2.6.4 Reconsideration of Hydrodynamic Volume Effect . . . . . . . 38
2.6.5 Promoter for Rubber Reinforcement by Filler . . . . . . . . . . 40
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Part II Analysis of Nanofiller Dispersion in Rubber Matrix
3 Principle and Practice of Three-Dimensional Transmission
Electron Microscopy (3D-TEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.1 Image Formation by Transmission Electron
Microscopy (TEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.2 Formation of Three-Dimensional Image by 3D-TEM . . . . . . . . . . 51
3.2.1 TEM and Tomography . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.2.2 Tomography Applied to TEM . . . . . . . . . . . . . . . . . . . . . 52
3.2.3 Notable Points on 3D-TEM Measurement . . . . . . . . . . . . . 55
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4 Nanofiller Dispersion in Rubber as Revealed by 3D-TEM . . . . . . . . 57
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.2 Particulate Silica Dispersion as Revealed by 3D-TEM . . . . . . . . . 58
4.2.1 Pretreatment of Rubber Sample Cross-Linked
by Sulfur/Accelerator System . . . . . . . . . . . . . . . . . . . . . . 58
4.2.2 3D-Imaging of Silica Dispersion and Its Analysis . . . . . . . 61
4.2.3 Visualization of Hydrophilic and Hydrophobic Silica
in Rubber Matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.3 Carbon Black Dispersion as Revealed by 3D-TEM . . . . . . . . . . . . 70
4.3.1 Importance of Carbon Black in Rubber
Reinforcement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4.3.2 3D-Imaging of Carbon Black Dispersion
and Its Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.3.3 Network Formation of Carbon Black
in Rubber Matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
4.4 Dispersion of the Other Fillers as Revealed by 3D-TEM . . . . . . . . 79
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
5 Reinforcing Mechanism of Rubber by Nanofiller . . . . . . . . . . . . . . . 83
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
5.2 Prehistory up to the Beginning of Discussions on Rubber
Reinforcement (Until the Early Second Half of the Twentieth
Century) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
5.3 Progress in the Modeling of Rubber Reinforcement
(Until the End of the Twentieth Century) . . . . . . . . . . . . . . . . . . . 86
5.4 Toward Nanofiller Networking in Rubber Matrix
(Early in the Twenty-First Century) . . . . . . . . . . . . . . . . . . . . . . . 88
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2.6.5 Promoter for Rubber Reinforcement by Filler . . . . . . . . . . 40
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Part II Analysis of Nanofiller Dispersion in Rubber Matrix
3 Principle and Practice of Three-Dimensional Transmission
Electron Microscopy (3D-TEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.1 Image Formation by Transmission Electron
Microscopy (TEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.2 Formation of Three-Dimensional Image by 3D-TEM . . . . . . . . . . 51
3.2.1 TEM and Tomography . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.2.2 Tomography Applied to TEM . . . . . . . . . . . . . . . . . . . . . 52
3.2.3 Notable Points on 3D-TEM Measurement . . . . . . . . . . . . . 55
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4 Nanofiller Dispersion in Rubber as Revealed by 3D-TEM . . . . . . . . 57
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.2 Particulate Silica Dispersion as Revealed by 3D-TEM . . . . . . . . . 58
4.2.1 Pretreatment of Rubber Sample Cross-Linked
by Sulfur/Accelerator System . . . . . . . . . . . . . . . . . . . . . . 58
4.2.2 3D-Imaging of Silica Dispersion and Its Analysis . . . . . . . 61
4.2.3 Visualization of Hydrophilic and Hydrophobic Silica
in Rubber Matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.3 Carbon Black Dispersion as Revealed by 3D-TEM . . . . . . . . . . . . 70
4.3.1 Importance of Carbon Black in Rubber
Reinforcement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4.3.2 3D-Imaging of Carbon Black Dispersion
and Its Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.3.3 Network Formation of Carbon Black
in Rubber Matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
4.4 Dispersion of the Other Fillers as Revealed by 3D-TEM . . . . . . . . 79
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
5 Reinforcing Mechanism of Rubber by Nanofiller . . . . . . . . . . . . . . . 83
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
5.2 Prehistory up to the Beginning of Discussions on Rubber
Reinforcement (Until the Early Second Half of the Twentieth
Century) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
5.3 Progress in the Modeling of Rubber Reinforcement
(Until the End of the Twentieth Century) . . . . . . . . . . . . . . . . . . . 86
5.4 Toward Nanofiller Networking in Rubber Matrix
(Early in the Twenty-First Century) . . . . . . . . . . . . . . . . . . . . . . . 88
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