Complexation of oppositely charged polyelectrolytes: effect of ion pair formation

Complexation in symmetric solutions of oppositely charged polyelectrolytes is studied theoretically. We include polyion crosslinking due to formation of thermoreversible ionic pairs. The electrostatic free energy is calculated within the Random Phase Approximation taking into account the structure of thermoreversible polyion clusters. The degree of ion association is obtained self-consistently from a modified law of mass action, which includes long-range electrostatic contributions. We analyze the relative importance of the three complexation driving forces: long-range electrostatics, ion association and van der Waals attraction. The conditions on the parameters of the system that ensure stability of the complex with addition of salt are determined

Weak Segregation Theory and Non-Conventional Morphologies in the Ternary ABC Triblock Copolymers

The Leibler weak segregation theory in molten diblock copolymers is generalized with due regard for the 2nd shell harmonics contributions defined in the paper and the phase diagrams are built for the linear and miktoarm ternary ABC triblock copolymers. The symmetric linear copolymers with the middle block non-selective with respect to the side ones are shown to undergo the continuous ODT not only into the lamellar phase but also into various non-conventional cubic phases (depending on the middle block composition it could be the simple cubic, face-centered cubic or non-centrosymmetric phase revealing the symmetry of space group No.214 first predicted to appear in molten block copolymers). For asymmetric linear ABC copolymers a region of compositions is found where the weakly segregated gyroid (double gyroid) phase exists between the planar hexagonal and lamellar or one of the non-conventional cubic phases up to the very critical point. In contrast, the miktoarm ABC block copolymers with one of its arm non-selective with respect to the two others are shown to reveal a pronounced tendency towards strong segregation, which is preceded by increase of stability of the conventional BCC phase and a peculiar weakly segregated BCC phase (BCC3), where the dominant harmonics belong to the 3rd co-ordination sphere of the reciprocal lattice. The validity region of the developed theory is discussed and outlined in the composition triangles both for linear and miktoarm copolymers.Comment: 61 pages, 12 figure

On Capabilities of Tracking Marine Surface Currents Using Artificial Film Slicks

It is known that films on the sea surface can appear due to ship pollution, river and collector drains, as well as natural biological processes. Marine film slicks can indicate various geophysical processes in the upper layer of the ocean and in the atmosphere. In particular, slick signatures in SAR-imagery of the sea surface at low and moderate wind speeds are often associated with marine currents. Apart from the current itself, other factors such as wind and the physical characteristics of films can significantly influence the dynamics of slick structures. In this paper, a prospective approach aimed at measuring surface currents is developed. The approach is based on the investigation of the geometry of artificial banded slicks formed under the action of marine currents and on the retrieval of the current characteristics from this geometry. The developed approach is applied to quasi stationary slick bands under conditions when the influence of the film spreading effects can be neglected. For the stationary part of the slick band where transition processes of the band formation, e.g., methods of application of surfactants on water, film spreading processes, possible wind transformation etc., become negligible, some empirical relations between the band geometrical characteristics and the characteristics of the surface currents are obtained. The advantage of the approach is a possibility of getting information concerning the spatial structure of marine currents along the entire slick band. The suggested approach can be efficient for remote sensing data verification

The Role of Micro Breaking of Small-Scale Wind Waves in Radar Backscattering from Sea Surface

The study of the microwave scattering mechanisms of the sea surface is extremely important for the development of radar sensing methods. Some time ago, Bragg (resonance) scattering of electromagnetic waves from the sea surface was proposed as the main mechanism of radar backscattering at moderate incidence angles of microwaves. However, it has been recently confirmed that Bragg scattering is often unable to correctly explain observational data and that some other physical mechanisms should be taken into consideration. The newly introduced additional scattering mechanism was characterized as non-polarized, or non-Bragg scattering, from quasi-specular facets appearing due to breaking wave crests, the latter usually occurring in moderate and strong winds. In this paper, it was determined experimentally that such non-polarized radar backscattering appeared not only for rough sea conditions in which wave crests strongly break and “white caps” occur, but also at very low wind velocities close to their threshold values for the wave generation process. The experiments were performed using two polarized Doppler radars. The experiments demonstrated that a polarization ratio, which characterizes relative contributions of non-polarized and Bragg components to the total backscatter, changed slightly with wind velocity and wind direction. Detailed analysis of radar Doppler shifts revealed two types of scatterers responsible for the non-polarized component. One type of scatterer, moving with the velocities of decimeter-scale wind waves, determined radar backscattering at low winds. We identified these scatterers as “microbreakers” and related them to nonlinear features in the profile of decimeter-scale waves, like bulges, toes and parasitic capillary ripples. The scatterers of the second type were associated with strong breaking, moved with the phase velocities of meter-scale breaking waves and appeared at moderate winds additionally to the “microbreakers”. Along with strong breakers, the impact of microbreaking in non-polarized backscattering at moderate winds remained significant; specifically the microbreakers were found to be responsible for about half of the non-polarized component of the radar return. The presence of surfactant films on the sea surface led to a significant suppression of the small-scale non-Bragg scattering and practically did not change the non-Bragg scatterer speed. This effect was explained by the fact that the nonlinear structures associated with dm-scale waves were strongly reduced in the presence of a film due to the cascade mechanism, even if the reduction of the amplitude of dm waves was weak. At the same time, the velocities of non-Bragg scatterers remained practically the same as in non-slick areas since the phase velocity of dm waves was not affected by the film

Surface Waves Prediction Based on Long-Range Acoustic Backscattering in a Mid-Frequency Range

Underwater acoustic echosounding for surface roughness parameters retrieval is studied in a frequency band that is relatively new for such purposes. During the described 2-weeks sea experiment, 1–3 kHz tonal pulses were emitted from an oceanographic platform, located on the northern Black Sea shelf. Doppler spectra of the resulting reverberation were studied. The frequency band of the acoustic system, selected for this study, is chosen due to the fact that the sound propagation range is large enough for remote sensing in a coastal zone, and the resolution cell size does not limit the research. Backscattering of acoustical signals was received for distances around two nautical miles. However, it turned to be quite difficult to interpret the obtained data since backscattering spectrum shape was influenced by a series of effects, resulting in a complicated link to wind waves and currents’ parameters. Significant wave height and dominant wave frequency were estimated as the result of such signals processed with the use of machine learning tools. A decision-tree-based mathematical regression model was trained to solve the inverse problem. Wind waves prediction is in a good agreement with direct measurements, made on the platform, and machine learning results allow physical interpretation

Surface Waves Prediction Based on Long-Range Acoustic Backscattering in a Mid-Frequency Range

Underwater acoustic echosounding for surface roughness parameters retrieval is studied in a frequency band that is relatively new for such purposes. During the described 2-weeks sea experiment, 1–3 kHz tonal pulses were emitted from an oceanographic platform, located on the northern Black Sea shelf. Doppler spectra of the resulting reverberation were studied. The frequency band of the acoustic system, selected for this study, is chosen due to the fact that the sound propagation range is large enough for remote sensing in a coastal zone, and the resolution cell size does not limit the research. Backscattering of acoustical signals was received for distances around two nautical miles. However, it turned to be quite difficult to interpret the obtained data since backscattering spectrum shape was influenced by a series of effects, resulting in a complicated link to wind waves and currents’ parameters. Significant wave height and dominant wave frequency were estimated as the result of such signals processed with the use of machine learning tools. A decision-tree-based mathematical regression model was trained to solve the inverse problem. Wind waves prediction is in a good agreement with direct measurements, made on the platform, and machine learning results allow physical interpretation