Hemodialysis membrane prepared from cellulose/N‐methylmorpholine‐N‐oxide solution. I. Effect of membrane preparation conditions on its permeation characteristics

Flat hemodialysis membranes were prepared from cellulose/N‐methylmorpholine‐N‐oxide (NMMO) solutions (dope) with different cellulose concentrations (6–8 wt %) by using a phase‐inversion method. The coagulant used was NMMO aqueous solution, of which the NMMO concentration and its temperature were varied in the range of 0 to 50 wt % and 5 to 60°C, respectively. The effects of these preparation conditions on the permeation characteristics, the ultrafiltration rate (UFR) of pure water, and sieving coefficient (SC) of dextran, were investigated. The decrease in cellulose concentration of the dope and the increases in both temperature and NMMO concentration of the coagulant gave a membrane with high UFR. Concerning the SC, the increase of the cellulose concentration and the decreases in both temperature and NMMO concentration gave a good result. Consequently, the membrane having the preferable UFR and SC as a hemodialysis membrane was obtained when the 8 wt % cellulose dope was coagulated in water at 5°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2302–2307, 2002     

Blend films of O‐carboxymethyl chitosan and cellulose in N‐methylmorpholine‐N‐oxide monohydrate

To introduce N‐methylmorpholine‐N‐oxide (NMMO) process to prepare antibacterial lyocell fiber, the blend films of O‐carboxymethyl chitosan (O‐CMCS) and cellulose were prepared. O‐CMCS in aqueous suspension with particles having a surface mean diameter of 2.24 μm was blended with cellulose in NMMO hydrate. The blend films with different O‐CMCS content were prepared with the blend solutions. SEM confirmed that O‐CMCS remained within the cellulose film in the particle. The mechanical properties of the blend films show little increased value when O‐CMCS was less 5%; however, it decreased sharply when O‐CMCS was over 8%. Thus, the optimum O‐CMCS content may give a good combination of antibacterial action and mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4601–4605, 2006     

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     

Rheological aspects of fiber spinning from cellulose solutions in N‐methylmorpholine‐N‐oxide

Based on rheological experiments with a cellulose solution in N‐methylmorpholine‐N‐oxide (NMMO), it was found that the shearing stress generated in the flowing viscoelastic fluid decreases with an l/d ratio in a rheometer capillary. This reduces the elastic response and the outflow of the fluid becomes more uniform. At constant temperature, the elongational viscosity of the solidified stream of the cellulose solution in NMMO is reduced with increase of the deformation rate, which makes it possible to increase the fiber‐formation velocity within the air zone. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1860–1868, 2001     

Preparation and oxygen permeation of U‐shaped perovskite hollow‐fiber membranes

The oxygen permeation of dense U‐shaped perovskite hollow‐fiber membranes based on Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ prepared by a phase inversion spinning process is reported. The perovskite hollow fibers with totally dense wall were obtained with the outer diameter of 1.147 mm and the inner diameter of 0.691 mm. The dependences of the oxygen permeation on the air flow rate on the shell side, the helium flow rate on the core side, the oxygen partial pressures, and the operating temperatures were experimentally investigated. According to the Wagner theory, it follows that the oxygen transport through the U‐shaped hollow‐fiber membrane is controlled by both surface reaction and bulk diffusion at the temperature ranges of 750–950°C. High oxygen permeation flux of 3.0 ml/(min cm²) was kept for about 250 h at 950°C under the conditions of the air feed flow rate of 150 ml/min and the helium flow rate of 50 ml/min. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Interactions of Ionic Liquids with Polysaccharides – 7: Thermal Stability of Cellulose in Ionic Liquids and N‐Methylmorpholine‐N‐oxide

The thermal behavior of cellulose dissolved in ionic liquids was studied in comparison to NMMO solutions. The cellulose solutions were characterized by reaction calorimetry and UV‐vis spectroscopy. Generation of chromophoric substances in cellulose/IL solutions is minimized by exposing to temperatures of above 100 °C for longer time periods. Dynamic calorimetric investigations revealed first thermal activities above 180 °C applying EMIMac and above 200 °C for BMIMCl and five other ILs tested. Moreover, even in the case of modified cellulose/IL solutions, e.g., activated charcoal, only a slight decline of onset temperatures was registered compared to modified cellulose/NMMO solutions.

     

Atomic force microscopy of cellulose membranes prepared from the N‐methylmorpholine‐N‐oxide/water solvent system

Cellulose membranes were obtained by solutions of cellulose being cast into a mixture of N‐methylmorpholine‐N‐oxide (NMMO) and water under different processing conditions. Atomic force microscopy (AFM) was used to investigate the surface structures of the membranes. The AFM method provided information on both the size and shape of the pores on the surface, as well as the roughness of the skin, through a computerized analysis of AFM micrographs. The results obtained showed that the surface morphologies were intrinsically associated with the permeation properties. For the cellulose membranes, increasing the NMMO concentration and the temperature of the coagulation bath led to higher fluxes and lower bovine serum albumin rejection. These were always correlated with higher values of the roughness parameters and larger pore sizes of the membrane surfaces. When the cellulose concentration of the casting solution was 11 wt %, the membrane showed a nodular structure with interconnected cavity channels between the agglomerated nodules. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3389–3395, 2002     

Activated carbon‐filled cellulose acetate hollow‐fiber membrane for cell immobilization and phenol degradation

The activated carbon‐filled cellulose acetate (CA) hollow‐fiber membranes were prepared by using phase‐inverse technique and subsequently characterized by scanning electronic microscopy (SEM), atomic force microscopy (AFM), dynamic mechanical analysis (DMA), thermal mechanical analysis (TMA), and tensile analysis. The SEM observation demonstrated that the activated carbon‐filled CA hollow‐fiber membranes possess four‐layer structure, which consists of an external skin dense layer, an external void layer, a central sponge layer, and an internal skin dense layer, whereas the pure CA hollow‐fiber membranes lack the macrovoid layer. As the measurement of AFM, the roughness of both internal and external surface of activated carbon‐filled fibers is much higher than that of pure CA fiber, respectively. Higher Young's modulus and storage modulus of filled membranes indicate that the activated carbon particles were homogeneously dispersed in the polymeric matrix. To investigate the feasibility of the newly developed hollow‐fiber membranes for cell immobilization cells and to evaluate the inhibitory effect of phenol on immobilized cells, Pseudomonas putida ATCC 17484 was chosen to be immobilized on both pure CA and activated carbon‐filled hollow‐fiber membranes. Batch experiments for phenol biodegradation were carried out for both free suspension and immobilized cells at the initial concentration of 1500 mg/L phenol. In the case of free suspension, neither cell growth nor phenol degradation occurred to any measurable extent up to 35 h. We found that both pure CA fiber and activated carbon‐filled fiber immobilization systems can completely degrade the phenol. However, the biodegradation rate of activated carbon‐filled fiber system was higher than that of pure CA fiber system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 695–707, 2000     

Development of thin‐film composite hollow‐fiber membranes from modified polyphenylene oxide for gas separation applications

The effect of sulfonation and bromination‐sulfonation on the gas transport properties of polyphenylene oxide has been investigated. These high‐performance modified polymers have been studied in the form of TFC membranes by solution coating on the skin side of polyetherimide hollow fibers. TFC membrane modules prepared from sulfonated‐brominated polyphenylene oxide as the active layer coated on polyetherimide hollow fibers. Stability of the TFC membranes was greatly improved when a wet feed stream was used instead of a dry one. Water vapor in the feed stream most likely prevented the active layer from stress cracking on drying. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 275–282, 2001     

Fundamental understanding of the effect of air‐gap distance on the fabrication of hollow fiber membranes

The objectives of this work are, fundamentally, to understand hollow fiber membrane formation from an engineering aspect, to develop the governing equations to describe the velocity profile of nascent hollow fiber during formation in the air gap region, and to predict fiber dimension as a function of air‐gap distance. We have derived the basic equations to relate the velocity profile of a nascent hollow fiber in the air‐gap region as a function of gravity, mass transfer, surface tension, drag forces, spinning stress, and rheological parameters of spinning solutions. Two simplified equations were also derived to predict the inner and outer diameters of hollow fibers. To prove our hypotheses, hollow fiber membranes were spun from 20 : 80 polybezimidazole/polyetherimide dopes with 25.6 wt % solid in N,N‐dimethylacetamide using water as the external and internal coagulants. We found that inner and outer diameters of as‐spun fibers are in agreement with our prediction. The effects of air‐gap distance or spin‐line stress on nascent fiber morphology, gas performance, and mechanical and thermal properties can be qualitatively explained by our mathematical equations. In short, the spin‐line stresses have positive or negative effects on membrane formation and separation performance. A high elongational stress may pull molecular chains or phase‐separated domains apart in the early stage of phase separation and create porosity, whereas a medium stress may induce molecular orientation and reduce membrane porosity or free volume. Scanning electron microscopic photographs, coefficient of thermal expansion, and gas selectivity data confirm these conclusions. T_g of dry‐jet wet‐spun fibers is lower than that of wet‐spun fibers, and T_g decreases with an increase in air‐gap distance possibly because of the reduction in free volume induced by gravity and elongational stress. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 379–395, 1999     

Dual action bactericides: Quaternary ammonium/N‐halamine‐functionalized cellulose fiber

Bi‐functional antibacterial material was prepared by co‐grafting N‐halamine and quaternary ammonium salt monomers from cellulose fiber. The grafted fiber was characterized by Fourier transform infrared spectra, and X‐ray photoelectron spectra. The N‐halamine derived from the precursor 4‐[(acryloxy)methyl]‐4‐ethyl‐2‐oxazolidinone via chlorination treatment and the oxidative chlorine (Cl⁺) leaching behavior were investigated. The antibacterial activities of singly (only QAs‐functionalized or only Cl⁺‐releasing) and dual (QAs‐functionalized and Cl⁺‐releasing) functional cellulose fibers were tested against Gram‐negative Escherichia coli and Gram‐positive Staphylococcus aureus. Compared to singly functionalized formulations, the bi‐functional cellulose fiber exhibited excellent and rapid bactericidal performance against both E. coli and S. aureus. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40070.     

Hemodialysis membrane prepared from cellulose/N‐methylmorpholine‐N‐oxide solution. II. Comparative studies on the permeation characteristics of membranes prepared from N‐methylmorpholine‐N‐oxide and cuprammonium solutions

Two kinds of regenerated cellulose membranes for hemodialysis were prepared from casting solutions of N‐methylmorpholine‐N‐oxide (NMMO) and cuprammonium (denoted NMMO membranes and cuprammonium membranes, respectively). The concentration of cellulose in the casting solution investigated was 6–8 wt %. The permeation characteristics of both membrane series were compared in terms of the ultrafiltration rate (UFR) of pure water, the sieving coefficient (SC) of dextran, and the solute permeabilities of urea, creatinine, and vitamin B₁₂. The UFR and SC of the NMMO membranes were strongly affected by the cellulose concentration of the casting solution, and NMMO was a preferable solvent for the production of cellulose membranes with high performance; the cuprammonium solution gave low‐performance membranes. The pore structures of both types of membranes were estimated with the Hagen–Poiseuille law. The results showed that the NMMO membranes had larger pore radius and smaller pore numbers than the cuprammonium membranes. The differences in the membrane pore structures led to the differences in the performance between the two membrane series. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 333–339, 2003     

Fabrication and characterization of PEI/PVP‐based carbon hollow fiber membranes for CO2/CH4 and CO2/N2 separation

Carbon hollow fiber membranes derived from polymer blend of polyetherimide and polyvinylpyrrolidone (PVP) were extensively prepared through stabilization under air atmosphere followed by carbonization under N₂ atmosphere. The effects of the PVP compositions on the thermal behavior, structure, and gas permeation properties were investigated thoroughly by means of differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction, and pure gas permeation apparatus. The experimental results indicate that the transport mechanism of small gas molecules of N₂, CO₂, and CH₄ is dominated by the molecular sieving effect. The gas permeation properties of the prepared carbon membranes have a strong dependency on PVP composition. The carbon membranes prepared from polymer blends with 6 wt % PVP demonstrated the highest CO₂/CH₄ and CO₂/N₂ selectivities of 55.33 and 41.50, respectively. © 2011 American Institute of Chemical Engineers AIChE J, 58: 3167–3175, 2012     

Highly scalable ZIF‐based mixed‐matrix hollow fiber membranes for advanced hydrocarbon separations

ZIF‐8/6FDA‐DAM, a proven mixed‐matrix material that demonstrated remarkably enhanced C₃H₆/C₃H₈ selectivity in dense film geometry, was extended to scalable hollow fiber geometry in the current work. We successfully formed dual‐layer ZIF‐8/6FDA‐DAM mixed‐matrix hollow fiber membranes with ZIF‐8 nanoparticle loading up to 30 wt % using the conventional dry‐jet/wet‐quench fiber spinning technique. The mixed‐matrix hollow fibers showed significantly enhanced C₃H₆/C₃H₈ selectivity that was consistent with mixed‐matrix dense films. Critical variables controlling successful formation of mixed‐matrix hollow fiber membranes with desirable morphology and attractive transport properties were discussed. Furthermore, the effects of coating materials on selectivity recovery of partially defective fibers were investigated. To our best knowledge, this is the first article reporting successful formation of high‐loading mixed‐matrix hollow fiber membranes with significantly enhanced selectivity for separation of condensable olefin/paraffin mixtures. Therefore, it represents a major step in the research area of advanced mixed‐matrix membranes. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2625–2635, 2014     

Polydimethylsiloxane/postmodified MIL‐53 composite layer coated on asymmetric hollow fiber membrane for improving gas separation performance

Composite layer containing postmodified MIL‐53 (P‐MIL‐53) was exploited to be coated on as‐fabricated asymmetric hollow fiber membrane for improving gas separation performance. The morphology and pore size distribution of P‐MIL‐53 particles were characterized by SEM and N₂ adsorption isotherm. The EDX mapping and FTIR spectra were performed to confirm the presence of P‐MIL‐53 deposited on the outer surface of hollow fiber membranes. The results of pure gas permeation measurement indicated that incorporation of P‐MIL‐53 particles in coating layer could improve permeation properties of hollow fiber membranes. By varying coating times and P‐MIL‐53 content, the membrane coated with PDMS/15%P‐MIL‐53 composite by three times achieved best performance. Compared to pure PDMS coated membrane, CO₂ permeance was enhanced from 29.96 GPU to 40.24 GPU and ideal selectivity of CO₂/N₂ and CO₂/CH₄ also increased from 23.28 and 26.95 to 28.08 and 32.03, respectively. The gas transport through composite membrane was governed by solution‐diffusion mechanism and CO₂ preferential adsorption of P‐MIL‐53 contributed to considerable increase of CO₂ solubility resulting in accelerated permeation rate. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44999.     

Preparation and properties of the single‐walled carbon nanotube/cellulose nanocomposites using N‐methylmorpholine‐N‐oxide monohydrate

Single‐walled carbon nanotube (SWNT)/cellulose nanocomposite films were prepared using N‐methylmorpholine‐N‐oxide (NMMO) monohydrate as a dispersing agent for the acid‐treated SWNTs (A‐SWNTs) as well as a cellulose solvent. The A‐SWNTs were dispersed in both NMMO monohydrate and the nanocomposite film (as confirmed by scanning electron microscopy) because of the strong hydrogen bonds of the A‐SWNTs with NMMO and cellulose. The mechanical properties, thermal properties, and electric conductivity of the nanocomposite films were improved by adding a small amount of the A‐SWNTs to the cellulose. For example, by adding 1 wt % of the A‐SWNTs to the cellulose, tensile strain at break point, Young's modulus, and toughness increased ～ 5.4, ～ 2.2, and ～ 6 times, respectively, the degradation temperature increased to 9°C as compared with those of the pure cellulose film, and the electric conductivities at ? (the wt % of A‐SWNTs in the composite) = 1 and 9 were 4.97 × 10^?4 and 3.74 × 10^?2 S/cm, respectively. Thus, the A‐SWNT/cellulose nanocomposites are a promising material and can be used for many applications, such as toughened Lyocell fibers, transparent electrodes, and soforth. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Teflon AF2400/Ultem composite hollow fiber membranes for alcohol dehydration by high‐temperature vapor permeation

High‐temperature vapor permeation has a stringent requirement of membrane stability under harsh feed environments. This work reports the design of Teflon AF2400/Ultem composite hollow fiber (HF) membranes for alcohol dehydration via vapor permeation. Fabrication parameters such as Teflon concentration and coating time were systematically investigated. Interestingly, the fabricated composite HF membranes possess an unusual surface with honeycomb‐like microstructure patterns. Owing to the Teflon protective layer, the newly developed composite HF shows a promising and stable separation performance with a flux of 4265 gm^?2 h^?1 and a separation factor of 383 for 95% isopropanol dehydration at 125°C. The composite HF also performs well under extreme vapor feed compositions from 87 to 99 wt % isopropanol. In addition, it exhibits impressive separation performance for the dehydration of ethanol and n‐butanol. This work may provide useful insights of designing thermal‐stable and high‐performance composite polymeric membranes for vapor permeation. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1747–1757, 2016     

Poly(vinylidene fluoride) hollow‐fiber membranes containing silver/graphene oxide dope with excellent filtration performance

In this study, an antifouling poly(vinylidene fluoride) (PVDF) hollow‐fiber membrane was fabricated by blending with silver‐loaded graphene oxide via phase inversion through a dry‐jet, wet‐spinning technique. The presence of graphene oxide endowed the blended membrane with a high antifouling ability for organic fouling. The permeation fluxes of the blended membrane was 3.3 and 2.9 times higher than those of a pristine PVDF membrane for filtering feed water containing protein and normal organic matter, respectively. On the other hand, the presence of silver improved the antibiofouling capability of the blended membrane. For the treatment of Escherichia coli suspension, the permeation flux of the blended membranes was 8.2 times as high as that of the pristine PVDF membrane. Additionally, the presented blended membrane improved the hydrophilicity and mechanical strength compared to those of the pristine PVDF membrane, with the water contact angle decreasing from 86.1 to 62.5° and the tensile strength increasing from 1.94 to 2.13 MPa. This study opens an avenue for the fabrication of membranes with high permeabilities and antifouling abilities through the blending of graphene‐based materials for water treatment. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44713.     

Pure H2 production through hollow fiber hydrogen‐selective MFI zeolite membranes using steam as sweep gas

Hollow fiber MFI zeolite membranes were modified by catalytic cracking deposition of methyldiethoxysilane to enhance their H₂/CO₂ separation performance and further used in high temperature water gas shift membrane reactor. Steam was used as the sweep gas in the MR for the production of pure H₂. Extensive investigations were conducted on MR performance by variations of temperature, feed pressure, sweep steam flow rate, and steam‐to‐CO ratio. CO conversion was obviously enhanced in the MR as compared with conventional packed‐bed reactor (PBR) due to the coupled effects of H₂ removal as well as counter‐diffusion of sweep steam. Significant increment in CO conversion for MR vs. PBR was obtained at relatively low temperature and steam‐to‐CO ratio. A high H₂ permeate purity of 98.2% could be achieved in the MR swept by steam. Moreover, the MR exhibited an excellent long‐term operating stability for 100 h in despite of the membrane quality. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3459–3469, 2015     

Exploration of ionic modification in dual‐layer hollow fiber membranes for long‐term high‐performance protein separation

Two types of ionic modification approaches (i.e., sulfonation and triethylamination) were applied with the aid of dual‐layer hollow fiber technology in this work to fine tune the pore size and pore size distribution, introduce the electrostatic interaction, and reduce membrane fouling for long‐term high‐performance protein separation. A binary protein mixture comprising bovine serum albumin (BSA) and hemoglobin (Hb) was separated in this work. The sulfonated fiber exhibits an improved BSA/Hb separation factor at pH = 6.8 compared with as‐spun fibers but at the expense of BSA sieving coefficient. On the other hand, the triethylaminated fiber reveals the best and most durable separation performance at pH = 4.8. Its BSA/Hb separation factor is maintained above 80 for 4 days and maximum BSA sieving coefficient reaches 33%. Therefore, this study documents that an intelligent combination of both size‐exclusion and electrostatic interaction can synergistically enhance protein separation performance in both purity and concentration. © 2008 American Institute of Chemical Engineers AIChE J, 2009