Citation: Yi-xin Liu, Er-qiang Chen. Thickening Kinetics of Monolayer Crystals of Low Molecular Weight Poly(ethylene oxide) Fractions on Mica Surfaces[J]. Acta Polymerica Sinica, ;2018, 0(9): 1212-1220. doi: 10.11777/j.issn1000-3304.2017.17333 shu

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, 2754093878@qq.com
Received Date: 18 December 2017
Revised Date: 16 January 2018
Available Online: 1 March 2018

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.
- Thin film crystallization,
- Folded-chain crystal,
- Thickening,
- Growth kinetics
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]
1. [1]
  Shule Liu . Application of SPC/E Water Model in Molecular Dynamics Teaching Experiments. University Chemistry, 2024, 39(4): 338-342. doi: 10.3866/PKU.DXHX202310029
2. [2]
  Yaling Chen . Basic Theory and Competitive Exam Analysis of Dynamic Isotope Effect. University Chemistry, 2024, 39(8): 403-410. doi: 10.3866/PKU.DXHX202311093
3. [3]
  Jiayu Gu , Siqi Wang , Jun Ling . Kinetics of Living Copolymerization: A Brief Discussion. University Chemistry, 2025, 40(4): 100-107. doi: 10.12461/PKU.DXHX202406012
4. [4]
  Jinfu Ma , Hui Lu , Jiandong Wu , Zhongli Zou . Teaching Design of Electrochemical Principles Course Based on “Cognitive Laws”: Kinetics of Electron Transfer Steps. University Chemistry, 2024, 39(3): 174-177. doi: 10.3866/PKU.DXHX202309052
5. [5]
  Yeyun Zhang , Ling Fan , Yanmei Wang , Zhenfeng Shang . Development and Application of Kinetic Reaction Flasks in Physical Chemistry Experimental Teaching. University Chemistry, 2024, 39(4): 100-106. doi: 10.3866/PKU.DXHX202308044
6. [6]
  Jiageng Li , Putrama . 数值积分耦合非线性最小二乘法一步确定反应动力学参数. University Chemistry, 2025, 40(6): 364-370. doi: 10.12461/PKU.DXHX202407098
7. [7]
  Xuzhen Wang , Xinkui Wang , Dongxu Tian , Wei Liu . Enhancing the Comprehensive Quality and Innovation Abilities of Graduate Students through a “Student-Centered, Dual Integration and Dual Drive” Teaching Model: A Case Study in the Course of Chemical Reaction Kinetics. University Chemistry, 2024, 39(6): 160-165. doi: 10.3866/PKU.DXHX202401074
8. [8]
  Dexin Tan , Limin Liang , Baoyi Lv , Huiwen Guan , Haicheng Chen , Yanli Wang . Exploring Reverse Teaching Practices in Physical Chemistry Experiment Courses: A Case Study on Chemical Reaction Kinetics. University Chemistry, 2024, 39(11): 79-86. doi: 10.12461/PKU.DXHX202403048
9. [9]
  Shanghua Li , Malin Li , Xiwen Chi , Xin Yin , Zhaodi Luo , Jihong Yu . 基于高离子迁移动力学的取向ZnQ分子筛保护层实现高稳定水系锌金属负极的构筑. Acta Physico-Chimica Sinica, 2025, 41(1): 2309003-. doi: 10.3866/PKU.WHXB202309003
10. [10]
  Jiajie Cai , Chang Cheng , Bowen Liu , Jianjun Zhang , Chuanjia Jiang , Bei Cheng . CdS/DBTSO-BDTO S型异质结光催化制氢及其电荷转移动力学. Acta Physico-Chimica Sinica, 2025, 41(8): 100084-. doi: 10.1016/j.actphy.2025.100084
11. [11]
  Yiying Yang , Dongju Zhang . Elucidating the Concepts of Thermodynamic Control and Kinetic Control in Chemical Reactions through Theoretical Chemistry Calculations: A Computational Chemistry Experiment on the Diels-Alder Reaction. University Chemistry, 2024, 39(3): 327-335. doi: 10.3866/PKU.DXHX202309074
12. [12]
  Yue Wu , Jun Li , Bo Zhang , Yan Yang , Haibo Li , Xian-Xi Zhang . Research on Kinetic and Thermodynamic Transformations of Organic-Inorganic Hybrid Materials for Fluorescent Anti-Counterfeiting Application information: Introducing a Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(6): 390-399. doi: 10.3866/PKU.DXHX202403028
13. [13]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . ZnO/D-A共轭聚合物S型异质结高效光催化产H₂O₂及其电荷转移动力学研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-. doi: 10.3866/PKU.WHXB202406027
14. [14]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
15. [15]
  Lijuan Wang , Yuping Ning , Jian Li , Sha Luo , Xiongfei Luo , Ruiwen Wang . Enhancing the Advanced Nature of Natural Product Chemistry Laboratory Courses with New Research Findings: A Case Study of the Application of Berberine Hydrochloride in Photodynamic Antimicrobial Films. University Chemistry, 2024, 39(11): 241-250. doi: 10.12461/PKU.DXHX202403017
16. [16]
  Yan Xiao , Shuling Li , Yifan Li , Jianing Fan , Linlin Shi . Discovering the Beauty of Life: Adding Some “Ingredients” to Crystals. University Chemistry, 2024, 39(6): 366-372. doi: 10.3866/PKU.DXHX202312025
17. [17]
  Tianqi Bai , Kun Huang , Fachen Liu , Ruochen Shi , Wencai Ren , Songfeng Pei , Peng Gao , Zhongfan Liu . 石墨烯厚膜热扩散系数与微观结构的关系. Acta Physico-Chimica Sinica, 2025, 41(3): 2404024-. doi: 10.3866/PKU.WHXB202404024
18. [18]
  Peiyu Zhang , Aixin Song , Jingcheng Hao , Jiwei Cui . 高频超声法制备聚多巴胺薄膜综合实验. University Chemistry, 2025, 40(6): 210-214. doi: 10.12461/PKU.DXHX202407081
19. [19]
  Xuewei Qian , Xingwen Sun , Houjin Li , Zhanxiang Liu , Yuan Zheng , Lin Wu , Shuanglian Cai , Ying Xiong , Guangao Yu , Qingwen Liu , Jie Han , Xin Du , Chengshan Yuan , Qihan Zhang , Shuyong Zhang , Jianrong Zhang . Basic Operations and Specification Suggestions for Organic Chemical Recrystallization Experiments. University Chemistry, 2025, 40(5): 66-75. doi: 10.12461/PKU.DXHX202503126
20. [20]
  Chengshan Yuan , Xiaolong Li , Xiuping Yang , Xiangfeng Shao , Zitong Liu , Xiaolei Wang , Yongwen Shen . Standardized Operational Guidelines for Mixed-Solvent Recrystallization in Organic Chemistry Experiment. University Chemistry, 2025, 40(5): 122-127. doi: 10.12461/PKU.DXHX202504073

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(156)
HTML views(12)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142