Macro-porous dolomite hollow fibers sintered at different temperatures toward widened applications

Ceramic hollow fibers from natural dolomite with different pore structures have been designed. The unique hollow fibers were produced by the phase inversion method and applying different sintering temperatures. The hollow fiber precursor presented coagulated polymers through the fiber thickness due to the high granulometric size of the used dolomite material (11.3–47.2 µm). The fiber sintered at 400 °C presented mechanical strength of 4.5 MPa and water permeability of 84.7 L h⁻¹ m⁻² kPa⁻¹. The increase in the sintering temperature up to 1250 °C resulted in fragile hollow fibers due to dolomite transformations that resulted in gas release and a significant mass loss of 33.7%. At 1350 °C, the liquid phase sintering mechanism occurred and the dolomite hollow fiber sintered at 1350 °C presented mechanical strength of 5.5 MPa and water permeability of 2219 L h⁻¹ m⁻² kPa⁻¹. Doloma dissolution in water was investigated and calcium concentration was increased from 0.72 (pure water) to 2.905 ppm for a contact time from 4 h between the fiber sintered at 1250 °C and pure water. However, this dissolution did not decrease the mechanical resistance of the fiber. These results suggest the potential of applying natural dolomite for producing low cost membranes or substrates. The hollow fiber sintered at 400 °C is suggested to be used as a proper separation medium, while the hollow fiber sintered at 1350 °C may be used as a substrate for the deposition of a separation layer to be used in gas separations. The high porosity of the fiber sintered at 1250 °C suggests its application as a support for the impregnation of functional materials. Thus, depending on the applied sintering temperature the dolomite membrane can be used in different applications.     

Effect of air-gap distance on the morphology and thermal properties of polyethersulfone hollow fibers

By using 30/70 polyethersulfone/NMP (N-methyl-2-pyrrolidone) solutions as an example, we have determined the role of air-gap distance on nascent fiber morphology, performance, and thermal properties. An increase in air-gap distance results in a hollow fiber with a less layer of fingerlike voids and a significant lower permeance. For the first time we have reported that the T_g of a dry-jet wet-spun fiber prepared from one-polymer/one-solvent systems is lower than that of a wet-spun fiber, and T_g decreases with an increase in air-gap distance. These interesting phenomena arise from the fact that different precipitation paths take place during the wet-spinning and dry-jet wet-spinning processes. Wet-spun fibers experience vigorous and almost instantaneous coagulations; it results in hollow fiber skins with a long-range random, unoriented chain entanglement, but loose structure. Dry-jet wet-spun fibers first go through a moisture-induced phase separation process and then a wet-phase inversion process; it results in external fiber skins with a short-range random, compact, and slightly oriented or stretched structure. As a result, the outskin of wet-spun fibers have a greater free volume and a higher first T_g than that of the dry-jet wet-spun ones. Both SEM (scanning electronic microscope) photomicrographs and DSC (differential scanning calorimeter) analyses support our conclusion. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1067–1077, 1997     

Phenol recovery with tributyl phosphate in a hollow fiber membrane contactor: Experimental and model analysis

The extraction and stripping of phenol using a solution of tributyl phosphate in kerosene in a hydrophobic polypropylene hollow fiber membrane contactor has been studied. The effect of the aqueous and the organic phase flow rates on the overall mass transfer coefficient for both extraction and stripping steps was investigated. Experimental values of the overall mass transfer coefficient were determined and compared with predicted values from the resistance in series model. Results showed that the overall mass transfer coefficients for extraction were about one order of magnitude greater than those measured during the stripping process. The experimental values were in good agreement with the predicted values for the extraction module. However, the predicted values were slightly overestimated for the stripping module. The individual mass transfer resistances were analyzed and the rate-controlling steps of mass transfer were also identified in both extraction and stripping modules. The major resistance in extraction and stripping was in the aqueous phase and in the membrane phase, respectively.     

Removal of As(V) by PVDF hollow fibers membrane contactors using Aliquat-336 as extractant

In this work, the removal of As(V) from an aqueous stream by non-dispersive solvent extraction in a hollow fibre membrane contactor was investigated. To this purpose, microporous hydrophobic poly(vinylidene fluoride) hollow fibres were prepared by the dry/wet spinning technique. Fibres were spun, changing the pore forming additives, to obtain micro-porous sponge-like structure membranes, with pore diameters of about 0.2 μm and porosity of 80%. The produced fibres were used to perform As(V) extraction experiments in a membrane contactor device, using Aliquat-336 as extractant. Different tests were carried out in order to study the effect of temperature, initial concentration, pH of the feed solution and membrane properties. The results showed that the extraction of As(V) by non-dispersive solvent extraction was influenced by the pH of the feed, with an optimum reached for neutral values, increased with the arsenic content in the feed and was not affected by temperature. The extraction was favoured by working with thinner membranes. The highest removal of arsenic achieved was around 70% after 6 h of operation. The produced fibres kept their performance for all the experimental activity, giving reproducible results with time.     

Enzyme immobilization onto renewable polymeric matrixes: Past,present, and future trends

In this review, we present an overview of the different renewable polymers that are currently being used as matrixes for enzyme immobilization and their properties and of new developments in biocatalysts preparation and applications. Polymers obtained from renewable resources have attracted much attention in recent years because they are environmentally friendly and available in large quantities from natural sources. Different methods for the immobilization of enzymes with these matrixes are reviewed, in particular: (1) binding to a prefabricated biopolymer, (2) entrapment, and (3) crosslinking of enzyme molecules. Emphasis is given to relatively recent developments, such as the use of novel supports, novel entrapment methods and protocols of polymer derivatization, and the crosslinking of enzymes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42125.     

Two‐dimensional simulation of hollow fiber membrane fabricated by phase inversion method

In the steady fabricating process, two‐dimensional hollow fiber membrane near the spinneret was numerically simulated using the finite element method (FEM). The unknown positions of free surface and moving interface were calculated simultaneously by the velocity and pressure fields. The effects of seven relevant parameters, i.e., inertia term, gravity term, dope flow rate, bore flow rate, dope viscosity, tensile force, end velocity and non‐Newtonian on the velocity and diameter profile were studied. On the basis of the simulated results, the inertia term in hollow fiber‐spinning process was safely neglected in low speed, while the effect of gravity was not be neglected. Besides, the outer diameter of the fibers increased with an increase of dope flow rate and bore flow rate; Large tensile force or large end velocity could cause large deformation in the air gap; larger viscous dope solution tended to make less deformation in the air gap. It was found that an increase of the dope flow rate at small dope flow rate resulted in an increase of the inner diameter, while at large dope flow rate, it decreased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2067–2074, 2006     

Preparation and characterization of polyvinylidene fluoride hollow fiber membranes for ultrafiltration

Polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared using the solvent spinning method. N,N-dimethylacetamide was the solvent and ethylene glycol was employed as non-solvent additive. The effect of the concentration of ethylene glycol in the PVDF spinning solution as well as the effect of ethanol either in the internal or the external coagulant on the morphology of the hollow fibers was investigated. The prepared membranes were characterized in terms of the liquid entry pressure of water measurements, the gas permeation tests, the scanning electron microscopy, the atomic force microscopy, and the solute transport experiments. Ultrafiltration experiments were conducted using polyethylene glycol and polyethylene oxides of different molecular weights cut-off as solutes. A comparative analysis was made between the membrane characteristic parameters obtained from the different characterization techniques.     

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     

Directed evolution: Past,present, and future

Directed evolution, the laboratory process by which biological entities with desired traits are created through iterative rounds of genetic diversification and library screening or selection, has become one of the most useful and widespread tools in basic and applied biology. From its roots in classical strain engineering and adaptive evolution, modern directed evolution came of age 20 years ago with the demonstration of repeated rounds of polymerase chain reaction (PCR)‐driven random mutagenesis and activity screening to improve protein properties. Since then, numerous techniques have been developed that have enabled the evolution of virtually any protein, pathway, network, or entire organism of interest. Here, we recount some of the major milestones in the history of directed evolution, highlight the most promising recent developments in the field, and discuss the future challenges and opportunities that lie ahead. © 2013 American Institute of Chemical Engineers AIChE J, 59: 1432–1440, 2013     

Separation of radioactive metal ions by hollow fiber-supported liquid membrane and permeability analysis

Extraction and stripping of uranium ions from nitrate media using a hollow fiber liquid membrane contactor was studied. In this study, tri-butyl phosphate (TBP) diluted in kerosene was used as extractant and sodium hydroxide was applied as a stripping solution. Uranium ions were extracted using TBP 5%(v/v) by rejecting thorium ions into raffinate with a maximum percentage of extraction for the uranium being 67%. The mathematical model was focused on the extraction side of the liquid membrane system. The permeability for each concentration of HNO₃ was investigated by mass transfer theory. When the concentration of HNO₃ increased, more uranium ions were extracted; however, when the concentration of uranium and thorium in the feed solution was increased, the percentage of extraction and stripping slightly decreased because the permeability decreases when the concentration of the feed solution increases due to membrane fouling and concentration polarization.     

Effect of coating and surface modification on water and organic solvent nanofiltration using ceramic hollow fiber membrane

Nanofiltration ceramic hollow fiber membranes were developed to simplify the manufacturing process and improve water and organic solvent permeation performance. The alumina hollow fiber support was prepared by a phase-inversion/sintering method, and a γ-Al₂O₃ sol was coated thereon as a selective layer. Polyvinyl alcohol and ethanol were used as the drying control chemical additive in the coating solution, so that a coating layer could be formed without defects in only one coating step. The coating layer thickness could be adjusted to 0.6–2 μm depending on the coating drawing speed. A sintering temperature of 350 °C was selected to provide both reasonable water permeability (6.91 LMH/bar) and rejection (a molecular weight cutoff of 1000 Da or less) and to form a stable γ-Al₂O₃ phase. In the case of a membrane that was surface-modified with (3-chloropropyl)-trimethoxysilane, the permeability of toluene and hexane was 2.3 and 4.3 LMH/bar, respectively. The newly developed ceramic membrane showed excellent permeability and separation properties, as well as potential effectiveness for organic solvent nanofiltration applications.     

Effects of pre-oxidant (KMnO4) on structure and performance of PVDF and PES membranes

The structure and performance of membrane materials are very important to the efficient and stable operation in membrane drinking water purification technology. Potassium permanganate (KMnO₄), which can change the characteristics of organic matters and control membrane surface fouling, has been widely used as pre-oxidant in the front of membrane drinking water process. This study investigates the evolution of membrane surface structure and performance when polyvinylidene fluoride (PVDF) and polyethersulfone (PES) were exposed to 10, 100 and 1000 mg·L^-1 KMnO₄ solution for 6 and 12 d, respectively. The aged membrane physicochemical characteristics such as membrane surface morphology, chemical composition, hydrophilicity, porosity and zeta potential were evaluated by modern analytical and testing instruments. The anti-fouling property of membrane surface was also investigated by the filtration-backwash experiment. The results indicated that the different concentrations and exposure time of KMnO₄ led to a different variation on PVDF and PES membrane surface structure and performance, which could further affect the membrane separation performance and the membrane fouling behaviors. The membrane surface pore size and porosity increased due to the dislodgment and degradation of membrane additive (PVP), which improved membrane permeability and enhanced the adsorption and deposition of pollutants in the membrane pores. With the increase of exposure time, the membrane surface pore size and porosity reduced for the reactions of chain scission and crosslinking on membrane materials, and the backwashing efficiency declined, leading to a more serious irreversible fouling. Compared with PVDF membranes, the formation of sulfonic group for PES membranes increased the negative charge on membrane surface due to the oxidation of KMnO₄. The present study provides some new insights for the regulation of the pre-oxidant dose and the selection of the membrane materials in KMnO₄ pre-oxidation combined with membrane filtration system.     

氯氟烃替代物的过去、现在和未来

该文对氯氟烃（CFCs）替代物的开发方法、发展现状进行了介绍。目前，开发出的CFCs替代物包括氢氯氟碳（HCFCs）、氢氟烃（HFCs）和氢氟烯烃（HFOs）。其中，HFOs环境性能优异，可在制冷和发泡领域实现对HFCs的替代。总结了HFOs的主要合成路线，并指出最佳的产业化路线。展望了CFCs替代物的未来发展趋势，由于HFOs的核心专利被国外发达国家所垄断，而且HFOs存在二次污染和易燃的风险，同时HFOs类物质的性能难以满足精密清洗、高端芯片先进制造、高压电器绝缘等领域的使用要求，因此，今后的研究重点在于，开发满足国家重大战略需求的新一代替代物，实现诸多领域CFCs的精准替代。     

Preparation and characterization of polyacrylonitrile-based membranes: Effects of internal coagulant on poly(acrylonitrileco-malefic acid) ultrafiltration hollow fiber membranes

Ultrafiltration hollow-fiber membranes (UHFMs) ofpoly(acrylonitrile-co-malefic acid) (PANCMA) were prepared by a dry-wet phase inversion process. The morphologies of inner surface and cross section for these hollow fibers were inspected with scanning electron microscopy. It was found that, by increasing the amount of solvent DMSO in internal coagulant, the number and size of macrovoid underneath the inner surface decreased. The water flux of the UHFMs also decreased while the bovine serum albumin rejection increased minutely. These results were interpreted based on the ternary phase diagrams for the PANCMA/DMSO/(H₂O+DMSO) system, which was obtained from the experimental cloud point measurements and empirical linearized cloud point relation. It was envisaged that the membrane surface could be further modified by the reaction of acid groups with poly(ethylene glycol).     

Fabrication and characterization of novel foaming polyurethane hollow fiber membrane

Foam-like materials had attracted great interest as promising absorbent. In this study, thermoplastic polyurethane(TPU) block sponge was synthesized. Polyester(PET) braid tubular reinforced polyurethane(PU) spongy hollow fiber membrane was prepared by a concentric circular spinning method. The method was woven from an outer coated water-blown PU separation layer and inner PET braid tubular. We have developed a simple and useful preparation technique for the PU spongy hollow fiber membrane. For the first time, the PU spongy hollow fiber membrane was prepared using a coating and controlled foaming technique. The influence of toluene isocyanate index on the physical properties, morphology, and structure of flexible PU sponge was discussed in terms of water contact angle(CA), pure water flux(PWF), Fourier Transform Infrared Analysis(FTIR),pressure-responsive property, and pull-out strength. The morphologies of the membranes were investigated by scanning electron microscopy. We have characterized the foams from an intuitive point of view and demonstrated that the dimensional morphology of the membrane was closely related to isocyanate index. The result showed that the surface cell size of the PU sponge hollow fiber membrane gradually decreased with an increase of the isocyanate index. Due to the elasticity of PU at room temperature, the pressure responsive characteristic of the membrane was prepared. When isocyanate index was 1.05, the interface bonding strength of PU spongy hollow fiber membranes reached as high as 0.37 MPa, porosity and PWF were 71.5% and 415.5 L·m~(-2)·h~(-1),respectively.     

Trade-off between thermodynamic enhancement and kinetic hindrance during phase inversion in the preparation of polysulfone membranes

Polysulfone membranes were prepared via the diffusion-induced phase inversion process from casting solutions consisting of polysulfone, dimethyformamide, and polyvinyl pyrrolidone as a polymeric additive. The effect of PVP added in casting solutions was analyzed by measuring the prepared membranes' morphology and water permeability. Variations in a casting solution's thermodynamic and kinetic properties caused by PVP addition suggest that the thermodynamic variation works in favor of the enhancement of demixing in the casting solution, but the rheological variation induces the opposite trend, or the delay of demixing. When prepared by the immersion coagulation into a water bath, the solidified membranes' structural and functional properties indicate that the coagulation of cast solutions was affected by the trade-offrelationship between thermodynamic enhancement and kinetic hindrance. With a small amount of PVP in the casting solution, the thermodynamic driving force played a major role on solution demixing, inducing the demixing enhancement, corresponding to the acceleration of phase separation due to the PVP's nonsolvent effect. Consequently, the PVP acts as a phase separation enhancer, resulting in both macropore enlargement and permeate flux increase. With more addition of PVP, however, the macropore structure and the water permeability were suppressed rather than enlarged or increased. These phenomena reflect that the demixing of the cast solution was delayed, with the kinetic hindrance offsetting the thermodynamic effect for phase separation enhancement.     

Preparation and Performance Evaluation of Polyethersulfone Hollow Fiber Membranes for Ultrafiltration Processes

In this article, polyethersulfone hollow fiber membranes were prepared using dry–jet–wet spinning process via phase inversion method. Effects of polyethersulfone and polyethylene glycol concentrations and coagulation bath temperature, air–gap distance, and take-up speed on morphology of the prepared membranes were investigated. Based on L₁₆ orthogonal array of Taguchi experimental design, 32 membranes were prepared. An experimental investigation on separation of the industrial oil from oily wastewater has been done. The results showed that synthesized polyethersulfone membranes was effective and suitable for the treatment of oily wastewater to achieve up to 66.6 and 95.0% removal of total organic carbon and oil–grease content, respectively, with a flux of 72.3 L/(m²h).     

SHS in the UK: Past, present, and future directions

The United Kingdom has played a small but significant role in the development of SHS. Parkin and Kuznetsov have studied the formation of complex oxides in external fields. Wood and Christanthou have studied the formation of intermetallic compounds and refractory materials by SHS. Perry, Thompson, and Green have made contributions to the synthesis of materials by solution phase auto-combustion reactions. The UK has also made contributions to the theory of SHS and the monitoring of SHS reactions by time resolved X-ray, neutron, and thermal imaging studies. The UK has been at the forefront in the development of a sub-class of SHS reactions termed solid state metathesis. Presented at the International Conference on Historical Aspects of SHS in Different Countries, October 22–27, 2007, Chernogolovka, Moscow, Russia.     

Polyvinylidene fluoride and polyetherimide hollow fiber membranes for CO2 stripping in membrane contactor

Porous polyvinylidene fluoride (PVDF) and polyetherimide (PEI) hollow fiber membranes incorporating polyethylene glycol (PEG) were prepared via spinning process for CO₂ membrane stripping. CO₂ loaded diethanolamine solution was used as liquid absorbent while N₂ was used as a strip gas. The characterization study of the fibers was carried out in terms of permeation test, contact angle measurement and liquid entry pressure (wetting pressure). Performance study via membrane contactor stripping was carried out at specific operating condition. The experimental results showed that PVDF membrane have high gas permeation, effective surface porosity and contact angle despite having lower liquid entry pressure in comparison with PEI membrane. PVDF-PEG membrane showed the highest stripping flux of 4.0 × 10⁻² mol m⁻² s⁻¹ at 0.7 ms⁻¹ compared to that of PEI membrane. Although the stripping flux for PEI-PEG membranes was slightly lower than PVDF membrane (e.g. 3.5 × 10⁻² mol m⁻² s⁻¹ at liquid velocity of 0.85 ms⁻¹), the membrane wetting pressure of PEI membrane is higher than hydrophobic PVDF membrane. Long term performance of both membranes showed severe flux reduction but started to level-off after 30 h of operation.