Stepwise strain-induced crystallization of soft composites prepared from natural rubber latex and silica generated in situ

Novel biphasic structured in situ silica filled natural rubber composites were focused on their strain-induced crystallization (SIC) behavior from the viewpoint of morphology. The composites were prepared by in situ silica filling in natural rubber (NR) latex using a sol–gel reaction of tetraethoxysilane. Simultaneous time-resolved wide-angle X-ray diffraction and tensile measurements revealed a relationship between the characteristic morphology and tensile stress–strain properties of the composites associating with the SIC. Results showed stepwise SIC behaviors of NR-based composites for the first time. Pure rubber phases in the biphasic structure were found to afford highly oriented amorphous segments and oriented crystallites. The generated crystallites worked as reinforcing fillers together with the in situ silica to result in high tensile stresses of the composites. The observed characteristics are useful for understanding a role of filler network in the reinforcement of rubber.

[1]  "Green" Nano-Composites Prepared from Natural Rubber and In Situ Silica , 2005 .

[2]  D. Long,et al.  Local Deformation in Carbon Black-Filled Polyisoprene Rubbers Studied by NMR and X-ray Diffraction , 2009 .

[3]  Frederick R. Eirich,et al.  Science and Technology of Rubber , 2012 .

[4]  T. Hahn International tables for crystallography , 2002 .

[5]  C. Gauthier,et al.  Parameters governing strain induced crystallization in filled natural rubber , 2007 .

[6]  K. P. Jones,et al.  Historical Development of the World Rubber Industry , 1992 .

[7]  G. Mitchell A wide-angle X-ray study of the development of molecular orientation in crosslinked natural rubber , 1984 .

[8]  Y. Ikeda,et al.  Reinforcement of General-Purpose Grade Rubbers by Silica Generated In Situ , 2000 .

[9]  Shinzo Kohjiya,et al.  Strain-induced crystallization of peroxide-crosslinked natural rubber , 2007 .

[10]  J. R. Katz Röntgenspektrographische Untersuchungen am gedehnten Kautschuk und ihre mögliche Bedeutung für das Problem der Dehnungseigenschaften dieser Substanz , 1925, Naturwissenschaften.

[11]  Y. Ikeda,et al.  Vulcanization: New Focus on a Traditional Technology by Small-Angle Neutron Scattering , 2009 .

[12]  W. Waddell,et al.  9 – The Science of Rubber Compounding , 2005 .

[13]  Shinzo Kohjiya,et al.  Comparative Study on Strain-Induced Crystallization Behavior of Peroxide Cross-Linked and Sulfur Cross-Linked Natural Rubber , 2008 .

[14]  B. Hsiao,et al.  Chain Dynamics and Strain-Induced Crystallization of Pre- and Postvulcanized Natural Rubber Latex Using Proton Multiple Quantum NMR and Uniaxial Deformation by in Situ Synchrotron X-ray Diffraction , 2012 .

[15]  M. R. Sethuraj,et al.  Natural rubber: biology, cultivation and technology. , 1992 .

[16]  C. Brinker,et al.  Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing , 1990 .

[17]  L. Bokobza Reinforcement of elastomeric networks by fillers , 2001 .

[18]  L. Alexander,et al.  X-Ray diffraction procedures for polycrystalline and amorphous materials , 1974 .

[19]  E. Giannelis,et al.  Effect of nanoclay on natural rubber microstructure , 2008 .

[20]  S. Kohjiya,et al.  Structural development of natural rubber during uniaxial stretching by in situ wide angle X-ray diffraction using a synchrotron radiation , 2002 .

[21]  Shinzo Kohjiya,et al.  Orientation and Crystallization of Natural Rubber Network As Revealed by WAXD Using Synchrotron Radiation , 2004 .

[22]  L. Bateman Polymers. (Book Reviews: The Chemistry and Physics of Rubber-Like Substances) , 1964 .

[23]  Shinzo Kohjiya,et al.  Effect of Network-Chain Length on Strain-Induced Crystallization of NR and IR Vulcanizates , 2004 .

[24]  P. Flory Principles of polymer chemistry , 1953 .

[25]  Shinzo Kohjiya,et al.  Nano‐Structural Observation of in situ Silica in Natural Rubber Matrix by Three Dimensional Transmission Electron Microscopy , 2004 .

[26]  Y. Ikeda,et al.  Nonuniformity in natural rubber as revealed by small-angle neutron scattering, small-angle X-ray scattering, and atomic force microscopy. , 2007, Biomacromolecules.

[27]  D. J. Montgomery,et al.  The physics of rubber elasticity , 1949 .

[28]  T. Hasegawa,et al.  Three-dimensional nano-structure of in situ silica in natural rubber as revealed by 3D-TEM/electron tomography , 2005 .

[29]  S. Kohjiya,et al.  Structural studies on crystalline polymer solids by high-resolution electron microscopy , 1995 .

[30]  Hanako Asai,et al.  Nonuniformity in Cross-Linked Natural Rubber as Revealed by Contrast-Variation Small-Angle Neutron Scattering , 2010 .

[31]  Christian Burger,et al.  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 , 2013 .

[32]  E. H. Andrews,et al.  Spherulite morphology in thin films of natural rubber , 1962, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[33]  S. C. Nyburg A statistical structure for crystalline rubber , 1954 .

[34]  J. E. Mark,et al.  Reinforcement of polydimethylsiloxane networks by in‐situ precipitation of silica: A new method for preparation of filled elastomers , 1982 .

[35]  Y. Ikeda,et al.  Novel biphasic structured composite prepared by in situ silica filling in natural rubber latex , 2012 .

[36]  B. Hsiao,et al.  Nano-Structural Elucidation in Carbon Black Loaded NR Vulcanizate by 3D-TEM and In Situ WAXD Measurements , 2007 .

[37]  C. Bawn,et al.  The chemistry and physics of rubber-like substances: Edited by L. Bateman MacLaren: London; Wiley: New York, 1963. xiv+784 pp. 168s , 1964 .

[38]  Shinzo Kohjiya,et al.  Visualization of nanostructure of soft matter by 3D-TEM : Nanoparticles in a natural rubber matrix , 2008 .

[39]  L. Mandelkern Crystallization of Polymers: Oriented crystallization and contractility , 2002 .

[40]  Shinzo Kohjiya,et al.  New Insights into Structural Development in Natural Rubber during Uniaxial Deformation by In Situ Synchrotron X-ray Diffraction , 2002 .

[41]  Harold P. Klug,et al.  X-Ray Diffraction Procedures: For Polycrystalline and Amorphous Materials, 2nd Edition , 1974 .

[42]  I. Šics,et al.  Mechanism of strain-induced crystallization in filled and unfilled natural rubber vulcanizates , 2005 .

[43]  Y. Nie,et al.  Large-scale orientation in a vulcanized stretched natural rubber network: proved by in situ synchrotron X-ray diffraction characterization. , 2010, The journal of physical chemistry. B.

[44]  A. Roberts,et al.  Natural rubber science and technology , 1988 .

[45]  B. Huneau STRAIN-INDUCED CRYSTALLIZATION OF NATURAL RUBBER: A REVIEW OF X-RAY DIFFRACTION INVESTIGATIONS , 2011 .

[46]  R. Ruoff,et al.  Processing–Morphology–Property Relationships and Composite Theory Analysis of Reduced Graphene Oxide/Natural Rubber Nanocomposites , 2012 .

[47]  P. Albouy,et al.  Effective Local Deformation in Stretched Filled Rubber , 2003 .