Unswollen layer of cross-linked polyisoprene at the solid interface

Shimomura, Shinichiro; Inutsuka, Manabu; Yamada, Norifumi L.; Tanaka, Keiji

doi:10.1016/j.polymer.2016.07.047

Cited by 21 publications

(33 citation statements)

References 63 publications

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“…Similar observations have been found in other work using neutron scattering and echo techniques. Shimomura et al 43 have identified that a tightly bound layer (about 5 nm) found in cross-linked polyisoprene on silica showed little or no penetration of deuterated n-hexane, a good solvent for polyisoprene. In the case of polybutadiene on carbon black, Jiang et al 42 found that a 0.5 nm layer of "inner" polymer was found to be near the particle surface and unswollen with deuterated toluene.…”

Section: ■ Discussionmentioning

confidence: 99%

Does Plasticizer Penetrate Tightly Bound Polymer in Adsorbed Poly(vinyl acetate) on Silica?

Hetayothin

Cabaniss²,

Blum

2017

Macromolecules

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When only tightly bound poly(vinyl acetate) (PVAc) was adsorbed on silica, the plasticizer, di(propylene glycol) dibenzoate (DPGDB), was not effective in lowering its glass transition. To determine why the plasticizer was not effective, we probed the behavior of the deuterated plasticizer di(propylene glycol) dibenzoate (DPGDB-d 10)/PVAc/silica system using deuterium (2H) solid state NMR and temperature-modulated differential scanning calorimetry (TMDSC). PVAc with 37% (w/w) of plasticizer/polymer was adsorbed on silica in adsorbed amounts of 2.60 and 0.76 mg PVAc/m2 silica. The dynamics of the plasticizer in the adsorbed PVAc was found to be more motionally heterogeneous than that observed in bulk samples. The NMR results provided firm evidence that when there is only a small amount of adsorbed polymer (e.g., only tightly bound polymer at less than 0.8 mg/m2), the plasticizer was effectively excluded from the polymer chains at the silica–polymer–air interface. When excluded from the tightly bound polymer, the plasticizer existed in an environment that was similar to that of pure plasticizer. At larger adsorbed amounts, the plasticizer was effective at lowering the T g of the adsorbed polymer.

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Section: ■ Discussionmentioning

confidence: 99%

Does Plasticizer Penetrate Tightly Bound Polymer in Adsorbed Poly(vinyl acetate) on Silica?

Hetayothin

Cabaniss²,

Blum

2017

Macromolecules

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“…By dispersing a small amount of fillers, such as carbon black and fibers, glass fibers, silica nanoparticles, talc, and so on, into a polymer matrix, multiple macroscopic properties of the polymer can be substantially improved. − Polymer chains adsorbed onto the filler, which generally exhibit different aggregation states and relaxation dynamics from those in the bulk, are believed to play crucial roles in the improvement of mechanical properties of polymer nanocomposites. − Such can be seen in the bulk glass transition temperature ( T g b ), elastic modulus, and rheological responses for polymer nanocomposites with respect to the bulk properties. − Over the past few decades, many efforts have been devoted to gaining a better understanding of the structural and dynamic properties of adsorbed polymer chains within the interfacial layer. ,,,− …”

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confidence: 99%

“…Meanwhile, many studies have suggested that the adsorption and relaxation processes of chains at the solid interface are much more complicated than previously thought. ,,− The relaxation dynamics can be faster for weakly, or loosely, adsorbed chains than for ones in direct contact with the solid surface. ,, This means that different techniques with various depths and time scale resolutions might detect the relaxation dynamics of different portions of adsorbed chains, revealing dynamic behaviors of adsorbed chains in more detail. Such techniques will lead to a better understanding of polymer behavior at interfaces.…”

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confidence: 99%

Dynamics Gradient of Polymer Chains near a Solid Interface

et al. 2019

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The relaxation dynamics of polyisoprene (PI) and nitrile butadiene rubber (NBR) chains at the SiO2 interface were directly probed as a function of distance from the SiO2 surface using time-resolved evanescent wave-induced fluorescence anisotropy, dielectric relaxation spectroscopy, and sum-frequency generation spectroscopy. We found the presence of the dynamics gradient of chains in the interfacial region with the SiO2 surface and tried to assign it to the two kinds of adsorbed chains, namely, loosely and strongly adsorbed, at the interface. The segmental relaxation of chains in the strongly adsorbed layer at the interface could be slower than that of bulk chains by more than 10 orders.

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“…In the field of composite materials composed of rubber polymers, the “bound rubber” concept, where an immobilized and insoluble polymer layer exists at the surface of inorganic fillers and plays an important role in the mechanical properties, has been widely accepted. , The interfacial layer is believed to consist of two types of chains with different conformations: “tightly” and “loosely” adsorbed chains. − ,− Tightly adsorbed chains are in direct contact with the solid surface and possess many adsorption points. In addition, there are chains that are partially adsorbed on the solid surface and connected to chains in the bulk phase.…”

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confidence: 99%

Adhesion Control of Elastomer Sheet on the Basis of Interfacial Segregation of Hyperbranched Polymer

et al. 2019

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Adhesion of a model rubbery material, crosslinked poly(dimethylsiloxane) (PDMS), onto a solid surface was studied by sum-frequency generation spectroscopy and X-ray photoelectron spectroscopy. To do so, here, we have focused on the adhesive deposit and insoluble layer. The former and latter were defined as the residual amount on the substrate after the peeling and residual layer after washing with a good solvent, respectively. The peel strength of a PDMS sheet adhered onto a glass plate increased with the contact time. Both adhesive deposit and insoluble layer also exhibited comparable contact time dependence. Once a hyperbranched polymer (HBP), which was segregated to the adhesive interface, was incorporated into PDMS, the peel strength and adhesive deposit decreased, although the thickness of the insoluble layer remained almost unchanged. These results suggest that the formation of loosely adsorbed chains on the solid surface, which possess not only trains but also many loop portions and tail parts, plays an important role in the macroscopic adhesion behavior of the PDMS sheet and the interfacial segregation of HBP can prevent it.

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Unswollen layer of cross-linked polyisoprene at the solid interface

Cited by 21 publications

References 63 publications

Does Plasticizer Penetrate Tightly Bound Polymer in Adsorbed Poly(vinyl acetate) on Silica?

Does Plasticizer Penetrate Tightly Bound Polymer in Adsorbed Poly(vinyl acetate) on Silica?

Dynamics Gradient of Polymer Chains near a Solid Interface

Adhesion Control of Elastomer Sheet on the Basis of Interfacial Segregation of Hyperbranched Polymer

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