Citation: Rong Yang, Hong-mei Li, Jing Jiang, Dong-shan Zhou. Study on Isothermal Crystallization Kinetics of Poly(ethylene oxide) Droplets by Fast Scanning Calorimetry[J]. Acta Polymerica Sinica, ;2018, 0(9): 1228-1235. doi: 10.11777/j.issn1000-3304.2018.18024 shu

Study on Isothermal Crystallization Kinetics of Poly(ethylene oxide) Droplets by Fast Scanning Calorimetry

Rong Yang ¹ ,
Hong-mei Li ¹ ,
Jing Jiang ^2,, ,
Dong-shan Zhou ^1,2,,

1.
Xinjiang Laboratory of Phase Transitions and Microstructures in Condensed Matter Physics, College of Physical Science and Technology, YiLi Normal University, Yining 835000
2.
School of Chemistry and Chemical Engineering, The State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210023

Corresponding author: Jing Jiang, juliejing@163.com Dong-shan Zhou, dzhou@nju.edu.cn
Received Date: 21 January 2017
Revised Date: 13 March 2018
Available Online: 26 June 2018

The isothermal crystallization kinetics of poly(ethylene oxide) (PEO) droplets was studied by fast scanning calorimetry (FSC) at a scanning rate up to 10000 K/s over a wide temperature range from its glass transition temperature to its melting temperature, and compared with that of PEO bulk sample. It was observed that the nucleation in PEO bulk sample during cooling is unavoidable even at a scanning rate of up to 50000 K/s because of numerous heterogeneity and the observation of an obvious cold crystallization peak in the subsequent heating curves. While the critical cooling rate is much slower when the sample was prepared by film dewetting and dispersed to several droplets smaller than 2 μm in diameter, and a fully amorphous sample could be obtained at a scanning rate of 10000 K/s. Isothermal crystallization of PEO bulk and that of droplets were studied in the time range from 10⁻² s to 10³ s at varied temperatures from 210 K to 310 K. The half crystallization time at each annealing temperature was calculated by fitting the enthalpy-time curve with a modified Avrami equation. It was found that the total crystallization rate of PEO droplets was systematically decreased by one magnitude in the whole temperature region. When the sample was dispersed into droplets of the size of several microns, the number of heterogeneity in each droplet was much less than that in the bulk or even heterogeneity-free in some droplets, with the average crystallization rate slowing down, especially in the low supercooling region, where heterogeneous nucleation is supposed to be dominant. The slowing down of crystallization rate was also observed at higher supercooling near T_g, where the homogeneous nucleation is considered to dominate the crystallization rate. Because of a slower homogeneous nucleation rate of PEO, the droplets sample with less heterogeneity mainly nucleated from homogeneous nucleation with a slower crystallization rate comparing to the unavoidable heterogeneous nucleation in bulk sample. The confinement of the droplet size may hinder the long-range diffusion of PEO chains and restricted the growth dimension under confinement, which could also be a reason for which a decrease in total crystallization rate of PEO droplets sample was observed.
- PEO,
- Confined crystallization,
- Fast scanning calorimetry,
- Isothermal crystallization
1. [1]
2. [2]
  Toda A, Androsch R, Schick C. Polymer, 2016, 91: 239 − 263
3. [3]
  Michell R M, Müller A J. Prog Polym Sci, 2016, 5455: 183 − 213
4. [4]
  Vayer M, Vital A. Eur Polym J, 2017: 132 − 139
5. [5]
  Ono T. Polymer, 2017, 116: 523 − 533
6. [6]
  Lee S. Polymer, 2016, 116: 540 − 548
7. [7]
  Michell R M, Lorenzo A T, Müller A J, Lin M C, Blaszczyk-Lezak I, Martín J, Mijangos C. Macromolecules, 2012, 45: 1517 − 1528
8. [8]
  Suzuki Y, Duran H, Steinhart M, Butt H J, Floudas G. Soft Matter, 2013, 9: 2621 − 2628
9. [9]
  Lin M C, Nandan B, Chen H L. Soft Matter, 2012, 8: 7306 − 7322
10. [10]
  Martín-Fabiani I, García-Gutiérrez M C, Rueda D R, Linares A, Hernández J J, Ezquerra T A, Reynolds M. ACS Appl Mater Interfaces, 2013, 5: 5324 − 5329
11. [11]
  Michell R M, Blaszczyk-Lezak I, Mijangos C, Müller A J. Macromol Symp, 2014, 337: 109 − 115
12. [12]
  Sanandaji N, Oka A, Haviland D B, Tholén E A, Hedenqvist M S, Gedde U W. Eur Polym, 2013, 49: 203 − 208
13. [13]
  Carvalho J L, Dalnoki-Veress S K. Eur Phys J, 2011, 34: 1 − 6
14. [14]
  Massa M V, Carvalho J L, Dalnoki-Veress K. Eur Phys J, 2003, 12: 111 − 117
15. [15]
  Zhang G, Lee P C, Jenkins S, Dooley J. Baer E Polymer, 2014, 55: 663 − 672
16. [16]
  Carr J M, Langhe D S, Ponting M T, Hiltner A, Baer E. J Mater Res, 2012, 27: 1326 − 50
17. [17]
  Huang C, Jiao L, Zeng J, Zhang J, Yang K, Wang Y. Phys Chem B, 2013, 117: 10665 − 10676
18. [18]
  Zeng J, Zhu Q, Lu X, He Y, Wang Y. Polym Chem, 2012, 3: 399 − 408
19. [19]
  Fu J, Wei Y, Xue L, Luan B, Pan C, Li B. Polymer, 2009, 50: 1588 − 1595
20. [20]
  van Riemsdyk A D. Ann Chim Phys, 1880, 20: 66 − 79
21. [21]
  Price F P. Nucleation in Polymer Crystallization. New York: Marcel Dekker, 1969. 405-488
22. [22]
  Vonnegut B. J Colloid Sci, 1948, 3: 563 − 569
23. [23]
  Turnbull D, Cech R. J Appl Phys, 1950, 21: 804 − 810
24. [24]
  Pound G M, La Mer V K. J Am Chem Soc, 1952, 74: 2323 − 2332
25. [25]
  Turnbull D, Cormia R. J Chem Phys, 1952, 20: 411 − 424
26. [26]
  Turnbull D, Cormia R. J Chem Phys, 1961, 34: 820 − 831
27. [27]
  Cormia R L, Price F P, Turnbull D. J Chem Phys, 1962, 37: 1333 − 1340
28. [28]
  Burns J, Turnbull D. J Appl Phys, 1966, 37: 4021 − 4026
29. [29]
  Koutsky J A, Walton A G, Baer E. J Appl Phys, 1967, 38: 1832 − 1839
30. [30]
  Gornick F, Ross G, Frolen L. J Polym Sci, Polym Part C Symp, 1967, 18: 79 − 91
31. [31]
  Su Y, Liu G, Xie B, Fu D, Wang D. Acc Chem Res, 2014, 47: 192 − 201
32. [32]
  Kailas L, Vasilev C, Audinot J N, Migeon H N, Hobbs J K. Macromolecules, 2007, 40: 7223 − 7230
33. [33]
  Carvalho J, Dalnoki-Veress K. Eur Phys J E, 2011, 34: 1 − 6
34. [34]
  Massa M V, Dalnoki-Veress K. Phys Rev Lett, 2004, 92: 1 − 4
35. [35]
  Massa M V, Lee M, Dalnoki-Veress S K. J Polym Sci, Part B: Polym Phys, 2005, 43: 3438 − 3443
36. [36]
  Massa M V, Carvalho J, Dalnoki-Veress K. Phys Rev Lett, 2006, 97: 1 − 4
37. [37]
  Carvalho J, Massa M V, Dalnoki-Veress K. J Polym Sci, Part B: Polym Phys, 2006, 44: 3448 − 3452
38. [38]
  Carvalho J, Dalnoki-Veress K. Phys Rev Lett, 2010, 105: 1 − 4
39. [39]
  Adamovsky S A, Minakov A A, Schick C. Thermochim Acta, 2003, 403(1): 55 − 63
40. [40]
  Adamovsky S, Schick C. Thermochim Acta, 2004, 415(2): 1 − 7
41. [41]
  de Santis F, Adamovsky S, Titomanlio G, Schick C. Macromolecules, 2006, 39(7): 2562 − 2567
42. [42]
  de Santis F, Adamovsky S, Titomanlio G, Schick C. Macromolecules, 2007, 40(25): 9026 − 9031
43. [43]
  Minakov A A, van Herwaarden A W, Wien W, Wurm A, Schick C. Thermochim Acta, 2007, 461(1-2): 96 − 106
44. [44]
  Minakov A A, Wurm A, Schick C. Eur Phys J E, 2007, 23(1): 43 − 53
45. [45]
  Zhuravlev E, Schmelzer J W P, Wunderlich B, Schick C. Polymer, 2011, 52(9): 1983 − 1997
46. [46]
  Mileva D, Androsch R, Zhuravlev E, Schick C, Wunderlich B. Polymer, 2012, 53(2): 277 − 282
47. [47]
  Massa M V, Carvalho J L, Dalnoki-Veress K. Eur Phys J, 2003, 12: 111 − 117
48. [48]
  Evgeny Z, Jürn W P, Alexander S. Cryst Growth Des, 2015, 15: 786 − 798
49. [49]
  Rhoades AM, Williams J L, Androsch R. Thermochim Acta, 2014: 112 − 120
50. [50]
  Mollova A, Androsch R, Mileva D, Schick C, Benhamida A. Macromolecules, 2013, 46: 828 − 835
51. [51]
  de Santis F, Adamovsky S, Titomanlio G, Schick C. Macromolecules, 2007, 40: 9026 − 9031
52. [52]
  Pyda M, Nowak-Pyda E, Heeg J, Huth H, Minakov A, Di Lorenzo M L, Schick C, Wunderlich B. Polym Sci, 2006, 44: 1364 − 1377
53. [53]
  Zhuravlev E, Schmelzer J W P, Wunderlich B, Schick C. Polymer, 2011, 52: 1983 − 1997
1. [1]
  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
2. [2]
  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
3. [3]
  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
4. [4]
  Ruiying Zhao , Shuheng Luo , Jinke Li , Junjie Zhang , Min Zhu , Yang Li , Yanhong Bai , Yinhuan Li , Lijuan Wang . Ultrasonic-Assisted Synthesis of Rosacetal: A Comprehensive Research-Oriented Organic Chemistry Experiment. University Chemistry, 2025, 40(11): 300-309. doi: 10.12461/PKU.DXHX202412075
5. [5]
  Jinfeng Chu , Lan Jin , Yu-Fei Song . Exploration and Practice of Flipped Classroom in Inorganic Chemistry Experiment: a Case Study on the Preparation of Inorganic Crystalline Compounds. University Chemistry, 2024, 39(2): 248-254. doi: 10.3866/PKU.DXHX202308016
6. [6]
  Shi-Yu Lu , Wenzhao Dou , Jun Zhang , Ling Wang , Chunjie Wu , Huan Yi , Rong Wang , Meng Jin . Amorphous-Crystalline Interfaces Coupling of CrS/CoS₂ Few-Layer Heterojunction with Optimized Crystallinity Boosted for Water-Splitting and Methanol-Assisted Energy-Saving Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(8): 2308024-0. doi: 10.3866/PKU.WHXB202308024
7. [7]
  Wei Zhong , Dan Zheng , Yuanxin Ou , Aiyun Meng , Yaorong Su . Simultaneously Improving Inter-Plane Crystallization and Incorporating K Atoms in g-C₃N₄ Photocatalyst for Highly-Efficient H₂O₂ Photosynthesis. Acta Physico-Chimica Sinica, 2024, 40(11): 2406005-0. doi: 10.3866/PKU.WHXB202406005
8. [8]
  Heng Chen , Longhui Nie , Kai Xu , Yiqiong Yang , Caihong Fang . Remarkable Photocatalytic H₂O₂ Production Efficiency over Ultrathin g-C₃N₄ Nanosheet with Large Surface Area and Enhanced Crystallinity by Two-Step Calcination. Acta Physico-Chimica Sinica, 2024, 40(11): 2406019-0. doi: 10.3866/PKU.WHXB202406019
9. [9]
  Chengqian Mao , Yanghan Chen , Haotong Bai , Junru Huang , Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014
10. [10]
  Zehua Zhao , Xiaoyan An , Jinrong Xu , Ling Yang , Hao Zhao , Zhongyun Wu . Independent Development and Application of Calorimetric Experiment Data Acquisition and Processing Software. University Chemistry, 2025, 40(11): 402-408. doi: 10.12461/PKU.DXHX202505045
11. [11]
  Zhen FAN , Jiayan WANG , Wenhao ZHU , Xiuchun ZHANG , Yang WANG , Hao LI , Zeyuan WANG , Songzhi ZHENG , Weihai SUN . Fabrication of CsPbBr₃ perovskite solar cells using buried polyvinylidene fluorideinterface modification method. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2464-2478. doi: 10.11862/CJIC.20250191
12. [12]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
13. [13]
  Jiaxin Su , Jiaqi Zhang , Shuming Chai , Yankun Wang , Sibo Wang , Yuanxing Fang . Optimizing Poly(heptazine imide) Photoanodes Using Binary Molten Salt Synthesis for Water Oxidation Reaction. Acta Physico-Chimica Sinica, 2024, 40(12): 2408012-0. doi: 10.3866/PKU.WHXB202408012
14. [14]
  Bolin Sun , Jie Chen , Ling Zhou . 乙烯型卤代烃的亲核取代反应. University Chemistry, 2025, 40(8): 152-157. doi: 10.12461/PKU.DXHX202410032
15. [15]
  Zongfei YANG , Xiaosen ZHAO , Jing LI , Wenchang ZHUANG . Research advances in heteropolyoxoniobates. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 465-480. doi: 10.11862/CJIC.20230306
16. [16]
  Min LIU , Huapeng RUAN , Zhongtao FENG , Xue DONG , Haiyan CUI , Xinping WANG . Neutral boron-containing radical dimers. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 123-130. doi: 10.11862/CJIC.20240362
17. [17]
  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
18. [18]
  Hong Zheng , Xin Peng , Chunwang Yi . The Tale of Caprolactam Cyclic Oligomers: The Ever-changing Life of “Princess Cyclo”. University Chemistry, 2024, 39(9): 40-47. doi: 10.12461/PKU.DXHX202403058
19. [19]
  Hongxia Yan , Rui Wu , Weixu Feng , Yan Zhao , Yi Yan . Innovation Inspired by Classical Chemistry: Luminescent Hyperbranched Polysiloxanes. University Chemistry, 2025, 40(4): 154-159. doi: 10.12461/PKU.DXHX202409010
20. [20]
  Huirong BAO , Jun YANG , Xiaomiao FENG . Preparation and electrochemical properties of NiCoP/polypyrrole/carbon cloth by electrodeposition. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1083-1093. doi: 10.11862/CJIC.20250008

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(260)
HTML views(47)

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