RESUMO
The noise power spectrum of the thermally activated motion of an AFM cantilever has been analyzed with respect to viscoelastic and hydrodynamic coupling between the cantilever and a substrate surface. Spheres with radii between 5 and 25 microm were glued to the cantilever to provide a well-defined geometry. The cantilever is modeled as a harmonic resonator with a frequency-dependent complex drag coefficient xi(omega). The variation of the drag coefficient xi(omega) with the tip-sample distance, D, and the sphere radius, R, can be expressed as a function of the single dimensionless parameter D/ R. However, this scaling breaks down close to the surface. There are two sources of a frequency dependence of xi(omega), which are viscoelastic memory and hydrodynamics. Viscoelastic relaxation is observed when the surface is covered with a soft polymer layer. In the absence of such a soft layer one still finds a frequency dependence of xi(omega) which is caused by hydrodynamics. At large substrate-cantilever distances, the drag coefficient increases with frequency because of inertial effects. At small distances, on the other hand, the drag coefficient decreases with increasing frequency, which is explained by the reflection of shear waves from the substrate surface. In liquids, inertial effects can be important when performing dynamic AFM experiments.
RESUMO
Phase diagrams of unpolymerized and UV-polymerized 2-ethyl hexyl acrylate (EHA) mixtures with the liquid crystal E7 are established using optical microscopy and differential scanning calorimetry. Both diagrams show upper critical solution temperature behavior. From 50 to 90 wt % liquid crystal (LC), the (I+I) phase located between the (N+I) and (I) phases was clearly shown. The nematic phase inside the droplets exhibits a twisted radial structure indicating that homeotropic anchoring occurs at the polymer interface. The experimental phase diagrams were successfully analyzed using a model based on the Flory-Huggins theory of isotropic mixing supplemented with the Maier-Saupe theory of nematic order. The LC solubility limit in the polymer matrix and the fractional amount of LC contained in the droplets were deduced from the calorimetric measurements. For the specific composition EHA/E7 (50:50), the scattering and morphological properties of the films were studied as a function of time elapsed after UV exposure. Drastic changes in the size, shape, spatial distribution, and number density of nematic droplets were observed and analyzed in terms of coalescence/diffusion phenomena.
RESUMO
The phase behavior of blends of polymers and smectic-A liquid crystals (LCs) is investigated using Flory-Huggins and Maier-Saupe-McMillan theories. Various examples are considered to depict the effects of the architecture and the size of the polymer together with the nature of anisotropic ordering forces on the phase diagram. The strength of these forces is characterized by a parameter alpha which is directly related to the temperature of the smectic-nematic transition. Three cases are considered depending on the value of alpha, and the corresponding phase diagrams are constructed. Substantial differences are observed in these diagrams, and the reasons for these differences are discussed. A comparative study is performed between mixtures of polymers and LCs, where the polymer is made of linear and crosslinked chains. The LC consists either of molecules with nematic ordering only or of molecules presenting both nematic and smectic-A ordering. Blends where polymer matrices are cross-linked networks are also examined. Remarkable properties are found in the nature of the phase diagrams for such mixtures. In general, it is observed that the ordering forces favor unmixing with a stronger effect for the higher smectic-A ordering. Spinodal curves are also reported for these mixtures. The effects of fluctuations near the transition temperatures are briefly discussed.