Tetrahydrofuran Research Articles

Synthesis of ultra-stretchable thermoelectric nanofibrous membrane based on wet-electrospun Polyurethane/MWCNTs composites

Electrospinning is a versatile method used to create nanofiber membranes with surface-to-volume ratios much higher than those achievable with other film fabrication methods. This technique allows the control of nanofiber morphology, including diameter, shape, and orientation. Such nanostructuring can enhance the thermoelectric performance of composite materials due to quantum confinement and filtering effects. However, the thermoelectric efficiency of a typical electrospun composite is limited due to the insulating nature of the polymer matrix. Therefore, many researchers have combined electrospinning with other techniques or post-treatments to accomplish higher thermoelectric performance. In this study, a new strategy to prepare a stretchable thermoelectric nanofibrous membrane is proposed. The ternary composite of Thermoplastic Polyurethane (TPU)/Multi Wall Carbon Nanotubes (MWCNTs)/Poly(3,4-ethylenedioxythiophene)polystyrene sulfonate (PEDOT: PSS) is obtained by electrospinning of TPU/MWCNTs solution in coagulation bath of PEDOT: PSS water dispersion. The nonsolvent-induced phase separation (NISP) phenomenon, and consequently, the formation of CNTs/PEDOT: PSS/CNTs electrically-conductive chains, were controlled by tuning the concentrations from binary solvents. The optimal value of the Power Factor, 4.28 μW m⁻1 K⁻2, was obtained for 0.12% MWCNTs and a 1:4 ratio of Tetrahydrofuran (THF) to N, N-Dimethylformamide (DMF) in the binary solvent. The sample exhibits a high value of electrical conductivity of 85 S m⁻1 and shows a strain range of 190 %. This study demonstrates the significant potential of the wet-spinning method for producing wearable and sustainable thermoelectric devices, offering an alternative to conventional devices that raise concerns regarding resource scarcity and environmental impact.

Fast Interfacial Defluorination Kinetics Enables Stable Cycling of Low-Temperature Lithium Metal Batteries.

The development of low-temperature lithium metal batteries (LMBs) encounters significant challenges because of severe dendritic lithium growth during the charging/discharging processes. To date, the precise origin of lithium dendrite formation still remains elusive due to the intricate interplay between the highly reactive lithium metal anode and organic electrolytes. Herein, we unveil the critical role of interfacial defluorination kinetics of localized high-concentration electrolytes (LHCEs) in regulating lithium dendrite formation, thereby determining the performance of low-temperature LMBs. We investigate the impact of solvation structures of LHCEs on low-temperature LMBs by employing tetrahydrofuran (THF) and 2-methyltetrahydrofuran (2-MeTHF) as comparative solvents. The combination of comprehensive characterizations and theoretical simulations reveals that the THF-based LHCE featured with a strong solvation strength exhibits fast interfacial defluorination reaction kinetics, thus leading to the formation of an amorphous and inorganic-rich solid-electrolyte interphase (SEI) that can effectively suppress the growth of lithium dendrites. As a result, the highly reversible Li metal anode achieves an exceptional Coulombic efficiency (CE) of up to ∼99.63% at a low temperature of -30 °C, thereby enabling stable cycling of low-temperature LMB full cells. These findings underscore the crucial role of electrolyte interfacial reaction kinetics in shaping SEI formation and provide valuable insights into the fundamental understanding of electrolyte chemistry in LMBs.

Can Aluminum Cations Promote Nucleation for THF Hydrate Growth?

Rapid nucleation of tetrahydrofuran (THF) hydrate is essential for developing a THF hydrate-based cold storage technology. Earlier works have hypothesized the role of aluminum complexes in initiating the nucleation of clathrate hydrates using aluminum metal electrodes and substrates. This study investigates if the nucleation promotional effect of hydrate can be achieved using the aluminum salt, AlCl3, due to the formation of aluminum aqua complexes in water. Metal chlorides NaCl and MgCl2 are also utilized to evaluate the effect of cation type in initiating nucleation, i.e., the effect of charge/radius ratio. The induction time is measured in a stirred reactor at various subcoolings and concentrations of 0.05, 0.1, 0.5, 1, and 2 wt %. The nucleation time is studied in two reactor configurations based on the nature of salt introduction in the THF solution, i.e., salt premixed in solution and salt injected inside the solution. The sudden rise in the reactor temperature due to hydrate formation is used as an indicator of hydrate formation. Results indicate that AlCl3 promotes hydrate nucleation as AlCl3 reduces induction time by 92.2% at 0.05 wt % concentration compared with water. Nearly instantaneous nucleation is also achieved by directly injecting AlCl3. MgCl2 and NaCl do not show a similar effect on induction time as AlCl3. The pH and Raman spectra measurements with and without salts are carried out to explain the effect of cations on the THF-water solution.

Solvent-doped PEDOT:PSS: Structural transformations towards enhanced electrical conductivity and transferable electromagnetic shields

The enhanced electrical conductivity of solvent-doped poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) is attributed to the screening effect between PSS and PEDOT chains. Yet, the precise manner in which this effect influences the crystalline structure and conformation of PEDOT:PSS remains unclear. In this study, we utilize Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and Grazing-incidence wide-angle X-ray scattering (GIWAXS) to examine the conformational changes and two-dimensional (2D) crystalline structure of PEDOT:PSS when doped with a variety of solvents, including dimethyl sulfoxide (DMSO), ethylene glycol (EG), dimethylformamide (DMF), methanol (MeOH), ethanol (EtOH), tetrahydrofuran (THF), and acetone. Our observations unveil that solvent doping improves the electrical conductivity of PEDOT:PSS by modifying its crystalline structure. This alteration leads to reduced inter-lamellar (d200) and π-π stacking (d010) distances, facilitating the formation of densely packed and well-ordered PEDOT crystallites in both face-on and edge-on orientations. Moreover, this doping process enhances the transferability and mechanical properties of drop-casted films, resulting in a flexible and transferable electromagnetic interference (EMI) shield with exceptional total shielding effectiveness (SET) of 35.70 dB and specific shielding effectiveness (SSE/t) of 7105.34 dB cm2.g−1.

Disentangling the Conformational Space and Structural Preferences of Tetrahydrofurfuryl Alcohol Using Rotational Spectroscopy and Computational Chemistry.

The influence of the hydroxymethyl (CH2OH) group on the tetrahydrofuran (THF) ring structure was investigated by disentangling the gas phase conformational landscape of the sugar analogue tetrahydrofurfuryl alcohol (THFA). By combining rotational spectroscopy (6-20 GHz) and quantum chemical calculations, transitions corresponding to two stable conformers of THFA and their 13C isotopologues were observed and assigned in the rotational spectrum. The positions of the C atoms were precisely determined to unambiguously distinguish between nearly isoenergetic pairs of conformers that differ in their ring configurations: envelope (E) versus twist (T). The rotational spectrum confirms that the E ring geometry is favoured when the CH2OH fragment lies gauche (-) to the THF backbone (OCCO ~-60°) whereas the T form is more stable for the gauche (+) alignment of the substituent (OCCO ~+60°). The observed spectral intensities suggest that conformational relaxation of the THF geometry (E↔T) to the more stable form readily occurs within the pairs of g- and g+ conformers which is consistent with the low barriers (1.5-1.7 kJ mol-1) for conversion determined via transition state calculations. Insights into the intramolecular hydrogen bonding and other weak interactions stabilizing the lowest energy structures of THFA were derived and rationalized using non-covalent interaction analyses.

Insights into the chemistry of Kubas’ chromium dihydrogen complexes

The structures of the complexes Cr(CO)3(PR3)2, (3) R = cyclohexyl and (4) isopropyl and their labile dihydrogen adducts Cr(η2-H2)(CO)3(PR3)2 (1) R = cyclohexyl and (2) isopropyl are calculated using density functional theory and compared to known structures of 3, Cr(η2-HC-CyPCy2)(CO)3(PCy3) (CSD code JOHNOJ) with an agostic CHCr interaction, and of 2, Cr(η2-H2)(CO)3(PiPr3)2 (CSD LEYCOH) with a very short HH distance. The TPSS functional with Grimme D3 dispersion, with a def2-TZVP basis set on all atoms and with the PCM solvent model for tetrahydrofuran (THF) reproduces fairly accurately the geometries, available vibrational spectra, and enthalpy of dihydrogen coordination in THF solution from literature experiments while other computational settings do not. This is a rare example of the calibration of theory with experiment for the Gibbs energy change in a solution phase reaction involving dihydrogen gas. The agostic form of the molecule is favoured in the crystal by intermolecular CHHC interactions as illustrated using Hirshfeld surface analysis and by the more compact size of this conformation.

Swelling Behaviors of Natural Rubber/Solvent Systems Based on the Extended Modified Double Lattice Model

AbstractSwelling experiments are conducted on nonfiller natural rubber using four solvents (toluene, cyclohexane, tetrahydrofuran (THF), and methylethylketone (MEK)) over temperatures from 10 to 70 °C. Toluene, cyclohexane, and THF, classified as effective solvents, show swelling ratios between 3 and 7, influenced by the crosslink density of the rubber. MEK, however, has a lower ratio of 1.5 to 2. Temperature has a minor impact on swelling compared to the crosslink density. The study evaluates the Extended Modified Double Lattice (EMDL) model for its mixing contribution in polymer network swelling, aiming to improve the Flory–Hüggins (FH) model. The superiority of EMDL above FH is in the boundary condition at the unvulcanized state, the former aligning its interaction energy with values from solvent activities in primary linear polymer/solvent solutions, unlike the FH model. The EMDL model also accounts for oriented interactions in polar solvents through a secondary lattice, linking specific interaction energy with solvent dipole moments. The study observes a nonlinear correlation between crosslinking density and sulfur amount, proposing a nonrandom mixing at lower sulfur concentrations. This model shows strong alignment with experimental data, suggesting that replacing the FH model's mixing contribution with the EMDL model could improve results with minimal additional complexity.

3D Printed P(VdF‐HFP)/SBA‐15 composite‐based gel polymer electrolyte versus commercial celgard: A comparative investigation on thermal stability and electrochemical performance for lithium‐ion battery application

AbstractThe current work reports on tailoring of 3D printed gel polymer electrolyte (GPE) employing poly(vinylidene fluoride‐co‐hexafluoropropylene) P(VdF‐HFP) as the host matrix and mesoporous Santa Barbara Amorphous‐15 (SBA‐15) mesoporous sieve as ceramic filler. Further, this work envisages an investigation on its physicochemical properties, thermal shrinkage behavior, and electrochemical performance. An effort has been undertaken to formulate 3D printable P(VdF‐HFP)/SBA‐15 composite‐based GPE ink with suitable rheological properties. The breath figure method is followed to investigate the influence of 1‐methyl‐2‐pyrrolidinone (NMP)/tetrahydrofuran (THF) mixture as a solvent on the porosity of 3D printed GPE, through which enhanced porosity is evident from scanning electron microscopy (SEM) analysis. The morphological analysis further confirms the hybrid porous structure facilitated by the addition of SBA‐15 into the P(VdF‐HFP) matrix. The 3D printed P(VdF‐HFP)/SBA‐15 (10%) composite‐based GPE shows promising ionic conductivity in the order of 0.2 × 10−4 S/cm at room temperature and demonstrates excellent dimensional thermal stability up to 175°C. The electrochemical measurement of 3D printed GPE is tested separately using 3D printed cathode half‐cell (3D printed LFP vs. Li+) and 3D printed anode half cell (3D printed LTO vs. Li+) with GPE as separator. Further, also tested with conventionally prepared electrode and the coin cell studies show discharge capacity of 3D printed P(VdF‐HFP)/SBA‐15 (10%) composite‐based GPE is comparable to commercial celgard separator. All these features speculate that the 3D printed fabricated in the current work may find potential application in lithium‐ion battery.

Optimizing Performance of PVC Gel Actuators: Temperature Influence and Characterizations

PVC gels are in high demand for actuators, so choosing the optimal route for preparing PVC gel is crucial. In this study, PVC gel samples were prepared using polymer PVC, plasticizer Di-butyl adipate (DBA), and solvent tetrahydrofuran (THF) at temperatures ranging from 40°C to 70°C. The samples obtained at different temperatures were labeled as PVC40, PVC50, PVC60, and PVC70. Rheological properties of all PVC gel samples were analyzed, revealing, that the rheological behavior of the PVC70 gel sample differed significantly from the others due to THF evaporation at 70°C, resulting in inadequate PVC gel preparation. However, PVC40, PVC50, and PVC60 gel samples were chosen for further characterizations, including scanning electron microscopy (SEM), actuation, and mechanical properties evaluation. Moreover, a self-assembled setup was fabricated using electrodes and PVC gel to test the performance of the planar actuator. The maximum displacement of PVC60 was measured at approximately 0.74 mm, with a response time of 0.75 sec under an applied voltage of 1000V. It was observed that the homogeneity of the gel and the solubility of the raw materials, based on resin were influenced by the reaction temperature, suggesting that uniformity could be achieved through dipole-dipole interactions or hydrogen bonding between PVC and DBA (Cl-H…. O=C). Finally, our findings have the potential to contribute to the development of innovative PVC gel actuators.

Isolation of the Antifungal Compound Alliodorin from the Heartwood of Cordia elaeagnoides A. DC. and the In Silico Analysis of the Laccase.

Cordia elaeagnoides A. DC. is an endemic species of Mexico valued for its timber. Renowned for its durability, resistance, and versatile applications in medicine, this tree holds significant commercial importance. Tetrahydrofuran (THF) extract from the heartwood of C. elaeagnoides was studied. Through chromatographic column purification, the compound 8-(2,5-Dihydroxyphenyl)-2,6-dimethylocta-2,6-dienal, also known as alliodorin, was successfully isolated. Identification of alliodorin was confirmed through comprehensive analysis utilizing NMR, IR, and mass spectrometry techniques. Inhibition tests were conducted using both the THF extract and alliodorin against the rotting fungus Trametes versicolor (L.) Lloyd, employing the agar well diffusion assay. Remarkably, alliodorin exhibited 100% inhibition with a median lethal concentration of 0.079 mg/mL and a total lethal concentration of 0.127 mg/mL, in comparison to the commercial fungicide benomyl, which requires a concentration of 1 mg/mL. In silico analysis through molecular docking on the laccase enzyme was proposed in order to explain the inhibitory activity against the fungus T. versicolor, as this enzyme is one of the main sources of nutrients and development for the fungus. Based on these findings, we deduced that alliodorin holds promise as a potent antifungal agent, potentially applicable in a wide array of technological and environmentally friendly initiatives.

Ni(I) and Ni(II) Bis(trimethylsilyl)amides Obtained in Pursuit of the Elusive Structure of Ni{N(SiMe3)2}2.

Salt metathesis routes to five new -N(SiMe3)2 nickel derivatives were studied to illuminate their mode of formation, structures, and spectroscopy. The reaction between NiI2 and K{N(SiMe3)2} afforded the Ni(II) and Ni(I) complexes [K][Ni{N(SiMe3)2}3] (1) and [K][Ni{N(SiMe3)2}2] (2). Dissolving 1 in tetrahydrofuran (THF) gave the Ni(II) species [K(THF)2][Ni{N(SiMe3)2}3] (3). The Ni(I) salt [K(DME)][Ni2{N(SiMe3)2}3] (4) was obtained by using NiCl2(DME) (DME = 1,2-dimethoxyethane) as the nickel source rather than NiI2. The isolation of the Ni(I) complexes 2 and 4 highlights the tendency for K{N(SiMe3)2} to function as a reducing agent. Introduction of adventitious O2 to solutions of [K][Ni{N(SiMe3)2}2] (2) gave the nickel inverse crown ether (ICE) species [K2][O(Ni{N(SiMe3)2}2)2] (5). Complex 5 is the first ICE complex of nickel and is one of four known ICE complexes for the 3d metals. The experimental results indicate that the reduced Ni(I) bis(trimethylsilyl)amides are relatively easily generated, whereas Ni(III) derivatives that might be expected from a disproportionation of a Ni(II) derivative are apparently not yet isolable by the above routes. Overall, the new species crystallize readily from the reaction mixtures, but under ambient conditions, they begin to decompose as solids within ca. 24 h, which hinders their characterization.

Rational solvent selection for the preparation of industrial monolithic supported liquid-phase (SLP) olefin hydroformylation catalyst

Heterogenisation of the hydroformylation (HyFo) process converting C4 olefins and syngas (CO/H2) to n-pentanal can substantially reduce its carbon footprint by simplifying downstream processing. Current upscaling efforts include constructing a pilot plant containing a Rh-diphosphite-stabilized supported liquid-phase (SLP) catalyst. The air-sensitive nature of the catalyst requires in-situ impregnation of the porous support material with the liquid phase components (Rh-precursor, ligand, stabiliser) entailing the use of large quantities of an organic solvent. Environment, health, and safety (EHS) as well as regulatory aspects prompt the search for an alternative to dichloromethane (DCM), which was used as standard solvent for lab-scale studies. To obtain alternatives to DCM, the replacement solvent methyl tert-butyl ether (MTBE) and in-silico screening of more than 5000 solvent candidates has been performed covering boiling points and solubility predictions by COSMO-RS as well as carcinogenicity- and mutagenicity predictions by quantitative structure–activity relationship (QSAR) models. The final list of solvent candidates contained unsaturated compounds (alkenes, alkynes) in addition to ether- and ester-functionalized​ solvents, which are typically recommended as DCM replacements. Sufficiently high solubilities of ligand and stabiliser to prepare the desired SLP catalyst were experimentally determined in the following solvents: methyl propionate (MP), dimethoxymethane (DMM), MTBE, tetrahydrofuran (THF) and DCM for benchmarking, and a monolithic SLP catalyst prepared with MTBE demonstrated to perform equally well in the HyFo reaction of 1-butene as the benchmark catalyst prepared using DCM solvent. Overall, the study demonstrates a practical approach for selecting solvents with a greener profile for making catalyst systems applicable for large-scale production.

Supramolecular solvent-based liquid–liquid microextraction (SUPRAS-LLME) of Sudan dyes from food and water samples with HPLC

Utilizing the environmentally friendly technique of supramolecular solvent-based microextraction (SUPRAS-LLME), Sudan I-IV dyes were successfully isolated and enriched from food and natural water samples. The optimization of the microextraction process was carried out by studying the effects of various parameters such as pH (6.0), supramolecular volume (100 μL), tetrahydrofuran (THF) volume (200 μL), ultrasonication temperature (40 °C), and vortex time (1.0 min). Extraction efficiency ranged between 82 % and 109 %, while other analytical parameters such as the limits of detection (LOD) were determined to be 0.23, 0.51, 0.42, and 0.39 μg L−1 for Sudan I, II, III, and IV, respectively. The total figure of merits for the presented SUPRAS-LLME method includes a limits of quantification (LOQ) of 0.78, 1.70, 1.41, and 1.30 μg L−1, a relative standard deviation (RSD%) of 3.4, 6.1, 2.9, and 4.4 (n = 10), a linear range of 5–1000 μg L−1 for all Sudan dyes, a pre-concentration factor (PF) of 15, 10, 10, and 17, and a determination coefficient (R2) of 0.9994, 0.9965, 0.9955, and 0.9946, for Sudan I, II, III, and IV, respectively. The environmental friendliness of the method was confirmed by evaluating the greenness of the method with the AGREE metric tool. A sustainable and environmentally friendly option for the extraction of Sudan dyes from food and water samples is offered by this SUPRAS-LLME method.

Elucidating the Mechanism of Tetrahydrofuran-Diol Formation through Os(VI)-Catalyzed Oxidative Cyclization of 5,6-Dihydroxyalkenes Ligated by Citric Acid.

A computational study is reported here on the mechanism of tetrahydrofuran (THF)-diol formation from the Os(VI)-catalyzed oxidative cyclization of 5,6-dihydroxyalkene ligated with citric acid and in the presence of Bro̷nsted acid. Initiated by Os(VI) dioxo citrate formation, coordination of co-oxidant pyridine-N-oxide (PNO) and protonation of its oxo group generate the active catalyst. The catalytic cycle commences through successive steps, including dihydroxyalkene addition to the active catalyst in a concerted mechanism to form hexacoordinated alkoxy-protonated PNO-complexed Os(VI) bisglycolate as a turnover-limiting step (TLS), cyclization to Os(IV) THF-diolate, reoxidation to Os(VI) THF-diolate, and hydrolysis via a dissociative mechanism to furnish the THF-diol and regenerate the active species, sustaining the catalytic cycle through an Os(VI)/Os(IV) cycle. Despite the overall exergonic nature of catalytic cycle (ΔGrcycle = -45.0 kcal/mol), the TLS is accelerated by the formation of an open-valence 16-electron Os(VI) intermediate but decelerated by the undesired formation of a saturated/hexacoordinate 18-electron Os(VI) intermediate. Bro̷nsted acid plays crucial roles in the formation of Os(VI) citrate and the active catalyst, impediment of the second cycle, and the cyclization step. Additionally, besides its role as a co-oxidant, and in the presence of acid, PNO is found to assist the insertion of dihydroxyalkene and, importantly, in releasing the THF-diol to regenerate the active intermediate.

Investigation of AC and DC Electrical Conductivity in Ethyl Cellulose (EC) and Poly Methyl Methacrylate (PMMA) Polyblends

The study of AC and DC electrical conductivity is crucial for understanding the behavior of charge carriers within materials and their mobility. Ethyl cellulose (EC) stands out among cellulose ethers due to its favorable electrical, mechanical, and weathering properties. Poly Methyl Methacrylate (PMMA) is a thermoplastic known for its rigidity, transparency, and outdoor durability, making it a valuable material. Despite being insulating materials, both EC and PMMA exhibit limited free charge carriers and low mobility. In this research, AC and DC electrical properties of Ethyl Cellulose (EC), Poly Methyl Methacrylate (PMMA), and their blends doped with tetrahydrofuran (THF) film were investigated using isothermal evaporation techniques. The investigation focused on the effects of temperature, electric field, and frequency on electrical conduction mechanisms. Measurements were conducted across frequencies ranging from 1 KHz to 1 MHz at temperatures between 323 K and 373 K. Results indicate that AC electrical conductivity of Ethyl Cellulose (EC), Poly Methyl Methacrylate (PMMA), and their blend (EC/PMMA) increases with higher frequencies of the applied electric field. Meanwhile, DC electrical conductivity of Ethyl Cellulose (EC), Poly Methyl Methacrylate (PMMA), and their blend (EC/PMMA) rises with increasing temperature. X-ray diffraction (XRD) analysis further supports these conductivity changes in the blend.

Mapping the Influence of Solvent Composition over the Characteristics of Polylactic Acid Nanofibers Fabricated by Electrospinning

AbstractThis study investigated the solubility of poly(lactic acid) (PLA) in various solvents (to achieve an 8 % (w/v) polymer solution) and its impact on the morphology of electrospun PLA nanofibers. Several solvents, such as dichloromethane (DCM), chloroform (CHL), tetrahydrofuran (THF), acetone (AC), acetonitrile (ACTNR), dimethylformamide (DMF), dimethylacetamide (DMAc), ethylene glycol (ETGLY), distilled water (WATER), methanol (MEOH), formic acid (FA), and n‐hexane (NHX) were used in their pure and binary forms at several ratios (4 : 1, 2 : 1, 1 : 1, 1 : 2, 1 : 3, and 1 : 4). The study aims to explore the correlation between PLA solubility and its electrospinnability using solvents mapped from the Teas graph across different parameter zones and chemical groups. Hansen solubility parameters, including dispersion cohesion fractional solubility parameter (fd), the polar cohesion fractional solubility parameter (fp) was employed to identify the most effective solvents for PLA dissolution. Teas graph analysis highlighted a correlation between PLA solubility and solvent proximity to Hansen solubility parameters. Additionally, the solubility time varied between 1 hour and 24 hours. Polar solvents such as DCM, CHL, THF, ACTNR, and FA were able to dissolve 8 % (w/v) of PLA at different times, but only very high and effective dissolution of PLA was achieved in pure DCM and CHL whereas FA dissolved PLA in 24 hours, which resulted in the slowest solubility rate. Several structures of nanofibers, such as smooth, heterogenous, porous, fibrous, and beaded, were observed and discussed accordingly in terms of solvent type and ratio. The average nanofiber diameter ranged between 0.18 μm and 3.81 μm. Moreover, physical tests, including surface tension, density, viscosity, and conductivity, were conducted on solvent systems and CHL displayed higher viscosity, while ACTNR had the lowest viscosity and highest conductivity among pure solvents. According to the results of our study, it is possible to design further studies with the aim of deciding which solvents or binary forms should be applied to dissolve PLA within a certain time. The desired structure can be easily arranged to be used as a filter, biomimicking tissue environment, drug delivery system, or extra.

Enhancing the performance of optoelectronic potential of CuO/Al nanoplats in a PVC for medium voltage cables applications

This study investigates the potential of incorporating CuO and Al nanoplates into a polyvinyl chloride (PVC) matrix to enhance the performance of medium voltage cables. The incorporation of nanoparticles into the PVC insulation material aims to improve the electrical, dielectric, and optical properties of the cable. The nanocomposite films were synthesized by dissolving PVC in tetrahydrofuran (THF) solvent and adding a mixture of 5 wt% CuO and Al nanoparticles. Fourier-transform infrared spectroscopy (FTIR) analysis confirmed the successful incorporation of the nanoparticles into the PVC matrix. The optical properties of the PVC/AlNPs and PVC/CuONPs + AlNPs nanocomposite films were characterized, revealing a decrease in band gap energy (4.35 eV) and Urbach tail energy (0.3702 eV) for the PVC/CuONPs + AlNPs film compared to the PVC/AlNPs film (4.5 eV and 0.41816 eV, respectively). Additionally, the PVC/CuONPs + AlNPs film exhibited higher absorption coefficients and increased electron delocalization and conjugation (carbon cluster value of 62.53). The dielectric properties of the CuONPs + AlNPs nanocomposites were investigated, with the sample containing 1.5% AlNPs demonstrating the highest AC conductivity (2.029 × 10−3 S/m), dielectric constant, and dielectric loss across the frequency range. Simulations of electric field distribution revealed that the PVC/CuONPs+1.5% AlNPs nanocomposite cable exhibited a more uniform electric field distribution compared to the PVC market cable, contributing to a reduction in electrostatic tension and a relative permittivity increase from 2.25 to 2.35. The electric potential distribution along the cable radius remained similar for both cable samples. These findings demonstrate the potential of nanocomposite insulation materials in enhancing the performance of medium voltage cables, paving the way for improved reliability, longevity, and efficiency.

Prediction of the univariant two-phase coexistence line of the tetrahydrofuran hydrate from computer simulation.

In this work, the univariant two-phase coexistence line of the tetrahydrofuran (THF) hydrate is determined from 100 to 1000bar by molecular dynamics simulations. This study is carried out by putting in contact a THF hydrate phase with a stoichiometric aqueous solution phase. Following the direct coexistence technique, the pressure is fixed, and the coexistence line is determined by analyzing if the hydrate phase grows or melts at different values of temperature. Water is described using the well-known TIP4P/Ice model. We have used two different models of THF based on the transferable parameters for phase equilibria-united atom approach (TraPPE-UA), the original (flexible) TraPPe-UA model and a rigid and planar version of it. Overall, at high pressures, small differences are observed in the results obtained by both models. However, large differences are observed in the computational efforts required by the simulations performed using both models, being the rigid and planar version much faster than the original one. The effect of the unlike dispersive interactions between the water and THF molecules is also analyzed at 250bar using the rigid and planar THF model. In particular, we modify the Berthelot combining rule via a parameter ξO-THF that controls the unlike water-THF dispersive interactions. We analyze the effect on the dissociation temperature of the hydrate when ξO-THF is modified from 1.0 (original Berthelot combining rule) to 1.4 (modified Berthelot combining rule). We use the optimized value ξO-THF = 1.4 and the rigid THF model in a transferable way to predict the dissociation temperatures at other pressures. We find excellent agreement between computer simulation predictions and experimental data taken from the literature.

Randomly cross-linked amphiphilic copolymer networks of n-butyl acrylate and N,N-dimethylacrylamide: synthesis and characterization

Abstract Five randomly cross-linked amphiphilic copolymer networks (ACPN) were prepared via the free radical cross-linking copolymerization of the hydrophobic n-butyl acrylate (BuA) and the hydrophilic N,N-dimethylacrylamide (DMAAm), in the presence of a small amount (5 mol% with respect to the sum of BuA plus DMAAm monomers) of the hydrophobic 1,6-hexanediol diacrylate (HexDA) cross-linker, initiated by 4,4ʹ-azobis(4-cyanovaleric acid) in 1,4-dioxane at a 10 % w/v total monomer concentration. The five ACPNs differed in their BuA content, fixed at 10, 30, 50, 70 and 90 mol%. The two homopolymer networks, BuA and DMAAm, were also prepared using the same polymerization method. Thus, this study involved a total of seven polymer networks, forming a homologous series with BuA contents ranging from 0 to 100 mol%. These networks were characterized in terms of their degrees of swelling in tetrahydrofuran (THF) and water, their mechanical properties in water, and their adhesion to human skin. The degrees of swelling (DS) of the networks in THF were higher than those in water because THF is a non-selective solvent, whereas water is selective for the hydrophilic DMAAm units. The DSs in THF increased with the network content in the less polar BuA units, while the opposite was true for the DSs in water which decreased with the content in the hydrophobic BuA units from 11 (0 mol% BuA) down to 1.1 (100 mol% BuA). A maximum in the elastic modulus was observed for the hydrogel with 50 mol% BuA, reflecting the opposing effects of polymer composition in soft polymer (polyBuA) content and hydrogel water content. In contrast, the tensile strain at break increased monotonically with the hydrogel BuA content, reaching a remarkable ∼900 % for the hydrogel with 90 mol% BuA. Finally, the adhesion of the ACPNs, both in their dried and hydrated states, onto human skin was explored. The adhesion of the hydrated samples onto skin was stronger than that of the dried ones. The hydrated ACPN with 30 mol% BuA exhibited the strongest adhesion onto skin, attributable to the best combination of a rather high content in polar DMAAm units (70 mol%), and a rather low aqueous DS (∼2.5), with the low DS value causing only a small dilution in the DMAAm units participating in the polar interactions with skin. The present work demonstrates that, even in this synthetically simple ACPN system, the multiple effects of ACPN composition on a certain property, in some cases opposing and in some other cooperating, lead to a rather complicated behavior. In particular, as the BuA content increases, some properties display maxima (elastic modulus, stress at break and fracture energy of hydrated ACPNs, and adhesion of hydrated ACPNs onto skin) while some other properties exhibit monotonic increases (strain at break of hydrated ACPNs, and adhesion of dried ACPNs onto skin). Thus, the optimal ACPN for a particular application will highly depend on the property best-serving the particular application, e.g., the ACPNs with 30, 50 and 90 mol% BuA for strongest wet adhesion to skin, stiffest hydrogel response, and highest hydrogel extensibility and toughness, respectively.

A systematic approach for screening green entrainers combining the environmental-health-safety indexes and separation performance

Here we propose a new approach for extractive distillation (ED) process design, integrating environmental-health-safety (EHS) indexes as early as during the entrainer screening phase. Typically, safety and environmental factors are addressed later in the design process, often during optimization or in a sequential evaluation after cost-based optimization. However, in this study, we propose for the early incorporation of EHS considerations during the entrainer screening phase. This involves assessing the entrainer suitability using traditional metrics alongside additional EHS criteria, such as lethal dose (LD50) and flash point. Two azeotropic mixtures, i.e., tetrahydrofuran (THF)/ethanol (EtOH) and THF/methanol (MeOH), are chosen to exemplify our proposed methodology. Among the 1432 screened entrainers, the top 10 entrainers were identified based on separation index. These candidates were then subjected to further evaluation based on EHS criteria. Ethylenediamine (EDA) emerged as the optimal choice for the separation of THF/MeOH and THF/EtOH mixtures, demonstrating commendable EHS performance. Both separation processes were successfully simulated using Aspen Plus, which confirms the validity and suitability of the screened entrainer.