Self-doped sulfonated polyaniline ultrafiltration membranes with enhanced chlorine resistance and antifouling properties

Membranes heavily rely on chlorination to diminish (bio)fouling, but chlorination can also lead to membrane degradation. We developed sulfonated polyaniline (S-PANI) ultrafiltration (UF) membranes with improved chlorine resistance and intrinsic antifouling properties. The S-PANI membranes were synthesized through Non-solvent Induced Phase Separation (NIPS). Membrane performance was evaluated under harsh chlorine conditions (250 ppm sodium hypochlorite for 3 days under different pH conditions). The S-PANI membranes showed improved chlorine resistance including a stable performance without changes in model foulant BSA rejection. In contrast, PANI membranes suffered critical structural damage with complete leakage and commercial PES membranes showed a 76% increase in pure water flux and a noticeable change in BSA rejection. Small changes in S-PANI membrane performance could be linked to membrane structural changes with pH, as confirmed by SEM, IR spectroscopy, and contact angle measurements. Additionally, the S-PANI membranes showed better antifouling properties with a high flux recovery ratio in comparison to PANI membranes using alginic acid, humic acid, and BSA model foulants. Chemical cleaning by sodium hypochlorite re-instated the transport properties to its initial condition. Overall, the developed S-PANI membranes have a high chlorine tolerance and enhanced antifouling properties making them promising for a range of UF membrane applications.     

Change of membrane performance due to chlorination of crosslinked polyamide membranes

A systematic investigation of the relationship between chlorine exposure of a thin film composite crosslinked polyamide membrane (LE membrane, FilmTec©) and changes in membrane performance (water flux and salt rejection) is discussed here. Performance change of crosslinked polyamide membranes due to chlorination depended on pH and concentration of chlorine in the soaking bath. Membranes chlorinated at low pH and high chlorine concentration showed flux decreases at an early stage of filtration and then increases with filtration time. On the other hand, membranes chlorinated at high pH and low chlorine concentration showed flux increases at an early stage and then decreases with filtration time. Performance of chlorinated polyamide membranes was determined by the balance between rearrangement of polymer chains and the distortion of the chains due to chlorination. A conceptual model of performance change was proposed consistent with the chlorination of polyamide membranes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5895–5902, 2006     

Change of chemical composition and hydrogen bonding behavior due to chlorination of crosslinked polyamide membranes

The effect of membrane exposure to hypochlorite oxidant on property changes (chemical composition and hydrogen bonding behavior) of four FilmTec© thin film composite crosslinked polyamide membranes has been investigated. Crosslinking densities of the membranes were about 25–35%, with about 3–4 chlorines bound to the repeating unit of the polyamide membranes. This was equivalent to ～ 39% of all nitrogens being chlorinated in the polyamide membranes assuming the amide nitrogen is the dominant reaction site with chlorine. FTIR spectra showed the amide I band (C?O stretching peak at 1663 cm^?1) of polyamide membranes shifted to higher wave‐numbers and the peak intensity of the amide II band (N? H bending peak at 1541 cm^?1) decreased after chlorination. The peak shift and decrease of peak intensity resulted from breakage of hydrogen bonds between C?O and N? H groups within the polymers. The XPS and FTIR analytical analysis showed that there is no difference in the chlorine attack of polyamide membranes of higher or lower crosslinking density, and that the chlorination breaks and weakens hydrogen bonding. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface-tailoring chlorine resistant materials and strategies for polyamide thin film composite reverse osmosis membranes

Polyamide thin film composite membranes have dominated current reverse osmosis market on account of their excellent separation performances compared to the integrally skinned counterparts. Despite their very promising separation performance, chlorine-induced degradation resulted from the susceptibility of polyamide toward chlorine attack has been regarded as the Achilles’s heel of polyamide thin film composite. The free chlorine species present during chlorine treatment can impair membrane performance through chlorination and depolymerization of the polyamide selective layer. From material point of view, a chemically stable membrane is crucial for the sustainable application of membrane separation process as it warrants a longer membrane lifespan and reduces the cost involved in membrane replacement. Various strategies, particularly those involved membrane material optimization and surface modifications, have been established to address this issue. This review discusses membrane degradation by free chlorine attack and its correlation with the surface chemistry of polyamide. The advancement in the development of chlorine resistant polyamide thin film composite membranes is reviewed based on the state-of-the-art surface modifications and tailoring approaches which include the in situ and post-fabrication membrane modifications using a broad range of functional materials. The challenges and future directions in this field are also highlighted.     

Flux enhancement of thin film composite RO membrane by controlled chlorine treatment

A major stumbling block in polyamide thin film composite RO membrane performance is its incompatibility with chlorine and oxidizing agents. The amide bond of the membrane is highly vulnerable to chlorine attack. Two reactions are possible with chlorine exposure i.e. N-H bond chlorination and/or aromatic ring chlorination. In this way, chlorine may cause degradation/modification in the membrane leading to deterioration in performance.However, low concentration of chlorine up to a certain time may give synergistic effect on membrane and improve its performance. Chlorine solution, if exposed to membrane for certain time gives enhancement in trans-membrane flux of the membrane.The same solution if exposed for more time deteriorates ultra-thin polyamide layer of TFC membrane. Conspicuously, the membrane with poor salt rejection and flux benefited more as compared to the membrane with better performance. In the present study, membranes with different salt rejection and flux were taken and exposed to the inorganic chlorine solution. The inorganic chlorine solutions were made by dissolving sodium hypochlorite in pH buffer. The different solutions were made by varying pH to investigate the pH dependence. The membrane samples were kept in solution for different time durations. The exposure time was monitored and the exposure level was taken in terms of ppm h (ppm chlorine solution exposed to membrane for a fixed time in h). With the same chlorine concentration, effect of varying pH was studied. Spiral wound TFC membrane modules were also subjected to chlorine solution to study its effect.     

New chlorine‐resistant polyamide reverse osmosis membrane with hollow fiber configuration

New asymmetric hollow fiber reverse osmosis (RO) membrane was developed from a new chlorine‐resistant copolyamide [4T‐PIP(30)] with a piperazine moiety by a conventional phase‐separation method. The new 4T‐PIP(30) hollow fiber membrane has the same low‐pressure RO performance as cellulose triacetate hollow fiber membrane (FR = 205 L/m² day, Rj = 99.6%) and superior chlorine resistance as well as pH resistance to conventional aramid RO membranes. Structural analysis and viscoelastic study revealed that the new hollow fiber consisted of a top skin, dense layer, and microporous layer, and that it began to decrease its elasticity at 80°C in water, which is possibly related to its good and stable RO performance around room temperature. Several kinds of RO modules were made from the new hollow fiber membranes, for which RO performances were stable for 2 years in chlorinated feed water desalination (the free residual chlorine ranged from 0.l to 1.1 mg/L). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 517–527, 2001     

氧化石墨烯掺杂反渗透混合基质膜制备及性能

由于芳香族聚酰胺反渗透膜在抗污染性以及耐氯性方面存在不足,限制了其在海水淡化等方面的应用。采用往油相中添加氧化石墨烯（GO）的二次界面聚合法改性了商业反渗透膜,评价了GO掺杂反渗透混合基质膜的分离性能和耐氯性能,并用接触角仪、Zeta电位仪、扫描电镜和原子力显微镜等仪器表征了膜的亲水性能、荷电性能以及膜表面形貌。结果表明,GO的添加提高了膜的分离性能、耐氯性能和亲水性能;当GO添加量为30 mg·L^-1时,膜的通量为（77.7±0.9） L·m^-2·h^-1,膜的截留率为97.6%±0.5%,相比商业膜分别提高了38.4%和4.5%。当氯化强度低于4800 mg·L^-1·h时,膜的水通量和盐截留率变化不明显。     

Preparation of graphene oxide/polyamide composite nanofiltration membranes for enhancing stability and separation efficiency

Polyamide (PA) NF membranes are synthesized on a hollow fiber support by the interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC). Then, GO is coated on the PA layer to decorate the NF membrane surface (denoted GO/PA-NF). This strategy aims to improve the hydrophilicity, chlorine resistance and separation stability of the membrane. The optimization, chemical composition, morphology, and hydrophilicity of the synthesized GO/PA-NF membrane are characterized. Results indicate that the optimized GO/PA-NF in terms of rejection rate and flux are with 0.05 wt% GO. The rejection of GO/PA-NF for Na2SO₄ and MgSO₄ is 99.4% and 96.9%, respectively. Even if the GO/PA-NF is immersed in 1000 ppm NaClO solution for 48 h, the NF membrane still maintains stable salt rejection. The developed NF membranes exhibit excellent treatment performance on dying wastewater. The permeate flux and rejection of GO/PA-NF toward Congo red solution are determined to be 44.2 L/m²h and 100%, respectively. Compared with the PA membrane, GO/PA-NF presents a higher rejection for Na₂SO₄ (99.4%) and a lower rejection for NaCl (less than 20%), which shows that the NF membranes have a better divalent/monovalent salt separation performance. This study highlights the superior performance of GO/PA-NF and shows its high potential for application in wastewater treatment.     

聚电解质静电沉积改性制备高性能反渗透膜

利用次氯酸钠溶液对商品反渗透膜表面进行氯化处理,然后将聚阳离子电解质壳聚糖通过静电吸附作用沉积在RO膜的表面,系统地研究了氯化过程的pH、氯化时间、次氯酸钠浓度、壳聚糖浓度及其沉积时间对膜性能的影响,以制备出高通量、高截留率的RO膜。在压力1.55 MPa、原料液温度（298±1）K的条件下,测定RO膜处理2000 μg·g^-1氯化钠溶液的水通量和截留率。结果表明,当pH=9、氯化时间为30 min、次氯酸钠浓度为1000 mg·L^-1时,水通量较原膜提高了约19.89%,截留率略有提高;当壳聚糖浓度为0.1%（质量分数）、沉积时间为30 min时,改性膜的接触角降低到34.88°,亲水性提高,水通量较氯化后的RO膜几乎保持不变,为60.55 L·m^-2·h^-1,截留率达到了99.56%。经过氯化和沉积改性后的RO膜水通量和截留率均得到了提高。     

Preparation of antibacterial biocompatible polycaprolactone/keratin nanofibrous mats by electrospinning

Keratin-based materials are widely used in biomedical applications due to excellent biocompatibility and biodegradability. In this study, keratin was extracted from waste wool fibers and blended with polycaprolactone (PCL) to produce PCL/keratin nanofibrous mats by electrospinning. The electrospun PCL/keratin nanofibrous mats were chlorinated in diluted sodium hypochlorite solution to endow antibacterial properties. The prepared nanofibrous mats were characterized by scanning electron microscopy, X-ray photoelectron, and Fourier infrared spectroscopy. The effect of the chlorination time on the active chlorine loading of the mats was investigated. The chlorinated PCL/keratin nanofibrous mats with 0.78 ± 0.009 wt% active chlorine displayed potent antibacterial activity against Gram-positive Staphylococcus aureus (ATCC 6538) and Gram-negative Escherichia coli O157:H7 (ATCC 43895) with 6.88 and 6.81 log reductions, respectively. It was found that the mats were compatible with mouse fibroblast cells (L929). The chlorinated PCL/keratin nanofibrous mats might find promising applications in the biomedical field.     

Green lignin-based polyester nanofiltration membranes with ethanol and chlorine resistance

As the main water treatment material, polymeric membranes inevitably suffer from membrane fouling. In this work, novel lignin-based polyester composite nanofiltration membranes (NFM) with ethanol and chlorine resistance were fabricated via interfacial polymerization. Lignin alkali (LA), a green lignin derivative, typically treated as chemical waste in the paper industry, was employed as the aqueous monomer, trimesoyl chloride (TMC) is served as the organic monomer. The structure and separation properties of the lignin-based NFM were studied, revealing that the dense polyester separation layer may show good performance for dye removal. The rejections of the optimized LA/TMC-3 membrane with an excellent permeation flux of 13.9 kg m^?2?h^?1 for rose Bengal sodium salt, brilliant blue, congo red, rhodamine B, MgSO₄, and NaCl are 97.6%, 97.3%, 97.8%, 71.34%, 51.4%, and 31.8%, respectively. Moreover, the LA/TMC-3 membrane also shows long-term tolerance in ethanol and sodium hypochlorite solution; the rejection of LA/TMC-3 to dye only decreases 8% after 8 days when immersed in alcohol, while the normalized rejection maintains 94% after 4000 ppm-hours of continuous exposure to chlorine. This lignin-based polyester membrane may broaden the sustainable utilization sphere of lignin derivatives, at that provide a referable direction for the development of membrane materials.     

聚丙烯水相悬浮热氯化

研究了等规聚丙烯(IPP)水相悬浮热氯化,考察了氯化时间和温度、IPP粒径、搅拌转速、通氯速率等条件对氯化反应的影响。发现氯含量随氯化温度的升高而增大,随IPP粒径的减小而呈线性增大;在IPP充分分散条件下搅拌和通氯速率对氯化几无影响。扫描电镜(SEM)照片显示,氯化反应首先发生在粒子表面,氯化产物将粒子表面孔隙填充,增加了氯向粒子内部扩散的阻力,致使粒子内部的氯化反应缓慢。     

A CASE STUDY FOR CONTROL STRUCTURE SELECTION: CHLORINATION STAGE IN THE BLEACHING PROCESS OF A PULP AND PAPER PLANT

The minimization of chlorinated organic compounds in the effluents of the chlorination unit of a pulp mill is proposed by the use of a control structure for the chlorination unit. Bleached pulp properties are related to the unbleached pulp properties: lignin content, brightness, and viscosity, as well as the amount of chlorinated organics in the bleachery effluent. The best feasible control pairings are studied by RGA and SVD methods. Kappa number of the bleached pulp (a measure of lignin content) and percent consistency of the pulp to be bleached; residual chlorine (which affects the amount of chlorinated organics discharged) and percent chlorine/pulp ratio adapted in the chlorination stage; and exit pulp viscosity (which directly affects strength and tear resistance of the paper) and residence time in the chlorinator are chosen to be the best pairings.     

A novel perforated electrode flow through cell design for chlorine generation

Chlorination remains a predominant method for disinfecting drinking water. Electrogeneration of chlorine has the potential to become the favoured method of chlorine production if costs can be lowered and chlorine generation efficiencies can be improved. A novel perforated electrode flow through (PEFT) cell design has been developed to address these problems. The electrodes were made from low-cost graphite sheets and stainless steel mesh and separated by a non-conducting fabric membrane. This electrode configuration allows reduction of electrode separation to 0.1 mm or less, minimizing cell resistance and increasing electrical efficiency. The new PEFT configuration generates hypochlorite from a 0.5 mol L⁻¹ brine at a current efficiency of better than 60%. As an inline in situ device, it produces chlorine concentrations known to be sufficient to disinfect water, from chloride concentrations as low as 0.004 mol L⁻¹ (available in most natural waters) by a single pass of the water through the cell operating at 11 V. The possibility of a portable device operated by a 12-V battery is indicated.     

Head-to-head polymers: 19. Chlorination of cis-1,4-polybutadiene

Chlorination of cis-1,4-polybutadiene (PB) has been studied in detail. It was found that chlorination must be carried out in an oxygen free atmosphere at polymer concentrations below 0.5%, and at temperatures below room temperature in mixed solvents with dichloromethane as the major component. In the initial stage of chlorine addition to the double bonds of cis-1,4-polybutadiene, block structures of chlorinated segments are formed. The chlorine addition to the cis-butadiene units was not stereospecific and the final chlorination product had nearly a 1:1 ratio of the threo- and erythro structure of the CHCICHCI-units. Microphase separation in partially chlorinated PB was observed by d.s.c., dynamic-mechanical measurement, and transmission electron microscopy. It was concluded that partially chlorinated PB, whose degree of chlorination was lower than 65 mole %, was composed of almost pure cis-1,4-PB domains and a separate phase which consists ofCH₂CHCICHCICH₂units with perhaps as much as 10% of cis-1,4-PB units incorporated in this phase. If the degree of chlorination is more than 90 mole % one phase exists.     

Effect of hypochlorite treatment on performance of hollow fiber membrane prepared from polyethersulfone/N‐methyl‐2‐pyrrolidone/tetronic 1307 solution

Polyethersulfone (PES) hollow fiber membrane was prepared by blending with nonionic surfactant Tetronic 1307 to improve its hydrophilicity. The membranes were posttreated by hypochlorite solution of 10, 100, 500, and 2000 ppm. The effect of hypochlorite treatment on the performance of PES membrane was investigated. Experimental results showed that the water permeability of treated membrane was two to three times higher than that of untreated membrane in case of blend membrane prepared from PES/N‐methyl‐2‐pyrrolidone (NMP)/Tetronic 1307 solution. On the other hand, hypochlorite treatment has no effect on water permeability of the membrane prepared from PES/NMP solution. Elemental analysis and ATR–FTIR measurement results indicated that hypochlorite treatment led to decomposition and leaching out of Tetronic 1307 component from the membrane. The change of membrane surface structure by the hypochlorite treatment was confirmed by atomic force microscopy measurement. The hypochlorite treatment brought about no significant impact on the mechanical property of the membranes. This indicated that the hypochlorite treatment of PES membrane prepared with surfactant was a useful way to improve the water permeability without the decrease of membrane strength. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

5－氯水杨酸的合成研究

比较了氯气直接氯代法和次氯酸叔丁酯法合成５氯水杨酸的合成条件和产物的纯度。认为直接氯代法生成物杂质较多而不易分离，但生产成本较低；而次氯酸叔丁酯法的产物所含杂质较少，但叔丁醇及溶剂易挥发，回收率低，生产成本较高     

5－氯水杨酸的合成研究

比较了氯气直接氯代法和次氯酸叔丁酯法合成５ 氯水杨酸的合成条件和产物的纯度。认为直接氯代法生成物杂质较多而不易分离，但生产成本较低；而次氯酸叔丁酯法的产物所含杂质较少，但叔丁醇及溶剂易挥发，回收率低，生产成本较高     

IMPROVED PEEL STRENGTH IN VULCANIZED SBR RUBBER ROUGHENED BEFORE CHLORINATION WITH TRICHLOROISOCYANURIC ACID

The effectiveness of chlorination as surface treatment to improve the adhesion of synthetic vulcanized styrene-butadiene rubber (SBR) depends on several experimental variables. Solutions of trichloroisocyanuric acid (TCI) in methyl ethyl ketone (MEK) have been used as effective chlorination agents for several rubbers. In this study, the influence of roughening prior to chlorination treatment of a SBR rubber (R2) and the durability of the modifications produced as the time after chlorination increased have been considered. Two concentrations of the chlorination agent (0.5 and 2 wt% TCI/MEK) have been used and the chlorination treatment was applied on the R2 rubber surface using a brush. Characterization of the treated surfaces was carried out using contact angle measurements, ATR-IR spectroscopy and Scanning Electron Microscopy (SEM). T-peel tests of treated R2 rubber/polyurethane adhesive joints have been carried out to determine the adhesion properties. Roughening was an effective treatment to remove paraffin waxes (antiadherent moieties) from the R2 rubber surface. When the chlorination is produced on the roughened R2 rubber, more noticeable chemical and morphological modifications were produced, and higher adhesion was obtained. On the other hand, TCI particles appeared on the roughened and unroughened chlorinated R2 rubber surface, and the size of these TCI particles were decreased by increasing the time after treatment. Furthermore, similar peel strength values were obtained for time after halogenation higher than 2 hours; for shorter time, a decrease in peel strength was found by increasing the time, due to the migration of paraffin wax to the rubber surface.     

Improved peel strength in vulcanized sbr rubber roughened before chlorination with trichloroisocyanuric acid

The effectiveness of chlorination as surface treatment to improve the adhesion of synthetic vulcanized styrene-butadiene rubber (SBR) depends on several experimental variables. Solutions of trichloroisocyanuric acid (TCI) in methyl ethyl ketone (MEK) have been used as effective chlorination agents for several rubbers. In this study, the influence of roughening prior to chlorination treatment of a SBR rubber (R2) and the durability of the modifications produced as the time after chlorination increased have been considered. Two concentrations of the chlorination agent (0.5 and 2 wt% TCI/MEK) have been used and the chlorination treatment was applied on the R2 rubber surface using a brush. Characterization of the treated surfaces was carried out using contact angle measurements, ATR-IR spectroscopy and Scanning Electron Microscopy (SEM). T-peel tests of treated R2 rubber/polyurethane adhesive joints have been carried out to determine the adhesion properties. Roughening was an effective treatment to remove paraffin waxes (antiadherent moieties) from the R2 rubber surface. When the chlorination is produced on the roughened R2 rubber, more noticeable chemical and morphological modifications were produced, and higher adhesion was obtained. On the other hand, TCI particles appeared on the roughened and unroughened chlorinated R2 rubber surface, and the size of these TCI particles were decreased by increasing the time after treatment. Furthermore, similar peel strength values were obtained for time after halogenation higher than 2 hours; for shorter time, a decrease in peel strength was found by increasing the time, due to the migration of paraffin wax to the rubber surface.