用相转换法制备非对称膜的凝胶动力学研究

本文采用了一套先进的实验装置来测定用相转换法制备非对称膜的凝胶速度，得到了和Ｓｔｒａｔｈｍａｎｎ等人不同的结果。实验结果及理论分析表明，凝胶动力学过程不能简单地用一个Ｆｉｃｋ扩散定律来描述。本文提出可以用凝胶速度常数Ｋ来表征凝胶速度和生态的膜结构。     

Effect of surfactant on morphology and pore size of polysulfone membrane

The skin layer structure can be changed by adjusting the diffusion rate of the non-solvent into the polymer solution between membrane and coagulation bath through adding surfactant into either coagulation bath or dope solution. When adding SDS in coagulation bath, the variation trend of apparent diffusion coefficient during phase separation and scanning electron microscopy morphology of resultant membranes indicated that, at the beginning SDS migrated to the membrane-bath interface during phase separation process, playing a role as mechanical barrier within 0.15 wt% SDS concentration. Once the SDS concentration exceeds CMC, the remaining SDS will form micelles act as a carrier, hence, the phase separation rate accelerated. The membranes were characterized roughness parameters, obtained by the atomic force microscopic technique. While adding surfactant in the dope solution, compared with SDS addition into the coagulation bath, apparent diffusion coefficient and SEM morphology showed the similar trend, and the excellent range of SDS concentration is 0.08 wt%-0.1 wt%. As changing the nature of surfactant in the dope solution, we found that, with the increase of surfactant hydrophile-lipophile balance (HLB) value, the rate of phase separation speeds up, the size of macrovoid increases, flux increases gradually and rejection is weakened.     

Stabilization of supported liquid membranes by gelation with PVC

This article describes the gelation by PVC of supported liquid membranes (SLMs) for nitrate removal using a quaternary ammonium salt as carrier. Untreated SLMs with this carrier are very unstable. To improve their stability, the LM-phase was gelled with polyvinyl chloride as gel-forming polymer. Both homogeneous gelations of the LM-phase as well as the application of an interfacial gel layer are described. In all cases, no improvement of the stability could be observed. For both types of gelation, the initial nitrate flux decreased while the flux after 1 day of degradation was almost zero. The flux decrease is the result of a decrease of the diffusion rate of carrier complex as a result of the presence of the gel network and the thickness of the applied gel layer. The absence of any stability improvement might indicate that the loss of LM-phase from these membranes is due to dissolution of carrier or membrane solvent and not a result of emulsion formation only. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1205–1216, 1997     

The kinetic study for asymmetric membrane formation via phase-inversion process

The kinetics of membrane formation by phase inversion was studied emphasizing the rate of solvent diffusion from a polymer solution during the phase separation. Diffusional behavior of the solvent can be considered Fickian. Membrane morphologies were shown to be strongly dependent on the rate of solvent diffusion, indicating that mass-transfer rates of solvent and nonsolvent during phase separation are crucial for determining the final membrane structure for the following system: polysulfone (polymer), dimethyl acetamide (solvent), and ethanol (gelation medium). Specific reference to the mechanism of macrovoid formation was explored. Macrovoid formation was found to be proportional to the square root of time, suggesting that it is governed by a diffusion process. In addition, latex particles of coagulated polymer formed by the nucleation and growth of a concentrated polymer phase was observed inside the macrovoids. Such a result implies that the macrovoids grow by a diffusive flow which results from the growth of the polymer lean phase during binodal decomposition. © 1996 John Wiley & Sons, Inc.     

Effect of ethylene glycol monobutyl ether on skin layer formation kinetics of asymmetric membranes

The present work was concerned with skin layer formation kinetics of Polyethersulfone with Cardo (PES‐C) asymmetric membranes by the phase inversion method. Gelation process was observed using an online optical microscope–CCD camera experimental system, the result indicated that a single linear correlation between square value of precipitation front move (X²) and time (t) did not exist for the whole gelation process, which was different from the traditional conclusion. The effect of Ethylene glycol monobutyl ether (EGME) on skin layer gelation process was investigated, and the skin layer formation kinetics equation was determined, which could be described with gelation rate constant equation. The gelation rate constant decreased with the increase of concentration of EGME. EGME concentrations affected the viscous flow activation energy, and the increase of viscous flow activation energy led to the decrease of gelation rate. The change trend of the gelation rate was exactly the same as that of the flux. The results helped to understand the asymmetric membrane skin layer formation process better, which was important for controlling the membrane separation properties and designing the membranes for a specific application. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of magnetic casting on the permeability and anti-fouling properties of a novel iron oxide/alumina/polysulfone mixed matrix membrane

Novel mixed matrix membranes (MMMs) were fabricated using Fe₃O₄, and Al₂O₃ nanoparticles (NPs) were added to the polysulfone (PSf) and N-methylpyrrolidone (NMP) solution. The nanocomposite membranes were fabricated using the NIPS (non-solvent induced phase separation) method. In order to create preferential permeation pathways for water across the MMMs, membrane formation is accomplished with an external magnetic field. Using magnetic casting cause the targeted placement of NPs in the best location and orientation. The performance of the prepared membranes was examined in terms of pure water flux and fouling parameters. Magnetic casting considerably increased pure water flux and decreased the total resistance of the optimum mixed matrix membrane, which contains 0.2% wt. of Fe₃O₄ NPs to 1175 L/m²h and 13.4 * 10¹¹ (m⁻¹), respectively. This is explained by the ordering of magnetic nanoparticles on the membrane sub-layer cast under the magnetic field of 500 mT, which changed the sub-layer structure. Less rough membrane surface of the mixed matrix membranes offered preferable anti-fouling properties against fouling by BSA proteins. The characterization of fabricated membranes was carried out using field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), energy dispersive X-ray (EDX), and water contact angle measurement methods.     

Effects of operation conditions,solvent and gelation bath on morphology and performance of PPESK asymmetric ultrafiltration membrane

The effect of gelation temperature, evaporation time, solvent and gelation bath on the structure and performance of poly(phthalazinone ether sulfone ketone) (PPESK) asymmetric ultrafiltration membrane via phase inversion are investigated; the relationship between gelation thickness of dope solutions (X) and time for several polymer solutions with different solvents and gelation bath by online optical microscope–CCD camera experimental system (OM–CC system) are obtained. The results show that gelation temperature has much stronger influence on aperture opening ratio of membrane surface (AOR) and average diameter of membrane surface (AD) than evaporation time, whereas evaporation time has greater effect on the structure factor of membrane cross-section (S). Bovine serum albumin rejection (R) is mainly determined by surface structure; however, pure water flux (J) is controlled not only by the structure of surface and cross-section, but also the connectivity of the pores. PPESK membranes with fine performance can be fabricated under appropriate gelation temperature and evaporation time. In addition, the membrane structure and performance vary widely when various solvents and gelation bath are employed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

聚偏氟乙烯中空纤维膜的制备

本丈研究了聚偏氟乙烯（PVDF）中空纤维微滤膜的制备。采用亲水聚合物材料（如PMMA、改性聚醚硅油等）对聚偏氟乙烯材料进行共混改性,显著提高了膜材料的亲水性;同时由于材料性质的改变,导致膜材料在成膜时的凝胶特性和相转化发生变化,所成膜的孔径、通水量、孔隙率、表面性能等也发生改变。通过选择合适的共混体系,可制备出高性能、高孔隙率、表面亲水的聚偏氟乙烯中空纤维膜。     

Self-assembled microstructured polymeric and ceramic surfaces

Self-assembled microstructures were manufactured by dip coating of substrates with unfilled and filler-loaded preceramic polymer mixtures in the presence of a solvent and a non-solvent. The nature of the polymers was characterized by their solubility parameters. Variation of the polymer/polymer ratio and the volume fraction of the solvent and/or non-solvent led to different surface structures. Studies of the structure formation mechanism indicate that demixing processes of the polymers are responsible for self-assembly in filler-free mixtures. In filler-loaded mixtures the structure formation process, however, is more complex. The micro-structured polymeric coatings obtained from filler loaded systems were converted into polymer derived ceramic coatings under shape retention. High specific surface areas were measured after thermal conversion.     

Phase behavior and morphological studies of polyimide/PVP/solvent/water systems by phase inversion

The solubility gaps for poly(vinyl pyrrolidone) (PVP) in four polyimide solutions (NMP, DMF, GBL, DMSO) were determined by cloud point measurement and correlated with χ_PI/Solvent and Δδ_PVP/Solvent. Membranes prepared with NMP and DMF systems showed a tendency of suppressing fingerlike structure with addition of PVP. On the other hand, membranes prepared with GBL and DMSO systems showed an inclination toward inducing macrovoid formation. These effects of PVP on the membrane morphology were explained by means of miscibility gap, viscosity of the polymer solution, polymer–polymer phase separation, and overall porosity. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3481–3488, 2001     

聚砜超滤膜凝胶过程研究——Ⅱ.平衡分配常数的表征

用高效液相色谱,以涂敷聚砜的玻璃微球为固定相;水、或丙三醇的水溶液、或丙酸水溶液为流动相;聚砜的七种良溶剂,15种添加剂为样品从测定的保留时间计算了平衡分配常数K_S。K_2能表征聚矾铸膜液在凝胶过程中,良溶剂与凝胶介质双向扩散速度之比;K_S的对数与正构醇、酸和酯的碳原子数n 成直线关系;K_S还和铸膜液的雾点有很好的相关性。并能以K_S 推测膜性能。     

Effects of polymer solvents on the performance of cellulose acetate membranes in methanol/methyl tertiary butyl ether separation

The performances of cellulose acetate membranes prepared with casting solutions, with acetone, dimethylformamide (DMF), and N‐methylpyrrolidone (NMP) as solvents, were studied in a series of methanol/methyl tertiary butyl ether separation experiments. The flux and selectivity of the membrane samples were affected by the type of solvent used to prepare the casting solution. The sample with DMF consistently gave the highest selectivity and lowest flux, followed by the samples with NMP and acetone. The differences in the performances were attributed to the effects of the volatility and evaporation rates of the solvents. Scanning electron microscopy and atomic force microscopy techniques were used for comparing the morphologies of the membranes. In addition, we used Raman spectroscopy as a novel technique to study the sorption selectivities of the membrane samples prepared with the three different solvents. In a parallel study, the relation between the polymer concentration in the casting solution and the morphology and performance of the membrane samples was studied. Under similar preparation conditions, the morphology of the membrane changed from being porous to being dense when the membrane was prepared with casting solutions with increasing polymer concentration. Also, the selectivity increased and the permeability decreased with increasing polymer concentration in the casting solution. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2882–2895, 2001     

Studies on phase separation rate in porous polyimide membrane formation by immersion precipitation

Phase separation rate during porous membrane formation by immersion precipitation was investigated by light scattering in a polyimide/N‐Methylpyrrolidone (NMP)/water system. In the light scattering measurement, plots of scattered intensity against scattered angle showed maxima in all cases, which indicated that phase separation occurred by a spinodal decomposition (SD). Characteristic properties of the early stage of SD, such as an apparent diffusion coefficient D_app and an interphase periodic distance Λ, were obtained. The growth process of Λ was also followed by light scattering. The growth rate had the same tendency as D_app when water content in the nonsolvent bath and the polymer concentration in the cast solution were changed. The pore size of the final membrane increased with decreasing water content, which was opposite to the tendency of Λ growth rate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 292–296, 2003     

Influence of hydroxyl‐terminated polybutadiene additives on the poly(ether sulfone) ultra‐filtration membranes

Hydroxyl‐terminated polybutadiene (HTPB) was blended into a poly(ether sulfone) (PES) casting solution used to prepare ultra‐filtration (UF) membranes via the phase inversion technique. The membranes were then characterized by contact angle (CA) measurements and UF experiments. The CA was increased with the addition of HTPB in the PES membrane and also by lowering the gelation bath temperature. It was observed that the CA was lower for membranes prepared with N‐methyl‐2‐pyrrolidinone (NMP) as the solvent than those using N,N‐dimethylacetamide (DMAc) as solvent. The flux values were higher for membranes made using a 4°C gelation bath when compared with the ambient temperature ((25 ± 1)°C) irrespective of the cast solvents, NMP or DMAc. The flux values were much higher and the solute separations were lower for the HTPB‐based PES membranes than for the pure PES membrane, when the membranes were cast with DMAc as a solvent. On the other hand, both flux and separation values were much lower for the HTPB‐based PES membranes than for the pure PES membrane, when the membranes were cast using NMP. Atomic force microscopy and scanning electron microscopy were used for morphological characterization and the correlation of topography/photography with the performance data was also examined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2292–2303, 2006     

Microporous polyvinylidene fluoride hollow fiber membrane contactors for CO2 stripping: Effect of PEG-400 in spinning dope

In order to develop the structure of microporous PVDF membranes, PEG-400 was introduced into the polymer dope as a non-solvent additive. The hollow fiber membranes were prepared via a wet phase-inversion process and then used in the membrane contactor modules for CO₂ stripping from water. By addition of different amounts of PEG-400, cloud points of the polymer dope were obtained to examine phase-inversion behavior. From FESEM analysis, the membrane structure changed from a finger-like to an approximately sponge-like morphology with the addition of 4 wt.% of PEG-400. The prepared membranes presented smaller mean pore size (0.13 μm) and significantly higher wetting pressure (550 kPa) compared to the plain membrane. From CO₂ stripping test, at water velocity of 0.4 m/s, the PVDF membranes prepared by 4% PEG-400 demonstrated an approximate CO₂ stripping flux of 4.5 × 10⁻⁵ (mol/m² s) which is 125% higher than the flux of the plain membrane. It could be concluded that structurally developed hydrophobic PVDF hollow fiber membranes can be prepared by a controlled phase-inversion process to enhance the performance of gas–liquid membrane contactor.     

聚间苯二甲酰间苯二胺平板膜的制备及其性能研究

以聚间苯二甲酰间苯二胺（PMIA）为制膜原料,氯化锂（LiCl）、聚乙二醇（PEG-400）和聚乙烯吡咯烷酮（PVP）为添加剂,通过非溶剂诱导相转化法制备了PMIA平板膜,系统考察了聚合物浓度、添加剂种类和含量对PMIA膜结构和性能的影响。结果表明,聚合物浓度和LiCl含量增加,铸膜液黏度增大,导致膜孔径减小,纯水通量降低。而PEG含量的增加,使得聚合物链呈现舒展状态,膜孔径增大,纯水通量升高,亲水性增强。随着PVP含量的增加,膜的纯水通量先升高后降低,膜的亲水性变差。当PMIA的质量分数为9%,LiCl的质量分数为2.8%,PVP的质量分数为1.2%时,膜的纯水通量高达1421.55 L·m^-2·h^-1·bar^-1,对牛血清蛋白（BSA）的截留率为80%,展现出较高的渗透性,为制备高性能膜材料提供了新的思路。     

聚间苯二甲酰间苯二胺平板膜的制备及其性能研究

以聚间苯二甲酰间苯二胺（PMIA）为制膜原料,氯化锂（LiCl）、聚乙二醇（PEG-400）和聚乙烯吡咯烷酮（PVP）为添加剂,通过非溶剂诱导相转化法制备了PMIA平板膜,系统考察了聚合物浓度、添加剂种类和含量对PMIA膜结构和性能的影响。结果表明,聚合物浓度和LiCl含量增加,铸膜液黏度增大,导致膜孔径减小,纯水通量降低。而PEG含量的增加,使得聚合物链呈现舒展状态,膜孔径增大,纯水通量升高,亲水性增强。随着PVP含量的增加,膜的纯水通量先升高后降低,膜的亲水性变差。当PMIA的质量分数为9%,LiCl的质量分数为2.8%,PVP的质量分数为1.2%时,膜的纯水通量高达1421.55 L·m^-2·h^-1·bar^-1,对牛血清蛋白（BSA）的截留率为80%,展现出较高的渗透性,为制备高性能膜材料提供了新的思路。     

Improvement of porous polyvinylidene fluoride-co-hexafluropropylene hollow fiber membranes for sweeping gas membrane distillation of ethylene glycol solution

Porous polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) hollow fiber membranes were fabricated through a wet spinning process. In order to improve the membrane structure, composition of the polymer solution was adjusted by studying ternary phase diagrams of polymer/solvent/non-solvent. The prepared membranes were used for sweeping gas membrane distillation (SGMD) of 20 wt% ethylene glycol (EG) aqueous solution. The membranes were characterized by different tests such as N₂ permeation, overall porosity, critical water entry pressure (CEP_w), water contact angle and collapsing pressure. From FESEM examination, addition of 3 wt% glycerol in the PVDF-HFP solution, produced membranes with smaller finger-likes cavities, higher surface porosity and smaller pore sizes. Increasing the polymer concentration up to 21 wt% resulted in a dense spongy structure which could significantly reduce the N₂ permeance. The membrane prepared by 3 wt% glycerol and 17 wt% polymer demonstrated an improved structure with mean pore size of 18 nm and a high surface porosity of 872 m^-1. CEP_w of 350 kPa and overall porosity of 84% were also obtained for the improved membrane. Collapsing pressure of the membranes relatively improved by increasing the polymer concentration. From the SGMD test, the developed membrane represented a maximum permeate flux of 28 kg·m^-2·h^-1 which is almost 19% higher than the flux of plain membrane. During 120 h of a long-term SGMD operation, a gradual flux reduction of 30% was noticed. In addition, EG rejection reduced from 100% to around 99.5% during 120 h of the operation.     

溶胀辊轧法PVDF膜表面的疏水强化：溶胀剂的影响

提出了一种简便、低成本的聚偏氟乙烯（PVDF）微孔膜表面疏水增强方法——溶胀辊轧法,以微结构辊筒对表面喷涂溶胀剂的PVDF成品微孔膜辊轧后,采用浸没凝胶法成膜。以N-甲基吡咯烷酮/水（非溶剂）为溶胀体系,采用扫描电子显微镜（SEM）、原子力显微镜（AFM）、水接触角（WCA）、最大孔径、平均孔径、N₂通量、耐磨性、液体穿透压（LEP）等表征手段,系统地研究了溶胀剂体系、溶胀剂容量对PVDF微孔膜结构与性能的影响。结果表明：辊轧膜表面呈现微米-亚微米层次特征,溶胀辊轧操作起到了疏水增强、透过能力提升的效果。溶胀剂中水（非溶剂）质量分数为6%、喷涂密度为0.03mL/cm²时,膜性能最优。连续运行30h的真空膜蒸馏（VMD）对比实验表明,辊轧膜较未辊轧膜具有更高的产水通量、脱盐率及更好的耐污染性能。该方法为低成本、连续化进行成品膜表面疏水强化提供了一种新选择。     

Improvement of porous polyvinylidene fluoride-co-hexafluropropylene hollow fiber membranes for sweeping gas membrane distillation of ethylene glycol solution

Porous polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) hollow fiber membranes were fabricated through a wet spinning process. In order to improve the membrane structure, composition of the polymer solution was adjusted by studying ternary phase diagrams of polymer/solvent/non-solvent. The prepared membranes were used for sweeping gas membrane distillation (SGMD) of 20 wt% ethylene glycol (EG) aqueous solution. The membranes were characterized by different tests such as N₂ permeation, overall porosity, critical water entry pressure (CEP_w), water contact angle and collapsing pressure. From FESEM examination, addition of 3 wt% glycerol in the PVDF-HFP solution, produced membranes with smaller finger-likes cavities, higher surface porosity and smaller pore sizes. Increasing the polymer concentration up to 21 wt% resulted in a dense spongy structure which could significantly reduce the N₂ permeance. The membrane prepared by 3 wt% glycerol and 17 wt% polymer demonstrated an improved structure with mean pore size of 18 nm and a high surface porosity of 872 m⁻¹. CEP_w of 350 kPa and overall porosity of 84% were also obtained for the improved membrane. Collapsing pressure of the membranes relatively improved by increasing the polymer concentration. From the SGMD test, the developed membrane represented a maximum permeate flux of 28 kg·m⁻²·h⁻¹ which is almost 19% higher than the flux of plain membrane. During 120 h of a long-term SGMD operation, a gradual flux reduction of 30% was noticed. In addition, EG rejection reduced from 100% to around 99.5% during 120 h of the operation.