Influence of the vulcanization system on the dynamics and structure of natural rubber: Comparative study by means of broadband dielectric spectroscopy and solid-state NMR spectroscopy

被引:50
作者
Hernandez, Marianella [1 ,2 ]
Valentin, Juan L. [2 ]
Lopez-Manchado, Miguel A. [2 ]
Ezquerra, Tiberio A. [3 ]
机构
[1] Delft Univ Technol, Fac Aerosp Engn, Novel Aerosp Mat Grp, NL-2629 HS Delft, Netherlands
[2] CSIC, Inst Ciencia & Tecnol Polimeros, E-28006 Madrid, Spain
[3] CSIC, Inst Estruct Mat, E-28006 Madrid, Spain
关键词
Natural rubber; Vulcanization; Broadband dielectric spectroscopy; Proton multiple-quantum NMR; Segmental dynamics; Structure; STRAIN-INDUCED CRYSTALLIZATION; MULTIPLE-QUANTUM NMR; CROSS-LINK DENSITY; SEGMENTAL DYNAMICS; MOLECULAR-DYNAMICS; NETWORK STRUCTURE; CHAIN DYNAMICS; SILICATE NANOCOMPOSITES; PEROXIDE VULCANIZATION; TEMPERATURE-DEPENDENCE;
D O I
10.1016/j.eurpolymj.2015.04.021
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
A study on the effects of the curing systems on the dynamics and network structure of Natural rubber (NR) is performed by using broadband dielectric spectroscopy (BDS) and proton multiple-quantum NMR Sulfur-cured systems present a regtricted segmental dynamics, whereas peroxide-cured systems have the fastest dynamics. Network structure also affects the segmental dynamics of NR. Peroxide-cured networks seem to have more heterogeneous spatial distribution of cross-links, while sulfur-cured networks have inhomogeneities at larger length scales associated to ZnO particles. These structural dissimilarities possibly explain the segmental dynamics behavior and fragility strength of NR. This investigation shows that BDS and NMR are complementary approaches for studying the dynamics and structure of NR. The correspondence between both techniques confirms that the segmental dynamics of vulcanized NR is not solely affected by the number of crosslinks, but also by their spatial distribution and nature of these junctions, e.g. C-C or sulfidic bridges with different lengths. (C) 2015 Elsevier Ltd. All rights reserved.
引用
收藏
页码:90 / 103
页数:14
相关论文
共 55 条
  • [1] Double quantum NMR applied to polymer networks with low concentration of pendant chains
    Acosta, Rodolfo H.
    Vega, Daniel A.
    Villar, Marcelo A.
    Monti, Gustavo A.
    Valles, Enrique M.
    [J]. MACROMOLECULES, 2006, 39 (14) : 4788 - 4792
  • [2] Transiently Trapped Entanglements in Model Polymer Networks
    Acosta, Rodolfo H.
    Monti, Gustavo A.
    Villar, Marcelo A.
    Valles, Enrique M.
    Vega, Daniel A.
    [J]. MACROMOLECULES, 2009, 42 (13) : 4674 - 4680
  • [3] Alliger G., 1964, VULCANIZATION ELASTO
  • [4] Viscoelastic behavior of poly(methyl methacrylate) networks with different cross-linking degrees
    Alves, NM
    Ribelles, JLG
    Gómez-Tejedor, JA
    Mano, JF
    [J]. MACROMOLECULES, 2004, 37 (10) : 3735 - 3744
  • [5] Thermoplastic elastomers based on ionomeric polyblends of zinc salts of maleated polypropylene and maleated EPDM rubber
    Antony, P
    Bandyopadhyay, S
    De, SK
    [J]. POLYMER ENGINEERING AND SCIENCE, 1999, 39 (05) : 963 - 974
  • [6] MOLECULAR-DYNAMICS IN BULK CIS-POLYISOPRENE AS STUDIED BY DIELECTRIC-SPECTROSCOPY
    BOESE, D
    KREMER, F
    [J]. MACROMOLECULES, 1990, 23 (03) : 829 - 835
  • [7] NONEXPONENTIAL RELAXATIONS IN STRONG AND FRAGILE GLASS FORMERS
    BOHMER, R
    NGAI, KL
    ANGELL, CA
    PLAZEK, DJ
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1993, 99 (05) : 4201 - 4209
  • [8] Brydson J.A., 1988, RUBBERY MAT THEIR CO, P469
  • [9] Molecular ordering and the direct measurement of weak proton-proton dipolar interactions in a rubber network
    Callaghan, PT
    Samulski, ET
    [J]. MACROMOLECULES, 1997, 30 (01) : 113 - 122
  • [10] Molecular dynamics of natural rubber as revealed by dielectric spectroscopy: The role of natural cross-linking
    Carretero-Gonzalez, Javier
    Ezquerra, Tiberio A.
    Amnuaypornsri, Sureerut
    Toki, Shigeyuki
    Verdejo, Raquel
    Sanz, Alejandro
    Sakdapipanich, Jitladda
    Hsiao, Benjamin S.
    Lopez-Manchado, Miguel A.
    [J]. SOFT MATTER, 2010, 6 (15) : 3636 - 3642