TiO2-incorporated polyelectrolyte composite membrane with transformable hydrophilicity/hydrophobicity for nanofiltration separation

The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane. In this work, a hydrophilic PDA-[PDDA/TiO₂]⁺Cl^- membrane was prepared by a one-step codeposition of poly(diallyldimethylammonium chloride) (PDDA) polyelectrolyte solution containing positively charged TiO₂@ PDDA nanoparticles with the assistance of dopamine (DA). Such positively charged membrane can be transformed into a hydrophobic membrane PDA-[PDDA/TiO₂]⁺PFO^- via the counterion exchange between Cl^- and PFO^- (perfluorooctanoate). The transformation between hydrophilicity and hydrophobicity is reversible. For both hydrophilic and hydrophobic membranes, the nanofiltration performances were respectively investigated by the aqueous solution and ethanol solution of dyes including methyl blue (MB), Congo red (CR) and Evans blue (EB), and as well metal salt aqueous solution. The consecutive running stability and anti-fouling performance of both hydrophilic and hydrophobic membranes were explored. The results revealed that both membranes showed high nanofiltration performances for retention of dyes in (non)aqueous solution. For the hydrophilic membrane, the rejection of salts in a sequence is MgSO₄ > Na₂SO₄ > MgCl₂ > NaCl. Moreover, both     

New one-step process for preparation of microporous composite polysulfone/polyurethane hollow-fiber membranes

Microporous composite polysulfone/polyurethane hollow-fiber membranes were prepared by using a low reactivity polyurethane prepolymer in the casting solution and precipitating the membrane in a precipitation solution containing a polymerization catalyst. The catalyst was used to promote the polymerization of prepolymer at the membrane/precipitation solution interface causing formation of an interfacial interpenetrating polymer network. As a result, an ultra-thin layer of hydrophilic polysulfone/ polyurethane composite polymer was constituted in situ on the surface of the polysulfone microporous substrate during membrane formation. Membranes with nominal pore sizes ranging from 0.1–0.45 μm were prepared using this technique. The resulting membranes exhibited excellent fluxes and very low protein adsorption characteristics.     

二氧化钛调控基膜结构对氧化石墨烯复合膜性能的影响

以聚醚砜(PES)超滤膜为基膜,通过聚多巴胺(PDA)表面改性后压力沉积不同量的二氧化钛(TiO₂)纳米粒子作为基底,再沉积氧化石墨烯(GO)片层制得TiO₂/GO复合分离膜,重点考察基膜表面形貌对GO膜分离性能的影响。通过扫描电子显微镜、接触角测试仪、固体表面Zeta电位分析仪、X射线衍射分析仪等对有无TiO₂沉积层的GO复合膜进行表征,并考察TiO₂沉积量对GO复合膜分离性能的影响。结果表明,TiO₂纳米粒子以团簇状态均匀分布在改性的超滤膜表面,随TiO₂沉积量的增加,团簇密度增大,GO沉积后表层的峰谷结构更为明显,但表层的层间距并无明显改变。TiO₂/GO复合膜的水通量随TiO₂沉积量的增加而明显增大,TiO₂的沉积对GO沉积量低的复合膜通量的影响更明显,当GO沉积量为4.11μg/cm2,TiO₂沉积量为20.55μg/cm2时,复合膜的水通量较无TiO     

共混改性法对有机分离膜影响进展

有机聚合物如聚砜类、聚偏氟乙烯类、醋酸纤维素类、聚烯烃类等具有优良特性,是重要的膜材料。然而,膜污染问题限制了膜的应用。共混改性法操作简单,改性和成膜同时进行,效果稳定,通过共混改性法对有机聚合物膜进行膜改性可以有效降低膜污染。一方面通过共混亲水性聚合物、两亲性聚合物、两性离子聚合物对有机聚合物膜进行膜改性,制备改性膜的防污性和渗透性等性能均有不同程度的提升;另一方面,共混如TiO₂、SiO₂、碳纳米管（CNTs）、Al₂O₃、氧化石墨烯（GO）和ZrO₂等无机纳米粒子也可以制备高性能分离膜。本文从以上两方面综述了共混改性法的研究进展和存在的问题,并指出了通过共混改性提升膜的抗污染等性能是今后主要的发展趋势。     

Photocatalytic inactivation of Escherischia coli: Effect of concentration of TiO2 and microorganism, nature, and intensity of UV irradiation

The efficiency of photocatalytic disinfection, used to inactivate Escherischia coli K12 under different physico-chemical parameters, was examined. The photocatalyst chosen was the semiconductor TiO₂ degussa P25 and the irradiation was produced by an HPK 125 lamp. The effect of titania concentration was investigated using two E. coli concentrations. The photocatalyst concentration ranged from 0.1 to 2.5 g/L. The evolution of E. coli inactivation as function of time was discussed depending on the E. coli and TiO₂ concentrations. The optimal concentration of the photocatalyst, 0.25 g/L, is lower than that necessary to absorb all photons and to degrade the organic compounds. Some hypotheses are presented to explain this behaviour. The effect of the different domains of UV light (UVA, UVB, and UVC) was also studied and modification of the light irradiation intensity is discussed. No bacteria photolysis was obtained with UVA but the use UVC had, on the contrary, a detrimental effect on bacteria survival. The addition of titania at a low concentration, 0.25 g/L, improved the inactivation of E. coli in the presence of UVA and UVB, but a detrimental effect was observed under UVC. The disinfection efficiency increases as a function of light intensity, whatever the photocatalytic conditions (different TiO₂ concentrations and different UV domains). No bacterial growth was observed after disinfection, whether the system contained titania or not.     

Efficient destruction of pathogenic bacteria with AgBr/TiO2 under visible light irradiation

The photocatalytic inactivation of pathogenic bacteria in water was investigated systematically with AgBr/TiO₂ under visible light (λ > 420 nm) irradiation. The catalyst was found to be highly effective for the killing of Escherichia coli, a Gram-negative bacterium, and Staphylococcus aureus, a Gram-positive bacterium. The decomposition of the cell wall and cell membrane was directly observed by TEM and further confirmed by K⁺ leakage from the inactivated bacteria. A possible cell damage mechanism by visible light-driven AgBr/TiO₂ is proposed. In addition, the effects of pH, inorganic ions on bacterial photocatalytic inactivation were investigated. The electrostatic force interaction of the bacteria–catalyst is crucial for the efficiency of disinfection. Moreover, AgBr/TiO₂ supported on porous nickel showed much higher bactericidal activity than fixed P25 TiO₂ under visible or near UV light irradiation.     

Characterization of Surface Modification of Polyethersulfone Membrane

Surface modification of polyethersulfone (PES) membrane surfaces using UV/ozone pretreatment with subsequent grafting and interfacial polymerization on membrane surface was investigated in order to improve the resistance of membrane surface to protein adsorption. The surface modifications were evaluated in terms of hydrophilicity, chemical composition of the surface and static protein adsorption. In both methods, poly(vinyl alcohol) (PVA), poly(ethylene glycol) (PEG) and chitosan were chosen as hydrophilic polymers to chemically modify the commercial virgin PES membrane to render it more hydrophilic as these materials have excellent hydrophilic property. Modified PES membranes were characterized by contact angle and XPS. Contact angles of modified PES membranes were reduced by 19 to 58% of that of the virgin PES membrane. PES membrane modified with PEG shows higher wettability than other hydrophilic materials with the highest contact angle reduction shown for UV/ozone pretreated, PEG grafted PES membrane surface. In general, XPS spectra supported that the PES membranes were successfully modified by both grafting with UV/ozone pretreatment and interfacial polymerization methods. The results of the static protein adsorption experiments showed all surface modifications led to reduction in protein adsorption on PES membranes; the highest protein adsorption reduction occurred with membrane modified by UV/ozone pretreatment followed by PES grafting, which corresponded to the highest contact angle reduction. However, there seems to be no clear correlation between contact angle reduction and reduction in protein adsorption in the case that involved chitosan. Nevertheless, membranes modified with chitosan do show higher reduction in protein adsorption than membranes modified with other materials under the same conditions.     

Modified polyether-sulfone membrane: a mini review

Polyethersulfone has been widely used as a promising material in medical applications and waste-treatment membranes since it provides excellent mechanical and thermal properties. Hydrophobicity of polyethersulfone is considered one main disadvantage of using this material because hydrophobic surface causes biofouling effects to the membrane which is always thought to be a serious limitation to the use of polyethersulfone in membrane technology. Chemical modification to the material is a promising solution to this problem. More specifically surface modification is an excellent technique to introduce hydrophilic properties and functional groups to the polyethersulfone membrane surface. This review covers chemical modifications of the polyethersulfone and covers different methods used to enhance the hydrophilicity of polyethersulfone membrane. In particular, the addition of amino functional groups to polyethersulfone is used as a fundamental method either to introduce hydrophilic properties or introduce nanomaterials to the surface of polyethersulfone membrane. This work reviews also previous research reports explored the use of amino functionalized polyethersulfone with different nanomaterials to induce biological activity and reduce fouling effects of the fabricated membrane.     

Highly hydrophobic oil−water separation membrane: reutilization of waste reverse osmosis membrane

The increasing applications of seawater desalination technology have led to the wide usage of polyamide reverse osmosis membranes, resulting in a large number of wasted reverse osmosis membranes. In this work, the base nonwoven layer of the wasted reverse osmosis membrane was successfully modified into the hydrophobic membrane via surface deposition strategy including TiO₂ and 1H,1H,2H,2H-perfluorooctyltrichlorosilane (PFOTS), respectively. Various techniques were applied to characterize the obtained membranes, which were then used to separate the oil–water system. The optimally modified membrane displayed good hydrophobicity with a contact angle of 135.2° ± 0.3°, and its oil–water separation performance was as high as 97.8%. After 20 recycle tests, the oil–water separation performance remained more than 96%, which was attributed to the film adhesion of the anchored TiO₂ and PFOTS layer on the surface. This work might provide a new avenue for recycling the wasted reverse osmosis membrane used in oily wastewater purification.     

Performance of a newly developed hydrophilic additive blended with different ultrafiltration base polymers

The capability of modifying ultrafiltration (UF) membranes with different base‐polymers using a newly synthesized hydrophilic additive was investigated in this study. Five typical base‐polymers were tested: cellulose acetate (CA), polyetherimide (PEI), polyethersulfone (PES), polysulfone (PS), and polyvinylidene fluoride (PVDF). The changes in characteristics and performance of the membranes were analyzed using scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle analysis, and solute transport tests. It was found that the effect of the hydrophilic additive was different for each polymer. Higher additive contents resulted in higher permeation flux. A visible effect on water content and permeability was obtained but the impact was not shown clearly in contact angles, possibly the additive's concentration was not sufficiently high at the surface. In term of flux enhancement the PES and PVDF membranes benefited the most by the addition of the hydrophilic additive. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

光催化剂TiO2改性的研究进展

TiO₂具有光催化性能好、化学性质稳定、毒性低、价格低廉等优点,但由于禁带较宽,只对紫外光有响应,且电子和空穴容易复合,导致光催化活性和效率降低。本文介绍了TiO₂的几种主要改性方法的最新研究进展。表面沉积贵金属、半导体复合、染料敏化可以降低TiO₂的禁带宽度,增加其响应波长,提高太阳光的利用率。离子掺杂可使得TiO₂晶体表面产生缺陷,抑制光生电子和空穴的复合,增加表面活性中心的数量。碳纳米管和石墨烯掺杂则能够提高TiO₂对可见光的吸收率,扩大光响应范围,同时加快电子传输,减少载流子复合,提高催化效率。指出石墨烯作为新型掺杂材料具有很大的发展潜力,TiO₂基多组分复合型光催化剂可获得比单种组分表面改性或者掺杂TiO₂更好的效果。最后介绍了TiO₂表面的亲/疏水改性研究进展。     

Characteristics and performance of new types of ultrafiltration membranes with chemically modified surfaces

A special “quo;coating”quo; technique for making new types of surface modified ultrafiltration membranes has been developed and evaluated. The preparation procedure comprises the following principle:

A suitable ultrafiltration support membrane made by the traditional phase inversion process is surface coated with an aqueous solution containing a hydrophilic polymer and/or monomer having reactive groups and a catalyst (the coating step). The membrane material is selected from the class of fluorine containing polymers. By raising the temperature, the hydrophilic components are chemically bonded to the membrane material at the exposed surface by an addition reaction (the curing step).

Using this method you can impart hydrophilic properties to an otherwise hydrophobic, high resistant synthetic polymeric ultrafiltration membrane.

The properties of the final membrane depend on the characteristics of the support membranes, the composition of the coating solution and the amount applied and the reaction conditions. The technique seems more or less universal - e.g. it is possible to make a series of membranes with different cut-off values.

Results from measurements on different test solutions and on relevant industrial products are described. Characterization is done by measuring hydraulic permeability and rejection of dextrans and proteins. Flux stability and fouling tendency have been examined using different model foulants.

Membrane surface structures are characterized by SEM-studies. Analytical investigations using infrared spectroscopy (FTIR/ATR) and X-ray photoelectron spectroscopy (ESCA) have been tried to get some information about the chemistry of the coating.

The main advantages of the new membranes are that higher flux values compared to a standard polyethersulfone UF membrane are generally obtained - e.g. on whey flux improvements in the order for 20 – 50% have been observed and for fermentation broths fluxes can be several times greater compared to results using the standard membrane.

Some of these new membranes are now commercially available and are supplied by DDS FILTRATION, designated ETNA series.     

Characterization of composite membranes by their non-equilibrium thermodynamic transport parameters

Composite reverse osmosis membranes were prepared by interfacially polymerizing aromatic polyamide discriminating layers on the inside surface of microporous polyethersulfone hollow fibers and on the surface of flat sheet polysulfone ultrafilters. The salt rejection and flux of these membranes were measured at various feed pressures. From these measurements, the membrane reflection coefficients, salt permeances and hydraulic permeances were estimated. Neither the polysulfone ultrafilters nor the microporous polyethersulfone hollow fibers possessed any inherent salt rejecting capability. Both had a hydraulic permeance at least two orders of magnitude greater than that of the respective composite membranes. Consequently, it was concluded that the estimated transport parameters for both composite membranes were characteristics exclusively of thier polyamide discriminating layers. Comparison of these transport parameters generated insight into structural and functional aspects of the membrane that could not be visualized by scanning electron microscopy.     

Effect of adding a smart potassium ion-responsive copolymer into polysulfone support membrane on the performance of thin-film composite nanofiltration membrane

Thin-film composite (TFC) nanofiltration (NF) membranes were fabricated via the interfacial polymerization of piperazine (PIP) and 1,3,5-benzenetricart)oiiyl trichloride on polysulfone (PSf) support membranes blended with K^+-responsive poly(N-isopropylacryamideco- acryloylamidobenzo-15-crown-5)(P(NIPAM-co- AAB15C5)). Membranes were characterized by attenuated total reflection Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscope, scanning electron microscope, contact angle, and filtration tests. The results showed that:(1) Under K^+-free conditions, the blended P(NIPAM-co-AAB15C5)/PSf supports had porous and hydrophilic surfaces, thereby producing NF membranes with smooth surfaces and low MgSO4 rejections;(2) With K^+ in the PIP solution, the surface roughness and water permeability of the resultant NF membrane were increased due to the K^+-induced transition of low-content P(NIPAM-co-AAB15C5) from hydrophilic to hydrophobic;(3) After a curing treatment at 95℃, the improved NF membrane achieved an even higher pure water permeability of 10.97 L·m^-2·h^-1 - bar1 under 200 psi. Overall, this study provides a novel method to improve the performance of NF membranes and helps understand the influence of supports on TFC membranes.     

Reduced Fouling of Ultrafiltration Membranes Via Surface Fluorination

Abstract

The fouling resistance of a polysulfone membrane can be improved by fluorination. In the filtration of potato waste streams, fluorination of polysulfone membranes has improved both the initial flux and fouling rates of the treated membranes. Selectivities of the membranes as measured by COD and total organic nitrogen rejection were not affected by the fluorination process.

The fluorination process adds both fluorine and oxygen to the surface, and the increased oxygen and fluorine on the surface of the membrane increase the hydrophilic nature of the membrane. This increase of hydrophilicity reduces the rate of adsorption of hydrophobic foulants to the surface, decreasing the fouling rate. Increased hydrophilicity also decreases the capillary pressure and permits permeate flow through smaller pores.     

Innovative hydrophobic/hydrophilic perfluoropolyether (PFPE)/polyvinylidene fluoride (PVDF) composite membrane for vacuum membrane distillation

Though membrane distillation (MD) has gained more and more attention in the field of desalination, the wetting phenomenon was still a non-negligible problem. In this work, a method combined dip-coating and UV in situ polymerization for preparing hydrophobic/hydrophilic perfluoropolyether (PFPE)/polyvinylidene fluoride composite membranes. This composite membrane consisted of a top thin hydrophobic coating layer and hydrophilic substrate membrane. In terms of anti-wetting properties, contact angle and liquid entry pressure of all composite membranes (except for those based on 0.45 μm) exceeded 160° and 0.3 MPa, respectively. In particular, the desalination performance was tested in vacuum membrane distillation tests by feeding 3.5% (mass) saline solution (NaCl) at 60 ℃. The composite membranes with larger support pore size and lower PFPE content had higher membrane distillation flux. And for stability tests (testing the 0.22 μm membrane coated by 5% (mass) PFPE), the highest MD flux 29.08 kg·m^-2·h^-1 and stable salt rejection (over 99.99%) during the period. Except that, the effects of coating material concentration and pore sizes of substrate membrane were also investigated for surface morphology and topography, porosity, mechanical strength and pore size characteristics. This work provided a simple and effective alternative to prepare excellent hydrophobic composite membranes for MD applications.     

The kinetics of phenol decomposition under UV irradiation with and without H2O2 on TiO2, Fe–TiO2 and Fe–C–TiO2 photocatalysts

H₂O₂ used in the photo-Fenton reaction with iron catalyst can accelerate the oxidation of Fe²⁺ to Fe³⁺ under UV irradiation and in the dark (in the so called dark Fenton process). It was proved that conversion of phenol under UV irradiation in the presence of H₂O₂ predominantly produces highly hydrophilic products and catechol, which can accelerate the rate of phenol decomposition. However, while H₂O₂ under UV irradiation could decompose phenol to highly hydrophilic products and dihydroxybenzenes in a very short time, complete mineralization proceeded rather slowly. When H₂O₂ is used for phenol decomposition in the presence of TiO₂ and Fe–TiO₂, decrease of OH radicals formed on the surface of TiO₂ and Fe–TiO₂ has been observed and photodecomposition of phenol is slowed down. In case of phenol decomposition under UV irradiation on Fe–C–TiO₂ photocatalyst in the presence of H₂O₂, marked acceleration of the decomposition rate is observed due to the photo-Fenton reactions: Fe²⁺ is likely oxidized to Fe³⁺, which is then efficiently recycled to Fe²⁺ by the intermediate products formed during phenol decomposition, such as hydroquinone (HQ) and catechol.     

Comparative performance study of polyethersulfone and polysulfone membranes for trypsin isolation from goat pancreas using affinity ultrafiltration

The comparative performance of polysulfone and polyethersulfone membranes (of 30 kDa MWCO) in isolation of trypsin from goat pancreas by affinity ultrafiltration is examined using cross-linked soybean trypsin inhibitor (STI) as affinity ligand, 0.1 M Tris–HCl as wash buffer and 0.5 M KCl–HCl as elution buffer in an unstirred, dead-ended module at 392.28 kPa (4 kg/cm²) transmembrane pressure and room temperature (ca. 30 °C) with 1:1 (v/v) ratio of pancreatic extract and wash buffer. No active trypsin was found to be detectably present in the washing phase permeate in any of the experiments, indicating good binding efficiency of the target enzyme with the ligand employed. The total protein recovery obtained with the polyethersulfone membrane (70%) is 1.5 times higher than that with the polysulfone (46%). Yields of active trypsin for the two membranes are, however, similar (74% for polyethersulfone and 70% for polysulfone) although comparable with earlier reported trypsin yield (from porcine pancreas). In both the washing and elution phases of affinity ultrafiltration, the polyethersulfone membrane facilitates consistently and substantially higher volumetric flux as well as permeated protein throughput than the polysulfone.     

Separation of propranolol enantiomers through membranes based on chiral derivatized polysulfone

The characterization of new synthesized chiral polymeric membranes, based in polysulfone polymer is here reported. Polysulfone was derivatized to chiral polysulfone, by bonding covalently the chiral carrier, N-dodecyl-4(R)-hydroxy-l-proline, to the polymer matrix. Two different chiral polysulfones, referred to as CPS_A and CPS_B, have been synthesized and used in the preparation of chiral polymeric membranes. However, as a consequence of the limited CPS_B solubility, only CPS_A resulted adequate to obtain useful membranes. Therefore, various chiral polysulfone membranes containing different amounts of CPS_A in unmodified polysulfone (PS) were prepared and properly characterized by scanning electron microscopy (SEM) and by enantioselective transport experiments of racemic propranolol. Dialysis transport experiments allowed us to determine the influence of the carrier content in the membrane on the transport rate and on enantiomer separation. Membranes containing a CPS_A/PS ratio of 1:3 showed an alpha value of 1.1 at 96 h of performance. Modelling of the propranolol transport rate is also performed.     

Fouling control in sugarcane juice ultrafiltration with surface modified polysulfone and polyethersulfone membranes

Commercial 50 and 100 kD polyethersulfone (PES) and polysulfone (PS) ultrafiltration membranes were surface modified by UV photografting of poly(ethylene glycol) methacrylate (PEGMA) monomer. The modified membranes were characterized by the degree of grafting, water flux and molecular weight cutoff (MWCO) rating. The flux and fouling of the modified and unmodified membranes were examined with sugarcane juice and its polysaccharide fraction. Under the conditions of this study, the modified membranes displayed a low degree of grafting (26-36 μg/cm²), which was independent of the UV exposure duration; however, both membrane water flux and MWCO rating were affected by the irradiation time. In the best case, the modified membranes exhibited lower fouling with sugarcane juice; furthermore, the propensity to foul also decreased. More significantly, juice flux recovery was almost complete for successive UF-cleaning cycles.