17 research outputs found
Influences of Recycled Polyethylene Terephthalate Microplastic on the Hygrothermal and Mechanical Performance of Plasterboard with Polymethylhydrosiloxane Content
New composites produced with recycled waste are needed to manufacture more sustainable construction materials. This paper aimed to analyze the hygrothermal and mechanical performance of plasterboard with a polymethylhydrosiloxane (PMHS) content, incorporating recycled PET microplastic waste and varying factors such as PMHS dose, homogenization time, and drying temperature after setting. A cube-centered experimental design matrix was performed. The crystal morphology, porosity, fluidity, water absorption, flexural strength, and thermal conductivity of plasterboards were measured. The results showed that incorporating recycled PET microplastics does not produce a significant difference in the absorption and flexural strength of plasterboards. However, the addition of recycled PET reduced the thermal conductivity of plasterboards by around 10%
Novel Polyelectrolytes Obtained by Direct Alkylation and Ion Replacement of a New Aromatic Polyamide Copolymer Bearing Pyridinyl Pendant Groups
The following work shows, for the first time, the synthesis and characterization of a new family of polyelectrolytes, along with their preliminary assessments in terms of desalin water treatment. These materials fall into the category of aromatic co-polyamides, which are obtained by the direct condensation of monomers 4,4′-oxydianiline (ODA), isophthaloyl chloride, and 3,5-diamino-N-(pyridin-4-ylmethyl)benzamide (PyMDA). Thereby, the charged nature exhibited by these materials was achieved through the quaternization of PyMDA moieties using linear iodoalkanes of different lengths (CnI with n = 1, 2, 4, and 6). After completing the quaternization process, polyelectrolytes were subjected to a one-step anion substitution process, where iodide counterions were replaced by bis(trifluoromethane)sulfonamide entities. For all the obtained materials, solubility tests were carried out, showing that those alkylated with methyl and ethyl chains exhibit high solubility in rutinary aprotic polar solvents, while those containing n-butyl and n-hexyl units resulted in the formation of insoluble gels. Due to the above, the latest were discarded from this study early on. The structural characterization of the initial neutral co-polyamide was carried out by means of infrared spectroscopy (FT-IR), nuclear magnetic resonance (1H, 13C-NMR), and size-exclusion chromatography (SEC), while the structure of methylated and ethylated polyelectrolytes was successfully confirmed through FT-IR, 1H, 13C, and 19F-NMR. Additionally, the thermal behavior of these materials was analyzed in terms of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), showing thermal degradation temperatures above 300 °C and glass transition temperatures (Tg) above 200 °C, resulting in polymers with outstanding thermal properties for water treatment applications. On the other hand, through the solvent-casting method, both neutral and charged polymers were found to be easily prepared into films, exhibiting a remarkably flexibility. The mechanical properties of the films were analyzed using the traction test, from which tensile strength values ranging between 83.5 and 87.9 Mpa, along with Young’s modulus values between 2.4 and 2.5 Gpa were obtained. Moreover, through contact angle measurements and absorption analysis by immersion, polyelectrolytes showed important changes in terms of affinity against polar and polar substances (water, n-heptane, and benzene), exhibiting a higher rejection regarding the neutral polymer. Finally, as a preliminary test against the seepage of saline waters, thin polymer films (from 11.4 to 17.1 µm) were deposited on top of commercial filter discs and tested as filters of saline solutions ([NaCl] = 1000 and 2000 ppm). These tests revealed a decrease of the salt concentration in the obtained filtrates, with retention values ranging between 6.2 and 20.3%, depending on the concentration of the former solution and the polymer used
Preparation of CuONPs@PVDF/Non-Woven Polyester Composite Membrane: Structural Influence of Nanoparticle Addition
Membrane distillation techniques have appeared as promising options for guaranteeing the availability of potable water in times of scarcity of this essential resource. For membrane preparation, polyvinylidene fluoride (PVDF) is preferred due to the easier synthesis procedures, with respect to other fluorine-based polymers. In this work, copper oxide nanoparticles (CuONPs) of different weight percent (wt %) embedded in PVDF membranes supported on non-woven polyester fabric (NWPET) were prepared by the phase inversion method, and characterized by spectroscopy (ATR-FTIR, Raman) and electron microscopy techniques (SEM). The PVDF deposited onto the NWPET was mostly composed of its polar β-phase (F(β) = 53%), which was determined from the ATR-FTIR spectrum. The F(β) value remained constant throughout the whole range of added CuONP concentrations (2–10 wt %), as was determined from the ATR-FTIR spectrum. The absence of signals corresponding to CuONPs in the ATR-FTIR spectra and the appearance of peaks at 297, 360, and 630 cm−1 in the Raman spectra of the membranes suggest that the CuONPs are preferably located in the inner PVDF membrane, but not on its surface. The membrane morphologies were characterized by SEM. From the obtained SEM micrographs, a decrease and increase in the amount of micropores and nanopores, respectively, near the surface and intercalated in the finger-like layer were observed. As a result of the CuONP addition, the nanopores in the sponge-like layer decreased in size. The values of water contact angle (WCA) measurements showed a decreasing trend, from 94° to 80°, upon the addition of CuONPs (2–10 wt %), indicating a diminishment in the hydrophobicity degree of the membranes. Apparently, the increase in the amount of nanopores near the surface decreased the membrane roughness, so it became less hydrophobic
PVDF Composite Membranes with Hydrophobically-Capped CuONPs for Direct-Contact Membrane Distillation
Water scarcity is an imminent problem that humanity is beginning to attempt to solve. Among the several technologies that have been developed to mitigate water scarcity, membrane distillation is of particular note. In the present work, CuO nanoparticles capped with 1-octanethiol (CuONPs@CH) or 1H,1H,2H,2H-perfluorodecanethiol (CuONPs@CF) are prepared. The nanoparticles are characterized by FT-IR and TGA methods. Two weight losses are observed in both cases, with the decomposition of the organic fragments beginning at 158 °C and 230 °C for CuONPs@CF and CuONPs@CH, respectively. Flat sheet PVDF composite membranes containing nanoparticles are prepared by the casting solution method using nanoparticle concentrations that ranged between 2–20% with a non-woven polyester fabric as support. The obtained membranes showed a thickness of 240 ± 40 μm. According to water contact angle (87° for CuONPs@CH and 95° for CuONPs@CF, both at 10% w.t) and roughness (12 pixel for CuONPs@CH and 14 pixels for CuONPs@CF, both at 10% w.t) determinations, the hydrophobicity of membranes changed due to a decrease in surface energy, while, for naked CuONPs, the roughness factor represents the main role. Membranes prepared with capped nanoparticles showed similar porosity (60–64%). SEM micrographs show asymmetric porous membranes with a 200-nm surface pore diameter. The largest finger-like pores in the membranes prepared with CuONPs, CuONPs@CH and CuONPs@CF had values of 63 ± 10 μm, 32 ± 8 μm, and 45 ± 10 μm, respectively. These membranes were submitted to a direct contact membrane distillation module and flux values of 1.8, 2.7, and 3.9 kg(m2·h)−1 at ΔT = 30 °C were obtained for the CuONPs, CuONPs@CH, and CuONPs@CF, respectively. The membranes showed 100% salt rejection during the testing time (240 min)
PANI Branches onto Donor-Acceptor Copolymers: Synthesis, Characterization and Electroluminescent Properties of New 2D-Materials
A new series of two-dimensional statistical conjugated polymers based on aniline and 9,9-dihexylfluorene as donor units and benzo- or naphtho-quinoxaline/thiadiazole derivatives as acceptor moieties, possessing PANI segments as side chains, were designed and synthesized. To investigate the effects of the perpendicular PANI branches on the properties of the main chain, the optical, electrochemical, morphological and electroluminescence properties were studied. The 2D materials tend to possess lower molecular weights and to absorb and to emit light red-shifted compared to the trunk 1D-polymers, in the yellow-red region of the visible spectrum. The 1D- and 2D-conjugated polymers present optical band gaps ranging from 2.15–2.55 eV, HOMO energy levels between −5.37 and −5.60 eV and LUMO energy levels between −3.02 and −3.29 eV. OLED devices based on these copolymers were fabricated. Although the performances were far from optimal due to the high turn-on voltages for which electroluminescence phenomena occur, a maximum luminescence of 55,100 cd/m2 together with a current density of 65 mA/cm2 at 18.5 V were recorded for a 2D-copolymer, PAFC6TBQ-PANI
Novel aromatic polyimides derived from 2,8-di(3-aminophenyl)dibenzofuran. Synthesis, characterization and evaluation of properties
Publisher Copyright: © The Royal Society of Chemistry 2015.Three aromatic polyimides (PIs) were prepared from a new aromatic diamine monomer derived from the rigid ring dibenzofuran. All PIs were obtained in high yield and the inherent viscosities were in the range of 0.60 and 0.74 dL g-1. Polyimides derived from 4,4′-hexafluoroisopropyliden diphthalic anhydride (6FDA) and 4,4′-(dimethylsilanediyl) diphthalic anhydride (SiDA) showed excellent solubility in a variety of aprotic polar organic solvents. All PIs showed high thermal stability with thermal decomposition temperature (TDT10%) between 555-590 °C and the glass transition temperatures (Tg) values were between 290 and 315 °C. Polymeric films were obtained from PI-6FDA and PI-SiDA solutions and then contact angle and surface free energy were tested in order to know the hydrophobicity of materials. Likewise, permeability and selectivity analyses were developed where PI-6FDA film offered a reasonably acceptable balance of permselectivity with values close to the Robeson upper-bound (1991), in particular for the CO2/CH4 gas pair.Peer reviewe
Spraying Fluorinated Silicon Oxide Nanoparticles on CuONPs@CF-PVDF Membrane: A Simple Method to Achieve Superhydrophobic Surfaces and High Flux in Direct Contact Membrane Distillation
Desalinization of seawater can be achieved by membrane distillation techniques (MD). In MD, the membranes should be resistant to fouling, robust for extended operating time, and preferably provide a superhydrophobic surface. In this work, we report the preparation and characterization of a robust and superhydrophobic polyvinylidene fluoride membrane containing fluoroalkyl-capped CuONPs (CuONPs@CF) in the inner and fluorinated capped silicon oxide nanoparticles (SiO2NPs@CF) on its surface. SiO2NPs@CF with a mean diameter of 225 ± 20 nm were prepared by the sol method using 1H,1H,2H,2H-perfluorodecyltriethoxysilane as a capping agent. Surface modification of the membrane was carried out by spraying SiO2NPs@CF (5% wt.) dispersed in a mixture of dimethyl formamide (DMF) and ethanol (EtOH) at different DMF/EtOH % v/v ratios (0, 5, 10, 20, and 50). While ethanol dispersed the nanoparticles in the spraying solution, DMF dissolved the PVDF on the surface and retained the sprayed nanoparticles. According to SEM micrographs and water contact angle measurements, the best results were achieved by depositing the nanoparticles at 10% v/v of DMF/EtOH. Under these conditions, a SiO2NPs covered surface was observed with a water contact angle of 168.5°. The water contact angle was retained after the sonication of the membrane, indicating that the modification was successfully achieved. The membrane with SiO2NPs@CF showed a flux of 14.3 kg(m2·h)−1, 3.4 times higher than the unmodified version. The method presented herein avoids the complicated modification procedure offered by chemical step modification and, due to its simplicity, could be scalable to a commercial membrane
Polymers of intrinsic microporosity containing aryl-phthalimide moieties: synthesis, modeling, and membrane gas transport properties
Producción CientíficaHigh-performance polymers for membrane gas separation require the careful design of the structure-porous relationship. In this work, five phthalimide-based polymers of intrinsic microporosity (PIMs) were obtained via the double nucleophilic aromatic substitution with the commercially available 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethylspirobisindane (TTSBI) monomer. The phthalimide monomers were synthesized considering different sizes and positions of the alkyl-substituents to evaluate their influence on the physical properties of the polymers and their potential use as gas separation membranes. Four polymers were soluble in the low-boiling solvents chloroform and tetrahydrofuran, facilitating the casting of self-standing films to evaluate their gas separation properties. The thermally stable membranes showed 5% weight lost between 537 °C and 549 °C. As powders, these four polymers showed apparent BET surface areas ranging from 434 to 661 m2 g−1. The experimental BET surface areas correlated with those obtained by molecular simulation models of the synthesized polymers. A linear function is proposed as a tool to predict, with a known uncertainty, the surface area values of this type of polymer from the corresponding computational models. As a trend, increasing the volume of the ortho-substituent in the aryl-phthalimide group increases the permeability of the membranes, reaching generally better performances than Matrimid® and close to those of PIM-1, considering their place on the Robeson diagrams of the O2/N2, CO2/CH4 and CO2/N2 gas pairs. Aging studies between 63 and 122 days showed a decrease in permeability, accompanied by the typical increase in selectivity that tends to move the data parallel to the upper Robeson limits.Agencia Nacional de Investigación y Desarrollo (ANID) by Fondecyt project number 1190772.
Universidad de Valladolid, proyecto PROYEMER-2021-05.
MCIN/AEI/10.13039/501100011033 and “European Union NextGenerationEU/PRTR”, Grant TED2021-131170A-I00.
PID2019-109403RB-C21/AEI/10.13039/50110001103
Synthesis and Characterization of a 2,3-Dialkoxynaphthalene-Based Conjugated Copolymer via Direct Arylation Polymerization (DAP) for Organic Electronics
Poly[(5,5’-(2,3-bis(2-ethylhexyloxy)naphthalene-1,4-diyl)bis(thiophene-2,2′-diyl))-alt-(2,1,3-benzothiadiazole-4,7-diyl)] (PEHONDTBT) was synthesized for the first time and through direct arylation polymerization (DAP) for use as p-donor material in organic solar cells. Optimized reaction protocol leads to a donor-acceptor conjugated polymer in good yield, with less structural defects than its analog obtained from Suzuki polycondensation, and with similar or even higher molecular weight than other previously reported polymers based on the 2,3-dialkoxynaphthalene monomer. The batch-to-batch repeatability of the optimized DAP conditions for the synthesis of PEHONDTBT was proved, showing the robustness of the synthetic strategy. The structure of PEHONDTBT was corroborated by NMR, exhibiting good solubility in common organic solvents, good film-forming ability, and thermal stability. PEHONDTBT film presented an absorption band centered at 498 nm, a band gap of 2.15 eV, and HOMO and LUMO energy levels of −5.31 eV and −3.17 eV, respectively. Theoretical calculations were performed to understand the regioselectivity in the synthesis of PEHONDTBT and to rationalize its optoelectronic properties. Bilayer heterojunction organic photovoltaic devices with PEHONDTBT as the donor layer were fabricated to test their photovoltaic performance, affording low power-conversion efficiency in the preliminary studies