Citation: Xiao-Yan Yang, Shao-Shuai Liu, Alexander V. Korobko, Stephen J. Picken, Nicolaas A. M. Besseling. Changes of the Molecular Mobility of Poly(ε-caprolactone) upon Drawing, Studied by Dielectric Relaxation Spectroscopy[J]. Chinese Journal of Polymer Science, ;2018, 36(5): 665-674. doi: 10.1007/s10118-018-2030-1 shu

Changes of the Molecular Mobility of Poly(ε-caprolactone) upon Drawing, Studied by Dielectric Relaxation Spectroscopy

a.
Lucky Research Institute, China Lucky Group Corporation, Baoding 071054, China
b.
Department of Chemical Engineering, Delft University of Technology, 2628 BL Delft, and Dutch Polymer Institute(DPI), 5600 AX Eindhoven, the Netherlands

Corresponding author: Xiao-Yan Yang, hsiaoyen_yang@hotmail.com
Received Date: 19 July 2017
Accepted Date: 30 August 2017
Available Online: 15 January 2018

Dielectric relaxation spectroscopy (DRS) of poly(ε-caprolactone) with different draw ratios showed that the mobility of polymer chains in the amorphous part decreases as the draw ratio increases. The activation energy of the α process, which corresponds to the dynamic glass transition, increases upon drawing. The enlarged gap between the activation energies of the α process and the β process results in a change of continuity at the crossover between the high temperature a process and the α and β processes. At low drawing ratios the a process connects with the β process, while at the highest drawing ratio in our measurements, the a process is continuous with the α process. This is consistent with X-ray diffraction results that indicate that upon drawing the polymer chains in the amorphous part align and densify upon drawing. As the draw ratio increases, the α relaxation broadens and decreases its intensity, indicating an increasing heterogeneity. We observed slope changes in the α traces, when the temperature decreases below that at which τ_α ≈ 1 s. This may indicate the glass transition from the 'rubbery' state to the non-equilibrium glassy state.
- Semicrystalline polymer,
- Dielectric relaxation spectroscopy,
- Molecular mobility
1. [1]
  Omid Y., Hamid G.. Development of a simple model to characterize the complex constrained polymer chains in polymer nanocomposites at the interphase of amorphous/semicrystalline ethylene vinyl acetate and nanosheets[J]. J. Compos. Mater., 2016,51(2):179-186.
2. [2]
  Perez-de-Eulate N. G., Di Lisio V., Cangialosi D.. Glass Transition and Molecular Dynamics in Polystyrene Nanospheres by Fast Scanning Calorimetry[J]. ACS Macro Lett., 2017,6(6):859-863.
3. [3]
  Sharma R. P., Green P. F.. Role of "Hard" and "soft" confinement on polymer dynamics at the nanoscale[J]. ACS Macro Lett., 2017,6(9):908-914. doi: 10.1021/acsmacrolett.7b00374
4. [4]
  Lee K. H., Kim H. Y., Khil M. S., Ra Y. M., Lee D. R.. Characterization of nano-structured poly(ε-caprolactone) nonwoven mats via electrospinning[J]. Polymer., 2003,44(4):1287-1294. doi: 10.1016/S0032-3861(02)00820-0
5. [5]
  Chen Z., Cao L., Wang L., Zhu H., Jiang H.. Effect of fiber structure on the properties of the electrospun hybrid membranes composed of poly(ε-caprolactone) and gelatin[J]. J. Appl. Polym. Sci., 2013,127(6):4225-4232. doi: 10.1002/app.38000
6. [6]
  Bernards D. A., Bhisitkul R. B., Wynn P., Steedman M. R., Lee O. T., Wong F., Thoongsuwan S., Desai T. A.. Ocular Biocompatibility and Structural Integrity of Micro-and Nanostructured Poly(caprolactone) Films[J]. J. Ocul. Pharmacol. Th., 2013,29(2):249-257. doi: 10.1089/jop.2012.0152
7. [7]
  Shan G. F., Yang W., Yang M. B., Xie B. H., Fu Q., Mai Y. W.. Investigation on tensile deformation behavior of semi-crystalline polymers[J]. J. Macromol. Sci. B, 2009,48(7):799-811.
8. [8]
  Li H., Zhou W., Ji Y., Hong Z., Miao B., Li X., Zhang J., Qi Z., Wang X., Li L., Li Z. M.. Spatial distribution of crystal orientation in neck propagation:An in-situ microscopic infrared imaging study on polyethylene[J]. Polymer, 2013,54(2):972-979. doi: 10.1016/j.polymer.2012.12.012
9. [9]
  Li J. X., Cheung W. L., Chan C. M.. On deformation mechanisms of β-polypropylene 3.Lamella structures after necking and cold drawing[J]. Polymer, 1999,40(13):3641-3656. doi: 10.1016/S0032-3861(98)00578-3
10. [10]
  Peterlin A.. Molecular model of drawing polyethylene and polypropylene[J]. J. Mater. Sci., 1971,6(6):490-508. doi: 10.1007/BF00550305
11. [11]
  Van Aerle N. A. J. M., Braam A. W. M.. A structural study on solid state drawing of solution-crystallized ultra-high molecular weight polyethylene[J]. J. Mater. Sci., 1988,23(12):4429-4436. doi: 10.1007/BF00551941
12. [12]
  Mcrae M. A., Maddams W. F., Preedy J. E.. An infra-red spectroscopic and X-ray diffraction study of cold-drawn high density polyethylene samples[J]. J. Mater. Sci., 1976,11(11):2036-2044. doi: 10.1007/PL00020329
13. [13]
  Flory P. J., Yoon D. Y.. Molecular morphology in semicrystalline polymers[J]. Nature, 1978,272(5650):226-229. doi: 10.1038/272226a0
14. [14]
  Nozue Y., Shinohara Y., Ogawa Y., Takamizawa T., Sakurai T., Kasahara T., Yamaguchi N., Yagi N., Amemiya Y.. Deformation behavior of banded spherulite during drawing investigated by simultaneous microbeam SAXS-WAXS and POM measurement[J]. Polymer, 2010,51(1):222-231. doi: 10.1016/j.polymer.2009.11.031
15. [15]
  Li J. X., Cheung W. L.. On the deformation mechanisms of β-polypropylene:1.Effect of necking on β-phase PP crystals[J]. Polymer, 1998,39(26):6935-6940. doi: 10.1016/S0032-3861(98)00144-X
16. [16]
  Zhao Y., Keroack D., Prudȼhomme R.. Crystallization under strain and resultant orientation of poly(ε-caprolactone) in miscible blends[J]. Macromolecules, 1999,32(4):1218-1225. doi: 10.1021/ma981416o
17. [17]
  Pieruccini M., Ezquerra T. A., Lanza M.. Phenomenological model for the confined dynamics in semicrystalline polymers:the multiple α relaxation in cold-crystallized poly(ethylene terephthalate)[J]. J. Chem. Phys., 2007,127(10). doi: 10.1063/1.2771166
18. [18]
  Hakme, C. ; Stevenson, I. ; David, L. ; Sixou, B. ; Voice, A. ; Seytre, G. ; Boiteux, G. Molecular mobility in poly(ethylene naphthalene 2, 6 dicarboxylate) (PEN) dielectric films. Proceeding of the 2004 IEEE International Conference on Solid Dielectrics. 2004, Vol. 1, 37-40.
19. [19]
  Hakme C., Stevenson I., David L., Seytre G., Boiteux G.. Effect of orientation and crystallization on dielectric and mechanical relaxations in uniaxially stretched poly(ethylene naphthalene 2, 6 dicarboxylate) (PEN) films[J]. J. Non-Cryst. Solids, 2006,352(42-49):4746-4752. doi: 10.1016/j.jnoncrysol.2006.01.126
20. [20]
  Nogales A., Denchev Z., Šics I., Ezquerra T. A.. Influence of the crystalline structure in the segmental mobility of semicrystalline polymers:poly(ethylene naphthalene-2, 6-dicarboxylate)[J]. Macromoleculs, 2000,33(25):9367-9375. doi: 10.1021/ma001066h
21. [21]
  Frübing P., Kremmer A., Gerhard-Multhaupt R., Spanoudaki A., Pissis P.. Relaxation processes at the glass transition in polyamide 11:from rigidity to viscoelasticity[J]. J. Chem. Phys., 2006,125(21). doi: 10.1063/1.2360266
22. [22]
  Donth, E. The glass transition: relaxation dynamics in liquids and disordered materials, Springer-Verlag Berlin Heidelberg, New York, 2001, p. 199.
23. [23]
  Grimau M., Laredo E., Pérez Y. M., Bello C. A.. Study of dielectric relaxation modes in poly(ε-caprolactone):molecular weight, water sorption, and merging effects[J]. J. Chem. Phys., 2001,114(15):6417-6425.
24. [24]
  Scönhals, A. ; Kremer, F., in "Broadband dielectric spectroscopy" ed. by Kremer, F. ; Scönhals, A., Springer-Verlag Berlin Heidelberg, New York, 2003, p. 59.
25. [25]
  Alcock B., Cabrera N. O., Barkoula N. M., Raynolds C. T., Govaert L. E., Peijs T.. The effect of temperature and strain rate on the mechanical properties of highly oriented polypropylene tapes and all-polypropylene composites[J]. Compos. Sci. Technol., 2007,67(10):2061-2070. doi: 10.1016/j.compscitech.2006.11.012
26. [26]
  Qiu Z., Yang W., Ikehara T., Nishi T.. Miscibility and crystallization behavior of biodegradable blends of two aliphatic polyesters.Poly(3-hydroxybutyrate-co-hydroxyvalerate) and poly(ε-caprolactone)[J]. Polymer, 2005,46(25):11814-11819. doi: 10.1016/j.polymer.2005.10.058
27. [27]
  Crescenzi V., Manzini G., Calzolari G., Borri C.. Thermodynamics of fusion of poly-β-propiolactone and poly-ε-caprolactone.comparative analysis of the melting of aliphatic polylactone and polyester chains[J]. Eur. Polym. J., 1972,8(3):449-463. doi: 10.1016/0014-3057(72)90109-7
28. [28]
  Bello A., Laredo E., Grimau M.. Comparison of analysis of dielectric spectra of PCL in the ε^* and the M* formalism[J]. J. Non-Cryst. Solids., 2007,353(47-51):4283-4287. doi: 10.1016/j.jnoncrysol.2007.08.041
29. [29]
  Serra R. S. I. J., Ivirico L. E., Dueñas J. M. M., Balado A. A., Ribelles J. L. G., Sánchez M. S.. Segmental dynamics in poly(ε-caprolactone)/poly(L-lactide) copolymer networks[J]. J. Polym. Sci., Part B:Polym. Phys., 2009,47(2):183-193. doi: 10.1002/polb.v47:2
30. [30]
  Lee H., Paeng K., Swallen S. F., Ediger M. D.. Direct measurement of molecular mobility in actively deformed polymer glasses[J]. Science, 2009,323(5911):231-234. doi: 10.1126/science.1165995
31. [31]
  Suljovrujić, E. Dielectric studies of molecular β-relaxation in low density polyethylene:the influence of drawing and ionizing radiation. Polymer 2002, 43(22), 5969-5978. (Note:the β and γ relaxations in the reference are the α and β relaxations in this paper, respectively)
32. [32]
  Adam G., Gibbs J. H.. On the temperature dependence of cooperative relaxation properties in glass-forming liquids[J]. J. Chem. Phys., 1965,143(1):139-146.
33. [33]
  Schröter K., Unger R., Reissig S., Garwe F., Kahle S., Beiner M., Donth E.. Dielectric spectroscopy in the αβ splitting region of glass transition in poly(ethyl methacrylate) and poly(n-butyl methacrylate):different evaluation methods and experimental conditions[J]. Macromolecules, 1998,31(25):8966-8972. doi: 10.1021/ma9713318
34. [34]
  Hansen C., Stickel F., Berger T., Richert R., Fischer E. W.. Dynamics of glass-forming liquids.Ⅲ. Comparing the dielectric α-and β-relaxation of 1-propanol and ο-terphenyl[J]. J. Chem. Phys., 1997,107(4):1086-1093. doi: 10.1063/1.474456
35. [35]
  Smith G. D., Bedrov D.. Relationship between the α-and β-relaxation processes in amorphous polymers:Insight from atomistic molecular dynamics simulations of 1, 4-polybutadiene melts and blends[J]. J. Polym. Sci., Part B:Polym. Phys., 2007,45(6):627-643. doi: 10.1002/(ISSN)1099-0488
36. [36]
  Götze, W. in "Liquid, Freezing and the Glass Transition", ed. by Hansen, J. P. ; Levesque, D. ; Zinn-Justin, J., North-Hollond, Amsterdam, 1991, p. 287.
37. [37]
  Saiter J. M., Grenet J., Saiter E. A., Delbreilh L.. Glass Transition temperature and value of the relaxation time at T_g in vitreous polymers[J]. Macromol. Symp., 2007,258(1):152-161. doi: 10.1002/(ISSN)1521-3900
38. [38]
  Li J. X., Cheung W. L., Chan C. M.. On deformation mechanisms of β-polypropylene 2.changes of lamellar structure caused by tensile load[J]. Polymer, 1999,40(8):2089-2102. doi: 10.1016/S0032-3861(98)00412-1
39. [39]
  Murthy N. S., Minor H., Bednarczyk C.. Structure of the amorphous phase in oriented polymers[J]. Macromolecules, 1993,26(7):1712-1721. doi: 10.1021/ma00059a034
40. [40]
  Liedermann K.. A simple formula for the temperature dependence of the relaxation frequency in glassy systems[J]. Collid. Polym. Sci., 1996,274(1):20-26. doi: 10.1007/BF00658905
41. [41]
  Kremer F. ; Huwe A. ; Schönhals A. ; Różański S. A., in "Broadband dielectric spectroscopy" ed. by Kremer, F. ; Scönhals, A., Springer-Verlag Berlin Heidelberg, New York, 2003, p. 171.
42. [42]
  Arndt M., Stannarius R., Groothues H., Hempel E., Kremer F.. Length Scale of Cooperativity in the Dynamic Glass Transition[J]. Phys. Rev. Lett., 1997,79(11):2077-2080. doi: 10.1103/PhysRevLett.79.2077
1. [1]
  Yan Cheng , Hua-Peng Ruan , Yan Peng , Longhe Li , Zhenqiang Xie , Lang Liu , Shiyong Zhang , Hengyun Ye , Zhao-Bo Hu . Magnetic, dielectric and luminescence synergetic switchable effects in molecular material [Et₃NCH₂Cl]₂[MnBr₄]. Chinese Chemical Letters, 2024, 35(4): 108554-. doi: 10.1016/j.cclet.2023.108554
2. [2]
  Jing Chen , Peisi Xie , Pengfei Wu , Yu He , Zian Lin , Zongwei Cai . MALDI coupled with laser-postionization and trapped ion mobility spectrometry contribute to the enhanced detection of lipids in cancer cell spheroids. Chinese Chemical Letters, 2024, 35(4): 108895-. doi: 10.1016/j.cclet.2023.108895
3. [3]
  Fang-Yuan Chen , Wen-Chao Geng , Kang Cai , Dong-Sheng Guo . Molecular recognition of cyclophanes in water. Chinese Chemical Letters, 2024, 35(5): 109161-. doi: 10.1016/j.cclet.2023.109161
4. [4]
  Haixia Wu , Kailu Guo . Sulfur reduction reaction mechanism elucidated with in situ Raman spectroscopy. Chinese Chemical Letters, 2025, 36(6): 110654-. doi: 10.1016/j.cclet.2024.110654
5. [5]
  Hongdao LI , Shengjian ZHANG , Hongmei DONG . Magnetic relaxation and luminescent behavior in nitronyl nitroxide-based annuluses of rare-earth ions. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 972-978. doi: 10.11862/CJIC.20230411
6. [6]
  Zhao-Bo Hu , Ling-Ao Gui , Long-He Li , Tong-Tong Xiao , Adam T. Hand , Pagnareach Tin , Mykhaylo Ozerov , Yan Peng , Zhongwen Ouyang , Zhenxing Wang , Zi-Ling Xue , You Song . Co^Ⅱ single-ion magnet and its multi-dimensional aggregations: Influence of the structural rigidity on magnetic relaxation process. Chinese Chemical Letters, 2025, 36(2): 109600-. doi: 10.1016/j.cclet.2024.109600
7. [7]
  Jiajia Zhuang , Chunyu Cui , Changjiang Li , Gang Luo , Jiaping Tong , Di Sun . Counter-ion effect to the Ising-type magnetic anisotropy and magnetic relaxation in trigonal bipyramidal Co(Ⅱ) complexes. Chinese Chemical Letters, 2025, 36(7): 110091-. doi: 10.1016/j.cclet.2024.110091
8. [8]
  Xiaoman Dang , Zhiying Wu , Tangxin Xiao , Zhouyu Wang , Leyong Wang . Highly robust supramolecular polymer networks crosslinked by metallacycles. Chinese Chemical Letters, 2024, 35(12): 110208-. doi: 10.1016/j.cclet.2024.110208
9. [9]
  Yaohua Li , Qi Cao , Xuanhua Li . Tailoring the configuration of polymer passivators in perovskite solar cells. Chinese Journal of Structural Chemistry, 2025, 44(2): 100413-100413. doi: 10.1016/j.cjsc.2024.100413
10. [10]
  Dayang Xie , Qiannan Cao , Huapan Fang , Yanhui Li , Huayu Tian . Applications and challenges of biomedical polymer materials in pulmonary diseases. Chinese Chemical Letters, 2026, 37(2): 111032-. doi: 10.1016/j.cclet.2025.111032
11. [11]
  Zhi-Long Li , Hao-Fei Ni , Bo Zhuang , Kun Ding , Da-Wei Fu , Qiang Guo , Meng-Meng Lun . Halogen substitution strategy for regulating the photoluminescence and dielectric response of ferroelastics. Chinese Chemical Letters, 2026, 37(4): 110755-. doi: 10.1016/j.cclet.2024.110755
12. [12]
  Caihong Mao , Yanfeng He , Xiaohan Wang , Yan Cai , Xiaobo Hu . Synthesis and molecular recognition characteristics of a tetrapodal benzene cage. Chinese Chemical Letters, 2024, 35(8): 109362-. doi: 10.1016/j.cclet.2023.109362
13. [13]
  Cheng-Da Zhao , Huan Yao , Shi-Yao Li , Fangfang Du , Li-Li Wang , Liu-Pan Yang . Amide naphthotubes: Biomimetic macrocycles for selective molecular recognition. Chinese Chemical Letters, 2024, 35(4): 108879-. doi: 10.1016/j.cclet.2023.108879
14. [14]
  Yanwei Duan , Qing Yang . Molecular targets and their application examples for interrupting chitin biosynthesis. Chinese Chemical Letters, 2025, 36(4): 109905-. doi: 10.1016/j.cclet.2024.109905
15. [15]
  Li-Ming Cao , Chun-Ting He . Molecular enhancement of platinum electrocatalysts for hydrogen evolution. Chinese Journal of Structural Chemistry, 2026, 45(3): 100814-100814. doi: 10.1016/j.cjsc.2025.100814
16. [16]
  Ling-Hao Zhao , Hai-Wei Yan , Jian-Shuang Jiang , Xu Zhang , Xiang Yuan , Ya-Nan Yang , Pei-Cheng Zhang . Effective assignment of positional isomers in dimeric shikonin and its analogs by ¹H NMR spectroscopy. Chinese Chemical Letters, 2024, 35(5): 108863-. doi: 10.1016/j.cclet.2023.108863
17. [17]
  Chengde Wang , Liping Huang , Shanshan Wang , Lihao Wu , Yi Wang , Jun Dong . A distinction of gliomas at cellular and tissue level by surface-enhanced Raman scattering spectroscopy. Chinese Chemical Letters, 2024, 35(5): 109383-. doi: 10.1016/j.cclet.2023.109383
18. [18]
  Manyu Zhu , Fei Liang , Lie Wu , Zihao Li , Chen Wang , Shule Liu , Xiue Jiang . Revealing the difference of Stark tuning rate between interface and bulk by surface-enhanced infrared absorption spectroscopy. Chinese Chemical Letters, 2025, 36(2): 109962-. doi: 10.1016/j.cclet.2024.109962
19. [19]
  Hao Li , Hanzhi Lu , Linlin Hu , Xueli Zhang , Hua Shao , Fulun Li , Yanfei Shen . Dynamic surface-enhanced Raman spectroscopy-based metabolic profiling: A novel pathway to overcoming antifungal resistance. Chinese Chemical Letters, 2025, 36(7): 110342-. doi: 10.1016/j.cclet.2024.110342
20. [20]
  Feiyan Ma , Haomiao Dou , Danni Luo , Ying Yan , Jie Zhou , Guangda Xu , Yue Wang , Longshan Zhao . Recent advances in chiral recognition based on surface-enhanced Raman scattering spectroscopy. Chinese Chemical Letters, 2026, 37(4): 111632-. doi: 10.1016/j.cclet.2025.111632

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(1993)
HTML views(96)

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