Interfacial interface anisotropy

In this respect, a theory that takes into account the deformation of one droplet (Doi and Ohta 1991) can be applied to describe the shear and normal stress transients. According to this model, blend morphology is characterized by a scalar (referring to a specific interfacial area) and a tensor (characterizing interface anisotropy). These parameters may be expressed in two equations—one describing the stresses of the interfacial structures and the other for the evaluation of the scalar and interface tensor. For immiscible blends with Newtonian or weakly viscoelastic fluids and an increase in shear, the droplets deform into fibrils while maintaining their initial diameter, d. In comparison, in a highly elastic matrix where droplet shape is... 

Equations [84] and [85] suggest that the droplet size in the steady state is essentially determined by competition of the interfacial tension and the viscous shear stress, as considered in the classical Taylor theory " for an instability criterion of a single droplet. However, the behavior of the normal stress difference (eqn [83b]) is not fully understood from this theory. Concerning this point, Doi and Ohta proposed a phenomenological model for the interface anisotropy and spedfic interfacial area in blends having the characteristic length determined only by the shear. The predictions of the Doi-Ohta model are consistent with the experimental observation (eqns [83]-[85]) as well as the scaling behavior observed for... 

The orientational structure of water near a metal surface has obvious consequences for the electrostatic potential across an interface, since any orientational anisotropy creates an electric field that interacts with the metal electrons. Hydrogen bonds are formed mainly within the adsorbate layer but also between the adsorbate and the second layer. Fig. 3 already shows quite clearly that the requirements of hydrogen bond maximization and minimization of interfacial dipoles lead to preferentially planar orientations. On the metal surface, this behavior is modified because of the anisotropy of the water/metal interactions which favors adsorption with the oxygen end towards the metal phase. 

Rotational dynamics of a fluorescent dye adsorbed at the interface provides useful information concerning the rigidity of the microenvironment of liquid-liquid interfaee in terms of the interfacial viscosity. The rotational relaxation time of the rhodamine B dye was studied by time-resolved total internal reflection fluorescent anisotropy. In-plane... 

A recent analysis by Kastritseas etal. (2004c) suggested that in both cases the magnitude of the thermal shock-induced stresses was overestimated as the anisotropic character of the materials was not taken into account. If material anisotropy is accounted for, then both (15.36) and (15.37) cannot predict A Tc accurately even for the largest possible value of the thermal shock-induced stresses (corresponding to a maximum value of the stress reduction factor, A = 0.66). To explain the discrepancy, it was proposed that the interfacial properties may be affected by the shock due to the biaxial nature of the induced stress field, which dictates that a tensile thermal stress component that acts perpendicular to the fibre-matrix interface is present for the duration of the shock. 

The general thermodynamic requirement for the stability of an interface between two phases is a positive - Gibbs energy of formation, because otherwise the interface would either fluctuate or disappear. Since the molecular forces on either side of an interface possess a specific anisotropy the structure of the utmost surface layers differs from that inside the phases (see -> double layer). For these interfacial regions the term -> interphase is also used. 

Dynamic fluorescence anisotropy is based on rotational reorientation of the excited dipole of a probe molecule, and its correlation time(s) should depend on local environments around the molecule. For a dye molecule in an isotropic medium, three-dimensional rotational reorientation of the excited dipole takes place freely [10]. At a water/oil interface, on the other hand, the out-of-plane motion of a probe molecule should be frozen when the dye is adsorbed on a sharp water/oil interface (i.e., two-dimensional in respect to the molecular size of a probe), while such a motion will be allowed for a relatively thick water/oil interface (i.e., three-dimensional) [11,12]. Thus, by observing rotational freedom of a dye molecule (i.e., excited dipole), one can discuss the thickness of a water/oil interface the correlation time(s) provides information about the chemi-cal/physical characteristics of the interface, including the dynamical behavioiu of the interfacial structure. Dynamic fluorescence anisotropy measurements are thus expected... 

Three-Dimensional Model. On the other hand, if the interfacial layer is thick enough compared to the molecular size of SRIOI and if SRIOI molecules adsorbed on the interface are weakly oriented, the rotational motions of SRIOI take place in three dimensions, similar to those in a bulk phase. If this is the case, the contribution of the fluorescence with the excited dipole moment of SR 101 directed along the z-axis cannot be neglected, so that the time profile of the total fluorescence intensity must be proportional to / (0 + 2/i(t). Thus, fluorescence dynamic anisotropy is given by Equation (15), as is well known for that in a macroscopically isotropic system [10,13] ... 

In this case, r(0) and the magic angle are calculated to be 0.4 and 54.7°, respectively. The thickness of a water/oil interfacial layer would be evaluated through TIR fluorescence anisotropy measurements and the value(s) provides information about characteristic features at a water/oil interface. 

It is worth noting that water/oil interfacial structures would be governed by various factors, so that a complementary study other than fluorescence dynamic anisotropy is required to obtain further detailed information about the characteristics at a water/oil interface. As a new and novel approach, therefore, excitation energy transfer d3mamics and the relevant structural (fractal) dimension analysis were introduced to elucidate the structure of a water/oil interface [4],... 

Although the structural differences between the water/CClq and water/DCE interfaces are not so large, the chemical and/or physical nature of the organic phase itself reflects on the photophysical properties of a probe molecule, indicating the novelty of the present experimental approaches. Systematic investigations are important to reveal factors governing structural and physical characteristics of water/oil interfaces. Therefore, we introduced fluorescence dynamic anisotropy and excitation energy transfer measurements to other water/oil interfacial systems the data are summarized in Table 12.3. The results are discussed in terms of the relationship between the interfacial stracture and the polarity at the water/oil interfaces (Section 12.6). 

Ellipsometry Spectroscopic ellipsometry Imaging ellipsometry Adsorbed amounts/coverages phase transitions thickness and refractive indices. Identification of interfacial molecules. Domain formation eind shape (coexisting phases) internal structure of condensed phases resolution O (1 gm). For interpretation in terms of molecular structure model profiles across the Interface are needed. Problems mono-layer anisotropy, and different profiles may match the experimental data additional (independent) information required. 

A rigorous kinetic description of interfacial catalysis has been hampered by the ill-defined physical chemistry of the lipid—water interface (Martinek et ai, 1989). Traditional kinetic assumptions are undermined by the anisotropy and inhomogeneity of the substrate aggregate. For example, the differential partitioning of reactants (enzyme, calcium ion, substrate) and products (lysolecithins, fatty acids) between the two bulk phases prevents direct measurement of enzyme and substrate concentrations. This complicates dissection of the multiple equilibria that contribute to the observed rate constants. Only recently has it become possible to describe clearly the activity of SPLA2S in terms of traditional Michaelis— Menten kinetics. Such a description required the development of methods to reduce experimentally the number of equilibrium states available to the enzyme (Berg etai, 1991). 

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