Influence of coagulation bath on morphology of cellulose membranes prepared by NMMO method

To control the morphology of cellulose membranes used for separation, they were prepared by the NMMO method using water, methanol, ethanol and their binary solution as coagulation baths. Morphologies of the surface and cross section of dry membranes were observed. The pore structure parameters of wet membranes were determined. By comparison, the process and mechanism of pore formation in dry membranes were suggested, and the relativity of cellulose crystal size to average pore diameter in wet membranes and their influences were discussed. The results show that the morphology of dry membranes is clearly varied with coagulation baths, while the porosity of wet membranes is almost constant. Porous structures can appear in the compact region of dry membranes due to swelling from water. These pores have a virtual effect on the average pore diameter of wet membranes. By changing the composition of coagulation baths, the microstructure of cellulose membranes in a dry or wet environment can be adjusted separately. __________ Translated from Journal of Chemical Engineering of Chinese Universities, 2007, 21(3): 398–403 [译自: 高校化学工程学报]     

凝固浴组成对NMMO法纤维素膜形貌的影响

为实现对分离用纤维素膜形貌的控制,采用NMMO法,分别以水、甲醇、乙醇和由它们配制的双组分溶液为凝固浴,制备了纤维素膜,观察了干膜的表面和断面形貌,测定了湿膜的孔结构参数,在对比基础上分析了干膜中微孔的形成过程与机制,探讨了纤维素结晶尺度与湿膜平均孔径的相关性和影响因素.研究表明,不同凝固浴制备出的纤维素膜在干态形貌上差别明显.纤维素膜的湿态孔隙率基本不受凝固浴组成影响,而干态下的致密区域在水溶胀后呈现多孔结构,对湿膜平均孔径影响很大.通过改变凝固浴组成,可分别或协同地调控纤维素膜的干态或湿态结构.     

Preparation of hydrophobic flat sheet membranes from PVDF-HFP copolymer for enhancing the oxygen permeance in nitrogen/oxygen gas mixture

In this study, poly(vinilydene fluoride-co-hexafluoropropylene)(PVDF-HFP) was used for preparation of hydrophobic membranes using non-solvent induced phase inversion(NIPS) technique. PVDF-HFP copolymer with concentrations of 10 wt% and 12 wt% was prepared to investigate the effect of polymer concentration on pore structure,morphology, hydrophobicity and performance of prepared membranes. Besides, the use of two coagulation baths with the effects of parameters such as coagulant time, polymer type and concentration, and the amount of nonsolvent were studied. The performance of prepared membranes was evaluated based on the permeability and selectivity of oxygen and nitrogen from a gas mixture of nitrogen/oxygen under operating conditions of feed flow rate(1–5 L·min~(-1)), inlet pressure to membrane module(0.1–0.5 MPa) and temperatures between 25 and 45 °C. The results showed that the use of two coagulation baths with different compositions of distillated water and isopropanol,coagulant time, polymer type and concentration, and the amount of non-solvent additive have the most effect on pore structure, morphology, thickness, roughness and crystallinity of fabricated membranes. Porosity ranges for the three fabricated membranes were determined, where the maximum porosity was 73.889% and the minimum value was 56.837%. Also, the maximum and minimum average thicknesses of membrane were 320.85 μm and115 μm. Besides, the values of 4.7504 × 10~(-7) mol· m~(-2)· s~(-1)· Pa~(-1), 0.525 and 902.126 nm were achieved for maximum oxygen permeance, O_2/N_2 selectivity and roughness, respectively.     

PAN原丝成形过程中孔隙结构的形成和演变

采用干湿法纺丝在梯级凝固成形条件和后续工艺下得到聚丙烯腈(PAN)原丝,利用扫描电镜、氮气吸附等方法测试研究了PAN原丝中孔隙的形成和演变。结果表明:在凝固成形阶段,PAN原丝内孔隙的形成是溶剂和非溶剂双扩散及PAN相分离双重作用的结果;PAN原丝经过沸水拉伸、干燥致密化、饱和蒸汽拉伸和热定型等处理,其纤维密度、结晶度增大,力学性能提高,其孔隙平均孔径、孔隙体积和孔隙含量均逐渐减小;PAN原丝内闭合孔隙经过拉伸后会形成新的开放孔隙,开放孔隙在干燥致密化后闭合和消失。     

Preparation and gas separation properties of asymmetric polysulfone membranes by a dual bath method

Defect-free skinned asymmetric gas separation membranes were prepared by a dual bath coagulation method that is a wet/wet phase inversion technique. The membranes were cast from a polysulfone/N,N-dimethylacetamide solution. In two sequent nonsolvent baths, the first bath using iso-propanol (IPA) leads to the formation of a dense skin top layer and the second bath using water makes the actual polymer precipitation. The top skin layer thickness was governed by changing the immersion time of the first IPA bath. We suggest that the growth rate of the skin layer is to be determined by a diffusion process.     

Dry-jet wet electrospinning of native cellulose microfibers with macroporous structures from ionic liquids

In this study, we have provided a review of electrospun cellulose micro/nanofibers from ionic liquids (ILs) and cosolvents from which we identify a lack of previous studies focusing on the structural morphology of the dry-jet wet electrospun native cellulose fibers from ILs. We have therefore aimed to investigate factors influencing the structural morphology of cellulose/IL electrospun fibers and investigate the coagulation parameters on this morphology. The electrospinning of 10% w/v cellulose/([C2MIM][OAc]/MIM) (1/1, v/v) solution was shown to produce macroporous fibers with average diameters of 2.8 ± 1.4 μm with pore sizes from 100 to 200 nm. We have found that coagulation bath type and immersion time affect the morphological structure of the electrospun fibers. The fiber spinnability, formation, and morphological structure are mainly dependent on the method used to collect and coagulate/solidify the fibers. The physical properties of the dissolved cellulose were measured and these are discussed in terms of the solution spinnability. The structural morphology of the electrospun cellulose fibers was characterized by scanning electron microscopy, and finally the extraction of IL from the fiber body was confirmed by nuclear magnetic resonance. The electrospun cellulose fibers morphology shows the formation of both micron and nanometer sized fibers with different morphological “macroporous” structures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47153.     

Polyamide‐imide nanofiltration hollow fiber membranes with elongation‐induced nano‐pore evolution

The molecular design of nanoporous membranes with desired morphology and selectivity has attracted significant interest over the past few decades. A major problem in their applications is the trade‐off between sieving property and permeability. Here, we report the discovery of elongation‐induced nano‐pore evolution during the external stretching of a novel polyamide‐imide nanofiltration hollow fiber membrane in a dry‐jet wet‐spinning process that simultaneously leads to a decreased pore size but increased pure water permeability. The molecular weight cutoff, pore size, and pore size distribution were finely tuned using this approach. AFM and polarized FTIR verified the nano‐pore morphological evolution and an enhanced molecular orientation in the surface skin layer. The resultant nanofiltration membranes exhibit highly effective fractionation of the monovalent and divalent ions of NaCl/Na₂SO₄ binary salt solutions. More than 99.5% glutathione can be rejected by the nanofiltration membranes at neutral pH, offering the feasibility of recovering this tripeptide. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Effect of ethanol in the coagulation bath on the structure and performance of PVDF-g-PEGMA/PVDF membrane

This report investigated the effect of ethanol content in the coagulation bath on the surface composition, membrane pore size structure, pure water flux, and permeability of the amphiphilic polymer polyvinylidene fluoride (PVDF)-g-poly (ethylene glycol) methyl ether methacrylate (PEGMA)-modified PVDF membrane. The study found that pore size and their distribution and, as a result, membrane permeability, can also be easily controlled by adjusting ethanol content in the coagulation bath. Membrane water fluxes formed by the coagulation baths with 0, 10, 20, and 30% of ethanol were 1843.65, 2774.61, 4391.88, and 5142.35 L (m⁻²·h⁻¹). When the content of ethanol in the coagulation bath is high, the surface enrichment of PEGMA slightly decreases, and the surface becomes rougher. Thus, the decrease of the hydrophilic functional groups on the surface of the membrane and the increase of the roughness leads to the deterioration of the hydrophilicity of the membranes surface. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47380.     

Poly(vinyl chloride) hollow‐fiber membranes for ultrafiltration applications: Effects of the internal coagulant composition

Poly(vinyl chloride) (PVC) hollow‐fiber membranes were spun by a dry/wet phase‐inversion technique from dopes containing 15 wt % PVC to achieve membranes with different pore sizes for ultrafiltration (UF) applications. The effects of the N,N‐dimethylacetamide (DMAc) concentration in the internal coagulant on the structural morphology, separation performance, and mechanical properties of the produced PVC hollow fibers were investigated. The PVC membranes were characterized by scanning electron microscopy, average pore size, pore size distribution, void volume fraction measurements, and solubility parameter difference. Moreover, the UF experiments were conducted with pure water and aqueous solutions of poly(vinyl pyrrolidone) as feeds. The mechanical properties of the PVC hollow‐fiber membranes were discussed in terms of the tensile strength and Young's modulus. It was found that the PVC membrane morphology changed from thin, fingerlike macrovoids at the inner edge to fully spongelike structure with DMAc concentration in the internal coagulant. The effective pores showed a wide distribution, between 0.2 and 1.1 μm, for the membranes prepared with H₂O as the internal coagulant and a narrow distribution, between 0.114 and 0.135 μm, with 50 wt % DMAc. The results illustrate that the difference in the membrane performances was dependent on the DMAc concentration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of dense cellulose film for membrane application

Regenerated cellulose films were prepared with environmentally friendly process by utilized N‐methylmorpholine‐N‐oxide (NMMO)‐Cellulose system. To prepare a dense cellulose film for membrane application, some parameter process which influence porous forming such as cellulose DP, cellulose concentration, addition NMMO in coagulation bath, coagulation bath temperature, and drying condition were investigated. We resumed that the porosity and pore size of cellulose membrane decrease with lower cellulose DP, higher cellulose concentration, addition of NMMO in coagulation bath, applying room temperature in coagulation bath and drying, and applying vacuum on drying process resulted in membranes with porosity in range of 24–41% and pore size 13.4–20.2 nm. The main factor for controlling porosity and pore size of dense cellulose membrane was coagulation process condition especially addition of NMMO into coagulation bath. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanically adaptive cellulose‐poly(acrylic acid) polymeric composites in wet–dry cycles

Polymeric composites consisting of cellulose and poly(acrylic acid) (PAA) are prepared by coagulation/bulk polymerization method. Scanning electron microscopy and thermal gravimetric analysis are used to investigate the homogeneity and the heat‐induced water loss of the composites, respectively. The water absorbed in the composites has strong hydrogen bonding with the polymer chains, as determined by differential scanning calorimetry. The mechanical and structural properties of the composites vary reversibly when the composites are applied into specifically explored wet–dry cycles, which are comprehensively measured by dynamic mechanic analysis, wide‐angle X‐ray diffraction, and Fourier transform infrared. It is unprecedented to explore the cellulose‐PAA composites as a mechanical adaptive material. The cellulose and the PAA chemically react with each other. Most of the cellulose content remains in amorphous state. Thus, the water molecules can diffuse into the composites, leading to the wet–dry mechanical adaptability of the composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphology and properties of cellulose/chitin blends membranes from NaOH/thiourea aqueous solution

Blend membranes of chitin/cellulose from 12 : 50 to 12 : 250 were successfully prepared from cotton linters in 1.5M NaOH/0.65M thirourea solution system. Two coagulation systems were used to compare with each other, one coagulating by 5 wt % H₂SO₄ (system H), and the other by 5 wt % CaCl₂ and then 5 wt % H₂SO₄ (system C). The morphology, crystallinity, thermal stabilities, and mechanical properties of the blend membranes were investigated by electron scanning microscopy, atomic absorption spectrophotometer, infrared spectroscope, elemental analysis, X‐ray diffraction, different scanning calorimeter, and tensile tests. The cellulose/chitin blends exhibited a certain level of miscibility in the weight ratios tested. There were great differences between the two blends H coagulated with H₂SO₄ and C coagulated with CaCl₂ and H₂SO₄, respectively. The membranes H have a denser structure, higher thermal stability, tensile strength (σ_b), and crystallinity (χ_c), and values of σ_b (90 MPa for chitin/cellulose 12 : 150) were significantly superior to that of both chitin and regenerated cellulose membrane. However, the blend membranes C have much better breaking elongations (?) than that of membranes H, and relatively large pore size (2r_e = 210 μm), owing to the removal of a water‐soluble calcium complex of chitin as pore former from the membranes C. When the percentage content of chitin in the blends was from 5 to 7.5%, the values of breaking elongation for the blend membranes H and C all were higher than that of unblend membranes, respectively. The blends provide a promising way for application of chitin as a functional film or fiber in wet and dry states without derivates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2025–2032, 2002     

Structures and gas separation properties of asymmetric polysulfone membranes made by dry,wet, and dry/wet phase inversion

Integrally skinned asymmetric gas separation membranes were prepared by (i) dry, (ii) wet, and (iii) dry/wet phase inversion processes. The membranes were cast from a polysulfone/methylene chloride/1,1,2-trichloroethane/2-methyl-2-butanol casting system. Wet and dry/wet phase inversion membranes were quenched in methanol. Membranes made by dry/wet phase inversion using convective evaporation showed optimum gas separation performance. The average O₂/N₂ and He/N₂ selectivities of these membranes were within 85% of those determined for a dense, solution-cast polysulfone film, suggesting that the ultrathin skin layers were essentially defect free. The average apparent skin layer thickness of all samples tested was 270 Å. Scanning electron photomicrographs revealed that optimum membranes made by dry/wet phase inversion consist of an ultrathin skin layer, a tightly packed nodular transition layer, and an open-cell, sponge-like substructure. Dry/wet phase inversion membranes prepared by free-standing evaporation resulted either in high flux and low selectivity membranes or essentially defect-free membranes with fluxes lower than those made by convective evaporation. Dry-phase inversion membranes exhibited extremely low gas fluxes due to thick (17.5 μm) skin layers. On the other hand, wet phase inversion membranes showed O₂/N₂ selectivities < 1, indicating that gas transport was determined by pore flow through skin layer defects.     

Morphology and performance control of PLLA-based porous membranes by phase separation

The structure, porosity and crystallization behavior of poly (L-lactic acid) and poly (L-lactic acid)/polyurethane porous membranes, prepared from ethanol/dioxane and ethanol/water coagulation baths through immersion precipitation, have been systematically investigated. The diffusion rate between solvent and nonsolvent as well as the equilibrium phase diagram of PLLA/solvent/nonsolvent system were also well studied. It has been proved that the ultimate structure and performance of the membranes could be mediated under control by suitable adjustment on phase separation behavior of the ternary system through varying coagulation bath compositions. The results show that the presence of lower ratio of dioxane in ethanol baths endows the resulting membranes with uniform sponge-like structure, higher porosity and crystallinity due to the moderate solidification and crystallization of PLLA, while increasing the water concentration tends to have a modestly opposite effect and obtains membranes with irregular finger-like structure, lower porosity and crystallinity. Under the same coagulation baths, PLLA/PU membranes possess slightly larger pores size and porosity than pure PLLA membranes, but the presence of PU appears to have no effect on the crystallinity of PLLA.     

Electrospun nanofibrous polyvinylidene fluoride-co-hexafluoropropylene membranes for oil–water separation

Effective separation of oil from water is of significant importance globally for various applications such as wastewater treatment, oil spill cleanup, and oil purification. Among the numerous approaches for oil removal, membrane separation is considered one of the most promising approaches due to its selectivity and ease of operation. Electrospinning is a promising technique for producing polymeric membranes with tunable structures with interconnected pores, large surface area, and high porosity. In this study, hydrophobic poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibrous membranes were electrospun and used for this purpose. The effects of various parameters (e.g., polymer concentration, applied voltage, tip to collector distance, and feed rate) were investigated to find the optimum electrospinning conditions. Further, the electrospun membranes were characterized according to average fiber diameter, morphology, average pore size, and wettability to identify the combinations most likely to succeed in oil–water filtration. The physical–chemical properties of the membranes (i.e., thickness, areal density, porosity, average pore size, water/oil contact angle, hydrostatic pressure head, and oil filtration flux) were studied based on standard test methods. The separation efficiency of eight electrospun membranes with various pore sizes and average fiber diameters were tested for diesel/water mixtures. A linear relation was found between the initial oil flux and the average pore size of the membranes. The maximum oil filtration flux of about 224 L/m²/h, achieving over 75% oil recovery in 10 min, was obtained for the electrospun membrane with the average pore size of 4.5 μm. The membranes were successfully used for eight consecutive oil–water separation cycles without noticeable loss of flux.     

Electrochemical and electrokinetic characterization of cellulose acetate polymeric membranes

The electrochemical and electrokinetic aspects of cellulose acetate membranes of varying pore structure and desalting abilities have been investigated. The electrochemical studies included measurement of conductance and membrane potential for various membrane electrolyte systems. The electrokinetic characterization was made from streaming potential measurements. The data obtained are explained in terms of interfacial double layer phenomena prevalent in porous permselective barrier systems. The average pore diameter evaluated independently is also presented and an attempt has been made to understand the solute–water transport in terms of weak ionic character of membrane surface.     

Study on the control of pore sizes of membranes using chemical methods: Part III. The performance of carbonates and bicarbonates in the membrane-making process by the chemical reaction

In this paper, polyvinylidene fluoride (PVDF)/polymethyl acrilate (PMMA)/cellulose acetate (CA) blend UF membranes were prepared by chemical reaction introduced phase-inversion method. The results of the experiment show that: (1) The membrane pore size distribution is more uniform due to the presence of carbonates or bicarbonates in the coagulation bath; (2) No more than the stoichiometric ratio amount of carbonates or bicarbonates in the coagulation bath can effectively improve the membrane pore size distribution and make the pore size of membrane more uniform; (3) The membrane prepared by carbonates solution as a working solution in coagulation bath possess superior performance than that by bicarbonates.     

Sulfonated polyphenylsulfone asymmetric membranes: Effect of coagulation bath (acetic acid‐NaHCO3/isopropanol) on morphology and antifouling properties

Sulfonated polyphenylsulfone porous asymmetric membranes, S‐PPSU with different sulfonation degrees, 21, 33, 50 wt %, were prepared by phase inversion. Two different coagulation baths were explored for asymmetric membrane preparation: acetone/isopropanol and acetic acid (AA)‐NaHCO₃/isopropanol. The latter bath allows better morphology control for the nucleation and pore formation of the membrane. Scanning electron microscopy of membranes shows that pore interconnectivity is improved, when the mixture of AA‐NaHCO₃/isopropanol was used for asymmetric S‐PPSU ultrafiltration membranes preparation. S‐PPSU asymmetric membranes show an increasing hydrophilicity with increasing sulfonation degree. Asymmetric membrane antifouling properties improve as the concentration of sulfonic groups increases in the membrane showing twice the flux recovery ratio and lower BSA protein absorption in static and dynamic flux tests. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44502.     

Effects of solubility parameter differences among PEG,PVP and CA on the preparation of ultrafiltration membranes: Impacts of solvents and additives on morphology,permeability and fouling performances

The effects of two different hydrophilic additives and two solvents on the membrane morphological structure,permeability property and anti-fouling performances of cellulose acetate (CA) ultrafiltration membranes were investigated.During the phase-inversion process,cellulose acetate was selected as a membrane forming polymer;polyethylene glycol (PEG) and polyvinyl pyrrolidone (PVP) were used as additives;acetone (Ac):N,N-Dimethylacetamide (DMAc) andN,N-Dimethylformamide (DMF) were used as solvents;and deionized (DI) water was used in the coagulation bath.All the prepared membranes were characterized in terms of hydraulic permeability (Pm),membrane resistance,average pore radius,and hydrophilicity.The top surface and crosssectional view of the prepared membranes were also observed by using field emission scanning electron microscopy.Membrane fouling and rejection experimentations were done using a stirred batch-cell filtration set-up.The experimental studies of fouling/rinsing cycles,rejection,and permeate fluxes were used to investigate the effect of PEG and PVP additives and effect of the two solvents on the fabricated membranes using bovine serum albumin (BSA) as a model protein.