Search Results (19)

Today, reducing carbon footprints requires the development of technologies to utilize CO₂, particularly by converting it into valuable chemical products. One approach is plasma-catalytic CO₂ splitting into CO and O₂. The task of separating such a ternary mixture is nontrivial and requires the development of an efficient method. In this paper, we have developed a comprehensive scheme for the separation of a CO₂/CO/O₂ mixture using membrane technology. The novelty of this work lies in the development of a complete scheme for separating the products of plasma-chemical decomposition of CO₂ to produce a CO concentrate. The calculations utilized the principle of a reasonable balance between the recovery rate and the energy consumption of the separation process. This scheme allows production of a CO stream with a purity of 99%. To achieve this goal, we have proposed the sequential use of CO₂-selective membranes based on polysiloxane with oligoethyleneoxide side groups (M-PEG), followed by polysulfone (PSF) hollow-fiber membranes to separate CO and O₂. For these membranes, we measured the CO permeability for the first time and obtained the selectivity for CO₂/CO and O₂/CO. The potential of membrane separation was demonstrated through a three-stage process, which includes recycling of the CO removal stream and concentration after CO₂ plasmolysis. This process was calculated to yield a highly pure CO stream containing 99 mol% with a recovery rate of 47.9–69.4%. The specific energy consumption for the separation process was 30.31–0.83 kWh per 1 m³ of feed mixture, and the required membrane area was between 0.1 m² for M-PEG and 42.5–107 m² for PSF, respectively. Full article

The pervaporation properties of membranes based on comb-like polysiloxanes when C₂-C₄ alcohols are removed from water were studied for the first time. It was established that membranes based on comb-like polysiloxanes with linear aliphatic and organosilicon substituents have increased permeability selectivity for C₃₊ alcohols. The obtained results were interpreted from the point of view of the solubility of the components of the separated mixture in polysiloxanes. It was shown that membranes based on polysiloxanes with linear substituents have increased butanol/water permeability selectivity (2.5–3.7). The achieved selectivity values correspond to the level of highly selective zeolite membranes, which allows for a reduction in energy consumption for the pervaporation removal of butanol by more than two times. Full article

The scope of this work was to develop a thin-film composite (TFC) membrane for the separation of CO₂/CO mixtures, which are relevant for many processes of gas processing and gasification of carbon-based feedstock. Special attention was given to the development of highly permeable porous polysulfone (PSF) supports (more than 26,000 GPU for CO₂) since both the selective and support layers contribute significantly to the overall performance of the TFC membrane. The PSF porous support is widely used in commercial and lab-scale TFC membranes, and its porous structure and other exploitation parameters are set during the non-solvent-induced phase separation (NIPS) process. Since the casting solution properties (e.g., viscosity) and the interactions in a three-component system (polymer, solvent, and non-solvent) play noticeable roles in the NIPS process, polysulfone samples in a wide range of molecular weights (M_w = 76,000–122,000 g·mol⁻¹) with terminal hydroxyl groups were synthesized for the first time. Commercial PSF with predominantly terminal chlorine groups (Ultrason^® S 6010) was used as a reference. The PSF samples were characterized by NMR, DSC, and TGA methods, and the Hansen solubility parameters were calculated. It was found that increasing the ratio of terminal –OH over –Cl groups improved the “solubility” of PSF in N-methyl-2-pyrrolidone (NMP) and water. A direct dependence of the gas permeance of porous supports on the coagulation rate of the casting solution was identified for the first time. It was shown that the use of synthesized PSF (M_w = 76,000 g·mol⁻¹, M_w/M_n = 3.0, (–OH):(–Cl) ratio of 4.7:1) enabled a porous support with a CO₂ permeance of 26,700 GPU to be obtained, while the support formed from a commercial PSF Ultrason^® S 6010 (M_w = 68,000 g·mol⁻¹, M_w/M_n = 1.7, (–OH):(–Cl) ratio of 1:1.9) under the same conditions demonstrated 4300 GPU. The siloxane-based materials were used for the selective layer since the thin films based on rubbery polymers do not undergo the same accelerating physical aging as glassy polymers. Two types of materials were screened for the selective layer: synthesized polymethyltrifluoroethylacrylate siloxane-polydecylmethylsiloxane (50F3) copolymer, and polydimethylsiloxane (PDMS). 50F3 siloxane was studied for gas separation applications for the first time. It was shown that the permeance of composite membranes based on high-performance porous supports from the PSF samples synthesized was 3.5 times higher than that from similar composite membranes based on supports from a commercial Ultrason^® S 6010 PSF with a permeance value of 4300 GPU for CO₂. It was found that the enhanced gas permeance of composite membranes based on the highly permeable porous PSF supports developed was observed for both 50F3 polysiloxane and commercial PDMS. At the same time, the CO₂/CO selectivity of the composite membranes with a 50F3-selective layer (9.1–9.3) is 1.5 times higher than that of composite membranes with a PDMS-selective layer. This makes the F-containing 50F3 polysiloxane a promising polymer for CO₂/CO separation. Full article

Background: Glioblastoma multiforme (GBM) is the most common highly aggressive, primary malignant brain tumor in adults. Current experimental strategies include photodynamic therapy (PDT) and new drug delivery technologies such as nanoparticles, which could play a key role in the treatment, diagnosis, and imaging of brain tumors. Objectives: The purpose of this study was to test the efficacy of PDT using AGuIX-TPP, a polysiloxane-based nanoparticle (AGuIX) that contains TPP (5,10,15,20-tetraphenyl-21H,23H-porphine), in biological models of glioblastoma multiforme and to investigate the vascular mechanisms of action at multiple complexity levels. Methods: PDT effects were studied in monolayer and spheroid cell culture, as well as tumors in chicken chorioallantoic membranes (CAMs) and in mice were studied. Results: Treatment was effective in both endothelial ECRF and glioma U87 cells, as well as in the inhibition of growth of the glioma spheroids. PDT using AGuIX-TPP inhibited U87 tumors growing in CAM and destroyed their vascularization. The U87 tumors were also grown in nude mice. Their vascular network, as well as oxygen partial pressure, were assessed using ultrasound and EPR oximetry. The treatment damaged tumor vessels and slightly decreased oxygen levels. Conclusions: PDT with AGuIX-TPP was effective against glioma cells, spheroids, and tumors; however, in mice, its efficacy appeared to be strongly related to the presence of blood vessels in the tumor before the treatment. Full article

In this work, a Pd(II)-C,N-cyclometalated complex was grafted to polysiloxanes via azide–alkyne cycloaddition. The obtained polymer–metal complex (Pd-PDMS) acts as a catalyst in the Suzuki–Miyaura reaction. Pd-PDMS was drop-casted onto a carbon fiber support, and the resulting membrane demonstrated catalytic activity in the cross-coupling reaction without yield loss after several catalytic cycles. The catalytic membrane allows for easy catalyst recycling and provides ultra-low palladium levels in Suzuki–Miyaura reaction products. Full article

The development of membrane materials with high transport and separation properties for the removal of higher hydrocarbons from gas mixtures is an important and complex task. This work examines the effect of a cross-linking agent on the structure and transport properties of polydecylmethylsiloxane (C10), a material characterized by high selectivity towards C₃₊ hydrocarbons. C10 was cross-linked with various diene hydrocarbons, such as 1,7-octadiene (C10-OD), 1,9-decadiene (C10-DD), 1,11-dodecadiene (C10-DdD), and vinyl-terminated polysiloxanes, of different molecular weights: 500 g/mol (C10-Sil500) and 25,000 g/mol (C10-Sil25-OD). Using a number of characterization methods (IR-spectroscopy, WAXS, DSC, toluene sorption, and gas permeability), it was revealed that a change in the type and length of the cross-linking agent (at the same mole concentration of cross-linking agent) led to a significant change in the structure of the polymer material. The nature of cross-linking agent affected the arrangement of the decyl side-groups of the polymer, resulting in noticeable differences in the solubility, diffusivity, permeability, and selectivity of tested gases (N₂, CH₄, C₂H₆, and C₄H₁₀). For instance, an increase in the length of the hydrocarbon cross-linker was associated with a drop of n-butane permeability from 5510 (C10-OD) to 3000 Barrer (C10-DdD); however, the transition to a polysiloxane cross-linker led to an increase in corresponded permeability up to 8200 Barrer (C10-Sil25-OD). The n-butane/nitrogen selectivity was significantly higher for diene-type cross-linkers, and the maximum value was achieved for 1,7-octadiene (α(C₄H₁₀/N₂) = 104). Full article

We have synthesized cubic and linear polysiloxanes containing polyoxyethylene branches (ASiP-Cu) using tetraethoxysilane, polyoxyethylene glycol, and copper chloride as precursors; the products are stable to self-condensation. The effect of copper chloride content on the chemical structure of ASiP-Cu has been established. A special study was aimed at defining the modifying effect of ASiP-Cu on the sorption characteristics of membranes based on microporous, optically transparent block copolymers (OBCs). These OBCs were produced using 2,4-toluene diisocyanate and block copolymers of ethylene and propylene oxides. The study demonstrated significantly increased sorption capacity of the modified polymers. On the basis of the modified microporous block copolymers and 1-(2-pyridylazo)-2-naphthol (PAN) analytical reagent, an analytical test system has been developed. Additionally, the modified OBCs have the benefit of high diffusion permeability for molecules of organic dyes and metal ions. It has been shown that the volume of voids and structural features of their internal cavities contribute to the complex formation reaction involving PAN and copper chloride. Full article

Waterproof breathable functional membranes have broad application prospects in the field of outdoors textiles. The fluorine-containing microporous membranes of the mainstream functional products easily cause harm to the environment, and thus, the fluorine-free environmental nanofibrous membranes are an important development direction for functional membranes. In this subject, the electrospun polyacrylonitrile nanofibrous membranes were first hydrophobically modified by amino functional modified polysiloxane (AMP), followed by in situ cross-linking modified with 4, 4’-methyl diphenylene diisocyanate (MDI). The fluorine-free modification by AMP altered the surface of the membranes from hydrophilic to hydrophobic, and greatly improved the waterproof properties with the hydrostatic pressure reaching to 87.6 kPa. In addition, the formation of bonding points and the in situ preparation of polyuria through the reaction between the isocyanate in MDI and the amino group in AMP, could improve the mechanical properties effectively. When using AMP with the concentration of 1 wt% and MDI with the concentration of 2 wt%, the relatively good comprehensive performance was obtained with good water resistance (93.8 kPa), modest vapor permeability (4.7 kg m⁻² d⁻¹) and air permeability (12.7 mm/s). Based on these testing data, the modified nanofibrous membranes had excellent waterproof and breathable properties, which has future potential in outdoor sports apparel. Full article

In spite of its versatility, the emulsion templating method is rather uncommon for the preparation of porous silicones. In this contribution, two siloxane-containing stabilizers, designed to be soluble in polar (water) and non-polar (toluene) solvents, respectively, were used in low concentrations to produce stable emulsions, wherein polysiloxane gels were obtained by UV-photoinitiated thiol-ene click cross-linking. The stabilizers exhibited negative interfacial tension, as measured by Wilhelmy plate tensiometry. The emulsion gels evolved into porous silicones (xerogels), with tunable morphology and properties. According to TEM and SEM investigations, the emulsion template was preserved in the final materials. Several parameters (e.g., the structure of the polysiloxane precursors, composition of the emulsion gels, nature of the continuous phase, cross-linking conditions, or additives) can be varied in order to obtain porous elastic materials with desired properties, such as Janus membranes, absorbent monoliths, all-polymer porous composites, or silicone-swollen gels. The feasibility of these types of materials was tested, and exemplary porous silicones were briefly characterized by contact angle measurements, mechanical testing, and absorption tests. The proposed method is simple, fast, and economic, uses very little amounts of stabilizers, and can be adjusted as a green technique. In this contribution, all the silicon-based materials with a convenient design were prepared in house. Full article

Zwitterionic polymers as crucial antifouling materials exhibit excellent antifouling performance due to their strong hydration ability. The structure–property relationship at the molecular level still remains to be elucidated. In this work, the surface hydration ability of three antifouling polymer membranes grafting on polysiloxane membranes Poly(sulfobetaine methacrylate) (T4-SB), poly(3-(methacryloyloxy)propane-1-sulfonate) (T4-SP), and poly(2-(dimethylamino)ethyl methacrylate) (T4-DM) was investigated. An orderly packed, and tightly bound surface hydration layer above T4-SP and T4-SB antifouling membranes was found by means of analyzing the dipole orientation distribution, diffusion coefficient, and average residence time. To further understand the surface hydration ability of three antifouling membranes, the surface structure, density profile, roughness, and area percentage of hydrophilic surface combining electrostatic potential, RDFs, SDFs, and noncovalent interactions of three polymers’ monomers were studied. It was concluded that the broadest distribution of electrostatic potential on the surface and the nature of anionic SO3- groups led to the following antifouling order of T4-SB > T4-SP > T4-DM. We hope that this work will gain some insight for the rational design and optimization of ecofriendly antifouling materials. Full article

The application of gas-liquid membrane contactors for ethane-ethylene separation seems to offer a good alternative to conventional energy-intensive processes. This work aims to develop new hydrophobic composite membranes with active ethylene carriers and to demonstrate their potential for ethylene/ethane separation in gas-liquid membrane contactors. For the first time, hybrid membrane materials based on polyoctylmethylsiloxane (POMS) and silver tetrafluoroborate, with a Si:Ag ratio of 10:0.11 and 10:2.2, have been obtained. This technique allowed us to obtain POMS-based membranes with silver nanoparticles (8 nm), which are dispersed in the polymer matrix. The dispersion of silver in the POMS matrix is confirmed by the data IR-spectroscopy, wide-angle X-ray diffraction, and X-ray fluorescence analyses. These membranes combine the hydrophobicity of POMS and the selectivity of silver ions toward ethylene. It was shown that ethylene sorption at 600 mbar rises from 0.89 cm³(STP)/g to 3.212 cm³(STP)/g with an increase of Ag content in POMS from 0 to 9 wt%. Moreover, the membrane acquires an increased sorption affinity for ethylene. The ethylene/ethane sorption selectivity of POMS is 0.64; for the membrane with 9 wt% silver nanoparticles, the ethylene/ethane sorption selectivity was 2.46. Based on the hybrid material, POMS-Ag, composite membranes were developed on a polyvinylidene fluoride (PVDF) porous support, with a selective layer thickness of 5–10 µm. The transport properties of the membranes were studied by separating a binary mixture of ethylene/ethane at 20/80% vol. It has been shown that the addition of silver nanoparticles to the POMS matrix leads to a decrease in the ethylene permeability, but ethylene/ethane selectivity increases from 0.9 (POMS) to 1.3 (9 wt% Ag). It was noted that when the POMS-Ag membrane is exposed to the gas mixture flow for 3 h, the selectivity increases to 1.3 (0.5 wt% Ag) and 2.3 (9 wt% Ag) due to an increase in ethylene permeability. Testing of the obtained membranes in a gas-liquid contactor showed that the introduction of silver into the POMS matrix makes it possible to intensify the process of ethylene mass transfer by more than 1.5 times. Full article

This study focuses on the development of porous ceramer and SiOC composites which are suitable for microfiltration applications, using a mixture of polysiloxanes as the preceramic precursor. The properties of the membranes—such as their pore size, hydrophilicity, specific surface area, and mechanical resistance—were tailored in a one-step process, according to the choice of pyrolysis temperatures (600–1000 °C) and the incorporation of micro- (SiC) and nanofillers (TiO₂). Lower pyrolysis temperatures (<700 °C) allowed the incorporation of TiO₂ in its photocatalytically active anatase phase, enabling the study of its photocatalytic decomposition. The produced materials showed low photocatalytic activity; however, a high adsorption capacity for methylene blue was observed, which could be suitable for dye-removal applications. The membrane performance was evaluated in terms of its maximum flexural strength, water permeation, and separation of an oil-in-water emulsion. The mechanical resistance increased with an increase of the pyrolysis temperature, as the preceramic precursor underwent the ceramization process. Water fluxes varying from 2.5 to 370 L/m²·h (2 bar) were obtained according to the membrane pore sizes and surface characteristics. Oil-rejection ratios of 81–98% were obtained at an initial oil concentration of 1000 mg/L, indicating a potential application of the produced PDC membranes in the treatment of oily wastewater. Full article

Traditional fertilizers and their intensive use cause different environmental problems and new strategies are necessary to deal with these aspects. In this sense, foliar nanofertilization is a new technology postulated as one of the most promising for use in the near future. This type of fertilization has many environmental advantages but there are different factors that require a solution, as it needs to be compatible with other additives. Membrane vesicles derived from plant material have been shown in preliminary studies to have great potential as nanocarriers of different micronutrients such as iron (Fe) or boron (B). A complete optimization of the fertilizer system based on nanocarriers encapsulating different elements from different approaches is key to obtaining a system that is suitable and profitable from an economic point of view. In this work, different physicochemical parameters such as size, potential Z or osmotic water permeability were measured in membrane vesicles obtained from Brassica oleracea L. to check the integrity of vesicles for further biotechnological application. Furthermore, different additives (polyether-modified-polysiloxane [PMP], Tween-20 and polyethylene glycol [PEG]) were added to vesicles at different concentrations of application to determine the effect on the integrity and functionality of the membranes. The results show that the functionality of the membrane vesicles was only reduced with polyether-modified-polysiloxane [PMP], but not altered by the rest of the additives. These analyses serve to support subsequent research to advance the implementation of this nanotechnology. Full article

The aim of the work was to purify model textile wastewater (MTW) using a two-stage membrane filtration process comprising nanofiltration (NF) and reverse osmosis (RO). For this purpose, a nanofiltration membrane TFC-SR3 (KOCH) and reverse osmosis membrane AG (GE Osmonics) were used. Each model wastewater contained a selected surfactant. The greatest decrease in flux in the initial phase of the process occurred for the detergents based on fatty-acid condensation products. An evident decrease in performance was observed with polysiloxane-based surfactants. No fouling effect and high flux values were observed for the wastewater containing a nonionic surfactant based on fatty alcohol ethoxylates. During RO, a significantly higher flux and lower resistance were observed for the feed that originally contained the anionic agent. For the MTW containing the nonionic surfactant, the conductivity reduction ranged from 84% to 92% depending on the concentrate ratio at the consecutive stages of RO. After treatment, the purified wastewater was reused in the process of dyeing cellulose fibers with reactive dyes. The research confirmed that textiles dyed with the use of RO filtrates did not differ in quality of dyeing from those dyed in pure deionized water. Full article

Within this study, new materials were synthesized and characterized based on polysiloxane modified with different ratios of N-acetyl-l-cysteine (NAC) and crosslinked via UV-assisted thiol-ene addition, in order to obtain efficient membranes able to resist bacterial adherence and biofilm formation. These membranes were subjected to in vitro testing for microbial adherence against S. pneumoniae using standardized tests. WISTAR rats were implanted for 4 weeks with crosslinked siloxane samples without and with NAC. A set of physical characterization methods was employed to assess the chemical structure and morphological aspects of the new synthetized materials before and after contact with the microbiological medium. Full article