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We report oscillations of current which accompany anodic deposition from Mn(II) solutions in a neutral acetic buffer and also cathodic birnessite deposition from alkaline permanganate solutions. We demonstrate that for both processes, oscillations appear at high enough overpotentials. The current oscillations are affected by solution convection. The results of rotating disc electrode experiments favor mixed control, with higher diffusion contribution in case of cathodic deposition. Electron microscopy combined with electron and X-ray diffraction and coulometric analysis is applied to assign oscillations to certain morphological features of the deposits. A pronounced difference in microstructure is found for anodic and cathodic deposits formed under oscillating growth conditions: "anodic" birnessite consists of parallel layers of small crystals, whereas "cathodic" birnessite is globular. This difference is interpreted with account for specific crystallographic features. Namely, the more ordered birnessite lattice formed by reduction of permanganate favors a preferentially lateral growth of thin lamellas, in contrast to birnessite having a pronounced interplane distortion, formed in the course of anodic deposition. We assign the periodic current decrease to diffusion limitations in growing porous layers and assume that the subsequent current increase in each period corresponds to dendrite-like growth of a low number of crystals located in the outer diffusion layer. [ABSTRACT FROM AUTHOR]

Mo-Zr-Si-B coatings were deposited by high-power impulse magnetron sputtering at a pulse frequency of 10, 50, and 200 Hz. The coating structure was studied by scanning electron microscopy, energy-dispersive spectroscopy, glow-discharge optical-emission spectroscopy, transmission electron microscopy, and X-ray diffraction. The mechanical characteristics, adhesive strength, coefficient of friction, wear resistance, resistance to cyclic-dynamic-impact loading, high-temperature oxidation resistance, and thermal stability of the coatings were determined. The coatings, obtained at 10 and 50 Hz, had an amorphous structure. Increasing the frequency to 200 Hz led to the formation of the h-MoSi2 phase. As the pulse frequency increased from 10 to 50 and 200 Hz, the deposition rate rose by 2.3 and 9.0 times, while hardness increased by 1.9 and 2.9 times, respectively. The Mo-Zr-Si-B coating deposited at 50 Hz was characterized by better wear resistance, resistance to cyclic-dynamic-impact loading, and oxidation resistance at 1500 °C. Thermal stability tests of the coating samples heated in the transmission electron microscope column showed that the coating deposited at 50 Hz remained amorphous in the temperature range of 20–1000 °C. Long-term annealing in a vacuum furnace at 1000 °C caused partial recrystallization and the formation of a nanocomposite structure, as well as an increased hardness from 15 to 37 GPa and an increased Young's modulus from 250 to 380 GPa, compared to those of the as-deposited coatings. [ABSTRACT FROM AUTHOR]

Highlights • The layered films made of hyaluronic acid (HA) and chitosan (CS) were prepared and characterized. • Formation of the CS/HA polyelectrolyte complex led to crystallization of the CS layer. • The CS/HA membranes showed high selectivity during the separation of water from the ethanol-water mixtures. • The membrane microstructure was observed to change during the pervaporation process using LVSEM. Abstract Self-supporting multilayer films containing a polyelectrolyte complex (PEC) were prepared by the sequential layering of sodium hyaluronate (HA, MW 5.4 × 104) and chitosan (CS, MW 1.6 × 105, the degree of deacetylation 0.80) in different orders. Imaging with low-voltage scanning electron microscopy (LVSEM) showed that the CS/HA films had a multilayer structure, while X-ray diffraction (XRD) indicated significant structuring of the CS layer near the PEC-CS region. Analysis of the thermal properties of the CS/HA films revealed differences in the structural organization and morphological features of the polymer layers and high thermal stability of the PEC layer. Testing of the transport properties of the CS/HA film in pervaporation (PV) separation using different compositions of ethanol-water mixtures indicated that the multilayer membrane was selective across a wide range of concentrations in the feed. Separation of an azeotropic ethanol-water mixture containing 5 wt% water yielded a permeate consisting of about 100 wt% water. LVSEM revealed that the membrane microstructure changed during the PV process due to membrane swelling and changes in the arrangement of the macromolecules during transport of the penetrant. The results support the use of CS/HA composite films as highly effective PV membranes. In addition to pervaporation separation, CS/HA multilayer films can also be used for drug delivery, tissue engineering, and wound healing applications. [ABSTRACT FROM AUTHOR]

We studied the effect of neutral polymer poly(vinyl alcohol) on the rheological properties and microstructure of highly charged mixed wormlike micelles of anionic and cationic surfactants, potassium oleate and n-octyltrimethylammonium bromide, without adding salt. It was shown that the polymer induces a hundredfold increase of viscosity and of longest relaxation time and the appearance of well-defined plateau modulus, which was assigned to interlacing of polymer and micellar chains. When the amount of added polymer exceeds 2 wt %, the rheological characteristics (the viscosity, the longest relaxation time, and the plateau modulus) level off because of microphase separation appearing as a result of the interplay of the segregation on the microscopic scale triggered by the energetic repulsion between polymer and surfactant components, on the one hand, and the translational entropy of counterions preventing the macroscopic phase separation, on the other hand. The formation of surfactant-rich and polymer-rich microphases was evidenced by small-angle neutron scattering and cryogenic transmission electron microscopy data. The results obtained open a new way to modify the rheological properties and the microstructure of wormlike micellar solutions. [ABSTRACT FROM AUTHOR]