Melting Temperature of Individual Electrospun Poly(vinylidene fluoride) Fibers Studied by AFM-based Local Thermal Analysis

Ze-Qian Wang; Zhen-Xing Zhong; Yu-Ying Ma; Xiao-Feng Lu; Ce Wang; Zhao-Hui Su

doi:10.1007/s10118-020-2476-9

Your Location：

Home >

Browse articles >

Melting Temperature of Individual Electrospun Poly(vinylidene fluoride) Fibers Studied by AFM-based Local Thermal Analysis

ARTICLE | Updated：2020-08-27

- Melting Temperature of Individual Electrospun Poly(vinylidene fluoride) Fibers Studied by AFM-based Local Thermal Analysis
- Chinese Journal of Polymer Science Vol. 39, Issue 2, Pages: 219-227(2021)
- Affiliations：
  
  a.State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  b.University of Science and Technology of China, Hefei 230026, China
  c.Alan G. MacDiarmid Institute, Jilin University, Changchun 130012, China
- Author bio：
  
  zhsu@ciac.ac.cn
- Funds：
- DOI：10.1007/s10118-020-2476-9
  CLC：
- Received：13 May 2020，
  
  Revised：2020-6-15，
  
  Accepted：01 July 2020，
  
  Online First：27 August 2020，
  
  Published：02 January 2021
- Accepted：
Scan QR Code
Wang, Z. Q.; Zhong, Z. X.; Ma, Y. Y.; Lu, X. F.; Wang, C.; Su, Z. H. Melting temperature of individual electrospun poly(vinylidene fluoride) fibers studied by AFM-based local thermal analysis. Chinese J. Polym. Sci. 2021, 39, 219–227

Ze-Qian Wang, Zhen-Xing Zhong, Yu-Ying Ma, et al. Melting Temperature of Individual Electrospun Poly(vinylidene fluoride) Fibers Studied by AFM-based Local Thermal Analysis[J]. Chinese Journal of Polymer Science, 2021, 39(2): 219-227.
Wang, Z. Q.; Zhong, Z. X.; Ma, Y. Y.; Lu, X. F.; Wang, C.; Su, Z. H. Melting temperature of individual electrospun poly(vinylidene fluoride) fibers studied by AFM-based local thermal analysis. Chinese J. Polym. Sci. 2021, 39, 219–227 DOI： 10.1007/s10118-020-2476-9.

Ze-Qian Wang, Zhen-Xing Zhong, Yu-Ying Ma, et al. Melting Temperature of Individual Electrospun Poly(vinylidene fluoride) Fibers Studied by AFM-based Local Thermal Analysis[J]. Chinese Journal of Polymer Science, 2021, 39(2): 219-227. DOI： 10.1007/s10118-020-2476-9.

摘要

Abstract

Thermal properties such as melting temperature can well reflect the microstructure of the polymer material

and have practical implications in the application of nanofibers. In this work

we investigated the melting temperature of individual electrospun poly(vinylidene fluoride) (PVDF) nanofibers with diameters ranging from smaller than 200 nm to greater than 2 μm by the local thermal analysis technique. The PVDF fibers obtained under four different conditions were found to crystallize into

and

phases

and the fiber mats showed typical values in the crystallinity and

with no significant difference among the four. However

analyses at single fiber level revealed broad distribution in diameter and

for the fibers produced under identical electrospinning condition. The

of individual nanofibers was found to remain constant at large diameters and increase quickly when reducing the fiber diameter toward the nanoscale

and

values of 220−230 °C were observed for the thinnest nanofibers

much higher than the typical values reported for bulk PVDF. The

and molecular orientation at different positions along a beaded fiber were analyzed

showing a similar distribution pattern with a minimum at the bead center and higher values when moving toward both directions. The results indicate that molecular orientation is the driving mechanism for the observed correlation between the

and the diameter of the nanofibers.

关键词

Keywords

references

Reneker, D. H.; Chun, I. . Nanometre diameter fibres of polymer, produced by electrospinning . Nanotechnology , 1996 . 7 216 - 223 . DOI: 10.1088/0957-4484/7/3/009 http://doi.org/10.1088/0957-4484/7/3/009 .

Gopal, R.; Kaur, S.; Ma, Z.; Chan, C.; Ramakrishna, S.; Matsuura, T. . Electrospun nanofibrous filtration membrane . J. Membr. Sci. , 2006 . 281 581 - 586 . DOI: 10.1016/j.memsci.2006.04.026 http://doi.org/10.1016/j.memsci.2006.04.026 .

Zhu, M.; Han, J.; Wang, F.; Shao, W.; Xiong, R.; Zhang, Q.; Pan, H.; Yang, Y.; Samal, S. K.; Zhang, F.; Huang, C. . Electrospun nanofibers membranes for effective air filtration . Macromol. Mater. Eng. , 2017 . 302 1600353 DOI: 10.1002/mame.201600353 http://doi.org/10.1002/mame.201600353 .

Al-Attabi, R.; Dumée, L. F.; Kong, L.; Schütz, J. A.; Morsi, Y. . High efficiency poly(acrylonitrile) electrospun nanofiber membranes for airborne nanomaterials filtration . Adv. Eng. Mater. , 2018 . 20 1700572 DOI: 10.1002/adem.201700572 http://doi.org/10.1002/adem.201700572 .

Zeng, J.; Xu, X.; Chen, X.; Liang, Q.; Bian, X.; Yang, L.; Jing, X. . Biodegradable electrospun fibers for drug delivery . J. Control. Release , 2003 . 92 227 - 231 . DOI: 10.1016/S0168-3659(03)00372-9 http://doi.org/10.1016/S0168-3659(03)00372-9 .

Hu, X.; Liu, S.; Zhou, G.; Huang, Y.; Xie, Z.; Jing, X. . Electrospinning of polymeric nanofibers for drug delivery applications . J. Control. Release , 2014 . 185 12 - 21 . DOI: 10.1016/j.jconrel.2014.04.018 http://doi.org/10.1016/j.jconrel.2014.04.018 .

Yang, F.; Murugan, R.; Wang, S.; Ramakrishna, S. . Electrospinning of nano/micro scale poly(L-lactic acid) aligned fibers and their potential in neural tissue engineering . Biomaterials , 2005 . 26 2603 - 2610 . DOI: 10.1016/j.biomaterials.2004.06.051 http://doi.org/10.1016/j.biomaterials.2004.06.051 .

Sill, T. J.; von Recum, H. A. . Electrospinning: applications in drug delivery and tissue engineering . Biomaterials , 2008 . 29 1989 - 2006 . DOI: 10.1016/j.biomaterials.2008.01.011 http://doi.org/10.1016/j.biomaterials.2008.01.011 .

Hu, J.; Kai, D.; Ye, H.; Tian, L.; Ding, X.; Ramakrishna, S.; Loh, X. J. . Electrospinning of poly(glycerol sebacate)-based nanofibers for nerve tissue engineering . Mater. Sci. Eng. , 2017 . 70 1089 - 1094 . DOI: 10.1016/j.msec.2016.03.035 http://doi.org/10.1016/j.msec.2016.03.035 .

Wong, S. C.; Baji, A.; Leng, S. . Effect of fiber diameter on tensile properties of electrospun poly( ε -caprolactone) . Polymer , 2008 . 49 4713 - 4722 . DOI: 10.1016/j.polymer.2008.08.022 http://doi.org/10.1016/j.polymer.2008.08.022 .

Pai, C. L.; Boyce, M. C.; Rutledge, G. C. . Mechanical properties of individual electrospun PA 6(3)T fibers and their variation with fiber diameter . Polymer , 2011 . 52 2295 - 2301 . DOI: 10.1016/j.polymer.2011.03.041 http://doi.org/10.1016/j.polymer.2011.03.041 .

Greenfeld, I.; Sui, X.; Wagner, H. D. . Stiffness, strength, and toughness of electrospun nanofibers: effect of flow-induced molecular orientation . Macromolecules , 2016 . 49 6518 - 6530 . DOI: 10.1021/acs.macromol.6b01204 http://doi.org/10.1021/acs.macromol.6b01204 .

Mathew, G.; Hong, J. P.; Rhee, J. M.; Leo, D. J.; Nah, C. . Preparation and anisotropic mechanical behavior of highly-oriented electrospun poly(butylene terephthalate) fibers . J. Appl. Polym. Sci. , 2006 . 101 2017 - 2021 . DOI: 10.1002/app.23762 http://doi.org/10.1002/app.23762 .

Chew, S. Y.; Hufnagel, T. C.; Lim, C. T.; Leong, K. W. . Mechanical properties of single electrospun drug-encapsulated nanofibres . Nanotechnology , 2006 . 17 3880 - 3891 . DOI: 10.1088/0957-4484/17/15/045 http://doi.org/10.1088/0957-4484/17/15/045 .

Chan, K. H. K.; Wong, S. Y.; Li, X.; Zhang, Y. Z.; Lim, P. C.; Lim, C. T.; Kotaki, M.; He, C. B. . Effect of molecular orientation on mechanical property of single electrospun fiber of poly . J. Phys. Chem. B , 2009 . 113 13179 - 13185 . DOI: 10.1021/jp905820h http://doi.org/10.1021/jp905820h .

Arinstein, A.; Zussman, E. . Electrospun polymer nanofibers: mechanical and thermodynamic perspectives . J. Polym. Sci., Part B: Polym. Phys. , 2011 . 49 691 - 707 . DOI: 10.1002/polb.22247 http://doi.org/10.1002/polb.22247 .

Stachewicz, U.; Bailey, R. J.; Wang, W.; Barber, A. H. . Size dependent mechanical properties of electrospun polymer fibers from a composite structure . Polymer , 2012 . 53 5132 - 5137 . DOI: 10.1016/j.polymer.2012.08.064 http://doi.org/10.1016/j.polymer.2012.08.064 .

Richard-Lacroix, M.; Pellerin, C. . Orientation and partial disentanglement in individual electrospun fibers: diameter dependence and correlation with mechanical properties . Macromolecules , 2015 . 48 4511 - 4519 . DOI: 10.1021/acs.macromol.5b00994 http://doi.org/10.1021/acs.macromol.5b00994 .

Papkov, D.; Zou, Y.; Andalib, M. N.; Goponenko, A.; Cheng, S. Z. D.; Dzenis, Y. A. . Simultaneously strong and tough ultrafine continuous nanofibers . ACS Nano , 2013 . 7 3324 - 3331 . DOI: 10.1021/nn400028p http://doi.org/10.1021/nn400028p .

Wang, W.; Barber, A. H. . Diameter-dependent melting behaviour in electrospun polymer fibres . Nanotechnology , 2010 . 21 225701 DOI: 10.1088/0957-4484/21/22/225701 http://doi.org/10.1088/0957-4484/21/22/225701 .

Doshi, J.; Reneker, D. H. . Electrospinning process and applications of electrospun fibers . J. Electrost. , 1995 . 35 151 - 160 . DOI: 10.1016/0304-3886(95)00041-8 http://doi.org/10.1016/0304-3886(95)00041-8 .

Wang, X.; Zhao, H.; Turng, L. S.; Li, Q. . Crystalline morphology of electrospun poly( ε -caprolactone) (PCL) nanofibers . Ind. Eng. Chem. Res. , 2013 . 52 4939 - 4949 . DOI: 10.1021/ie302185e http://doi.org/10.1021/ie302185e .

Kołbuk, D.; Sajkiewicz, P.; Kowalewski, T. A. . Optical birefringence and molecular orientation of electrospun polycaprolactone fibers by polarizing-interference microscopy . Eur. Polym. J. , 2012 . 48 275 - 283 . DOI: 10.1016/j.eurpolymj.2011.11.012 http://doi.org/10.1016/j.eurpolymj.2011.11.012 .

Damaraju, S. M.; Wu, S.; Jaffe, M.; Arinzeh, T. L. . Structural changes in PVDF fibers due to electrospinning and its effect on biological function . Biomed. Mater. , 2013 . 8 045007 DOI: 10.1088/1748-6041/8/4/045007 http://doi.org/10.1088/1748-6041/8/4/045007 .

Liu, Y.; Li, C.; Chen, S.; Wachtel, E.; Koga, T.; Sokolov, J. C.; Rafailovich, M. H. . Electrospinning of poly(ethylene- co -vinyl acetate)/clay nanocomposite fibers . J. Polym. Sci., Part B: Polym. Phys. , 2009 . 47 2501 - 2508 . DOI: 10.1002/polb.21877 http://doi.org/10.1002/polb.21877 .

Arinstein, A.; Liu, Y.; Rafailovich, M.; Zussman, E. . Shifting of the melting point for semi-crystalline polymer nanofibers . Europhys. Lett. , 2011 . 93 46001 DOI: 10.1209/0295-5075/93/46001 http://doi.org/10.1209/0295-5075/93/46001 .

Liu, Y.; Chen, S.; Zussman, E.; Korach, C. S.; Zhao, W.; Rafailovich, M. . Diameter-dependent modulus and melting behavior in electrospun semicrystalline polymer fibers . Macromolecules , 2011 . 44 4439 - 4444 . DOI: 10.1021/ma200262z http://doi.org/10.1021/ma200262z .

Zheng, Y. R.; Zhang, J.; Sun, X. L.; Li, H. H.; Ren, Z. J.; Yan, S. K. . Enhanced αγ′ transition of poly(vinylidene fluoride) by step crystallization and subsequent annealing . Chinese J. Polym. Sci. , 2018 . 36 598 - 603 . DOI: 10.1007/s10118-018-2040-z http://doi.org/10.1007/s10118-018-2040-z .

Baji, A.; Mai, Y. W.; Li, Q.; Liu, Y. . Electrospinning induced ferroelectricity in poly(vinylidene fluoride) fibers . Nanoscale , 2011 . 3 3068 - 3071 . DOI: 10.1039/c1nr10467e http://doi.org/10.1039/c1nr10467e .

Hansen, B. J.; Liu, Y.; Yang, R.; Wang, Z. L. . Hybrid nanogenerator for concurrently harvesting biomechanical and biochemical energy . ACS Nano , 2010 . 4 3647 - 3652 . DOI: 10.1021/nn100845b http://doi.org/10.1021/nn100845b .

Chang, C.; Tran, V. H.; Wang, J.; Fuh, Y. K.; Lin, L. . Direct-write piezoelectric polymeric nanogenerator with high energy conversion efficiency . Nano Lett. , 2010 . 10 726 - 731 . DOI: 10.1021/nl9040719 http://doi.org/10.1021/nl9040719 .

Zhou, J.; Berry, B.; Douglas, J. F.; Karim, A.; Snyder, C. R.; Soles, C. . Nanoscale thermal-mechanical probe determination of 'softening transitions' in thin polymer films . Nanotechnology , 2008 . 19 495703 DOI: 10.1088/0957-4484/19/49/495703 http://doi.org/10.1088/0957-4484/19/49/495703 .

Wu, X.; Shi, S.; Yu, Z.; Russell, T. P.; Wang, D. . AFM nanomechanical mapping and nanothermal analysis reveal enhanced crystallization at the surface of a semicrystalline polymer . Polymer , 2018 . 146 188 - 195 . DOI: 10.1016/j.polymer.2018.05.043 http://doi.org/10.1016/j.polymer.2018.05.043 .

Middendorf, D.; Bindrich, U.; Mischnick, P.; Franke, K.; Heinz, V. . AFM-based local thermal analysis is a suitable tool to characterize the impact of different grinding techniques on sucrose surface properties . J. Food Eng. , 2018 . 235 50 - 58 . DOI: 10.1016/j.jfoodeng.2018.04.021 http://doi.org/10.1016/j.jfoodeng.2018.04.021 .

Ago, M., Jakes, J. E.; Johansson, L.; Park, S.; Rojas, O. J. . Interfacial properties of lignin-based electrospun nanofibers and films reinforced with cellulose nanocrystals . ACS Appl. Mater. Interfaces , 2012 . 4 6849 - 6856 . DOI: 10.1021/am302008p http://doi.org/10.1021/am302008p .

Wang, Z.; Sun, B.; Lu, X.; Wang, C.; Su, Z. . Molecular orientation in individual electrospun nanofibers studied by polarized AFM-IR . Macromolecules , 2019 . 52 9639 - 9645 . DOI: 10.1021/acs.macromol.9b01778 http://doi.org/10.1021/acs.macromol.9b01778 .

Chowdhury, M.; Stylios, G. . Effect of experimental parameters on the morphology of electrospun Nylon 6 fibres . Int. J. Basic Appl. Sci. , 2010 . 10 70 - 78 . .

Lin, J.; Ding, B.; Yu, J.; Hsieh, Y. . Direct fabrication of highly nanoporous polystyrene fibers via electrospinning . ACS Appl. Mater. Interfaces , 2010 . 2 521 - 528 . DOI: 10.1021/am900736h http://doi.org/10.1021/am900736h .

Martins, P.; Lopes, A. C.; Lanceros-Mendez, S. . Electroactive phases of poly(vinylidene fluoride): determination, processing and applications . Prog. Polym. Sci. , 2014 . 39 683 - 706 . DOI: 10.1016/j.progpolymsci.2013.07.006 http://doi.org/10.1016/j.progpolymsci.2013.07.006 .

Boccaccio, T.; Bottino, A.; Capannelli, G.; Piaggio, P. . Characterization of PVDF membranes by vibrational spectroscopy . J. Membr. Sci. , 2002 . 210 315 - 329 . DOI: 10.1016/S0376-7388(02)00407-6 http://doi.org/10.1016/S0376-7388(02)00407-6 .

Kochervinskii, V. V. . The structure and properties of block poly(vinylidene fluoride) and systems based on it . Russ. Chem. Rev. , 1996 . 65 865 - 913 . DOI: 10.1070/RC1996v065n10ABEH000328 http://doi.org/10.1070/RC1996v065n10ABEH000328 .

Bormashenko, Y.; Pogreb, R.; Stanevsky, O.; Bormashenko, E. . Vibrational spectrum of PVDF and its interpretation . Polym. Test. , 2004 . 23 791 - 796 . DOI: 10.1016/j.polymertesting.2004.04.001 http://doi.org/10.1016/j.polymertesting.2004.04.001 .

Imamura, R.; Silva, A. B.; Gregorio Jr., R. . γ → β Phase transformation induced in poly(vinylidene fluoride) by stretching . J. Appl. Polym. Sci. , 2008 . 110 3242 - 3246 . DOI: 10.1002/app.28851 http://doi.org/10.1002/app.28851 .

Gregorio Jr., R. . Determination of the α , β , and γ crystalline phases of poly(vinylidene fluoride) films prepared at different conditions . J. Appl. Polym. Sci. , 2006 . 100 3272 - 3279 . DOI: 10.1002/app.23137 http://doi.org/10.1002/app.23137 .

Esterly, D. M.; Love, B. J. . Phase transformation to β -poly(vinylidene fluoride) by milling . J. Polym. Sci., Part B: Polym. Phys. , 2004 . 42 91 - 97 . DOI: 10.1002/polb.10613 http://doi.org/10.1002/polb.10613 .

Gregorio, J. R.; Cestari, M. . Effect of crystallization temperature on the crystalline phase content and morphology of poly(vinylidene fluoride) . J. Polym. Sci., Part B: Polym. Phys. , 1994 . 32 859 - 870 . .

Lee, S. H.; Cho, H. H. . Crystal structure and thermal properties of poly(vinylidene fluoride)-carbon fiber composite films with various drawing temperatures and speeds . Fibers Polym. , 2010 . 11 1146 - 1151 . DOI: 10.1007/s12221-010-1146-x http://doi.org/10.1007/s12221-010-1146-x .

Nakagawa, K.; Ishida, Y. . Annealing effects in poly(vinylidene fluoride) as revealed by specific volume measurements, differential scanning calorimetry, and electron microscopy . J. Polym. Sci., Polym. Phys. Ed. , 1973 . 11 2153 - 2171 . DOI: 10.1002/pol.1973.170110908 http://doi.org/10.1002/pol.1973.170110908 .

Maccone, P.; Brinati, G.; Arcella, V. . Environmental stress cracking of poly(vinylidene fluoride) in sodium hydroxide. Effect of chain regularity . Polym. Eng. Sci. , 2000 . 40 761 - 767 . .

Zhao, S.; Wu, X.; Wang, L.; Huang, Y. . Electrospinning of ethyl-cyanoethyl cellulose/tetrahydrofuran solutions . J. Appl. Polym. Sci. , 2004 . 91 242 - 246 . DOI: 10.1002/app.13196 http://doi.org/10.1002/app.13196 .

Ero-Phillips, O.; Jenkins, M.; Stamboulis, A. . Tailoring crystallinity of electrospun PLLA fibres by control of electrospinning parameters . Polymers , 2012 . 4 1331 - 1348 . DOI: 10.3390/polym4031331 http://doi.org/10.3390/polym4031331 .

Nandi, A. K.; Mandelkern, L. . The influence of chain structure on the equilibrium melting temperature of poly(vinylidene fluoride) . J. Polym. Sci., Part B: Polym. Phys. , 1991 . 29 1287 - 1297 . DOI: 10.1002/polb.1991.090291012 http://doi.org/10.1002/polb.1991.090291012 .

Cui, Z.; Hassankiadeh, N. T.; Zhuang, Y.; Drioli, E.; Lee, Y. M. . Crystalline polymorphism in poly(vinylidenefluoride) membranes . Prog. Polym. Sci. , 2015 . 51 94 - 126 . DOI: 10.1016/j.progpolymsci.2015.07.007 http://doi.org/10.1016/j.progpolymsci.2015.07.007 .

Richard-Lacroix, M.; Pellerin, C. . Molecular orientation in electrospun fibers: from mats to single fibers . Macromolecules , 2013 . 46 9473 - 9493 . DOI: 10.1021/ma401681m http://doi.org/10.1021/ma401681m .

Wang, C.; Tsou, S. Y.; Lin, H. S. . Brill transition of nylon-6 in electrospun nanofibers . Colloid Polym. Sci. , 2012 . 290 1799 - 1809 . DOI: 10.1007/s00396-012-2724-9 http://doi.org/10.1007/s00396-012-2724-9 .

Iguchi, M.; Tonami, H.; Kawai, T. . Crystallization of polyethylene under molecular orientation . Kolloid-Z.u.Z. Polymere , 1967 . 221 28 - 40 . DOI: 10.1007/BF02091921 http://doi.org/10.1007/BF02091921 .

Yan, J.; Xiao, C.; Wang, C.; Fu, H.; An, S.; Jiang, Y. . Crystalline structure changes of poly(vinylidene fluoride) fibers during stretching process . Acta Polymerica Sinica (in Chinese) , 2019 . 50 752 - 760 . .

Yoshioka, T.; Dersch, R.; Tsuji, M.; Schaper, A. K. . Orientation analysis of individual electrospun PE nanofibers by transmission electron microscopy . Polymer , 2010 . 51 2383 - 2389 . DOI: 10.1016/j.polymer.2010.03.031 http://doi.org/10.1016/j.polymer.2010.03.031 .

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Dielectric Constant Calculation of Poly(vinylidene fluoride) Based on Finite Field and Density Functional Theory

Matrix Effect on Polydiarylfluorenes Electrospun Hybrid Microfibers: From Morphology Tuning to High Explosive Detection Efficiency

Highly Transparent and Adhesive Poly(vinylidene difluoride) Films for Self-Powered Piezoelectric Touch Sensors

Squaramide-directed Cooperative One-dimensional Assembly in Telechelic Polydimethylsiloxane for Hierarchical Network Formation

Topology-regulated Co-assembly of Single Chain Polymer Nanoparticles and Block Copolymers into Hierarchical Micelle@Vesicle Composite Structures

Related Author

Jian Xu

Ming-Liang Wang

Cai-Zhen Zhu

Chao-Fan Chang

Ya-Dong Li

Lu-Kun Feng

Yong-Zhi Lin

Sheng-Jie Wang

Related Institution

Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences

College of Chemistry and Environmental Engineering, Shenzhen University

Frontiers Science Center for Flexible Electronics (FSCFE), Shaanxi Institute of Flexible Electronics (SIFE) & Shaanxi Institute of Biomedical Materials and Engineering (SIBME), Northwestern Polytechnical University (NPU)

Center for Supramolecular Optoelectronics (CSO), Key Laboratory of Flexible Electronics (KLOFE) and Institute of Advanced Materials (IAM), Nanjing Tech University (NanjingTech)

State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications

⁰