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聚乙烯醇水溶液二维定向凝固的微观组织演化

贾琳 王理林 申洁楠 张忠明 李俊杰 王锦程 王志军

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聚乙烯醇水溶液二维定向凝固的微观组织演化

贾琳, 王理林, 申洁楠, 张忠明, 李俊杰, 王锦程, 王志军

Microstructure evolution of polyvinyl alcohol aqueous solution solidated in two-dimensional direction

Jia Lin, Wang Li-Lin, Shen Jie-Nan, Zhang Zhong-Ming, Li Jun-Jie, Wang Jin-Cheng, Wang Zhi-Jun
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  • 为了深入探究定向多孔聚合物材料的微观组织形成机理,利用定向凝固原位实时观察手段,研究不同浓度及不同分子量聚乙烯醇(PVA)水溶液在不同抽拉速度下的定向凝固形貌演化.PVA水溶液的定向凝固形态在低浓度(1 wt%,2.5 wt%)和小分子量(Mw=24000)情况下,一次枝晶间距随着抽拉速度的增加而减小.随着PVA浓度和分子量的增加,一次枝晶间距随抽拉速度变化不明显,枝晶主轴尺寸则随速度增加呈现减小的趋势.与传统凝固形态形成机理相比,PVA水溶液的凝固形态由PVA分子的扩散引起的凝固界面不稳定性机理和PVA高分子链交联引起的局部相分离机理竞争决定.
    Porous polymers have received much attention in recent years because of their light quality,high strength,good permeability and easy-revisable.Various fabrication methods of porous polymers have been used in which ice templating is a process which can prepare porous materials with complex structures and fine microstructures.This method has been widely used to prepare porous polymers but it still has many problems,such as poor homogeneity of pore distribution and pore connectivity.To solve these problems,it is necessary to understand the morphology of ice crystal growth in the solidification process of polymer solution.In situ observation of directional solidification is adopted in this paper to study the morphology evolution during directional solidification of polyvinyl alcohol (PVA) aqueous solution with different concentrations and molecular weights under different pulling speeds.The experimental results show that the primary dendrite spacing of PVA aqueous solution decreases with the increase of pulling speed at low concentration (1 wt%,2.5 wt%).However,increasing PVA concentration does not result in significant change in primary dendrite spacing.The primary dendrite spacing varies with pulling speed whereas the dendritic primary arm tends to shrink with increasing velocity.The effects of PVA concentration and pulling speed on morphology are partly because of diffusion instability from the classical solidification theory.When the concentration of solution is 5 wt%,there is little change of primary dendrite spacing with the velocity,which is due to the suppressed diffusion instability by high concentration of the polymer solution and large viscosity.When the concentration of solution increases to 10 wt%,ice crystal morphology is seaweed-like,where the PVA molecules are enriched and crosslinked ahead the ice crystal,leading to the continuous bifurcation of the dendrites.For the solidification morphologies of the aqueous solutions with different PVA molecular weights,the primary dendrite spacing of PVA aqueous solution decreases with the increase of pulling speed at low molecular weight (Mw=24000).Increasing PVA molecular weight does not result in significant change in primary dendrite spacing.At the low PVA molecular weight,the interface shows cell morphology.With the increase of PVA molecular weight,the large chain length leads to the stronger interaction among them and suppressing their diffusion. The corresponding constitutional undercooling is strengthened,thereby promoting the interfacial instability and dendrite formation.From the classical solidification morphology formation mechanism it may be concluded that the solidification morphology of PVA aqueous solution is determined by the competition between the two different mechanisms,i.e., interface instability induced by diffusion of PVA molecule and the local phase separation from the crosslinking of PVA polymer chains.
      通信作者: 王志军, zhjwang@nwpu.edu.cn
    • 基金项目: 凝固技术国家重点实验室(批准号:158-QP-2016,SKLSP201627)资助的课题.
      Corresponding author: Wang Zhi-Jun, zhjwang@nwpu.edu.cn
    • Funds: Project supported by State Key Laboratory of Solidification Processing, China (Grant Nos. 158-QP-2016, SKLSP201627).
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    [26]

    Zhang L, Zhao J, Zhu J, He C, Wang H 2012 Soft Matter 40 10447

    [27]

    He H 2012 Ph. D. Dissertation (Chongqing:Chongqing University) (in Chinese)[何洪 2012 博士学位论文 (重庆:重庆大学)]

    [28]

    Doi M 2013 Soft Matter Physics (New York:Oxford University Press) p145

    [29]

    Utter B, Ragnarsson R, Bodenschatz E 2001 Phys. Rev. E 72 011601

    [30]

    Li J J, Wang J C, Xu Q, Yang G C 2007 Acta Phys. Sin. 56 1514 (in Chinese)[李俊杰, 王锦程, 许泉, 杨根仓 2007 物理学报 56 1514]

    [31]

    Gao H W, Yang R J, He J Y, et al. 2010 Acta Polym. Sin. 5 542 (in Chinese)[高瀚文, 杨荣杰, 何吉宇, 等 2010 高分子学报 5 542]

  • [1]

    Liu Q, Tang Z, Ou B, Zhou Z 2014 Mater. Chem. Phys. 144 213

    [2]

    Nemoto J, Uraki Y, Kishimoto T, Sano Y, Funada R, Obata N, Yabu H, Tanaka M, Shimomura M 2005 Bioresour. Technol. 96 1955

    [3]

    Adiga S P, Jin C, Curtiss L A, Monteriro-Riviere N A, Narayan R J 2009 Wires. Nanomed. Nanobi. 1 568

    [4]

    Colombo P 2006 Philos. Trans. R. Soc. London Ser. A 364 109

    [5]

    Karimi A, Wan M A W D 2015 Polym. Compos. 38 1135

    [6]

    Colosi C, Costantini M, Barbetta A, Pecci R, Bedini R, Dentini M 2012 Langmuir 29 82

    [7]

    Holloway J L, Lowman A M, Palmese G R 2013 Soft Matter 9 826

    [8]

    Li X, Kanjwal M A, Lin L, Chronakis L S 2013 Colloids Surf. B 103 182

    [9]

    Jiang X R, Guan J, Chen X, Shao Z Z 2010 Acta Chim. Sin. 68 1909 (in Chinese)[江霞蓉, 管娟, 陈新, 邵正中 2010 化学学报 68 1909]

    [10]

    Deville S 2008 Adv. Eng. Mater. 10 155

    [11]

    Deville S, Saiz E, Nalla R K, Tomsia A P 2006 Science 311 515

    [12]

    Deville S 2010 Materials 3 1913

    [13]

    Fukasawa T, Deng Z Y, Ando M, Ohji T, Goto Y 2001 J. Mater. Sci. 36 2523

    [14]

    Delattre B, Bai H, Ritchie R O, Coninck J D, Tomsia A P 2013 ACS Appl. Mater. Inter. 6 159

    [15]

    Kim S S, Seo I S, Yeum J H, Ji B C, Kim J H, Kwak J W, Yoon W S, Noh S K, Lyoo W S 2004 J. Appl. Polym. Sci. 92 1426

    [16]

    Ren L, Zeng Y P, Jiang D 2009 Ceram. Int. 35 1267

    [17]

    Zhang H, Hussain I, Brust M, Butler M F, Rannard S P, Cooper A I 2005 Nat. Mater. 4 787

    [18]

    Zhang H, Cooper A I 2007 Adv. Mater. 19 1529

    [19]

    Gutirrez M C, Garca-Carvajal Z Y, Jobbgy M, Rubio F, Yuste L, Rojo F, Ferrer M L, Monte F D 2007 Adv. Funct. Mat. 17 3505

    [20]

    Wu X, Liu Y, Li X, Wen P, Zhang Y, Long Y, Wang X, Guo Y, Xing F, Gao J 2010 Acta Biomater. 6 1167

    [21]

    Qian L, Zhang H 2011 J. Chem. Technol. Biotechnol. 86 172

    [22]

    Wang L L, Wang X B, Wang H Y, Lin X, Huang W D 2012 Acta Phys. Sin. 61 148104 (in Chinese)[王理林, 王贤斌, 王红艳, 林鑫, 黄卫东 2012 物理学报 61 148104]

    [23]

    Yu H L, Lin X, Li J J, Wang L L, Huang W D 2013 Acta Metall. Sin. 49 58 (in Chinese)[宇红雷, 林鑫, 李俊杰, 王理林, 黄卫东 2013 金属学报 49 58]

    [24]

    You J, Wang L, Wang Z, Li J, Wang J 2015 Rev. Sci. Instrum. 86 084901

    [25]

    Wang X B, Lin X, Wang L L, Bai B B, Wang M, Huang W D 2013 Acta Phys. Sin. 62 108103 (in Chinese)[王贤斌, 林鑫, 王理林, 白贝贝, 王猛, 黄卫东 2013 物理学报 62 108103]

    [26]

    Zhang L, Zhao J, Zhu J, He C, Wang H 2012 Soft Matter 40 10447

    [27]

    He H 2012 Ph. D. Dissertation (Chongqing:Chongqing University) (in Chinese)[何洪 2012 博士学位论文 (重庆:重庆大学)]

    [28]

    Doi M 2013 Soft Matter Physics (New York:Oxford University Press) p145

    [29]

    Utter B, Ragnarsson R, Bodenschatz E 2001 Phys. Rev. E 72 011601

    [30]

    Li J J, Wang J C, Xu Q, Yang G C 2007 Acta Phys. Sin. 56 1514 (in Chinese)[李俊杰, 王锦程, 许泉, 杨根仓 2007 物理学报 56 1514]

    [31]

    Gao H W, Yang R J, He J Y, et al. 2010 Acta Polym. Sin. 5 542 (in Chinese)[高瀚文, 杨荣杰, 何吉宇, 等 2010 高分子学报 5 542]

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  • 收稿日期:  2017-04-14
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  • 刊出日期:  2017-10-05

聚乙烯醇水溶液二维定向凝固的微观组织演化

  • 1. 西安理工大学材料科学与工程学院, 西安 710048;
  • 2. 西北工业大学, 凝固技术国家重点实验室, 西安 710072
  • 通信作者: 王志军, zhjwang@nwpu.edu.cn
    基金项目: 凝固技术国家重点实验室(批准号:158-QP-2016,SKLSP201627)资助的课题.

摘要: 为了深入探究定向多孔聚合物材料的微观组织形成机理,利用定向凝固原位实时观察手段,研究不同浓度及不同分子量聚乙烯醇(PVA)水溶液在不同抽拉速度下的定向凝固形貌演化.PVA水溶液的定向凝固形态在低浓度(1 wt%,2.5 wt%)和小分子量(Mw=24000)情况下,一次枝晶间距随着抽拉速度的增加而减小.随着PVA浓度和分子量的增加,一次枝晶间距随抽拉速度变化不明显,枝晶主轴尺寸则随速度增加呈现减小的趋势.与传统凝固形态形成机理相比,PVA水溶液的凝固形态由PVA分子的扩散引起的凝固界面不稳定性机理和PVA高分子链交联引起的局部相分离机理竞争决定.

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