Abstract: Poly(amidoamine) (PAMAM) dendrimers were incorporated into cross-linked poly(vinyl alcohol) (PVA) matrix to improve carbon dioxide (CO2) separation performance at elevated pressures. In our previous studies, PAMAM/PVA hybrid membranes showed high CO2 separation properties from CO2/H2 mixed gases. In this study, three types of organic Ti metal compounds were selected as PVA cross-linkers that were used to prepare PAMAM/cross-linked PVA hybrid membranes. Characterization of the PAMAM/cross-linked PVA hybrid membranes was conducted using nanoindentation and thermogravimetric analyses. The effects of the cross-linker and CO2 partial pressure in the feed gas on CO2 separation performance were discussed. H2O and CO2 sorption of the PAMAM/PVA hybrid membranes were investigated to explain the obtained CO2 separation efficiencies.
Abstract: Based on a two-step polymerization method, two sulfobetaine-based zwitterionic monomers, including 3-(methacryloylamino) propyl-dimethyl-(3-sulfopropyl) ammonium hydroxide (MPDSAH) and 2-(methacryloyloxyethyl) ethyl-dimethyl-(3-sulfopropyl) ammonium (MEDSA), were successfully grafted from poly(vinylidene fluoride) (PVDF) hollow fiber membrane surfaces in the presence of N,N′-methylene bisacrylamide (MBAA) as a cross-linking agent. The mechanical properties of the PVDF membrane were improved by the zwitterionic surface layers. The surface hydrophilicity of PVDF membranes was significantly enhanced and the polyMPDSAH-g-PVDF membrane showed a higher hydrophilicity due to the higher grafting amount. Compared to the polyMEDSA-g-PVDF membrane, the polyMPDSAH-g-PVDF membrane showed excellent significantly better anti-protein-fouling performance with a flux recovery ratio (RFR) higher than 90% during the cyclic filtration of a bovine serum albumin (BSA) solution. The polyMPDSAH-g-PVDF membrane showed an obvious electrolyte-responsive behavior and its protein-fouling-resistance performance was improved further during the filtration of the protein solution with 100 mmol/L of NaCl. After cleaned with a membrane cleaning solution for 16 days, the grafted MPDSAH layer on the PVDF membrane could be maintain without any chang; however, the polyMEDSA-g-PVDF membrane lost the grafted MEDSA layer after this treatment. Therefore, the amide group of sulfobetaine, which contributed significantly to the higher hydrophilicity and stability, was shown to be imperative in modifying the PVDF membrane for a stable anti-protein-fouling performance via the two-step polymerization method.
Abstract: Two nanofiltration membranes, a Dow NF 270 polyamide thin film and a TriSep TS 80 polyamide thin film, were investigated for their retention of ionic species when filtering mine influenced water streams at a range of acidic pH values. The functional iso-electric point of the membranes, characterized by changes in retention over a small pH range, were examined by filtering solutions of sodium sulphate. Both membranes showed changes in retention at pH 3, suggesting a zero net charge on the membranes at this pH. Copper mine drainage and synthetic solutions of mine influenced water were filtered using the same membranes. These solutions were characterized by pH values within 2 and 5, thus crossing the iso-electric point of both membranes. Retention of cations was maximized when the feed solution pH was less than the iso-electric point of the membrane. In these conditions, the membrane has a net positive charge, reducing the transmission rate of cations. From the recoveries of a range of cations, the suitability of nanofiltration was discussed relative to the compliance with mine water discharge criteria and the recovery of valuable commodity metals. The nanofiltration process was demonstrated to offer advantages in metal recovery from mine waste streams, concomitantly enabling discharge criteria for the filtrate disposal to be met.
Abstract: The present work is focused on the investigation of the performance and long-term stability of two composite palladium membranes under different operating conditions. One membrane (Pd/porous stainless steel (PSS)) is characterized by a ~10 µm-thick palladium layer on a porous stainless steel substrate, which is pretreated by means of surface modification and oxidation; the other membrane (Pd/Al2O3) is constituted by a ~7 µm-thick palladium layer on an asymmetric microporous Al2O3 substrate. The operating temperature and pressure ranges, used for studying the performance of these two kinds of membranes, are 350–450 °C and 200–800 kPa, respectively. The H2 permeances and the H2/N2 selectivities of both membranes were investigated and compared with literature data. At 400 °C and 200 kPa as pressure difference, Pd/PSS and Pd/Al2O3 membranes exhibited an H2/N2 ideal selectivity equal to 11700 and 6200, respectively, showing stability for 600 h. Thereafter, H2/N2 selectivity of both membranes progressively decreased and after around 2000 h, dropped dramatically to 55 and 310 for the Pd/PSS and Pd/Al2O3 membranes, respectively. As evidenced by Scanning Electron Microscope (SEM) analyses, the pinholes appear on the whole surface of the Pd/PSS membrane and this is probably due to release of sulphur from the graphite seal rings.
Abstract: In the research of new nanocomposite proton-conducting membranes, SnO2 ceramic powders with surface functionalization have been synthesized and adopted as additives in Nafion-based polymer systems. Different synthetic routes have been explored to obtain suitable, nanometer-sized sulphated tin oxide particles. Structural and morphological characteristics, as well as surface and bulk properties of the obtained oxide powders, have been determined by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared (FTIR) and Raman spectroscopies, N2 adsorption, and thermal gravimetric analysis (TGA). In addition, dynamic mechanical analysis (DMA), atomic force microscopy (AFM), thermal investigations, water uptake (WU) measurements, and ionic exchange capacity (IEC) tests have been used as characterization tools for the nanocomposite membranes. The nature of the tin oxide precursor, as well as the synthesis procedure, were found to play an important role in determining the morphology and the particle size distribution of the ceramic powder, this affecting the effective functionalization of the oxides. The incorporation of such particles, having sulphate groups on their surface, altered some peculiar properties of the resulting composite membrane, such as water content, thermo-mechanical, and morphological characteristics.
Abstract: The solidification behavior of poly(vinylidene fluoride) (PVDF) solution during membrane preparation by thermally induced phase separation (TIPS) was investigated. Apparatus newly developed in our laboratory was used to quantitatively measure membrane stiffness during phase separation. In this apparatus, a cooling polymer solution, placed on a stage, is moved upwards and the surface of the polymer solution contacts a sphere attached to the tip of a needle. The displacement of a blade spring attached to the needle is then measured by a laser displacement sensor. Different phase separation modes, such as liquid-liquid (L-L) phase separation and solid-liquid (S-L) phase separation (polymer crystallization) were investigated. In the case of S-L phase separation, the stiffness of the solution surface began to increase significantly just before termination of crystallization. In contrast, L-L phase separation delayed solidification of the solution. This was because mutual contact of the spherulites was obstructed by droplets of polymer-lean phase formed during L-L phase separation. Thus, the solidification rate was slower for the L-L phase separation system than for the S-L phase separation system.