Three-Dimensional Structure of a Nanocomposite Material Consisting of Two Kinds of Nanofillers and Rubbery Matrix Studied by Transmission Electron Microtomography

Jinnai, Hiroshi; Shinbori, Yuki; Kitaoka, Tatsuro; Akutagawa, Keizo; Mashita, Naruhiko; Nishi, Toshio

doi:10.1021/ma071102d

Cited by 76 publications

(43 citation statements)

References 42 publications

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“…TEMT has been proved to be useful for investigating 3D nanostructures in polymeric systems. [30][31][32] It was observed that 1D NWs of CN-TFMBE, which were grown at different depths within the polymer matrix, formed 1D NWs of different diameters. Thin wires (A in Fig.…”

Section: Resultsmentioning

confidence: 99%

Selected-area in situ generation of highly fluorescent organic nanowires embedded in a polymer film: the solvent-vapor-induced self-assembly process

Chung

Hirato

et al. 2010

J. Mater. Chem.

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The preparation of highly fluorescent one-dimensional (1D) nanostructures within a selected area of a solid substrate is a challenging requirement for the realization of optoelectronic nanodevices. We present a novel method for fabricating highly fluorescent organic nanowires (NWs) embedded in a variety of polymer films through the combined processes of photochemical lithography and solventvapor annealing (SVA). To achieve this, we designed and synthesized an acid-responsive organic fluorophore bearing a self-assembly moiety. The in situ self-assembly of this fluorophore into ultralong nanowires proceeds selectively in designated regions of the polymer matrix via a simple selected-area SVA process. The I-V electrical characteristics of 2-(3 0 ,5 0 -bis(trifluoromethyl)biphenyl-4-yl)-3-(6-3,5-bis(trifluoromethyl)phenyl)pyridine-3-yl)acrylonitrile (Py-CN-TFMBE) structures, selfassembled using the SVA method, were measured on a two-terminal electrode device. This unique fabrication approach, which combines photochemical lithography and SVA, eliminates the difficulties of transferring preformed 1D organic nanostructures to fixed locations on a substrate, thereby establishing a new method for the fabrication control of optoelectronic nanodevices.

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Section: Resultsmentioning

confidence: 99%

Selected-area in situ generation of highly fluorescent organic nanowires embedded in a polymer film: the solvent-vapor-induced self-assembly process

Chung

Hirato

et al. 2010

J. Mater. Chem.

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“…[48][49][50][56][57][58][59][60] When the particles are electrically conductive (e.g., carbon black), electrical resistance testing is another useful method to study the structure of the percolated filler network. [61][62][63][64] With the exception of transmission electron microtomography, 65,66 it is difficult to observe differences in the three-dimensional nature of jammed particle networks using microscopy. For example, the unmodified silica-filled SBR and the compound with 3.6 phr MPTMS added have very different extents of filler networking based on G versus strain amplitude data (Figure 4), yet TEM images of these two distinct compounds are quite similar as demonstrated in Figure 6.…”

Section: Flocculation Reinforcement and Glass Transition Effects 511mentioning

confidence: 99%

Flocculation, Reinforcement, and Glass Transition Effects in Silica-Filled Styrene-Butadiene Rubber

Robertson

Lin

Bogoslovov

et al. 2011

Rubber Chemistry and Technology

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The introduction of silanes to improve processability and properties of silica-reinforced rubber compounds is critical to the successful commercial use of silica as a filler in tires and other applications. The use of silanes to promote polymer-filler interactions is expected to limit the development of a percolated filler network and may also affect the mobility of polymer chains near the particles. Styrene-butadiene rubber (SBR) was reinforced with silica particles at a filler volume fraction of 0.19, and various levels of filler-filler shielding agent (n-octyltriethoxysilane) and polymerfiller coupling agent (3-mercaptopropyltrimethoxysilane) were incorporated. Both types of silane inhibited the filler flocculation process during annealing the uncured rubber materials, thus reducing the magnitude of the Payne effect. In contrast to the significant reinforcement effects noted in the strain-dependent shear modulus, the bulk modulus from hydrostatic compression was largely unaltered by the silanes. Addition of polymer-filler linkages using the coupling agent yielded bound rubber values up to 71%; however, this bound rubber exhibited glass transition behavior which was similar to the bulk SBR response, as determined by calorimetry and viscoelastic testing. Modifying the polymer-filler interface had a strong effect on the nature of the filler network, but it had very little influence on the segmental dynamics of polymer chains proximate to filler particles.

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“…The TEMT image contains richer structural information than the 2D TEM image. Using a Monte-Carlo simulation, spatial position of each silica particle was resolved 63,64 and displayed in Figure 3(c). Note that this protocol is necessary to evaluate 3D spatial distribution, e.g., the spatial correlation function of fillers, especially when individual fillers are too small to be clearly visualized but only regions of the fillers are obtained.…”

Section: D Morphological Studies Of Block Copolymersmentioning

confidence: 99%

Three-Dimensional Imaging in Polymer Science: Its Application to Block Copolymer Morphologies and Rubber Composites

Dohi¹,

Kimura²,

Kotani³

et al. 2007

Polym J

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ABSTRACT:New methods to visualize polymer morphologies in three-dimension (3D) in polymer science are reviewed. Here we concentrate on one of such 3D imaging technique, transmission electron microtomography (TEMT), and introduce some experimental studies using this novel technique. They are block copolymer morphologies during order-order transition between the two different morphologies and block copolymer thin film morphology also during morphological change due to confinement. Direct visualization of 3D structure of silica particle/rubber composite and related morphological analyses are shown. Subsequently, as a very hot topic of the 3D imaging, we show for the first time to characterize the morphological change in a silica particle/rubber composite upon stretching. It was found that the aggregates of silica particles were broken down upon stretching and many voids were generated near and between the silica particles. Local stress upon stretching inside the composite was inferred from the image intensity of the 3D reconstructed image. The local stress was found not only near the silica particles but also near the top of the voids. The observations indicated that the local stress increases the modulus, causing voids to form along the stretching direction. The thickness of the specimen after the stretching was also estimated from the 3D volume data, which turned out to be non-uniform and thinner than what is expected from the affine deformation. These experimental findings indicate that the rubber composite does not obey the assumption of the affine deformation at the nano-scale. Polymer materials are ubiquitous in our daily life. Such materials often consist of more than one species of polymers and thus become multi-component systems, such as in polymer blends, 1,2 block copolymers, 3 and fillers/polymer composites. 4 The multi-component systems often show phase-separated structures due to immiscibility of constituents. Studies to characterize such morphologies inside the materials have been growing intensively over the past few decades. Academic interest in complex fluids (to which polymeric systems belong) as well as the ceaseless industrial need for developing new materials motivates such studies.In academia, pattern formation and self-assembling processes of multi-component polymer systems are one of the most fascinating research themes in nonlinear, non-equilibrium phenomena.1 Likewise, nanometer-scale periodic structures formed in block copolymers in their equilibrium state are interesting because their self-assembly is driven by the subtle balance between the entropic block chain conformation and enthalpic interaction between the constituents. 3In industry, phase-separated polymer systems provide an important route to achieve superior physical properties. Hence, the structure-property relationship in multi-component polymeric materials is of significant importance, basic studies on which eventually render new designs of polymer materials satisfying the diverse requirements of industry.Filler/polymer comp...

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Three-Dimensional Structure of a Nanocomposite Material Consisting of Two Kinds of Nanofillers and Rubbery Matrix Studied by Transmission Electron Microtomography

Cited by 76 publications

References 42 publications

Selected-area in situ generation of highly fluorescent organic nanowires embedded in a polymer film: the solvent-vapor-induced self-assembly process

Selected-area in situ generation of highly fluorescent organic nanowires embedded in a polymer film: the solvent-vapor-induced self-assembly process

Flocculation, Reinforcement, and Glass Transition Effects in Silica-Filled Styrene-Butadiene Rubber

Three-Dimensional Imaging in Polymer Science: Its Application to Block Copolymer Morphologies and Rubber Composites

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