Citation: Zi-Jie Huang, Jing Jiang, Gi Xue, Dong-Shan Zhou. β-Phase Crystallization of Poly(vinylidene fluoride) in Poly(vinylidene fluoride)/Poly(ethyl methacrylate) Blends[J]. Chinese Journal of Polymer Science, ;2019, 37(1): 94-100. doi: 10.1007/s10118-019-2177-4 shu

β-Phase Crystallization of Poly(vinylidene fluoride) in Poly(vinylidene fluoride)/Poly(ethyl methacrylate) Blends

Zi-Jie Huang ^a ,
Jing Jiang ^a ,
Gi Xue ^a ,
Dong-Shan Zhou ^a,b,,

a.
Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Key Laboratory of High Performance Polymer Materials and Technology, and The State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, China
b.
School of Physical Science and Technology, Xinjiang Key Laboratory and Phase Transitions and Microstructures in Condensed Matters, Yili Normal University, Yining 835000, China

Corresponding author: Dong-Shan Zhou, dzhou@nju.edu.cn
Received Date: 31 May 2018
Revised Date: 27 July 2018
Accepted Date: 31 July 2018
Available Online: 30 August 2018

The nature of the crystalline phase of poly(vinylidene fluoride) (PVDF) in compatible blends with poly(ethyl methacrylate) (PEMA) was investigated by using X-ray diffraction (XRD), infrared microscopy (IR) and differential scanning calorimetry (DSC). The β phase of PVDF was observed after quenching from the melt and further annealing above the glass transition temperature over a composition range. The PVDF/PEMA blend with weight ratio of 3:2 has formed higher content of PVDF β crystals than others. By taking advantage of fast cooling rate of ultrafast differential scanning calorimeter (UFDSC), the quenching process of blends was modeled and tested simultaneously, and the melting behavior of β crystals in all blends was investigated. Three types of crystallization behavior of β phase PVDF in blends were found after quenching-annealing at different temperatures.
- β-Crystal of PVDF,
- Mesophase,
- PVDF/PEMA blend,
- Ultra-fast scanning calorimetry
1. [1]
  Abraham, K. M.; Alamgir, M. Li⁺-conductive solid polymer electrolytes with liquid-like conductivity. J. Electrochem. Soc. 1990, 137, 1657-1658. doi: 10.1149/1.2086749
2. [2]
  Passerini, S.; Rosolen, J. M.; Scrosati, B. Plasticized carbon electrodes of interest for lithium rocking chair batteries. J. Power Sources 1993, 45, 333-341. doi: 10.1016/0378-7753(93)80022-H
3. [3]
  Choe, H. S.; Giaccai, J.; Alamgir, M.; Abraham, K. M. Preparation and characterization of poly(vinyl sulfone)- and poly(vinylidene fluoride)-based electrolytes. Electrochim. Acta 1995, 40, 2289-2293. doi: 10.1016/0013-4686(95)00180-M
4. [4]
  Lovinger, A. J. Crystallization of the β phase of poly(vinylidene fluoride) from the melt. Polymer 1981, 22, 412-413. doi: 10.1016/0032-3861(81)90058-6
5. [5]
  Kim, J. C.; Yong, J. C.; Kim, Y. H. Factors determining the formation of the β crystalline phase of poly(vinylidene fluoride) in poly(vinylidene fluoride)-poly(methyl methacrylate) blends. Vib. Spectrosc 1995, 9, 147-159. doi: 10.1016/0924-2031(94)00092-U
6. [6]
  Salimi, A.; Yousefi, A. A. Analysis method: FTIR studies of β-phase crystal formation in stretched PVDF films. Polym. Test. 2003, 22, 699-704. doi: 10.1016/S0142-9418(03)00003-5
7. [7]
  Benz, M.; Euler, W. B.; Gregory, O. J. The role of solution phase water on the deposition of thin films of poly(vinylidene fluoride). Macromolecules 2002, 35, 2682-2688. doi: 10.1021/ma011744f
8. [8]
  Yang, J.; Wang, J.; Zhang, Q.; Chen, F.; Deng, H.; Wang, K.; Fu, Q. Cooperative effect of shear and nanoclay on the formation of polar phase in poly(vinylidene fluoride) and the resultant properties. Polymer 2011, 52), 4970-4978. doi: 10.1016/j.polymer.2011.08.051
9. [9]
  Li, M.; Stingelin, N.; Michels, J. J.; Spijkman, M. J.; Asadi, K.; Feldman, K.; Blom, P. W. M.; de Leeuw, D. M. Ferroelectric phase diagram of PVDF:PMMA. Macromolecules 2012, 45), 7477-7485. doi: 10.1021/ma301460h
10. [10]
  Sajkiewicz, P.; Wasiak, A.; Gocłowski, Z. Phase transitions during stretching of poly(vinylidene fluoride). Eur. Polym. J. 1999, 35, 423-429. doi: 10.1016/S0014-3057(98)00136-0
11. [11]
  Ferreira, A.; Costa, P.; Carvalho, H.; Nobrega, J. M.; Sencadas, V.; Lanceros-Mendez, S. Extrusion of poly(vinylidene fluoride) filaments: effect of the processing conditions and conductive inner core on the electroactive phase content and mechanical properties. J. Polym. Res. 2011, 18, 1653-1658. doi: 10.1007/s10965-011-9570-1
12. [12]
  Gonçalves, R.; Martins, P. M.; Caparrós, C.; Martins, P.; Benelmekki, M.; Botelho, G.; Lanceros-Mendez, S.; Lasheras, A.; Gutiérrez, J.; Barandiarán, J. M. Nucleation of the electroactive β-phase, dielectric and magnetic response of poly(vinylidene fluoride) composites with Fe₂O₃ nanoparticles. J. Non-Cryst. Solids 2013, 361, 93-99. doi: 10.1016/j.jnoncrysol.2012.11.003
13. [13]
  Voet, V. S. D.; Hermida-Merino, D.; ten Brinke, G.; Loos, K. Block copolymer route towards poly(vinylidene fluoride)/poly(methacrylic acid)/nickel nanocomposites. Rsc Advances 2013, 3, 7938-7946. doi: 10.1039/c3ra40365c
14. [14]
  Wu, Y.; Hsu, S. L.; Honeker, C.; Bravet, D. J.; Williams, D. S. The role of surface charge of nucleation agents on the crystallization behavior of poly(vinylidene fluoride). J. Phys. Chem. B 2012, 116, 7379-7388. doi: 10.1021/jp3043494
15. [15]
  Jia, N.; Xing, Q.; Xia, G.; Sun, J.; Song, R.; Huang, W. Enhanced β-crystalline phase in poly(vinylidene fluoride) films by polydopamine-coated BaTiO3 nanoparticles. Mater. Lett. 2015, 139, 212-215. doi: 10.1016/j.matlet.2014.10.069
16. [16]
  Yu, J. H.; Jiang, P. K.; Wu, C.; Wang, L. C.; Wu, X. F. Graphene nanocomposites based on poly(vinylidene fluoride): structure and properties. Polym. Compos. 2011, 32, 1483-1491. doi: 10.1002/pc.v32.10
17. [17]
  Leonard, C.; Halary, J. L.; Monnerie, L. Crystallization of poly(vinylidene fluoride) poly(methyl methacrylate) blends - Analysis of the molecular parameters controlling the nature of the poly(vinylinene fluoride) crystalline phase. Macromolecules 1988, 21, 2988-2994. doi: 10.1021/ma00188a016
18. [18]
  Guo, H. F.; Li, Z. S.; Dong, S. W.; Chen, W. J.; Deng, L.; Wang, Y. F.; Ying, D. J. Piezoelectric PU/PVDF electrospun scaffolds for wound healing applications. Colloid. Surface B 2012, 96, 29-36. doi: 10.1016/j.colsurfb.2012.03.014
19. [19]
  Chaudhari, S.; Sharma, Y.; Archana, P. S.; Jose, R.; Ramakrishna, S.; Mhaisalkar, S.; Srinivasan, M. Electrospun polyaniline nanofibers web electrodes for supercapacitors. J. Appl. Polym. Sci. 2013, 129 1660-1668. doi: 10.1002/app.v129.4
20. [20]
  Leonard, C.; Halary, J. L.; Monnerie, L.; Broussoux, D.; Servet, B.; Micheron, F. FTIR evidence of beta-crystal phase formation in PVDF PMMA blends. Polym. Comm. 1983, 24 110-114.
21. [21]
  Naber, R. C. G.; Tanase, C.; Blom, P. W. M.; Gelinck, G. H.; Marsman, A. W.; Touwslager, F. J.; Setayesh, S.; De Leeuw, D. M. High-performance solution-processed polymer ferroelectric field-effect transistors. Nat. Mater. 2005, 4, 243-248. doi: 10.1038/nmat1329
22. [22]
  Naber, R. C. G.; Asadi, K.; Blom, P. W. M.; De Leeuw, D. M.; De Boer, B. Organic nonvolatile memory devices based on ferroelectricity. Adv. Mater. 2010, 22, 933-945. doi: 10.1002/adma.200900759
23. [23]
  Khan, M. A.; Bhansali, U. S.; Alshareef, H. N. High-performance non-volatile organic ferroelectric memory on banknotes. Adv. Mater. 2012, 24, 2165-2170. doi: 10.1002/adma.201200626
24. [24]
  Asadi, K.; De Leeuw, D. M.; De Boer, B.; Blom, P. W. M. Organic non-volatile memories from ferroelectric phase-separated blends. Nat. Mater. 2008, 7, 547-550. doi: 10.1038/nmat2207
25. [25]
  Asadi, K.; Li, M.; Stingelin, N.; Blom, P. W. M.; De Leeuw, D. M. Crossbar memory array of organic bistable rectifying diodes for nonvolatile data storage. Appl. Phys. Lett. 2010, 97, 193308. doi: 10.1063/1.3508948
26. [26]
  Asadi, K.; Li, M.; Blom, P. W. M.; Kemerink, M.; De Leeuw, D. M. Organic ferroelectric opto-electronic memories. Mater. Today 2011, 14, 592-599. doi: 10.1016/S1369-7021(11)70300-5
27. [27]
  Feuillade, G.; Perche, P. Ion-conductive macromolecular gels and membranes for solid lithium cells. J. Appl. Electrochem. 1975, 5, 63-69. doi: 10.1007/BF00625960
28. [28]
  Han, H. S.; Kang, H. R.; Kim, S. W.; Kim, H. T. Phase-separated polymer electrolyte based on poly(vinyl chloride)/poly(ethyl methacrylate) blend. J. Power Sources 2002, 112, 461-468. doi: 10.1016/S0378-7753(02)00436-6
29. [29]
  Alsaigh, Z. Y.; Chen, P. Characterization of semicrystalline polymers by inverse gas-chromatography. 2. A blend of poly(vinylidene fluoride) and poly(ethylmethacrylate). Macromolecules 1991, 24, 3788-3795. doi: 10.1021/ma00013a008
30. [30]
  Jiang, J.; Zhuravlev, E.; Huang, Z.; Wei, L.; Xu, Q.; Shan, M.; Xue, G.; Zhou, D.; Schick, C.; Jiang, W. A transient polymorph transition of 4-cyano-4′-octyloxybiphenyl (8OCB) revealed by ultrafast differential scanning calorimetry (UFDSC). Soft Matter 2013, 9, 1488-1491. doi: 10.1039/C2SM27012A
31. [31]
  Jiang, J.; Zhuravlev, E.; Hu, W.-b.; Schick, C.; Zhou, D.-s. The effect of self-nucleation on isothermal crystallization kinetics of poly(butylene succinate) (PBS) investigated by differential fast scanning calorimetry. Chinese J. Polym. Sci. 2017, 35, 1009-1019. doi: 10.1007/s10118-017-1942-5
32. [32]
  Gregorio, R. Determination of the alpha, beta, and gamma crystalline phases of poly(vinylidene fluoride) films prepared at different conditions. J. Appl. Polym. Sci. 2006, 100, 3272-3279. doi: 10.1002/(ISSN)1097-4628
33. [33]
  Zhuravlev, E.; Schick, C. Fast scanning power compensated differential scanning nano-calorimeter: 1. The device. Thermochim. Acta 2010, 505, 1-13. doi: 10.1016/j.tca.2010.03.019
34. [34]
  Zhuravlev, E.; Schick, C. Fast scanning power compensated differential scanning nano-calorimeter: 2. Heat capacity analysis. Thermochim. Acta 2010, 505, 14-21.
35. [35]
  Gradys, A.; Sajkiewicz, P.; Zhuravlev, E.; Schick, C. Kinetics of isothermal and non-isothermal crystallization of poly(vinylidene fluoride) by fast scanning calorimetry. Polymer 2016, 82, 40-48. doi: 10.1016/j.polymer.2015.11.020
36. [36]
  Wei, L.; Jiang, J.; Shan, M.; Chen, W.; Deng, Y.; Xue, G.; Zhou, D. Integration of ultrafast scanning calorimetry with micro-Raman spectroscopy for investigation of metastable materials. Rev. Sci. Instrum. 2014, 85, 074901. doi: 10.1063/1.4889882
37. [37]
  Zhuravlev, E.; Schmelzer, J. W. P.; Wunderlich, B.; Schick, C. Kinetics of nucleation and crystallization in poly(epsilon caprolactone) (PCL). Polymer 2011, 52, 1983-1997. doi: 10.1016/j.polymer.2011.03.013
38. [38]
  Wunderlich, B. in Crystal structure, Morphology, Defects. Vol. 1. Academic Press, New York, 1973, 1-552.
39. [39]
  Hoffman, J. D.; Weeks, J. J. Melting process and the equilibrium melting temperature of polychlorotrifluoroethylene. Journal of Research of the National Bureau of Standards - A. Physics and Chemistry 1962, 66A, 13-28. doi: 10.6028/jres.066A.003
40. [40]
  Hellmuth, E.; Wunderlich, B. Superheating of linear high-polymer polyethylene crystals. J. Appl. Phys. 1965, 36, 3039-3044. doi: 10.1063/1.1702924
41. [41]
  Minakov, A.; Wurm, A.; Schick, C. Superheating in linear polymers studied by ultrafast nanocalorimetry. Eur. Polym. J. E 2007, 23, 43-53.
1. [1]
  Biao Fang , Runwei Mo . PVDF-based solid-state battery. Chinese Journal of Structural Chemistry, 2024, 43(8): 100347-100347. doi: 10.1016/j.cjsc.2024.100347
2. [2]
  Lingna Wang , Chenxin Tian , Ruobin Dai , Zhiwei Wang . Eco-friendly regeneration of end-of-life PVDF membrane with triethyl phosphate: Efficiency and mechanism. Chinese Chemical Letters, 2024, 35(9): 109356-. doi: 10.1016/j.cclet.2023.109356
3. [3]
  Jian Wang , Baohui Wang , Pin Ma , Yifei Zhang , Honghong Gong , Biyun Peng , Sen Liang , Yunchuan Xie , Hailong Wang . Regulation of uniformity and electric field distribution achieved highly energy storage performance in PVDF-based nanocomposites via continuous gradient structure. Chinese Chemical Letters, 2025, 36(4): 109714-. doi: 10.1016/j.cclet.2024.109714
4. [4]
  Xiaohan Zhang , Bo Xiao . Facilitating ultra-fast lithium ion diffusion in face-centered cubic oxides via over-stoichiometric face-sharing configurations. Chinese Journal of Structural Chemistry, 2025, 44(2): 100419-100419. doi: 10.1016/j.cjsc.2024.100419
5. [5]
  Wenli Xu , Yingzhao Zhang , Rui Wang , Chenyang Liu , Jialin Liu , Xiangyu Huo , Xinying Liu , He Zhang , Jianxu Ding . In-situ passivating surface defects of ultra-thin MAPbBr3 perovskite single crystal films for high performance photodetectors. Chinese Journal of Structural Chemistry, 2025, 44(1): 100454-100454. doi: 10.1016/j.cjsc.2024.100454
6. [6]
  Yuhuan Meng , Long Zhang , Lequan Wang , Junming Kang , Hongbin Lu . 20 nm-ultra-thin fluorosiloxane interphase layer enables dendrite-free, fast-charging, and flexible aqueous zinc metal batteries. Chinese Chemical Letters, 2024, 35(12): 110025-. doi: 10.1016/j.cclet.2024.110025
7. [7]
  Jiakun Bai , Junhui Jia , Aisen Li . An elastic organic crystal with piezochromic luminescent behavior. Chinese Journal of Structural Chemistry, 2024, 43(6): 100323-100323. doi: 10.1016/j.cjsc.2024.100323
8. [8]
  Peng Meng , Qian-Cheng Luo , Aidan Brock , Xiaodong Wang , Mahboobeh Shahbazi , Aaron Micallef , John McMurtrie , Dongchen Qi , Yan-Zhen Zheng , Jingsan Xu . Molar ratio induced crystal transformation from coordination complex to coordination polymers. Chinese Chemical Letters, 2024, 35(4): 108542-. doi: 10.1016/j.cclet.2023.108542
9. [9]
  Jun Lu , Jinrui Yan , Yaohao Guo , Junjie Qiu , Shuangliang Zhao , Bo Bao . Controlling solid form and crystal habit of triphenylmethanol by antisolvent crystallization in a microfluidic device. Chinese Chemical Letters, 2024, 35(4): 108876-. doi: 10.1016/j.cclet.2023.108876
10. [10]
  Ce Liang , Qiuhui Sun , Adel Al-Salihy , Mengxin Chen , Ping Xu . Recent advances in crystal phase induced surface-enhanced Raman scattering. Chinese Chemical Letters, 2024, 35(9): 109306-. doi: 10.1016/j.cclet.2023.109306
11. [11]
  Xiumei LI , Yanju HUANG , Bo LIU , Yaru PAN . Syntheses, crystal structures, and quantum chemistry calculation of two Ni(Ⅱ) coordination polymers. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 2031-2039. doi: 10.11862/CJIC.20240109
12. [12]
  Xiumei LI , Linlin LI , Bo LIU , Yaru PAN . Syntheses, crystal structures, and characterizations of two cadmium(Ⅱ) coordination polymers. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 613-623. doi: 10.11862/CJIC.20240273
13. [13]
  Chen Chen , Jinzhou Zheng , Chaoqin Chu , Qinkun Xiao , Chaozheng He , Xi Fu . An effective method for generating crystal structures based on the variational autoencoder and the diffusion model. Chinese Chemical Letters, 2025, 36(4): 109739-. doi: 10.1016/j.cclet.2024.109739
14. [14]
  Fengyu Zhang , Yali Liang , Zhangran Ye , Lei Deng , Yunna Guo , Ping Qiu , Peng Jia , Qiaobao Zhang , Liqiang Zhang . Enhanced electrochemical performance of nanoscale single crystal NMC811 modification by coating LiNbO₃. Chinese Chemical Letters, 2024, 35(5): 108655-. doi: 10.1016/j.cclet.2023.108655
15. [15]
  Na Wang , Wang Luo , Huaiyi Shen , Huakai Li , Zejiang Xu , Zhiyuan Yue , Chao Shi , Hengyun Ye , Leping Miao . Crystal engineering regulation achieving inverse temperature symmetry breaking ferroelasticity in a cationic displacement type hybrid perovskite system. Chinese Chemical Letters, 2024, 35(5): 108696-. doi: 10.1016/j.cclet.2023.108696
16. [16]
  Zhijia Zhang , Shihao Sun , Yuefang Chen , Yanhao Wei , Mengmeng Zhang , Chunsheng Li , Yan Sun , Shaofei Zhang , Yong Jiang . Epitaxial growth of Cu_2-xSe on Cu (220) crystal plane as high property anode for sodium storage. Chinese Chemical Letters, 2024, 35(7): 108922-. doi: 10.1016/j.cclet.2023.108922
17. [17]
  Min Chen , Boyu Peng , Xuyun Guo , Ye Zhu , Hanying Li . Polyethylene interfacial dielectric layer for organic semiconductor single crystal based field-effect transistors. Chinese Chemical Letters, 2024, 35(4): 109051-. doi: 10.1016/j.cclet.2023.109051
18. [18]
  Zhi-Yuan Yue , Hua-Kai Li , Na Wang , Shan-Shan Liu , Le-Ping Miao , Heng-Yun Ye , Chao Shi . Dehydration-triggered structural phase transition-associated ferroelectricity in a hybrid perovskite-type crystal. Chinese Chemical Letters, 2024, 35(10): 109355-. doi: 10.1016/j.cclet.2023.109355
19. [19]
  Chao LIU , Jiang WU , Zhaolei JIN . Synthesis, crystal structures, and antibacterial activities of two zinc(Ⅱ) complexes bearing 5-phenyl-1H-pyrazole group. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1986-1994. doi: 10.11862/CJIC.20240153
20. [20]
  Yang Li , Yihan Chen , Jiaxin Luo , Qihuan Li , Yiwu Quan , Yixiang Cheng . Enhanced circularly polarized luminescence emission promoted by achiral dichroic oligomers of F8BT in cholesteric liquid crystal. Chinese Chemical Letters, 2024, 35(11): 109864-. doi: 10.1016/j.cclet.2024.109864

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(815)
HTML views(27)

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