Preparation and application of stimuli-responsive PET TeMs: RAFT graft block copolymerisation of styrene and acrylic acid for the separation of water-oil emulsions.

Stimuli-responsive membranes play an important role in the fields of biomedicine, food and chemical industries, and environmental applications, including separation of water-oil emulsions. In this study, we present a method to fabricate pH-sensitive membranes using UV-initiated RAFT graft copolymerization of styrene (ST) and acrylic acid (AA) on poly(ethylene terephthalate) (PET) track-etched membranes (TeMs). The optimization of polymerization conditions led to successful grafting of polystyrene (PS) and poly(acrylic acid) (PAA) onto PET TeMs, resulting in membranes with stable hydrophobicity and pH change responsiveness. The membranes show a contact angle of 65° in basic environments (pH 9) and 97° in acidic environments (pH 2). The membranes were characterized by atomic force microscopy (AFM), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), thermogravimetric analyses (TGA), Fourier transform infrared spectroscopy (FTIR), contact angle (CA) methods. The PET TeMs-g-PS-g-PAA exhibited good performance in separating water-oil emulsions with a high efficiency of more than 90% and flux for direct chloroform-water 2500 L m-2 h-1 and reverse emulsions of benzene-water 1700 L m-2 h-1. This method of preparing stimuli-responsive membranes with controlled wettability and responsiveness to environmental pH provides versatility in their use in separating two types of emulsions: direct and reverse.

Effect of hydrophobized PET TeMs membrane pore-size on saline water treatment by direct contact membrane distillation.

This paper describes the desalination process by membrane distillation (MD) using track-etched membranes (TeMs). Hydrophobic track-etched membranes based on poly(ethylene terephthalate) (PET TeMs) with pore diameters from 700 to 1300 nm were prepared by UV-initiated graft polymerization of lauryl methacrylate (LMA) inside the nanochannels. Modified PET TeMs were investigated by Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and contact wetting angle (CA) measurements. Hydrophobic PET TeMs were tested for treating saline solutions of different concentrations by the direct contact membrane distillation (DCMD) method. The influence of membrane pore diameter and salt solution concentration on the water flux and rejection degree were investigated. Membranes with CA 94 ± 4° were tested in the direct contact membrane distillation (DCMD) of 7.5-30 g L-1 saline solution. Hydrophobic membranes with large pore sizes showed water fluxes in the range of 1.88 to 11.70 kg m-2 h-1 with salt rejection values of up to 91.4%.

Stimuli-Responsive Track-Etched Membranes for Separation of Water-Oil Emulsions.

In this work, we have developed a method for the preparation of pH-responsive track-etched membranes (TeMs) based on poly(ethylene terephthalate) (PET) with pore diameters of 2.0 ± 0.1 µm of cylindrical shape by RAFT block copolymerization of styrene (ST) and 4-vinylpyridine (4-VP) to be used in the separation of water-oil emulsions. The influence of the monomer concentration (1-4 vol%), the molar ratio of RAFT agent: initiator (1:2-1:100) and the grafting time (30-120 min) on the contact angle (CA) was studied. The optimal conditions for ST and 4-VP grafting were found. The obtained membranes showed pH-responsive properties: at pH 7-9, the membrane was hydrophobic with a CA of 95°; at pH 2, the CA decreased to 52°, which was due to the protonated grafted layer of poly-4-vinylpyridine (P4VP), which had an isoelectric point of pI = 3.2. The obtained membranes with controlled hydrophobic-hydrophilic properties were tested by separating the direct and reverse "oil-water" emulsions. The stability of the hydrophobic membrane was studied for 8 cycles. The degree of purification was in the range of 95-100%.

Graft Polymerization of Stearyl Methacrylate on PET Track-Etched Membranes for Oil-Water Separation.

In this article, results of PET track-etched membranes (PET TeMs) hydrophobized by photo-induced graft polymerization of stearyl methacrylate (SM) inside the pores were presented. The effects of monomer concentration, time of irradiation and the nature of the solvent on the degree of grafting and membrane morphology were investigated. The PET TeMs with pore diameters ranging from 350 nm (pore density of 1 × 108 pore/cm2) to 3.05 µm (pore density of 1 × 106 pore/cm2) were hydrophobized and tested for oil-water separation by using hexadecane-water and chloroform-water emulsions. Studies have shown high separation performance for membranes (up to 1100 mL/m2·s) with large pore diameters while achieving a high degree of purification.

Preparation of Hydrophobic PET Track-Etched Membranes for Separation of Oil-Water Emulsion.

The paper describes the separation of an oil-water emulsion by filtration using poly(ethylene terephthalate) track-etched membranes (PET TeMs) with regular pore geometry and narrow pore size distribution. PET TeMs were modified with trichloro(octyl)silane to increase their hydrophobic properties. Conditions for the modification of PET TeMs with trichloro(octyl)silane were investigated. The results of changes in the pore diameters and the contact angle depend on the concentration of trichloro(octyl)silane and the soaking time are presented. The obtained samples were characterized by FTIR, AFM, SEM-EDX and gas-permeability test. Chloroform-water and cetane-water emulsions have been used as a test liquid for oil-water separation.

Recent Progress in the Membrane Distillation and Impact of Track-Etched Membranes.

Membrane distillation (MD) is a rapidly developing field of research and finds applications in desalination of water, purification from nonvolatile substances, and concentration of various solutions. This review presents data from recent studies on the MD process, MD configuration, the type of membranes and membrane hydrophobization. Particular importance has been placed on the methods of hydrophobization and the use of track-etched membranes (TeMs) in the MD process. Hydrophobic TeMs based on poly(ethylene terephthalate) (PET), poly(vinylidene fluoride) (PVDF) and polycarbonate (PC) have been applied in the purification of water from salts and pesticides, as well as in the concentration of low-level liquid radioactive waste (LLLRW). Such membranes are characterized by a narrow pore size distribution, precise values of the number of pores per unit area and narrow thickness. These properties of membranes allow them to be used for more accurate water purification and as model membranes used to test theoretical models (for instance LEP prediction).

Modification of PET Ion-Track Membranes by Silica Nanoparticles for Direct Contact Membrane Distillation of Salt Solutions.

The paper describes desalination by membrane distillation (MD) using ion-track membranes. Poly(ethylene terephthalate) (PET) ion-track membranes were hydrophobized by the immobilization of hydrophobic vinyl-silica nanoparticles (Si NPs). Si NPs were synthesized by the sol-gel method, and the addition of the surfactant led to the formation of NPs with average size of 40 nm. The thermal initiator fixed to the surface of membranes allowed attachment of triethoxyvinyl silane Si NPs at the membrane surface. To further increase hydrophobicity, ethoxy groups were fluorinated. The morphology and chemical structure of prepared membranes were characterized by SEM, FTIR, XPS spectroscopy, and a gas permeability test. Hydrophobic properties were evaluated by contact angle (CA) and liquid entry pressure (LEP) measurements. Membranes with CA 125-143° were tested in direct contact membrane distillation (DCMD) of 30 g/L saline solution. Membranes showed water fluxes from 2.2 to 15.4 kg/(m2·h) with salt rejection values of 93-99%.

Functionalization of PET Track-Etched Membranes by UV-Induced Graft (co)Polymerization for Detection of Heavy Metal Ions in Water.

Nowadays, water quality monitoring is an essential task since environmental contamination and human exposure to heavy metals increased. Sensors that are able to detect ever lower concentrations of heavy metal ions with greater accuracy and speed are needed to effectively monitor water quality and prevent poisoning. This article shows studies of the modification of flexible track-etched membranes as the basis for the sensor with various polymers and their influence on the accuracy of detection of copper, cadmium, and lead ions in water. We report the UV-induced graft (co)polymerization of acrylic acid (AA) and 4-vinylpyridine (4-VPy) on poly(ethylene terephthalate) track-etched membrane (PET TeMs) and use them after platinum layer sputtering in square wave anodic stripping voltammetry (SW-ASV) for detection of Cu2+, Cd2+, and Pb2+. Optimal conditions leading to functionalization of the surface and retention of the pore structure were found. Modified membranes were characterized by SEM, FTIR, X-ray photoelectron spectroscopy (XPS) and colorimetric analysis. The dependence of the modification method on the sensitivity of the sensor was shown. Membrane modified with polyacrylic acid (PET TeMs-g-PAA), poly(4-vinylpyridine) (PET TeMs-g-P4VPy), and their copolymer (PET TeMs-g-P4VPy/PAA) with average grafting yield of 3% have been found to be sensitive to µg/L concentration of copper, lead, and cadmium ions. Limits of detection (LOD) for sensors based on PET TeMs-g-PAA are 2.22, 1.05, and 2.53 µg/L for Cu2+, Pb2+, and Cd2+, respectively. LODs for sensors based on PET TeMs-g-P4VPy are 5.23 µg/L (Cu2+), 1.78 µg/L (Pb2+), and 3.64 µg/L (Cd2+) µg/L. PET TeMs-g-P4VPy/PAA electrodes are found to be sensitive with LODs of 0.74 µg/L(Cu2+), 1.13 µg/L (Pb2+), and 2.07 µg/L(Cd2+). Thus, it was shown that the modification of membranes by copolymers with carboxylic and amino groups leads to more accurate detection of heavy metal ions, associated with the formation of more stable complexes.