Search Results (20)

Pressure-sensitive paint (PSP) is an important wind tunnel testing technology. Compared with conventional PSP, the performance and test accuracy of cryogenic PSP are still immature. Therefore, investigating how to improve the pressure sensitivity of cryogenic PSP and reduce the interference of temperature effect is of great significance. By studying the PSP luminescence characteristics at different time points, temperatures, and pressures, some interesting phenomena have been discovered. When the temperature reaches 323 K, PSP can accelerate aging, leading to significant and irreversible changes in coating performance. Additionally, the effect of temperature on the luminescence characteristics of PSP shows significant differences over time. This unusual phenomenon may be related to the microstructure change in PTMSP (PtTFPP) coatings over time. In the beginning, PTMSP coating has high activity and spacing between PtTFPP luminescence centers, which change significantly with the microstructure as the temperature decreases. This might result in a stronger concentration quenching of PtTFPP, which counteracts the expected enhancement of luminescence efficiency typically caused by the temperature decrease. After 72 h, the microstructure of the coating tends to be stable, and the effect of temperature on the fluorescence characteristics of PSP becomes a thermal quenching law similar to that of traditional PSP. This discovery can provide a more precise basis for correcting the temperature effect for cryogenic PSP coatings with varying service lives. Full article

The effect of the stereoregularity of poly(1-trimethylsilyl-1-propyne) [PTMSP] (cis-content from 50 to 90%) on physical aging was investigated by measurement of the gas permeability. Films from pure PTMSP as well as those with the addition of the antioxidant Irganox 1076 were exposed to the air. The permeability of pure PTMSP films increases with an increase in cis-stereoregularity and correlates with an increase in interchain distances (according to X-ray analysis). For pure PTMSP films, the most significant aging (up to 50% of permeability drop) was observed for polymers with mixed microstructure, and the slowest aging (10–30% of permeability drop) was observed for polymers with cis-regular structure. For PTMSP films with added Irganox 1076, some decrease in permeability with time is also observed. The addition of Irganox 1076 to PTMSP in mixed as well as cis-enriched configurations visibly slows down aging. In the case of cis-regular PTMSP with a slow aging rate, the introduction of an antioxidant does not provide any advantages. The high stability of cis-regular PTMSP demonstrates the possibility of obtaining more stable membrane materials with the highest equilibrium state of the polymer selective layer prepared by casting solution. Full article

The thermally activated relaxation of poly(1-trimethylsilyl-1-propyne) (PTMSP) samples of various cis-/trans-compositions (50–80% units of cis-configuration) in the presence of phenolic antioxidants of various structures was investigated. It was pointed out that polymers with a high content of cis-units exhibited greater thermal-oxidative stability due to the greater flexibility of the cis-enriched macrochains. The use of hindered phenols as antioxidants made it possible to prevent the process of thermally initiated oxidative degradation. At the same time, the most effective stabilizing agents were antioxidants with larger molecules such as Vulkanox BKF, Irganox 1010, and Irganox 1076. It was shown that the permeability coefficients of stabilized PTMSP during thermal treatment initially slightly decreased (by 20–30%), which, according to the X-ray diffraction data, was associated with an increase in the density of the macrochain packing, and during further heating remained practically unchanged. Note that for the cis-enriched samples, no signs of oxidation or decrease in the transport characteristics were observed during polymer heating for 240 h at 140 °C. Full article

This work was focused on the mitigation of physical aging in thin-film composite (TFC) membranes (selective layer ~1 μm) based on polymer intrinsic microporosity (PTMSP) by the introduction of both soft, branched polyethyleneimine (PEI), and rigid, porous aromatic framework PAF-11, polymer additives. Self-standing mixed-matrix membranes of thicknesses in the range of 20–30 μm were also prepared with the same polymer and fillers. Based on 450 days of monitoring, it was observed that the neat PTMSP composite membrane underwent a severe decline of its gas transport properties, and the resultant CO₂ permeance was 14% (5.2 m³ (STP)/(m²·h·bar)) from the initial value measured for the freshly cast sample (75 m³ (STP)/(m²·h·bar)). The introduction of branched polyethyleneimine followed by its cross-linking allowed to us to improve the TFC performance maintaining CO₂ permeance at the level of 30% comparing with day zero. However, the best results were achieved by the combination of porous, rigid and soft, branched polymeric additives that enabled us to preserve the transport characteristics of TFC membrane as 43% (47 m³ (STP)/(m²·h·bar) after 450 days) from its initial values (110 m³ (STP)/(m²·h·bar)). Experimental data were fitted using the Kohlrausch–Williams–Watts function, and the limiting (equilibrium) values of the CO₂ and N₂ permeances of the TFC membranes were estimated. The limit value of CO₂ permeance for neat PTMSP TFC membrane was found to be 5.2 m³ (STP)/(m²·h·bar), while the value of 34 m³(STP)/(m²·h·bar) or 12,600 GPU was achieved for TFC membrane containing 4 wt% cross-linked PEI, and 30 wt% PAF-11. Based on the N₂ adsorption isotherms data, it was calculated that the reduction of the free volume was 1.5–3 times higher in neat PTMSP compared to the modified one. Bearing in mind the pronounced mitigation of physical aging by the introduction of both types of fillers, the developed high-performance membranes have great potential as support for the coating of an ultrathin, selective layer for gas separation. Full article

In this work, perspective polymeric materials were developed for membrane contactor applications, e.g., for the dissolved oxygen removal from amine CO₂ capture solvents. Several polymeric blends based on poly[1-trimethylsilyl-1-propyne] (PTMSP) and poly[vinyltrimethylsilane] (PVTMS) were studied. The gas and water vapor sorption and permeability coefficients for the PTMSP/PVTMS blend membranes at different PVTMS contents (0–100%) were obtained under temperatures of 30 and 60 °C for the first time. As the PVTMS content increases, the O₂ and CO₂ permeabilities decrease by 160 and 195 times at 30 °C, respectively. The fractional accessible volume of the polymer blends decreases accordingly. The transport of the CO₂ capture solvent vapors through the PTMSP/PVTMS blend membranes were determined in thermo-pervaporation (TPV) mode using aqueous monoethanolamine (30%), N-methyldiethanolamine (40%), and 2-amino-2-methyl-1-propanol (30%) solutions as model amine solvents at 60 °C. The membranes demonstrated high pervaporation separation factors with respect to water, resulting in low amine losses. A joint analysis of the gas permeabilities and aqueous alkanolamine TPV data allowed us to conclude that the polymer blend composition of PTMSP/PVTMS 70/30 provides an optimal combination of a sufficiently high oxygen permeability and the pervaporation separation factor at a temperature of 60 °C. Full article

For the first time, membranes based on poly(1-trimethylsilyl-1-propyne) (PTMSP) with 5–50 wt% loading of hyper-crosslinked polystyrene sorbent particles (HCPS) were obtained; the membranes were investigated for the problem of effective removal of volatile organic compounds from aqueous solutions using vacuum pervaporation. The industrial HCPS sorbent Purolite Macronet™ MN200 was chosen due to its high sorption capacity for organic solvents. It has been found that the membranes are asymmetric when HCPS content is higher than 30 wt%; scanning electron microscopy of the cross-sections the membranes demonstrate that they have a clearly defined thin layer, consisting mainly of PTMSP, and a thick porous layer, consisting mainly of HCPS. The transport and separation characteristics of PTMSP membranes with different HCPS loading were studied during the pervaporation separation of binary and multicomponent mixtures of water with benzene, toluene and xylene. It was shown that the addition of HCPS up to 30 wt% not only increases the permeate fluxes by 4–7 times, but at the same time leads to 1.5–2 fold increase in the separation factor. It was possible to obtain separation factors exceeding 1000 for all studied mixtures at high permeate fluxes (0.5–1 kg/m²∙h) in pervaporation separation of binary solutions. Full article

The effect of phenolic antioxidant Irganox 1076 on the structure and gas permeation behavior of poly(1-trimethylsilyl-1-propyne) (PTMSP) was investigated. Isotropic films as well as thin film composite membranes (TFCM) from pure PTMSP and with added antioxidant (0.02 wt%) were prepared. PTMSP with antioxidant has a significantly higher thermal degradation stability in comparison to pure polymer. The thermal annealing of isotropic films of PTMSP with antioxidant was carried out at 140 °C. It revealed the stability of gas permeation properties for a minimum of up to 500 h of total heating time after a modest permeation values decrease in the first 48 h. X-ray diffraction data indicate a decrease in interchain distances during the heat treatment of isotropic films and indicate an increase in the packing density of macromolecules during thermally activated relaxation. Isotropic films and TFCMs from pure PTMSP and with antioxidant stabilizer were tested under conditions of constant O₂ and N₂ flow. The physical aging of thick and composite PTMSP membranes point out the necessity of thermal annealing for obtaining PTMSP-based membranes with predictable properties. Full article

A novel bilayer cation-exchange membrane—consisting of a thick layer of a pristine perfluorinated membrane MF-4SC (Russian equivalent of Nafion^®-117) and a thinner layer (1 μm) of the membrane, on a base of glassy polymer of internal microporosity poly(1-trimethylsilyl-1-propyne) (PTMSP)—was prepared and characterized. Using the physicochemical characteristics of one-layer membranes MF-4SC and PTMSP in 0.05 M HCl and NaCl solutions, the asymmetric current–voltage curves (CVC) of the bilayer composite were described with good accuracy up to the overlimiting regime, based on the “fine-porous membrane” model. The MF-4SC/PTMSP bilayer composite has a significant asymmetry of CVC that is promising for using it in electromembrane devices, such as membrane detectors, sensors, and diodes. Full article

Pressure-Sensitive Paint (PSP) is a powerful measurement technique to obtain pressure distribution on a model of interest by measuring the emission intensity of the PSP coating with a camera. Since a PSP coating is prepared by applying a solution containing an organic solvent, generally, by sprayer, the properties such as the pressure- and the temperature-sensitivity depends on the skill of the person applying it. This fabrication process is one of the barriers to use of the PSP technique because of the legal restrictions on the use of organic solvents. Thus, a sticker-like PSP coating is useful because it does not require the use of organic solvent and the applying skill. In this study, we have fabricated freestanding Pressure-Sensitive Nano-Sheet (PSNS) by a sacrificial layer process using a spin-coating method. We employed Pt(II) meso-tetra(pentafluorophenyl)porphine (PtTFPP) as a pressure-sensitive dye and poly(1-trimethylsilyl-propyne) (PTMSP) and poly(L-lactic acid) (PLLA) as a polymer binder; thus, the PSNS samples based on PTMSP and PLLA were prepared. The pressure- and the temperature-sensitivity, the lifetime of the luminescence, and the quantum yield of the fabricated PSNS have been investigated. The pressure-sensitivity of PTMSP-based PSNS is higher than that of PLLA-based PSNS. Conversely, the quantum yield of PLLA-based PSNS is higher than that of PTMSP-based PSNS. Full article

Fluorine-containing polymers occupy a peculiar niche among conventional polymers due to the unique combination of physicochemical properties. Direct surface fluorination of the polymeric materials is one of the approaches for the introduction of fluorine into the chemical structure that allows one to implement advantages of fluorinated polymers in a thin layer. Current review considers the influence of the surface interaction of the polymeric materials and membranes with elemental fluorine on gas, vapor and liquid transport as well as swelling and related phenomena. The increase in direct fluorination duration and concentration of fluorine in the fluorination mixture is shown to result mostly in a reduction of all penetrants permeability to a different extent, whereas selectivity of the selected gas pairs (He-H₂, H₂-CH₄, He-CH₄, CO₂-CH₄, O₂-N₂, etc.) increases. Separation parameters for the treated polymeric films approach Robeson’s upper bounds or overcome them. The most promising results were obtained for highly permeable polymer, polytrimethylsilylpropyne (PTMSP). The surface fluorination of rubbers in printing equipment leads to an improved chemical resistance of the materials towards organic solvents, moisturizing solutions and reduce diffusion of plasticizers, photosensitizers and other components of the polymeric blends. The direct fluorination technique can be also considered one of the approaches of fabrication of fuel cell membranes from non-fluorinated polymeric precursors that improves their methanol permeability, proton conductivity and oxidative stability. Full article

The influence of casting centrifugation process parameters, such as a rotation speed (ω), the amount of the film-forming solution (V), and its concentration (C) on transport properties of composite membranes were investigated. A number of composite membranes based on poly (1-trimethylsilylpropyne) (PTMSP) and micro- (MFFK-1) and ultrafiltration (UFFK) membranes were obtained using the spin-coating method. For the first time, an unexpected dependence of permeance and ideal selectivity on rotation speed had been discovered: the thickness of the selective layer decreases from 3.0 to 1.0 μm for MFFK-1 and from 1.7 to 1.1 μm for UFFK with an increase of spin coater rotation speed from 500 to 3000 rpm. However, the gas permeance of composite membranes in the range of 500–2000 rpm was reduced due to an increase of a penetration depth of PTMSP into a support layer porous structure (estimated by the EDX method). The permeance of the PTMSP/UFFK membranes was higher than PTMSP/MFFK-1 membranes due to a thinner selective layer and a lower penetration depth of polymer solution into the pores of the support. The highest CO₂/N₂ selectivity values were achieved as 5.65 ± 0.9 at CO₂ permeance 5600 ± 1000 GPU for PTMSP/UFFK membranes (C_PTMSP = 0.35%, V_solution = 1 mL, ω = 1000 rpm), and 6.1 ± 0.5 at CO₂ permeance 4090 ± 500 GPU for PTMSP/MFFK-1 membranes (C_PTMSP = 0.35%, V_solution = 1 mL, ω = 2000 rpm). Full article

The influence of hyper-crosslinked polystyrene (HCPS) Macronet^TM MN200 on the gas transport properties and aging of the highly permeable glassy polymer poly(1-trimethylsilyl-1-propyne) (PTMSP) was studied and analyzed in detail. The gas transport characteristics of dense PTMSP membranes containing 0–10.0 wt % HCPS were studied. It was shown that the introduction of a small amount of HCPS into the PTMSP matrix led to a 50–60% increase of the permeability coefficients of the material for light gases (N₂, O₂, CO₂) and slowed down the deterioration of polymer transport properties over time. The lowest reduction in gas permeability coefficients (50–57%) was found for PTMSP containing HCPS 5.0 wt % after annealing at 100 °C for 300 h. It was found that HCPS sorbed residues of tantalum-based polymerization catalyst from PTMSP. In order to investigate the influence of catalysts on transport and physical properties of PTMSP, we purified the latter from the polymerization catalyst by addition of 5 wt % HCPS into polymer/chloroform solution. It was shown that sorption on HCPS allowed for almost complete removal of tantalum compounds from PTMSP. The membrane made of PTMSP purified by HCPS demonstrated more stable transport characteristics compared to the membrane made of the initial polymer. HCPS has a complex effect on the aging process of PTMSP. The introduction of HCPS into the polymer matrix not only slowed down the physical aging of PTMSP, but also reduced chemical aging due to removal of active reagents. Full article

The mitigation of the physical aging of thin-film composite (TFC) poly[1-trimethylsilyl-1-propyne] (PTMSP) membranes was studied via the simultaneous application of a polymer-selective layer crosslinking and mixed-matrix membrane approach. For the first time, a recently developed highly porous activated carbon material (infrared (IR) pyrolyzed poly[acrylonitrile] (PAN) or IR-PAN-a) was investigated as an additive to a PTMSP-selective layer for the reduction of aging in TFC membranes. The total electric energy spent on the IR irradiation treatment of IR-PAN-a particles was twice lower than conventional heating. The flat-sheet porous microfiltration membrane MFFK-1 was used as a support, and the crosslinked PTMSP/PEI loaded with a porous filler was applied as a selective layer (0.8–1.8 µm thick) to the TFC membranes. The initial IR-PAN-a sample was additionally milled to obtain a milled IR-PAN-aM sample with a monomodal particle size distribution of 500–800 nm. It was shown that IR-PAN-a, as a filler material with a high surface area and pore volume (2450 m²/g and 1.06 cm³/g, respectively) and a well-developed sponge-like structure, leads to the increase of the N₂, O₂, and CO₂ permeance of PTMSP-based hybrid membrane material and the decrease of the aging of PTMSP. The simultaneous effect of crosslinking and the addition of a highly porous filler essentially improved the aging behavior of PTMSP-based TFC membranes. The monomodal and narrow particle size distribution of highly porous activated IR-pyrolyzed PAN is a key factor for the production of TFC membranes with reduced aging. The highest stability was achieved by the addition of a milled IR-PAN-aM sample (10 wt%). TFC membrane permeance was 6300 GPU (30% of initial permeance) after 11,000 h of aging at ambient laboratory conditions. Full article

In this work, a poly(1-trimethylsilyl-1-propyne) (PTMSP) mixed-matrix membrane was fabricated for the selective removal of 1-butanol from aqueous solutions through pervaporation. Silica nanoparticles (SNPs), which were surface-modified with surfactant hexadecyltrimethylammonium bromide (CTAB), were incorporated into the structure of the membrane. The modified membrane was characterized by thermogravimetry-differential scanning calorimetry (TG-DSC), contact angle measurements, and scanning electron microscope (SEM) analysis. It was found that the surface hydrophobicity of the membrane was improved when compared to neat PTMSP by contact angle measurement. It was confirmed by SEM analysis that a uniform distribution of surface-modified SNPs throughout the PTMSP membrane was achieved. The thermogravimetric analysis detected the thermal degradation of the modified PTMSP at 370 °C, which is comparable to neat PTMSP. The pervaporation measurements showed a maximum separation factor of 126 at 63 °C for 1.5 w/w% 1-butanol in the feed. The maximum total flux of approximately 1.74 mg·cm⁻²·min⁻¹ was observed with the highest inspected temperature of 63 °C and at the 1-butanol concentration in the feed 4.5 w/w%. The pervaporation transients showed that the addition of the surface-modified SNPs significantly enhanced the diffusivity of 1-butanol in the composite compared to the neat PTMSP membrane. This improvement was attributed to the influence of the well-dispersed SNPs in the PTMSP matrix, which introduced an additional path for diffusivity. Full article

In this work, the performance of new robust mixed matrix composite hollow fiber (MMCHF) membranes with a different selective layer composition is evaluated in the absence and presence of water vapor in CO₂/N₂ and CO₂/CH₄ separation. The selective layer of these membranes is made of highly permeable hydrophobic poly(trimethyl-1-silylpropine) (PTMSP) and hydrophilic chitosan-ionic liquid (IL-CS) hybrid matrices, respectively, filled with hydrophilic zeolite 4A particles in the first case and HKUST-1 nanoparticles in the second, coated over compatible supports. The effect of water vapor in the feed or using a commercial hydrophobic PDMSXA-10 HF membrane has also been studied for comparison. Mixed gas separation experiments were performed at values of 0 and 50% relative humidity (RH) in the feed and varying CO₂ concentration in N₂ and CH₄, respectively. The performance has been validated by a simple mathematical model considering the effect of temperature and relative humidity on membrane permeability. Full article