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4 result(s) for "Syrtsova, Daria A."
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Hydrophobic–Hydrophilic Properties and Characterization of PIM-1 Films Treated by Elemental Fluorine in Liquid Perfluorodecalin
A direct fluorination technique was applied for the surface treatment of PIM-1 films in a liquid phase (perfluorodecalin). The fluorinated samples were analyzed by various instrumental techniques. ATR-IR spectroscopy showed that the fluorination predominantly takes place in methylene- and methyl-groups. Cyano-groups, aromatic hydrogens and the aromatic structure of the PIM-1 repeat unit were shown to be relatively stable at the fluorination conditions. XPS confirmed that the concentration of fluorine, as well as oxygen, in the near surface layer (~1 nm) increases with fluorination time. C1s and O1s surface spectra of the fluorinated PIM-1 samples indicated an appearance of newly-formed C-F and C-O functional groups. Scanning electron microscopy and X-ray energy-dispersive spectroscopy of the fluorinated PIM-1 samples showed an increase of the fluorine concentration at the surface (~0.1–1 μm) with the treatment duration. Analysis of the slices of the PIM-1 films demonstrated a decline of the fluorine content within several microns of the film depth. The decline increased with the fluorination time. A model of fluorine concentration dependence on the film depth and treatment duration was suggested. A change in the specific free surface energy as a result of PIM-1 fluorination was revealed. The fluorination time was shown to affect the surface energy (γSV), providing its shift from a low value (25 mJ∙m−2), corresponding to tetrafluoroethylene, up to a relatively high value, corresponding to a hydrophilic surface.
Preparation of Hollow Fiber Membranes Based On Poly(4-methyl-1-pentene) for Gas Separation
New hollow fiber gas separation membranes with a non-porous selective layer based on poly(4-methyl-1-pentene) (PMP) granules have been obtained using the solution-free melt spinning process. The influence of the preparation conditions on the geometry of the obtained samples was studied. It was found that a spin head temperature of 280 °C and a specific mass throughput of 103 g mm−2 h−1 are optimal to obtain defect-free, thin-walled hollow fibers in a stable melt spinning process, using the given spinneret geometry and a winding speed of 25 m/min. The gas permeability and separation properties of new fibers were studied using CO2/N2 and CO2/CH4 mixtures, and it was found that the level of gas selectivity characteristic of homogeneous polymer films can be achieved. The features of the gas mixture components permeability below and above the PMP glass transition temperature have been experimentally studied in the range of CO2 concentrations from 10 to 90% vol. The temperature dependences of the permeability of the CO2/CH4/N2 mixture through the obtained HF based on PMP have been investigated, and the values of the apparent activation energies of the permeability have been calculated, which make it possible to predict the properties of membrane modules based on the obtained membranes in a wide temperature range.
Surface and Structural Characterization of PVTMS Films Treated by Elemental Fluorine in Liquid Perfluorodecalin
Poly(vinyl trimethylsilane) (PVTMS) films were subjected to direct surface fluorination in liquid medium (perfluorodecalin). The samples were investigated using several techniques: SEM-XEDS, XPS, ATR-IR, and contact angle measurement. The methods used allowed us to estimate chemical changes occurring because of the treatment. ATR-IR showed that most of the changes occurred in the Si(CH3)3 group. Monofluorinated Si(CH3)3 groups formed in the near-surface layer (Ge crystal, 0.66 µm penetration) after 30 min of fluorination, and then di- and trifluorinated groups appeared. Oxidation of the film with oxygen was also shown with the use of ZnSe crystal (2 µm penetration). The XPS method allowed an assessment of the ratio of the main elements at the surface of the fluorinated film. Two different exponential models were proposed to fit the experimental data of SEM-XEDS. Based on the model with the intercept, the depth of fluorination was estimated to be ≤1.1 µm, which is consistent with the result from the literature for the gas-phase fluorination. Contact angle measurements showed that oxidation of the PVTMS surface prevailed for the first 45 min of fluorination (surface hydrophilization) with a subsequent fluorine content increase and hydrophobization of the surface upon 60 min of fluorination.
Depth Profile Analysis of the Modified Layer of Poly(vinyltrimethylsilane) Films Treated by Direct-Current Discharge
Previously, we found that modification of the membrane surface from polyvinyltrimethylsilane (PVTMS) by treatment with low-temperature plasma induced by low pressure DC discharge leads to a significant increase in gas separation characteristics. To understand the mechanism of this phenomenon, in this article XPS combined with precision etching 10 keV beam of Ar2500+ clusters was used for depth profiling of PVTMS spin-coated films before and after DC discharge treatment. The etching craters depths were measured by stylus surface profiler. The average etching rate of the untreated PVTMS film by Ar2500+ clusters was defined (230 nm/min). It was found that the low temperature plasma treatment of PVTMS leads to a sharp increase in the oxygen concentration on a surface with a simultaneous decrease in the carbon content. The experimental data obtained indicate also that the treatment of PVTMS film by plasma leads not only to a change in the chemical structure of the surface, but also to the formation of a gradient subsurface layer with a thickness of about 50 nm.