/pdf/the-surface-chemistry-of-amorphous-silica-zhuravlev-model-4kfs2lx66q.pdf

The surface chemistry of amorphous silica. Zhuravlev model

The incorporation of silica nanoparticles into polyethylene increased the breakdown strength and voltage endurance significantly compared to the incorporation of micron scale fillers. In addition, dielectric spectroscopy showed a decrease in dielectric permittivity for the nanocomposite over the base polymer, and changes in the space charge distribution and dynamics have been documented. The most significant difference between micron scale and nanoscale fillers is the tremendous increase in interfacial area in nanocomposites. Because the interfacial region (interaction zone) is likely to be pivotal in controlling properties, the bonding between the silica and polyethylene was characterized using Fourier transformed infrared (FTTR) spectroscopy, electron paramagnetic resonance (EPR), and x-ray photoelectron spectroscopy (XPS). The picture which is emerging suggests that the enhanced interfacial zone, in addition to particle-polymer bonding, plays a very important role in determining the dielectric behavior of nanocomposites.

/pdf/polymer-nanocomposite-dielectrics-the-role-of-the-interface-3aw0skty7t.pdf

Polymer nanocomposite dielectrics-the role of the interface

High-resolution solid-state NMR techniques were used to investigate the surface structure of Cab-O-Sil fumed silica. 1H NMR results obtained from CRAMPS, MAS-only and relaxation studies reveal the existence of both hydrogen-bonded silanols and isolated silanols on the Cab-O-Sil surface. A systematic dehydration study of fumed silica was carried out, with results on the quantity of each type of silanol on the surface at various dehydration stages. 29Si CP-MAS experiments, including CP spin dynamics studies and various other relaxation studies, were employed to probe hydrogen bonding and the local structural environments of various hydroxyl groups of silica surfaces. 29Si CP-MAS experiments on water-treated and deuterium-exchanged Cab-O-Sil indicate the existence of interparticle silanols and internal silanols in fumed silica. 1H and 29Si NMR show that for fumed silica both isolated and hydrogen-bonded silanols are present on the surface of an untreated sample, in contrast to the case of silica gel, where a...

The Fumed Silica Surface: A Study by NMR

The catalytic conversion of m-cresol in the presence of H2 has been investigated on SiO2-supported Ni, Fe, and bimetallic Ni–Fe catalysts at 300 °C and atmospheric pressure. Over the monometallic Ni catalyst, the dominant product is 3-methylcyclohexanone while 3-methylcyclohexanol and toluene appear in smaller amounts, even at high conversions. By contrast, on Fe and Ni–Fe bimetallic catalysts, the dominant product is toluene while the hydrogenation products (3-methylcyclohexanone and 3-methylcyclohexanol) are practically negligible in the entire range of conversions. To explain these differences, we have proposed a deoxygenation path that starts with the tautomerization of m-cresol to an unstable ketone intermediate (3-methyl-3,5-cyclohexadienone). The fate of this intermediate is determined by the ability of the catalyst to either hydrogenate the carbonyl group or the ring. The former would mostly occur on Fe and Ni–Fe catalysts that contain an oxophilic metal (Fe), while the latter would occur on Ni, which has a higher affinity for the aromatic ring. Hydrogenation of the carbonyl group produces a very reactive unsaturated alcohol (3-methyl-3,5-cyclohexadienol), which can be easily dehydrated to toluene. This would explain the high selectivity of Fe and Ni–Fe to toluene. By contrast, hydrogenation of the ring would result in 3-methylcyclohexanone, which can be further hydrogenated to 3-methylcyclohexanol. On supports that contain acid sites, which are active for dehydration, the formation of toluene would occur via dehydration of the alcohol and subsequent dehydrogenation. On the catalysts investigated in this work, dehydration of the corresponding alcohol does not occur, so the only path to toluene is via hydrogenation of the carbonyl of the unstable ketone intermediate. In addition, to the products mentioned above, xylenol is also observed in significant yields, which indicate that transalkylation of m-cresol is another reaction path occurring on these catalysts.

Selective conversion of m-cresol to toluene over bimetallic Ni–Fe catalysts

A refined and generalized version of a previously suggested model of the silica surface, in which geminal silanols are situated on surface segments similar to (100)-type faces of the β-cristobalite structure and single silanols are situated on surface segments similar to corresponding (111)-type faces, is supported by extensive spectroscopic data In this model single silanols on the same (111)-type surface segment cannot form hydrogen bonds with each other Whether or not adjacent geminal silanols on the same (100)-type surface segment can form hydrogen bonds with each other depends on the relative orientation of their hydroxyl groups When two surface segments of either (100)- or (111)-type intersect convexly, hydroxyl groups cannot participate in hydrogen bonding across the intersection; but when two surface segments intersect concavely, those silanols situated at the intersection can form hydrogen bonds with their counterparts across the intersection All the hydrogen-bonding silanols in this generali

A Detailed Model of Local Structure and Silanol Hydrogen Bonding of Silica Gel Surfaces

Hydroxyls of silica powders

Proton spin–spin relaxation time measurements have been performed at 300 and 400 MHz on bound rubber-filler mixes resulting from the solvent extraction of silica-filled and silicafilled-modified polybutadiene, on the one hand, and of carbon black-filled and carbon blackfilled-modified styrene butadiene rubber, on the other hand. Two relaxation times are observed for all samples. They are ascribed to the occurrence of tightly and loosely bound rubber components, respectively. The effect of the grafting modification of the fillers on the formation of bound rubber and its two components is discussed. © 1992 John Wiley & Sons, Inc.

A. P. Legrand

Papers

Hydroxyls of silica powders

Application of NMR spectroscopy to the characterization of elastomer/filler interactions

Hydroxylation of Amorphous Fumed Silicas Demonstrated by IGC, Solid‐State NMR and IR Spectroscopies