Branched Polyvinyl Alcohol Hybrid Membrane for Acid Recovery via Diffusion Dialysis

A branched polymer was prepared by grafting allyltrimethylammonium chloride onto polyvinyl alcohol (PVA) via free‐radical polymerization. Afterwards, a series of hybrid membranes were prepared by sol‐gel cross‐linking between quaternary ammonium‐PVA and tetraethoxysilane. The obtained membranes were characterized in terms of infrared spectroscopy, ion exchange capacity, water uptake, linear expansion ratio, and acid resistance. The thermal properties of the membranes were investigated as well. The diffusion dialysis performances of the membranes were tested by using a simulated feed solution containing HCl and FeCl₂. The diffusion dialysis coefficients and the separation factors were much better than those of the commercial DF‐120 membrane.     

来瓦希尔骨架材料MIL-53(Al)填充PEBA膜渗透汽化分离水中苯胺

将来瓦希尔骨架材料MIL-53(Al)引入到聚醚共聚酰胺（PEBA-2533）高分子相中制备了不同填充量的PEBA/MIL-53(Al)杂化膜并用于渗透汽化分离水中微量苯胺。X-射线衍射结果证实MIL-53(Al)被成功合成。扫描电镜和激光粒度分析结果表明所制备MIL-53(Al)颗粒粒径在纳米尺度范围内。采用扫描电镜、红外光谱、X-射线衍射、差示扫描量热和水接触角对杂化膜进行了表征，并考察了杂化膜的溶胀行为和分离性能。结果表明，所得杂化膜的热稳定性较好。当MIL-53(Al)质量分数小于20%时，MIL-53(Al)在高分子相中分散均匀，继续增大填充量出现团聚现象。杂化膜的结晶度随MIL-53(Al)填充量的增加而降低。MIL-53(Al)的引入增强了杂化膜的疏水性和溶胀度。在料液温度为60℃、膜下游压力400Pa、料液苯胺质量分数为3.6%时，MIL-53(Al)质量分数为20%的杂化膜（M-20）综合分离性能最优，渗透通量达到2.15kg/(m²·h)，分离因子为264。12天的稳定性测试结果表明所得杂化膜分离性能无显著变化，能够满足渗透汽化应用要求。     

Layer-by-layer self-assembly of multifunctional enzymatic UF membranes

In order to eliminate membrane fouling and to ensure enzymatic hydrolysis of urea, multifunctional biocatalytic membranes were prepared by using urease (URE) and trypsin (TRY) enzymes on the sulfonated polysulfone (SPSf) ultrafiltration membrane via layer-by-layer (LbL) self-assembly method. The membrane architecture consisted of multilayer assembly with TRY and URE enzymes as the outer layer and inner sandwiched layer, respectively. Polyethyleneimine (PEI) and alginate (ALG) were used as cationic and anionic polyelectrolytes. Sulfonation and PEI deposition were successfully accomplished as confirmed by attenuated total reflectance Fourier transform infrared spectroscopy, differential scanning calorimetry (DSC) and scanning electron microscopy analysis, contact angle measurements, staining with toluidine blue and Congo red dyes and dead-end filtration experiments. A characteristic value of SPSf membrane with a high water permeability (1000 L/m².h.bar) and 95% bovine serum albumin (BSA) rejection was observed. In static conditions, URE activities of SPSf2-PEI-URE membrane were not affected by BSA fouling, while TRY immobilizations with increased concentrations (SPSf2-PEI-URE-PEI-ALG-TRY) significantly lowered the activity of URE. In dynamic conditions, each deposited layer exhibited individual resistance to flow that can be considered as irreversible fouling and caused 90% of flux decline for the SPSf2-PEI-URE-PEI-ALG-TRY membrane assembly. The recovery of the initial flux for the multilayered membrane at the end of six fouling and washing cycles was observed 85%. Moreover, at the end of 5 cycles, 78% of the URE initial activity of the multilayered membrane was preserved. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48750.     

Investigation on carbon nanotube oxide for anhydrous proton exchange membranes application

The widespread participation of polymers in the membrane preparation has been considering to be critical for the development of proton exchange membranes (PEMs). For the polymers without functional groups to conduct protons, the introduction of proton conduction carriers with the formation of composite membranes is an effective strategy to prepare PEMs with the outstanding proton conductivity. However, there remains a potential risk of the components leaking from composite membranes due to the lack of the interaction force. Here, the composite of carbon nanotube oxide (OCNT) assembling with cadmium telluride (CdTe) and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF₆) was introduced into the system of phosphoric acid (PA) doping poly(vinylidene fluoride) (PVDF) with the formation of PVDF/OCNT-CdTe-bmimPF₆/85%PA membranes. PA molecules are anchored by the inorganics of OCNT-CdTe-bmimPF₆ and are stabilized in membranes. The high and stable proton conductivity values at the elevated temperature are obtained comparing the reported PVDF/bmimPF₆/PA membranes. Specifically, the proton conductivity value reached 1.28 × 10⁻¹ S/cm at 160 °C and the value is stable 1.70 × 10⁻² S/cm at 120 °C lasting for 350 h. The fine stability in components could make the membranes extricate from the predicament of proton conductivity decline exceeding 120 °C under anhydrous conditions in PVDF/bmimPF₆/PA membranes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48833.     

Electrospinning superhydrophobic–superoleophilic PVDF-SiO2 nanofibers membrane for oil–water separation

Oil–water separation has attracted research interest due to the damages of oily wastewater caused to the environment and human beings. Electrospun fiber membrane has high oil–water separation performance. A nanofibers membrane with multi-stage roughness was prepared by electrospinning using poly(vinylidene fluoride)(PVDF)-silica blend solution as raw material. The result shows that the water contact angle (WCA) of the nanofibers membrane was promoted from 138.5 ± 1° to 150.0 ± 1.5° when the SiO₂ content was increased from 0 to 3 wt%. The nanofibers membranes exhibited excellent separation efficiency (99 ± 0.1%) under gravity drive, with high separation flux of 1857 ± 101 L·m⁻²·h⁻¹. More importantly, the obtained PVDF-SiO₂ nanofibers membranes showed excellent multi-cycle performance and stable chemical resistance, which would make them great advantages for the practical application of oil–water separation.     

Investigation of OSN properties of PDMS membrane for the retention of dilute solutes with potential industrial applications

Few commercially available membranes can be used for organic solvent nanofiltration (OSN). Applying OSN in chemical industries is nevertheless of high interest to cut with energy consumption linked to solvent recycling and soluble catalysts recovery. A commercial membrane, PERVAP4060, was used to investigate the retention of dilute solutes in toluene feeds and to mimic metathesis medium. The studied solutes were R-BINAP a neutral polyaromatic molecule used in metathesis chemistry, tetraoctylammonium bromide (ToABr), a charged molecule used as a homogeneous catalyst and n-hexadecane. Retention of polar ToABr (95%) was higher than that of neutral R-BINAP (80%). The transfer mechanism, either pore flow or solution-diffusion, was discussed. All the results obtained suggested that the transport is governed by the solution-diffusion mechanism. The measured retentions could be explained in terms of solubility affinities and diffusion coefficients. The stability and performances of PERVAP4060 were well established, showing the strong potential for industrial applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48359.     

A low pressure SWCNT-ENM sandwich membrane system for the removal of PPCPs from water

While carbon nanotubes are known as efficient adsorbents for removal of a number of contaminants from water, the possibility of their leaching into drinking water has prevented their application in water treatment. In this study, single walled carbon nanotubes (SWCNT) were sandwiched between two electrospun nanofibre membranes (ENM). The relatively small pore size of the ENM prevented the mechanically entangled nanotubes from passing through and contaminating the water. The performance of the SWCNT-ENM was evaluated in a lab-scale setup for the removal of PPCPs. For this purpose, a feed solution spiked with known concentrations of six PPCPs was passed through the membrane system. The target substances included acetaminophen (ACT), bezafibrate (BZF), iopromide (IOP), diclofenac (DCF), carbamazepine (CBZ), and sulphamethoxazole (SMX). The same test was also conducted using a single contaminant (ACT). Results demonstrated a decrease in the overall percent removal of PPCPs as feed flow rate and PPCP concentration increased. For multi-component feeds containing equal amounts of the aforementioned PPCPs, the overall percent removal decreased from 90.8% to 71.0% when increasing the feed concentration from 30 to 600 μg/L. Experiments using sandwiched powdered activated carbon (PAC) showed that the dynamic adsorption capacity of PPCPs by SWCNT-ENM was higher than that of PAC-ENM, and remained unaffected by the feed composition. In addition, the high porosity of this novel membrane allowed for flow of water with low resistance such that the trans-membrane pressure was found to be as low as 4 kPa at a pure water flux of 330 L/m²h.     

Enhancing the permeability of reverse osmosis membrane by embedding the star-like rigid supports in the substrate

Thin film composite (TFC) reverse osmosis (RO) membranes with high permeability have been prepared by interfacial polymerization based on tailoring the polysulfone (PSf) substrate structure by in situ embedded poly(p-phenylene terephthamide) (PPTA) star-like rigid supports. The star-like rigid supports were observed by the polarizing optical microscopy (POM) and transmission electron microscope (TEM). The surface properties of the substrates were investigated by FTIR, the water contact angle (WCA), FESEM and AFM. The WCA was decreased from 88.5° to 72.3° with the PPTA increasing from 0% to 8%, and the surface roughness increased from 24.2, 25.1, 33.5 and 58.6 nm, respectively. Furthermore, numerous interconnect micro-structures were constructed in the substrate when the PPTA content was up to 8%. The pure water flux of 8% PPTA/92%PSf substrate was up to 377.0 L m⁻² h⁻¹ and the flux decline rate was lowest (64%) after compacted at 5.5 MPa for 30 min. Otherwise, increasing the PPTA contents in the substrate enhanced the roughness, encouraged nanosheet formation and improved the permeability of TFC RO membranes. The pure water flux of the TFC RO membranes increased from 36.32 to 58.42 L m⁻² h⁻¹, where the NaCl rejection was about 99.5% at 5.5 MPa.