Augmenting the Efficacy of a Polyvinyl Alcohol Selective Layer Coated on Polyvinylidene Fluoride Support Membranes with Kaolinite Introduction for Improved Pervaporation Dehydration of Epichlorohydrin/Isopropanol/Water Ternary Systems.

Composite membranes with a polyvinyl alcohol (PVA) selective layer composed of well-dispersed hydrophilic kaolinite particles coated on a polyvinylidene fluoride (PVDF) support were developed. They were applied to the pervaporation dehydration of the industrially important epichlorohydrin (ECH)/isopropanol (IPA)/water ternary mixture. In comparison with raw kaolinite (RK), hydrophilic kaolinite (HK) enhanced the mechanical properties, hydrophilicity, and thermal stability of the PVA selective layer, as confirmed by universal testing, the contact angle, and TGA analyses, respectively. The pervaporation results revealed that the addition of HK particles significantly enhanced the separation factor (3-fold). Only a marginal reduction in flux was observed with ECH/IPA/water, 50/30/20 (w/w %) at 40 °C. An HK particle concentration of 4 wt.% with respect to PVA delivered the highest flux performance of 0.86 kg/m2h and achieved a separation factor of 116. The PVA-kaolinite composite membrane exhibited pronounced resistance to the ECH-containing feed, demonstrating a sustained flux and separation factor throughout an extended pervaporation stability test lasting 250 h.

Synergistic pervaporation dehydration of ethanol/water mixture: Exploring the potential of a covalently designed hybrid membrane structure of polyacrylic acid grafted carbon nitride and polyvinyl alcohol.

Polyacrylic acid (PAA) grafted CN sheet (P-g-CN) was synthesized to enhance the dispersive properties of carbon nitride (CN) in the membrane. A successful PAA grafting to the CN was confirmed from FTIR, TGA, and Zeta potential and XRD analyses. The A PVA membrane embedded P-g-CN, including a covalently constructed polymer-filler network, was developed to separate ethanol-water mixtures using pervaporation (PV). XPS study has confirmed a covalent attachment of P-g-CN sheets to the PVA matrix. Thereby, a defect-free membrane matrix was observed in the FESEM analysis. A 10 wt% loaded PVA-P-g-CN10 composite membrane was compared to the pristine PVA membrane, demonstrating improved PV dehydration performance. The flux decreased from 0.21 kg/m2h of pristine PVA membrane to 0.17 kg/m2h of PVA-P-g-CN10 membrane, while the separation factor improved from 49 to 176 in a 90/10 wt % ethanol/water feed at 40 °C. This improvement can be attributed to the selective diffusion of water through the P-g-CN interlayer spacing and tiny triangular nanopores in the s-triazine network, along with their dispersibility in the PVA matrix, resulting in well-ordered membrane morphology. Furthermore, PVA-P-g-CN10 exhibited higher water permeance (43.31-86.07 GPU) than ethanol (1.18-10.47 GPU) as the feed temperature increased from 30 to 70 °C, suggesting P-g-CN successfully inhibits swelling in the feed solution through proper interaction with PVA. In a long-term PV test lasting 250 h, the PVA-P-g-CN10 membrane displayed excellent structural stability and maintained its performance.

Hydrophilic and organophilic pervaporation of industrially important α,ß and α,ω-diols.

The distillation-based purification of α,ß and α,ω-diols is energy and resource intensive, as well as time consuming. Pervaporation separation is considered to be a remarkable energy efficient membrane technology for purification of diols. Thus, as a core pervaporation process, hydrophilic polyvinyl alcohol (PVA) membranes for the removal of water from 1,2-hexanediol (1,2-HDO) and organophilic polydimethylsiloxane-polysulfone (PDMS-PSF) membranes for the removal of isopropanol from 1,5 pentanediol (1,5-PDO) were employed. For 1,2-HDO/water separation using a feed having a 1 : 4 weight ratio of 1,2-HDO/water, the membrane prepared using 4 vol% glutaraldehyde (GA4) showed the best performance, yielding a flux of 0.59 kg m-2 h-1 and a separation factor of 175 at 40 °C. In the organophilic pervaporation separation of the 1,5-PDO/IPA feed having a 9 : 1 weight ratio of components, the PDMS membrane prepared with a molar ratio of TEOS alkoxy groups to PDMS hydroxyl groups of 70 yielded a flux of 0.12 kg m-2 h-1 and separation factor of 17 638 at 40 °C. Long term stability analysis found that both hydrophilic (PVA) and organophilic (PDMS) membranes retained excellent pervaporation output over 18 days' continuous exposure to the feed. Both the hydrophilic and organophilic membranes exhibited promising separation performance at elevated operating conditions, showing their great potential for purification of α,ß and α,ω-diols.

Stability and pervaporation characteristics of PVA and its blend with PVAm membranes in a ternary feed mixture containing highly reactive epichlorohydrin.

In order to find an alternative for classical distillation in the recovery of ECH/IPA from azeotropic ECH/IPA/water (50/30/20 w/w, %) mixtures, a pervaporation process has been applied. Membranes from the crosslinking of poly(vinyl alcohol)/poly(vinyl amine) (PVA/PVAm) were prepared, and then the membrane stability and pervaporation efficiency of the crosslinked PVA/PVAm membranes were studied for highly reactive ECH systems containing a ternary feed mixture. From the Fourier-transform infrared (FT-IR) spectroscopy analysis, it was observed that all of the membranes were chemically stable for 15 days of immersion in a 50 : 30 : 20 ECH/IPA/water (w/w, %) feed mixture at 60 °C. The degree of membrane swelling increased with increasing PVAm content in the membrane composition, water content in the feed composition, and feed temperature, which was attributed to the increase in the number of hydrophilic sites in the membrane. The field-emission scanning electron microscopy (FE-SEM) study revealed that higher PVAm content membranes (PVAm1.0 and PVAm1.5) show polymer phase extraction in ECH/IPA/water (50 : 30 : 20) (w/w, %) at 60 °C in long-term stability tests. The pervaporation dehydration characteristics for all of the membranes with the feed comprising an ECH/IPA/water (50 : 30 : 20 by weight) azeotropic mixture at 30 °C were examined and excellent pervaporation dehydration efficiency was found. Quantitatively, the flux increased from 0.025 to 0.32 kg (m2 h)-1 and the separation factor decreased from 1908 to 60 with increasing PVAm content in the blended membrane.

Mechanical and Thermal Properties of Epoxy Composites Containing Zirconia-Impregnated Halloysite Nanotubes with Different Loadings.

Epoxy resins are widely used in various industrial fields due to their low cost, good workability, heat resistance, and good mechanical strength. However, they suffer from brittleness, an issue that must be addressed for further applications. To solve this problem, additional fillers are needed to improve the mechanical and thermal properties of the resins; zirconia is one such filler. However, it has been reported that aggregation may occur in the epoxy composites as the amount of zirconia increases, preventing enhancement of the mechanical strength of the epoxy composites. Herein, to reduce the aggregation, zirconia was well dispersed on halloysite nanotubes (HNTs), which have high thermal and mechanical strength, by a conventional wet impregnation method. The HNTs were impregnated with zirconia at different loadings using zirconyl chloride octahydrate as a precursor. The mechanical and thermal strengths of the epoxy composites with these fillers were investigated. The zirconia-impregnated HNTs (Zr/HNT) were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and tunneling electron microscopy (TEM). The hardening conditions of the epoxy composites were analyzed by differential scanning calorimetry (DSC). The thermal strength of the epoxy composites was studied by thermomechanical analysis (TMA) and micro-calorimetry and the mechanical strength of the epoxy composites (flexural strength and tensile strength) was studied by using a universal testing machine (UTM). The mechanical and thermal strengths of the epoxy composites with Zr/HNT were improved compared to those of the epoxy composite with HNT, and also increased as the zirconia loading on HNT increased.

Ag-exchanged NaY zeolite introduced polyvinyl alcohol/polyacrylic acid mixed matrix membrane for pervaporation separation of water/isopropanol mixture.

Ag-exchanged NaY zeolite (Ag-NaZ) particles were prepared by ion exchange and introduced to a polyvinyl alcohol (PVA) membrane cross-linked with polyacrylic acid (PAA) for the pervaporation dehydration of an isopropanol (IPA) aqueous mixture. The Ag-exchanged NaY zeolite particles were characterized by FE-SEM, EDS, BET, and XRD studies. The prepared Ag-NaZ-loaded PVA/PAA composite membrane was characterized by FE-SEM, XRD, a swelling study, and contact angle measurements. Pervaporation characteristics were investigated in terms of Ag-NaZ concentrations within PVA/PAA membranes using diverse feed solution conditions. The preferential sorption of IPA/water mixtures for Ag-NaZ-introduced membranes were also determined by calculating the apparent activation energies of IPA and water permeation, respectively. As a result, flux and selectivity increased with the Ag-NaZ concentration to 5 wt% in the membrane. Optimum pervaporation performance was observed in a 5 wt% Ag-NaZ-incorporated membrane with a flux equal to 0.084 kg m-2 h-1 and a separation factor of 2717.9 at 40 °C from an 80 wt% IPA aqueous feed solution.