doi:10.11777/j.issn1000-3304.2017.17333

引用本文: 刘一新, 陈尔强. 云母表面低分子量聚氧乙烯单层片晶等温增厚动力学[J]. 高分子学报, 2018, (9): 1212-1220. doi: 10.11777/j.issn1000-3304.2017.17333 shu

Citation: Yi-xin Liu and Er-qiang Chen. Thickening Kinetics of Monolayer Crystals of Low Molecular Weight Poly(ethylene oxide) Fractions on Mica Surfaces[J]. Acta Polymerica Sinica, 2018, (9): 1212-1220. doi: 10.11777/j.issn1000-3304.2017.17333 shu

云母表面低分子量聚氧乙烯单层片晶等温增厚动力学

刘一新 ^{1
,
,} ,
陈尔强 ²

1.
聚合物分子工程国家重点实验室复旦大学高分子科学系　上海 200438
2.
高分子化学与物理教育部重点实验室北京大学化学与分子工程学院　北京 100871

通讯作者: 刘一新, E-mail: lyx@fudan.edu.cn

基金项目: 国家自然科学基金(基金号 21004013)资助项目

摘要: 采用附有热台的原子力显微镜(AFM)原位跟踪研究了2种低分子量聚氧乙烯(PEO)样品的单层片晶在云母表面的增厚行为. 实验发现表面平整的一次折叠链片晶在其熔点以下等温退火时，其内部陆续出现增厚区域(增厚粒子). 单个增厚粒子可在厚度和侧向尺寸2个维度同时生长. 其中，增厚粒子的厚度随时间的变化曲线呈S形，并具有显著的温度相关性. 基于在厚度维度满足成核机理的假设，可推导出厚度与时间的对数成正比关系. 据此关系可进一步求得片晶侧表面自由能，结果与文献报道一致，并且对于2种PEO样品的结果也相近，确认了我们提出的机理的合理性. 增厚粒子侧向尺寸随时间线性生长，生长速率与退火温度正相关，推测与片晶中的链滑移有关.

关键词:

薄膜结晶 /
片晶 /
增厚 /
生长动力学

English

Thickening Kinetics of Monolayer Crystals of Low Molecular Weight Poly(ethylene oxide) Fractions on Mica Surfaces

Yi-xin Liu ^{1,
,} ,
Er-qiang Chen ²

1.
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438
2.
Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871

Corresponding author: Yi-Xin Liu, E-mail: lyx@fudan.edu.cn

Received Date: 2017-12-18
Accepted Date: 2018-01-16
Available Online: 2018-09-01

Abstract: The thickening of monolayer crystals of low molecular weight poly(ethylene oxide) (PEO) fractions on mica surface are in situ monitored by an atomic force microscopy (AFM) coupled with a hot stage. Two PEO fractions, with different molecular weights (HPEO2K, M_n = 2000; HPEO3K, M_n = 3000), have been examined. It is found that thickening domains continuously emerge when smooth once-folded-chain crystals are annealed isothermally below their melting temperature. A single thickening domain can grow in thickness and lateral size simutaneously. The growth of the thickness of the thickening domain follows a sigmoidal curve and depends significantly on the annealing temperature. It is found that the thickness of the thickening domain grows linearly with the logarithm of time. Such linear relation implies that its underlying mechanism should be nucleation and growth, as confirmed by a theoretical derivation of the thickness of the thickening domain as a function of time based on this mechanism. For each annealing temperature, a linear regression between the thickness of the thickening domain and the logarithm of time is performed and the obtained reciprocal of the slope linearly depends on the reciprocal of the annealing temperature. Then the surface free energy of the lateral surface of the folded-chain crystals can be inferred from the relation between the reciprocal of the slope and the annealing temperature. In this study, the value of the lateral surface free energy is found to be 1.25 and 1.22 kJ/mol for HPEO2K and HPEO3K, respectively. These values agree well with each other and also with reported values, which further validates our proposed mechanism. The lateral size of the thickening domain grows linearly with time as long as its thickeness approaches the extended-chain crystal. Such type of growth resembles the direct growth of the polymer crystals from the melt. However, its reltation between the growth rate and the annealing temperature is quite different from that of the growth of polymer crystals: the growth rate increases with the annealing temperature in the thickening case while it decreases with the crystallization temperature in the crystallization case. It indicates that there is an activation process rather than a nucleation process during thickening, which has been attributed to the chain sliding diffusion within the folded-chain crystals.

Key words:

1. [1]
  Cheng S Z D. Phase Transitions in Polymers. The Role of Metastable States. Amsterdam: Elsevier Science, 2008. 78 – 91
2. [2]
  Keller A, Cheng S Z D. Polymer, 1998, 39: 4461 − 4487 doi: 10.1016/S0032-3861(97)10320-2
3. [3]
  Fischer E W, Schmidt G F. Angew Chem Int Ed, 1962, 1: 488 − 499 doi: 10.1002/(ISSN)1521-3773
4. [4]
  Wunderlich B. Macromolecular Physics Vol. 2. New York: Academic Press, 1976. 348 – 425
5. [5]
  Sanchez I C, Peterlin A, Eby R K, McCrackin, F L. J Appl Phys, 1974, 45: 4216 − 4219 doi: 10.1063/1.1663038
6. [6]
  Sanchez I C, Colson J P, Eby R K. J Appl Phys, 1973, 44: 4332 − 4339 doi: 10.1063/1.1661961
7. [7]
  Kovacs A J, Straupe C, Gonthier A. J Polym Sci, Polym Symp, 1977, 59: 31 − 54
8. [8]
  Kovacs A J, Gonthier A, Straupe C. J Polym Sci, Polym Symp, 1975, 50: 283 − 325
9. [9]
  Hikosaka M, Amano K, Rastogi S, Keller A. Macromolecules, 1997, 30: 2067 − 2074 doi: 10.1021/ma960746a
10. [10]
  Reiter G, Sommer J U. Polymer Crystallization: Observations, Concepts and Interpretations. Berlin Heidelberg: Springer-Verlag, 2003. Vol. 606, 131 – 152
11. [11]
  Zhai X, Zhang G, Ma Z, Tang X, Wang W. Macromol Chem Phys, 2007, 208: 651 − 657 doi: 10.1002/(ISSN)1521-3935
12. [12]
  Zhai X M, Wang W, Ma Z P, Wen X J, Yuan F, Tang X F, He B L. Macromolecules, 2005, 38: 1717 − 1722 doi: 10.1021/ma047764+
13. [13]
  Liu Y X, Li J F, Zhu D S, Chen E Q, Zhang H D. Macromolecules, 2009, 42: 2886 − 2890 doi: 10.1021/ma802806q
14. [14]
  Wang M, Gao H, Zha L, Chen E Q, Hu W. Macromolecules, 2013, 46: 164 − 171 doi: 10.1021/ma301926p
15. [15]
  Peterlin A. J Polym Sci, Part B: Polym Phys, 1963, 1: 279 − 284 doi: 10.1002/pol.1963.110010603
16. [16]
  Peterlin A. Polymer, 1965, 6: 25 − 34 doi: 10.1016/0032-3861(65)90076-5
17. [17]
  Ichida T, Tsuji M, Murakami S, Kawaguchi A, Katayama K. Colloid Polym Sci, 1985, 263: 293 − 300 doi: 10.1007/BF01412244
18. [18]
  Takahashi Y Tadokoro H. Macromolecules, 1973, 6: 672 − 675 doi: 10.1021/ma60035a005
19. [19]
  Turnbull D, Fisher J C. J Chem Phys, 1949, 17: 71 − 73 doi: 10.1063/1.1747055
20. [20]
  Liu Y X, Zhong L W, Su S Z, Chen E Q. Macromolecules, 2011, 44: 8819 − 8828 doi: 10.1021/ma201885g
21. [21]
  Buckley C P, Kovacs A J. Colloid Polym Sci, 1976, 254: 695 − 715 doi: 10.1007/BF01643767
22. [22]
  Point J J, Kovacs A J. Macromolecules, 1980, 13: 399 − 409 doi: 10.1021/ma60074a038
23. [23]
  Koutsky J A, Walton A G, Baer E. J Appl Phys, 1967, 38: 1832 − 1839 doi: 10.1063/1.1709769
24. [24]
  Liu Yixin(刘一新). Phase Selection Pathways and Morphological evolution in Polymer Crystallization: An Experimental and Theoretical Study on Low Molecular Weight Poly(ethylene oxide) Fractions(高分子结晶中的路径选择与形态演化: 对低分子量聚氧乙烯的一些实验和理论研究). Doctoral Dissertation of Peking Univeristy(北京大学博士学位论文), 2009
1. [1]
  夏楠 , 唐雄峰 , 温笑菁 , 张国梁 , 翟雪梅 , 王维 . 一个低分子量聚氧化乙烯从亚稳态的折叠链片晶向稳态的伸直链片晶转化增厚过程的研究. 高分子学报, 2011, (9): 1040-1052. doi: 10.3724/SP.J.1105.2011.10391
2. [2]
  温笑菁 , 王维 . SAXS研究四臂聚氧化乙烯片晶的增厚. 高分子学报, 2014, (3): 415-422. doi: 10.3724/SP.J.1105.2014.13307
3. [3]
  张彬 . 原子力显微镜研究高分子超薄膜结晶机理及功能化调控. 高分子学报, 2020, 51(3): 221-238. doi: 10.11777/j.issn1000-3304.2019.19185
4. [4]
  张子男 , 于逢源 , 张洪斌 , 俞炜 . 流场作用对聚丙烯结晶成核过程和晶体生长过程动力学的影响. 高分子学报, 2015, (4): 396-402. doi: 10.11777/j.issn1000-3304.2015.14314
5. [5]
  吕冬 , 卢影 , 门永锋 . 小角X射线散射技术在高分子表征中的应用. 高分子学报, 2021, 52(0): 0-0. doi: 10.11777/j.issn1000-3304.2020.20249
6. [6]
  王曦 , 刘朋生 , 姜勇 , 罗艳红 , 高峡 , 李林 . 原子力显微镜原位观察球晶界面上片晶的生长. 高分子学报, 2003, (5): 761-764.
7. [7]
  罗筱烈 , 张瑞云 , 马德柱 . 阻燃聚丙烯体系结晶动力学研究. 高分子学报, 1990, (1): 18-23.
8. [8]
  薛小芙 , 杨宝泉 , 李红云 , 莫志深 . 尼龙-1010非等温结晶动力学. 高分子学报, 1993, (5): 589-594.
9. [9]
  刘枭 , 魏千适 , 柴利国 , 周建军 , 严大东 , 闫寿科 , 李林 . 片晶折叠表面成核机制与结晶温度的相关性研究. 高分子学报, 2013, (5): 654-659. doi: 10.3724/SP.J.1105.2013.12416
10. [10]
  陈德文 , 徐愉 , 梁振华 . 光导薄膜表面静电荷积累过程的动力学特征. 高分子学报, 1986, (4): 264-269.
11. [11]
  李思佳 , 张万喜 , 蒋放 , 卢宇源 , 石彤非 , 安立佳 . 高分子薄膜去润湿孔增长动力学. 高分子学报, 2014, (9): 1174-1182. doi: 10.11777/j.issn1000-3304.2014.14095
12. [12]
  刘仪 , 许晓洲 , 莫松 , 韩刚 , 朱才镇 , 李翠华 , 范琳 . PMDA/ODA型聚酰亚胺薄膜的热氧化降解动力学研究. 高分子学报, 2020, 51(10): 1169-1177. doi: 10.11777/j.issn1000-3304.2020.20093
13. [13]
  申长雨 , 周应国 , 陈静波  . 半结晶聚合物注射成型中结晶动力学的数值模拟. 高分子学报, 2008, (8): 771-778. doi: 10.3724/SP.J.1105.2008.00771
14. [14]
  王玉忠 , 吴大诚 , 郑长义 . 用DSC研究阻燃PET的结晶性和结晶动力学. 高分子学报, 1993, (4): 497-501.
15. [15]
  . 一种典型半结晶型聚酰亚胺的非等温结晶动力学. 高分子学报, 2011, (11): 1273-1277. doi: 10.3724/SP.J.1105.2011.10319
16. [16]
  张志英 , 康文华 , 张春玲 . 高聚物的非等温结晶动力学——从不同速率的升温或降温DSC曲线解析结晶动力学参数. 高分子学报, 1992, (4): 500-503.
17. [17]
  刘冶球 , 祝亚非 , 许家瑞 . 聚丙烯-g-聚氨酯共聚物的非等温结晶动力学研究. 高分子学报, 2002, (5): 577-581.
18. [18]
  莫志深 . 一种研究聚合物非等温结晶动力学的方法. 高分子学报, 2008, (7): 656-661. doi: 10.3724/SP.J.1105.2008.00656
19. [19]
  周崇福 , 马敬红 , 梁伯润 , 姜润喜 , 任夕娟 . PET/LCP反应性共混物的非等温结晶动力学. 高分子学报, 2001, (5): 565-570.
20. [20]
  高光辉 , 李卫华 , 颜德岳 . 尼龙1218的等温及非等温结晶动力学研究. 高分子学报, 2004, (4): 465-470.
Figure 1. Morphological evolution of HPEO2K IF(1) crystals annealed at 26 ºC (top row) and HPEO3K IF(1) crystals annealed at 44 ºC (bottom row)

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Figure 2. Section profiles through centers of thickening domains: (a) HPEO2K IF(1) crystals annealed at 26 °C, and (b) HPEO3K IF(1) crystals annealed at 44 °C (H denotes the thickness of the PEO crystal.)

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Figure 3. Thicknesses of thickening domains (the thickness of IF(1) crystals has been subtracted) as a function of time for (a) HPEO2K and (b) HPEO3K (Each curve has been shifted in vertical direction for an appropriate amount.)

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Figure 4. Thicknesse of thickening domains as function of the logarithm of time for (a) HPEO2K and (b) HPEO3K

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Figure 5. b (defined in Eq. (10) ) as a function of the reciprocal of annealing temperature for (a) HPEO2K and (b) HPEO3K

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Figure 6. Lateral size of a thickening domain (HW) as a function of time (t) for HPEO2K IF(1) crystals annealed at 26 ºC

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Figure 7. (a) Lateral size at second stage of thickening process as a function of time at various annealing temperatures and (b) growth rate of lateral size as a function of annealing temperature for HPEO3K

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