Citation: Han Liu, Guang-Su Huang, Lai-Yun Wei, Jian Zeng, Xuan Fu, Cheng Huang, Jin-Rong Wu. Inhomogeneous Natural Network Promoting Strain-induced Crystallization: A Mesoscale Model of Natural Rubber[J]. Chinese Journal of Polymer Science, ;2019, 37(11): 1142-1151. doi: 10.1007/s10118-019-2267-3 shu

Inhomogeneous Natural Network Promoting Strain-induced Crystallization: A Mesoscale Model of Natural Rubber

College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, China

Corresponding author: Guang-Su Huang, guangsu-huang@hotmail.com Jin-Rong Wu, wujinrong@scu.edu.cn
Received Date: 18 February 2019
Revised Date: 21 March 2019
Available Online: 6 June 2019

Although synthetic rubbers show continuously improved mechanical properties, natural rubber (NR) remains irreplaceable in the rubber family due to its superior mechanical properties. A mainstream viewpoint regarding the superiority of NR is that NR possesses a natural network formed by linking the poly(cis-1,4-isoprene) chain terminals to protein and phospholipid aggregates; after vulcanization, the natural network additionally contributes to rubber mechanics by both increasing the network density and promoting the strain-induced crystallization (SIC) behavior. However, the reason why the natural network promotes SIC is still unclear; in particular, only using the increased network density cannot explain our finding that the NR shows smaller onset strain of SIC than Gel (the gel component of NR with higher network density) and even vulcanized NR. Herein, we point out that the inhomogeneous chain deformation is the alternative reason why SIC of NR takes place at smaller strain than that of Gel. More specifically, although the natural network is homogenous on the subchain length scale based on the proton double-quantum NMR results, it is essentially inhomogeneous on mesoscale (100 nm), as revealed by the small angle X-ray scattering analysis. This inhomogeneous network also leads to the mesoscale deformation inhomogeneity, as detected by the orientation of stearic acid (SA) probe, thus resulting in the smaller onset strain of SIC of NR. Based on the experimental results, a mesoscale model is proposed to qualitatively describe the crucial roles of inhomogeneous structure and deformation of natural network in NR’s mechanical properties, providing a clue from nature to guide the development of high-performance rubbers with controlled structures at mesoscale.
- Natural Rubber,
- Inhomogeneous natural network,
- Strain-induced crystallization,
- Mesoscale model
1. [1]
  Kohjiya, S; Ikeda, Y. Chemistry, Manufacture and applications of natural rubber. Cambridge, UK, Woodhead Publishing, 2014.
2. [2]
  Gent, A.; Kawahara, S.; Zhao, J. Crystallization and strength of natural rubber and synthetic cis-1,4-polyisoprene. Rubber Chem. Technol. 1998, 71, 668–678. doi: 10.5254/1.3538496
3. [3]
  Tanaka, Y. Structural characterization of natural polyisoprenes: Solve the mystery of natural rubber based on structural study. Rubber Chem. Technol. 2001, 74, 355–375. doi: 10.5254/1.3547643
4. [4]
  Tarachiwin, L.; Sakdapipanich, J.; Ute, K.; Kitayama, T.; Bamba, T.; Fukusaki, E.-i.; Kobayashi, A.; Tanaka, Y. Structural Characterization of α-terminal group of natural rubber. 1. Decomposition of branch-points by lipase and phosphatase treatments. Biomacromolecules 2005, 6, 1851–1857.
5. [5]
  Tarachiwin, L.; Sakdapipanich, J.; Ute, K.; Kitayama, T.; Tanaka, Y. Structural characterization of α-terminal group of natural rubber. 2. Decomposition of branch-points by phospholipase and chemical treatments. Biomacromolecules 2005, 6, 1858–1863. doi: 10.1021/bm058004p
6. [6]
  Karino, T.; Ikeda, Y.; Yasuda, Y.; Kohjiya, S.; Shibayama, M. Nonuniformity in natural rubber as revealed by small-angle neutron scattering, small-angle X-ray scattering, and atomic force microscopy. Biomacromolecules 2007, 8, 693-699. doi: 10.1021/bm060983d
7. [7]
  Toki, S.; Burger, C.; Hsiao, B. S.; Amnuaypornsri, S.; Sakdapipanich, J.; Tanaka, Y. Multi-scaled microstructures in natural rubber characterized by synchrotron X-ray Scattering and optical microscopy. J. Polym. Sci., Part B: Polym. Phys. 2008, 46, 2456–2464. doi: 10.1002/polb.v46:22
8. [8]
  Amnuaypornsri, S.; Sakdapipanich, J.; Toki, S.; Hsiao, B.; Ichikawa, N.; Tanaka, Y. Strain-induced crystallization of natural rubber: effect of proteins and phospholipids. Rubber Chem. Technol. 2008, 81, 753–766. doi: 10.5254/1.3548230
9. [9]
  Tanaka, Y.; Tarachiwin, L. Recent advances in structural characterization of natural rubber. Rubber Chem. Technol. 2009, 82, 283–314. doi: 10.5254/1.3548250
10. [10]
  Toki, S.; Hsiao, B. S.; Amnuaypornsri, S.; Sakdapipanich, J. New insights into the relationship between network structure and strain-induced crystallization in un-vulcanized and vulcanized natural rubber by synchrotron X-ray diffraction. Polymer 2009, 50, 2142–2148. doi: 10.1016/j.polymer.2009.03.001
11. [11]
  Che, J.; Burger C.; Toki, S.; Rong, L.; Hsiao, B. Crystal and crystallites structure of natural rubber and synthetic cis-1,4-polyisoprene by a new two dimensional wide angle X-ray diffraction simulation method. I. Strain-induced crystallization. Macromolecules 2013, 46, 4520–4528.
12. [12]
  Toki, S.; Che, J.; Rong, L.; Hsiao, B. S.; Amnuaypornsri, S.; Nimpaiboon, A.; Sakdapipanich, J. Entanglements and networks to strain-induced crystallization and stress-strain relations in natural rubber and synthetic polyisoprene at various temperatures. Macromolecules 2013, 46, 5238–5248. doi: 10.1021/ma400504k
13. [13]
  Liu, J.; Wang, S.; Tang, Z.; Huang, J; Guo, B.; Huang, G. Bioinspired engineering of two different types of sacrificial bonds into chemically cross-linked cis-1,4-polyisoprene toward a high-performance elastomer. Macromolecules 2016, 49, 8593–8604. doi: 10.1021/acs.macromol.6b01576
14. [14]
  Zhou, Y.; Kosugi, K.; Yamamoto, Y.; Kawahara, S. Effect of nonrubber components on the mechanical properties of natural rubber. Polym. Adv. Technol. 2017, 28, 159–165. doi: 10.1002/pat.3870
15. [15]
  Wu, J.; Qu, W.; Huang, G.; Wang, S.; Huang, C.; Liu, H. Super-resolution fluorescence imaging of spatial organization of proteins and lipids in natural rubber. Biomacromolecules 2017, 18, 1705–1712. doi: 10.1021/acs.biomac.6b01827
16. [16]
  Sainumsai, W.; Toki, S.; Amnuaypornsri, S.; Nimpaiboon, A.; Sakdapipanich, J.; Rong, L.; Hsiao, B.; Suchiva, K. Dependence of the onset of strain-induced crystallization of natural rubber and its synthetic analogue on crosslink and entanglement by using synchrotron X-Ray. Rubber Chem. Technol. 2017, 90, 728–742. doi: 10.5254/rct.18.82693
17. [17]
  Gabrielle, B.; Gomez, E.; Korb, J. Probing rubber cross-linking generation of industrial polymer networks at nanometer scale. J. Phys. Chem. B 2016, 120, 5581–5589.
18. [18]
  Valentin, J. L.; Posadas, P.; Fernandez-Torres, A.; Malmierca, M. A.; Gonzalez, L.; Chasse, W.; Saalwaechter, K. Inhomogeneities and chain dynamics in diene rubbers vulcanized with different cure systems. Macromolecules 2010, 43, 4210–4222. doi: 10.1021/ma1003437
19. [19]
  Tosaka, M.; Murakami, S.; Poompradub, S.; Kohjiya, S.; Ikeda, Y.; Toki, S.; Sics, I.; Hsiao, B. S. Orientation and crystallization of natural rubber network as revealed by WAXD using synchrotron radiation. Macromolecules 2004, 37, 3299–3309. doi: 10.1021/ma0355608
20. [20]
  Nie, Y. J.; Gao, H. H.; Yu, M. H.; Hu, Z. M.; Reiter, G.; Hu, W. B. Competition of crystal nucleation to fabricate the oriented semi-crystalline polymers. Polymer 2013, 54(13), 3402–3407. doi: 10.1016/j.polymer.2013.04.047
21. [21]
  Zhang, M. M.; Zha, L. Y.; Gao, H. H.; Nie, Y. J.; Hu, W. B. How polydispersity of network polymers influences strain-induced crystal nucleation in a rubber. Chinese J. Polym. Sci. 2014, 32(9), 1218–1223. doi: 10.1007/s10118-014-1495-9
22. [22]
  Weng, G.; Huang, G.; Qu, L.; Nie, Y.; Wu, J. Large-scale orientation in a vulcanized stretched natural rubber network: Proved by in situ synchrotron X-ray diffraction. J. Phys. Chem. B 2010, 114, 7179–7188.
23. [23]
  Ikeda, Y.; Higashitani, N.; Hijikata, K.; Kokubo, Y.; Morita, Y.; Shibayama, M.; Osaka, N.; Suzuki, T.; Endo, H.; Kohjiya, S. Vulcanization: New focus on a traditional technology by small-angle neutron scattering. Macromolecules 2009, 42, 2741–2748. doi: 10.1021/ma802730z
24. [24]
  Ikeda, Y.; Yasuda, Y.; Hijikata, K.; Tosaka, M.; Kohjiya, S. Comparative study on strain-induced crystallization behavior of peroxide cross-linked and sulfur cross-linked natural rubber. Macromolecules 2008, 41, 5876–5884. doi: 10.1021/ma800144u
25. [25]
  Suzuki, T.; Osaka, N.; Endo, H.; Shibayama, M.; Ikeda, Y.; Asai, H.; Higashitani, N.; Kokubo, Y.; Kohjiya, S. Nonuniformity in cross-linked natural rubber as revealed by contrast-variation small-angle neutron scattering. Macromolecules 2010, 43, 1556–1563. doi: 10.1021/ma9019416
26. [26]
  Toki, S.; Sics, I.; Ran, S. F.; Liu, L. Z.; Hsiao, B. S.; Murakami, S.; Senoo, K.; Kohjiya, S. New insights into structural development in natural rubber during uniaxial deformation by in situ synchrotron X-ray diffraction. Macromolecules 2002, 35, 6578–6584. doi: 10.1021/ma0205921
27. [27]
  Tosaka, M. A Route for the thermodynamic description of strain-induced crystallization in sulfur-cured natural rubber. Macromolecules 2009, 42, 6166–6174. doi: 10.1021/ma900954c
28. [28]
  Candau, N.; Laghmach, R.; Chazeau, L.; Chenal J.; Gauthier, C.; Biben, T.; Munch, E. Strain-induced crystallization of natural rubber and cross-link densities heterogeneities. Macromolecules 2014, 47, 5815–5824. doi: 10.1021/ma5006843
29. [29]
  Ran, S.; Fang, D.; Zong, X.; Hsiao, B. S.; Chu, B.; Cunniff, P. M. Structural changes during deformation of Kevlar fibers via on-line synchrotron SAXS/WAXD techniques. Polymer 2001,42, 1601–1612. doi: 10.1016/S0032-3861(00)00460-2
30. [30]
  Shibayama, M.; Kurokawa, H.; Nomura, S.; Muthukumar, M.; Stein, R.; Roy, S. Small-angle neutron scattering from poly(vinyl alcohol)-borate gels. Polymer 1992, 33, 2883–2890. doi: 10.1016/0032-3861(92)90072-5
31. [31]
  Ott, M.; Perez-Aparicio, R.; Schneider, H.; Sotta, P.; Saalwachter, K. Microscopic Study of chain deformation and orientation in uniaxially strained polymer networks: NMR results versus different network models. Macromolecules 2014, 47, 7597–7611. doi: 10.1021/ma5012655
32. [32]
  Saalwaechter, K. Proton Multiple-quantum NMR for the study of chain dynamics and structural constraints in polymeric soft materials. Progress in nuclear magnetic resonance spectroscopy 2007, 51, 1-35. doi: 10.1016/j.pnmrs.2007.01.001
33. [33]
  Saalwächte, K. Chain order and cross-link density of elastomers as investigated by proton multiple-quantum NMR. Macromolecules 2005, 38, 9650–9660. doi: 10.1021/ma051238g
34. [34]
  Pérez-Aparicio, R.; Schiewek, M.; López Valentín, J.; Schneider, H.; Long, D.; Saphiannikova, M.; Sotta, P.; Saalwächter, K.; Ott, M. Local chain deformation and overstrain in reinforced elastomers: An NMR study. Macromolecules 2013, 46, 5549–5560. doi: 10.1021/ma400921k
35. [35]
  Chasse, W.; Valentin, J.; Genesky, G.; Cohen, C.; Saalwachter, K. Precise dipolar coupling constant distribution analysis in proton multi-quantum NMR Elastomers. J. Chem. Phys. 2011, 134, 044907-044916. doi: 10.1063/1.3534856
36. [36]
  Naumovaa, A.; Tschierskeb, C; Saalwächtera, K. Orientation-dependent proton double-quantum NMR build-up function for soft materials with anisotropic mobility. Solid State Nucl. Mag. 2017, 82, 22–28. doi: 10.1016/j.ssnmr.2017.01.006
37. [37]
  Eriko Sato Matsuo, Michal Orkisz, Shao-Tang Sun, Yong Li, Toyoichi Tanaka. Origin of structural inhomogeneity in polymer gels. Macromolecules 1994, 27, 6791–6796. doi: 10.1021/ma00101a018
38. [38]
  Brostowitz, N.; Weiss, R.; Cavicchi, K. Facile fabrication of a shape memory polymer by swelling cross-linked natural rubber with stearic acid. ACS Macro Lett. 2014, 3, 374–377. doi: 10.1021/mz500131r
39. [39]
  Boue, F.; Bastide, J.; Buzier, M.; Collette, C.; Lapp, A.; Herz, J. Dynamics of permanent and temporary networks: Small angle neutron scattering measurements and related remarks on the classical models of rubber deformation. Prog. Colloid Polym. Sci. 1987, 75, 152–170.
40. [40]
  Wagner, M. H. Analysis of small-angle neutron scattering data on poly(dimethylsiloxane) network unfolding. Macromolecules 1994, 27, 5223–5226. doi: 10.1021/ma00096a056
1. [1]
  Peng Chen , Lijuan Liang , Yufei Zhu , Zhimin Xing , Zhenhua Jia , Teck-Peng Loh . Strategies for constructing seven-membered rings: Applications in natural product synthesis. Chinese Chemical Letters, 2024, 35(6): 109229-. doi: 10.1016/j.cclet.2023.109229
2. [2]
  Xiaoliu Liang , Chunliu Huang , Hui Liu , Hu Chen , Jiabao Shou , Hongwei Cheng , Gang Liu . Natural hydrogel dressings in wound care: Design, advances, and perspectives. Chinese Chemical Letters, 2024, 35(10): 109442-. doi: 10.1016/j.cclet.2023.109442
3. [3]
  Jia Chen , Yun Liu , Zerong Long , Yan Li , Hongdeng Qiu . Colorimetric detection of α-glucosidase activity using Ni-CeO₂ nanorods and its application to potential natural inhibitor screening. Chinese Chemical Letters, 2024, 35(9): 109463-. doi: 10.1016/j.cclet.2023.109463
4. [4]
  Deli Chen , Jiawen Li , Xudong Xu , Zhaocui Sun , Yun Yang , Minghui Xu , Hanqiao Liang , Junshan Yang , Hui Meng , Guoxu Ma , Jianhe Wei . Plant-microbial interactions inspired the discovery of novel sesquiterpenoid dimeric skeletons of hidden natural products from Hibiscus tiliaceus. Chinese Chemical Letters, 2024, 35(10): 109451-. doi: 10.1016/j.cclet.2023.109451
5. [5]
  Ying Gao , Rong Zhou , Qiwen Wang , Shaolong Qi , Yuanyuan Lv , Shuang Liu , Jie Shen , Guocan Yu . Natural killer cell membrane doped supramolecular nanoplatform with immuno-modulatory functions for immuno-enhanced tumor phototherapy. Chinese Chemical Letters, 2024, 35(10): 109521-. doi: 10.1016/j.cclet.2024.109521
6. [6]
  Tao Wei , Jiahao Lu , Pan Zhang , Qi Zhang , Guang Yang , Ruizhi Yang , Daifen Chen , Qian Wang , Yongfu Tang . An intermittent lithium deposition model based on bimetallic MOFs derivatives for dendrite-free lithium anode with ultrahigh areal capacity. Chinese Chemical Letters, 2024, 35(8): 109122-. doi: 10.1016/j.cclet.2023.109122
7. [7]
  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
8. [8]
  Chuan Li , Yangyang Han , Yanan Zhai , Ke Li , Xingzhong Liu , Zhuan Zhang , Cai Jia , Yongsheng Che . Phomaketals A and B, pentacyclic meroterpenoids from a eupC overexpressed mutant strain of Phoma sp.. Chinese Chemical Letters, 2024, 35(7): 109019-. doi: 10.1016/j.cclet.2023.109019
9. [9]
  Gang Lang , Jing Feng , Bo Feng , Junlan Hu , Zhiling Ran , Zhiting Zhou , Zhenju Jiang , Yunxiang He , Junling Guo . Supramolecular phenolic network-engineered C–CeO₂ nanofibers for simultaneous determination of isoniazid and hydrazine in biological fluids. Chinese Chemical Letters, 2024, 35(6): 109113-. doi: 10.1016/j.cclet.2023.109113
10. [10]
  Pingping Wang , Huixian Miao , Kechuan Sheng , Bin Wang , Fan Feng , Xuankun Cai , Wei Huang , Dayu Wu . Efficient blue-light-excitable copper(Ⅰ) coordination network phosphors for high-performance white LEDs. Chinese Chemical Letters, 2024, 35(4): 108600-. doi: 10.1016/j.cclet.2023.108600
11. [11]
  Jie XIE , Hongnan XU , Jianfeng LIAO , Ruoyu CHEN , Lin SUN , Zhong JIN . Nitrogen-doped 3D graphene-carbon nanotube network for efficient lithium storage. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1840-1849. doi: 10.11862/CJIC.20240216
12. [12]
  Wei-Yu Zhou , Zi-Han Xi , Ning-Ning Du , Li Ye , Ming-Hao Jiang , Jin-Le Hao , Bin Lin , Guo-Dong Yao , Xiao-Xiao Huang , Shao-Jiang Song . Rapid discovery of two unprecedented meroterpenoids from Daphne altaica Pall. using molecular networking integrated with MolNetEnhancer and Network Annotation Propagation. Chinese Chemical Letters, 2024, 35(8): 109030-. doi: 10.1016/j.cclet.2023.109030
13. [13]
  Tong Su , Yue Wang , Qizhen Zhu , Mengyao Xu , Ning Qiao , Bin Xu . Multiple conductive network for KTi₂(PO₄)₃ anode based on MXene as a binder for high-performance potassium storage. Chinese Chemical Letters, 2024, 35(8): 109191-. doi: 10.1016/j.cclet.2023.109191
14. [14]
  Hui Gu , Mingyue Gao , Kuan Shen , Tianli Zhang , Junhao Zhang , Xiangjun Zheng , Xingmei Guo , Yuanjun Liu , Fu Cao , Hongxing Gu , Qinghong Kong , Shenglin Xiong . F127 assisted fabrication of Ge/rGO/CNTs nanocomposites with three-dimensional network structure for efficient lithium storage. Chinese Chemical Letters, 2024, 35(9): 109273-. doi: 10.1016/j.cclet.2023.109273
15. [15]
  Yu He , Hao Jiang , Shaoxuan Yuan , Jiayi Lu , Qiang Sun . On-surface photo-induced dechlorination. Chinese Chemical Letters, 2024, 35(9): 109807-. doi: 10.1016/j.cclet.2024.109807
16. [16]
  Tian Cao , Xuyin Ding , Qiwen Peng , Min Zhang , Guoyue Shi . Intelligent laser-induced graphene sensor for multiplex probing catechol isomers. Chinese Chemical Letters, 2024, 35(7): 109238-. doi: 10.1016/j.cclet.2023.109238
17. [17]
  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
18. [18]
  Menglu Guo , Ying-Qi Song , Junfei Cheng , Guoqiang Dong , Xun Sun , Chunquan Sheng . Hydrophobic tagging-induced degradation of NAMPT in leukemia cells. Chinese Chemical Letters, 2024, 35(9): 109392-. doi: 10.1016/j.cclet.2023.109392
19. [19]
  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
20. [20]
  Ting Hu , Yuxuan Guo , Yixuan Meng , Ze Zhang , Ji Yu , Jianxin Cai , Zhenyu Yang . Uniform lithium deposition induced by copper phthalocyanine additive for durable lithium anode in lithium-sulfur batteries. Chinese Chemical Letters, 2024, 35(5): 108603-. doi: 10.1016/j.cclet.2023.108603

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(630)
HTML views(2)

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