Chem Int Ed,2013,52(4):1122-1127.
[20]杨纤,冯纯,陆国林,等.结晶驱动自组装的研究进展[J].功能高分子学报,2017,30(1):15-33.
[21]张朔,蔡春华,黄琦婧,等.分子间相互作用对聚肽共聚物/聚苯乙烯衍生物共混体系自组装形貌影响的研究[J].高分子学报,2018(1):109-118.
[22]周永丰.聚肽嵌段共聚物/均聚物共混自组装:一种构筑仿病毒粒子的方法[J].功能高分子学报,2018,31(2):95-97.
[23] CAI C,WANG L,LIN J.Self-assembly of polypeptide-based copolymers into diverse aggregates[J].Chem Commun,2011,47(40):11189-11203.
[24] CAI C,LI Y,LIN J,et al.Simulation-assisted self-assembly of multicomponent polymers into hierarchical assemblies with varied morphologies[J].Angew Chem Int Ed,2013,52(30):7732-7736
[25] ZHANG S,CAI C,GUAN Z,et al.Fabrication of virus-like particles with strip-pattern surface:A two-step selfassembly approach[J].Chin Chem Lett,2017,28(4):839-844
[26]杜振飞,许占文,林嘉平.多嵌段共聚物/纳米粒子杂化多级结构的光学性能[J].功能高分子学报,2017,30(3):249-258.
[27] YU Q,GUAN P,DONG Q,et al.Inverted size-dependence of surface-enhanced Raman scattering on gold nanohole and nanodisk arrays[J].Nano Lett,2008,8(7):1923-1928.
[28]赵子鑫,阿孜古丽·木尔赛力木,阿比旦·阿布都乃则尔,等.以聚乙二醇-b-聚四乙烯基吡啶为模板制备聚联苯胺微/纳米颗粒及其电容特性[J].功能高分子学报,2017,30(3):306-313.
[29]任伟,蒋晓菡,俞强.聚丙烯-聚乙二醇嵌段共聚物的制备及其对聚丙烯薄膜的表面改性[J].功能高分子学报,2015,28(4):386-392.
[30] CAI C,ZHU W,CHEN T,et al.Synthesis and self-assembly behavior of amphiphilic polypeptide-based brush-coil block copolymers[J].J Polym Sci Part A:Polym Chem,2009,47(22):5967-5978.
[31] XU J,XIA J,HONG S W,et al.Self-assembly of gradient concentric rings via solvent evaporation from a capillary bridge[J].Phys Rev Lett,2006,96(6):066104.
[32] YABU H,SHIMOMURA M.Preparation of self-organized mesoscale polymer patterns on a solid substrate:Continuous pattern formation from a receding meniscus[J].Adv Funct Mater,2005,15(4):575-581.
[33] JIANG N,SHANG J,DI X,et al.Formation mechanism of high-density,flattened polymer nano layers adsorbed on planar solids[J].Macromolecules,2014,47(8):2682-2689.
[34] CAI C,WANG L,LIN J,ZHANG X.Morphology transformation of hybrid micelles self-assembled from rod-coil block copolymer and nanoparticles[J].Langmuir,2012,28(9):4515-4524
[35] ZHU X,GUAN Z,LIN J,et al.Strip-pattern-spheres self-assembled from polypeptide-based polymer mixtures:Structure and defect features[J].Sci Rep,2016,6:29796.
[36]孔雪丽,王小凡,陈健壮,等.偶氮苯聚合物的光控图案化[J].功能高分子学报,2017,30(3):259-264.
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