4.5 Article

Role of aerosil dispersion on the activated kinetics of the LC1-xSilx system

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JOURNAL OF PHYSICAL CHEMISTRY B
卷 110, 期 51, 页码 26160-26169

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AMER CHEMICAL SOC
DOI: 10.1021/jp065209z

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This study explores the role of aerosil dispersion on activated phase transitions of bulk octylcyanobiphenyl (8CB) liquid crystals by performing heating rate-dependent experiments. Differential scanning calorimetry (DSC) was used at various heating ramp rates in order to probe the activated phase dynamics of the system. The system, LC(1-x)Sil(x), was prepared by mixing aerosil nanoparticles (7 nm in diameter) in the bulk 8CB by the solvent dispersion method (SDM). LC represents bulk 8CB, and Sil represents aerosil nanoparticles with concentration x in percent. The concentration of the aerosil nanoparticles (x) varied from 0 to 0.2 g/cm(3) in the bulk 8CB. Well-defined, endothermic peaks were found on a heating scan at melting and at the smectic-A to nematic (SmA-N) and nematic to isotropic (N-I) transitions. These peaks show a temperature shift and a change in their shapes and sizes in the presence of aerosil nanoparticles. In addition, an exothermic peak also appeared before the melting peak during the heating scan in the presence of aerosil nanoparticles. All transitions shifted significantly with different heating ramp rates, following an Arrhenius behavior, showing activated kinetics. The presence of aerosil nanoparticles caused a significant increase in the enthalpy and a decrease in the activation energy compared to the results found in bulk 8CB. This behavior can be explained by aerosil dispersion in the LC(1-x)Sil(x), inducing a disorder in the bulk 8CB. Infrared (IR) spectroscopy shows a shift to higher frequency for the broad peak at 1082 cm(-1), corresponding to an Si-O bond as the density of the aerosil increases, and can be explained in terms of surface and molecular interactions between aerosil nanoparticles and 8CB liquid crystal molecules.

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