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
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