Electrospinning of porous polylactic acid fibers during nonsolvent induced phase separation

In this study, porous micron‐sized fibers of polylactic acid (PLA) are fabricated via electrospinning of PLA‐dichloromethane (DCM)‐hexane systems with no post treatment involved. Several compositions from the liquid‐liquid phase separated region of the phase diagram of this ternary system are selected and their electrospinnability are investigated throughout their phase separation process before gelation. We show that under constant processing and ambient parameters, there is a phase separation shelf time for each composition wherein the viscoelasticity of the systems is optimum to produce long, uniform porous fibers. For the first time, we investigate the effect of aging time during phase separation on the morphology of the electrospun fibers using scanning electron microscopy (SEM). Based on our results, certain phase separated systems provide a range of viscosity allowing for the production of porous spherical micro beads or fibers via electrospraying and electrospinning, respectively. It is also shown that obtaining long, uniform fibers from electrospinning of highly phase separated systems, e.g., a gel, is not feasible due to the high degree of crystallinity of their polymer‐rich domains and the solid‐like yielding behavior. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44862.     

Structure control of asymmetric poly(vinyl butyral)‐TiO2 composite membrane prepared by nonsolvent induced phase separation

Poly(vinyl butyral) (PVB)‐TiO₂ composite hollow fiber membranes were prepared via nonsolvent induced phase separation (NIPS). The membrane had a skin layer on both the outer and inner surface at the initial stage after membrane preparation. However, the outer surface became porous with the passage of time, as the polymer in the membrane's outer surface was decomposed by the photocatalysis of TiO₂. The initial water permeability increased with the increase of TiO₂ content. Furthermore, for all the membranes, as time elapsed the water permeabilities increased and became constant after about 15 days, which was in accordance with the alteration on the membrane's outer surface. Despite decomposition of the polymer on the outer surface, particle rejection hardly changed because the inner surface kept the original structure. Thus, addition of TiO₂ to the membrane is a useful way to improve water permeability while maintaining particle rejection. The clear asymmetric structure with both porous structure at the outer surface and skin layer at the inner surface was achieved by the addition of TiO₂. Therefore, the addition of TiO₂ is a new method for achieving the high porosity at the outer surface of the hollow fiber membrane. In addition, tensile strength and elasticity kept constant over time and were higher than those of original PVB membranes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Factors controlling surface morphology of porous polystyrene membranes prepared by thermally induced phase separation

A special device for preparing porous polymer membranes through a thermally induced phase separation (TIPS) process was designed and machined; it included a solution container, a membrane‐forming platform, a coldplate, a temperature‐decreasing system and a temperature‐supervising system. Polystyrene was selected as the model polymer from which to prepare porous membranes using the device due to its better understood TIPS and good biocompatibility with cells. The major factors controlling surface morphology and cell size, ie volume fraction of polystyrene (ϕ₂), quench rate and solvent‐removing methods, were studied. Fixing the coldplate temperature, when ϕ₂ is as low as 0.045, provokes the formation of round pores on both the bottom and top surfaces of the membrane; when ϕ₂ = 0.16 no pores are formed on either surface; when ϕ₂ = 0.087 pores form on the top surface, but not on the bottom surface. When ϕ₂ = 0.087 the cell size is very small or no pores are formed on the bottom surface, whereas the top surface shows a regular decrease of the pore sizes and an increase of the pore number and pore area, along with a decrease of the coldplate temperature. The side near the coldplate is dense, and the dense layer aligns along the coldplate, while the side away from the coldplate is like a porous foam, the shape of which is isotropic and the surfaces are interconnected with each other three dimensionally. On the top surface of a membrane obtained by ethanol extraction, the cell size is enlarged and the cell number reduced, but the surface morphology and the whole area remained almost the same when compared to samples obtained by freeze drying in the same membrane‐forming conditions. The isotropic, uniformly distributed and round pores suggest that the mechanism of phase separation is a spinodal liquid–liquid decomposition under our research conditions. © 2000 Society of Chemical Industry     

Formation of a bicontinuous structure membrane of polyvinylidene fluoride in diphenyl ketone diluent via thermally induced phase separation

The polyvinylidene fluoride (PVDF)‐diphenyl ketone (DPK) mixture was studied as a new system to prepare PVDF membranes via thermally induced phase separation (TIPS). The phenomena of liquid–liquid phase separation was found in this mixture when the temperature of mixture was decreasing and the PVDF concentration was less than 30 wt %. Using DPK as diluent, PVDF membrane with bicontinuous structure was obtained without necessity to add a nonsolvent or a stretching process further. The phase diagram of PVDF‐DPK system was also constructed to help investigate the effect of PVDF concentration and coarsening temperature on morphology of resulting membrane. The experiments showed that high coarsening temperatures and low PVDF concentrations resulted in the formation of the large pore size membrane. The strength of the wet membrane was decreasing with decreasing PVDF concentration. On condition that the PVDF concentration was larger than 30 wt %, thermally induced solid–liquid separation occurred and bicontinuous structure disappeared. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fabrication of cellulose acetate ultrafiltration membrane with diphenyl ketone via thermally induced phase separation

With diphenyl ketone as diluent, cellulose acetate (CA) ultrafiltration (UF) membrane with a bicontinuous structure was prepared via thermally induced phase separation (TIPS) method. The liquid–liquid phase separation region of CA/diphenyl ketone system was measured and the maximum corresponding polymer concentration was approximately 53 wt %. The effects of polymer concentration, coarsening time and coarsening temperature on the morphologies, and mechanical properties of CA membranes were investigated systematically. As the polymer concentration increased from 15 to 30 wt %, the bicontinuous structure could be obtained and the tensile strength of CA membranes increased from 3.92 to 30.17 MPa. With the increase of coarsening time, the thickness of dense skin layer and the asymmetry of cross‐section reduced. However, excess coarsening rendered the membrane morphology evolved from a bicontinuous structure to a cellular structure. When the coarsening time was 5 min, the bicontinuous structure in cross‐section showed good interconnectivity and the dense skin layer exhibited a thin thickness of 2 μm. The fabricated CA hollow fiber UF membrane exhibited a high tensile strength of 31.00 MPa and rejection of 96.10% for dextran 20 kDa. It is indicated that diphenyl ketone is a competitive diluent to prepare CA membranes with excellent performance via TIPS. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42669.     

Optimization of structure and properties of polyphenylene sulfide porous membrane by controlling the process of thermally induced phase separation

Polyphenylene sulfide (PPS) porous membranes were successfully prepared from miscible blends of PPS and polyethersulfone (PES) via thermally induced phase separation followed by subsequent extraction of the PES diluent. The morphologies, crystalline structures, mechanical properties, pore structures and permeate fluxes of the PPS porous membranes obtained from different phase separation processes were characterized and are discussed. During the phase separation in the heating process, PPS and PES mainly underwent liquid–liquid phase separation, and then a nonhomogeneous porous structure with a mean pore size of 100 μm and a honeycomb‐like internal structure formed on the membrane surface. The phase separation of PPS/PES occurring in the cooling process was easier to control and the related pore diameter distribution was more regular. In the process of direct annealing, as the phase separation temperature decreased, the pore size distribution became more homogeneous and the mean diameter of the pores also decreased gradually. When the phase separation temperature decreased to 200 °C, PPS membranes with a network structure and a uniform as well as well‐interconnected porous structure could be obtained. In addition, the maximum permeation flux reached 1718.03 L m^–2 h^–1 when the phase separation temperature was 230 °C. The most probable pore diameter was 6.665 nm, and the permeate flux of this membrane was 2.00 L m^–2 h^–1; its tensile strength was 17.07 MPa. Finally, these PPS porous membranes with controllable pore structure as well as size can be widely used in the chemical industry and energy field for liquid purification. © 2020 Society of Chemical Industry     

Preparation of polypropylene microfiltration membranes via thermally induced (solid–liquid or liquid–liquid) phase separation method

Polypropylene (PP) hollow fiber microfiltration membranes with excellent performance were successfully prepared from the PP‐binary diluent system via thermally induced liquid–liquid (L–L) phase separation method. The binary diluent consisted of myristic acid and diphenyl carbonate. The effects of the binary diluent on phase separation and membrane structure were systematically investigated. With the decrease in the weight ratio of myristic acid to diphenyl carbonate, the Flory–Huggins interaction parameter between PP and the binary diluent became more positive, and the mechanism of phase separation changed from solid–liquid (S–L) to L–L. This resulted in the membrane structure changing from spherulitic to bicontinuous. Moreover, as the weight ratio of myristic acid to diphenyl carbonate decreased from 11/9 to 2/3, the L–L phase separation region kept enlarging while the viscosity of the whole system became higher. The pore size of the cross‐section increased due to the longer coarsening time while the surface pore size decreased due to the higher viscosity of the system. The bulk porosity of resultant PP membranes was mostly higher than 70% and pure water flux were generally larger than 650 L m^?2 h^?1. In addition, the PP hollow fiber microfiltration membrane possessed excellent mechanical properties (tensile strength of 3.47 MPa and elongation of 118%) and good separation performance (rejection to PEO (M_w = 1000 kDa) of 94.6%) when the weight ratio of myristic acid to diphenyl carbonate was 2/3. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42490.     

Polymerization induced viscoelastic phase separation of porous phenolic resin from solution

The porous structure evolution of thermosetting phenolic resin controlled by polymerization induced viscoelastic phase separation from solution was investigated in this work. The ultimate morphology and the evolution of a porous texture for the resol resin/solvent system were characterized by digital camera and optical microscopy. In-situ Fourier transform infrared spectroscopy and a rheological method were used to trace the curing reaction of the resol resin/solvent system. The impacts of solvent content and curing temperature on the foaming behavior were quantitatively and systematically investigated. Based on the relationship between the morphology evolution and curing dynamics, the foaming mechanism of the polymerization induced viscoelastic phase separation was elucidated. The present work provides new insight into the foaming mechanism of thermosetting materials and may be helpful for morphological control in the preparation of lightweight porous phenolic material. © 2016 Society of Chemical Industry     

Effects of nucleating agents on the porous structure of polyphenylene sulfide via thermally induced phase separation

The different molecular weight Polyethylene glycol (PEG) was chosen to be the nucleating agent to investigate the effects of nucleating agents on the porous structure of polyphenylene sulfide (PPS) via thermally induced phase separation (TIPS). The pore structures were changed with the addition of PEG, due to the different mechanism on pattern formation. Moreover, some effecting factors, such as the molecular weight and concentration of PEG, were used to control the pore structure and size. With addition of nucleating agent, it can be estimated that the pore size (radius) should be about 0.5 ～ 0.05 μm and the porosity should be above 70%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Formation of an interconnected lamellar structure in PVDF membranes with nanoparticles addition via solid‐liquid thermally induced phase separation

Novel microporous membranes were prepared via thermally induced solid‐liquid (S‐L) phase separation of mixtures containing poly(vinylidene fluoride) (PVDF)/diphenyl ketone (DPK)/nanoparticles [such as montmorillonite (MMT) and polytetrafluoroethylene (PTFE)] in diluted systems with a mass ratio of 29.7/70/0.3 wt %. The crystallization and melting characteristics of these diluted systems were investigated by polarizing optical microscopy (POM), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and wide angle X‐ray diffraction (WAXD). The nanoparticle structure and the interaction between PVDF chains and nanoparticle surfaces determined the crystallization behavior and morphology of the PVDF membrane. The addition of MMT and PTFE had a significant nucleation enhancement on the crystallization of PVDF accompanied by S‐L phase separation during the thermally induced phase separation (TIPS) process. It was observed that an interconnected lamellar structure was formed in these two membranes, leading to a higher tensile strength compared with that of the reference membrane without nanoparticles addition. Additionally, addition of MMT facilitates the fiber‐like β phase crystal formation, resulting in the highest elongation at break. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

泡沫分离法制备聚苯乙烯多孔微球

以一种新型、简单、高效的溶剂挥发法制备不同孔形态和粒径分布的聚苯乙烯微球。该方法利用机械搅拌和升温过程中溶剂挥发产生的泡沫,将油相液滴夹带进入泡沫相,使溶剂在气相中迅速挥发,诱导聚合物与非良溶剂发生相分离成孔。结果表明：随着聚合物与致孔剂用量比减小,微球结构形态由多孔演变到中空结构;聚乙烯醇（PVA）质量分数由1%增大至3%时,微球的平均粒径由52μm±23μm减小至23μm±20μm及转速由300r/min增大至700r/min时,微球粒径由107μm±40μm减小到45μm±20μm,但由于产生的泡沫量和泡沫形态不同影响了溶剂的挥发过程,故得到微球的多孔形态不同,增大PVA浓度得到的微球表面孔数目较少、孔径较大,而增大转速得到的微球孔数目较多。此外,该方法在油水相比≥1时,在泡沫中也能得到稳定规则的多孔微球,而传统的在水相中引发相分离的方法因水相无法完全分散油相,故无法成球。     

Effect of non‐reactive solvent on the formation and properties of porous epoxy thermosets formed via reaction‐induced phase separation

BACKGROUND: A reaction‐induced process for producing controlled‐porosity epoxy thermosets with the aid of solvents is presented. The curing reactions were carried out in diglycidyl ether of bisphenol A and 4,4′‐diaminodicyclohexylmethane systems in the presence of appropriate solvents. RESULTS: The phase separation during the polymerization with appropriate solvent was characterized using dynamic light scattering. Supercritical carbon dioxide was used to extract the solvent from the epoxy resin matrix. The morphology and the porosity within the epoxy thermosets were investigated using scanning electron microscopy and atomic force microscopy as a function of solvent content. The results showed that porous epoxy networks with average pore size ranging from 1 to 20 µm were obtained, and the size of pores could be varied by changing the solvent content. Thermal properties were investigated using differential scanning calorimetry and thermogravimetric analysis. The introduction of solvent decreased the glass transition temperature and the thermal stability of the epoxy thermosets but showed no influence on the degradation of the main networks. CONCLUSION: Porous epoxy thermosets have been successfully fabricated through a novel reaction‐induced phase separation process with the aid of appropriate solvents. They should open a wide range of opportunities for new applications. Copyright © 2008 Society of Chemical Industry     

Preparation of polyvinylidene fluoride membrane via a thermally induced phase separation using a mixed diluent

Polyvinylidene fluoride (PVDF) membranes were prepared via a thermally induced phase separation method with a mixed diluent (dibutylphthalate/dioctyl phthalate). The effects of PVDF concentration and cooling bath temperature (CBT) on the structure and properties of the membranes were investigated. Scanning electron microscopy photos showed that the cross‐section of all the membranes, regardless of PVDF concentration and CBT, presented a bi‐continuous structure with the spherulitic pattern; moreover, the spherulitic patterns became clear gradually from the top surface to the bottom surface, and the top surface was denser than the bottom surface. As a result, all the membranes exhibited an asymmetric structure. The membrane property measurement indicated that, as PVDF concentration increased from 25 to 35 wt %, the pure water flux (PWF) decreased from 342 to 80 L m^?2 h^?1, and the porosity decreased slightly, whereas the minimum bubble point pressure (BPP) increased, which indicates maximum pore size decreased. In addition, with the increase in CBT, the PWF increased, but, the minimum BPP and porosity decreased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Formation of microporous polymeric membranes via thermally induced phase separation: A review

A review of recent research related to microporous polymeric membranes formed via thermally induced phase separation (TIPS) and the morphologies of these membranes is presented. A summary of polymers and suitable diluents that can be used to prepare these microporous membranes via TIPS are summarized. The effects of different kinds of polymer materials, diluent types, cooling conditions, extractants and additive agents on the morphology and performance of TIPS membranes are also discussed. Finally new developments in TIPS technology are summarized.

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Preparation of porous membrane by combined use of thermally induced phase separation and immersion precipitation

By immersion in the cooled nonsolvent, PMMA porous membrane was prepared by the combined use of thermally induced phase separation (TIPS) and immersion precipitation. As nonsolvent, water with low mutual affinity with cyclohexanol (diluent) and methanol with high affinity were used. In the case of water, the porous structure was formed by TIPS immediately after the immersion. Near the top surface contacted with the nonsolvent, the thin skin layer was formed due to the outflow of the diluent. After the long immersion period, macrovoids were formed near the top surface due to the penetration of the nonsolvent. Thus, TIPS and the immersion precipitation occurred serially. On the contrary, TIPS and the immersion precipitation occurred simultaneously in the case of methanol because the inflow of methanol was fast. Therefore, the membrane obtained after the short immersion period had the larger pores near the top surface due to the nonsolvent induced phase separation and the smaller pores near the bottom surface due to TIPS. These two modes of the phase separations were confirmed by the changes in light transmittance through the polymer solutions.     

蒸汽诱导相分离法制备具有规整微孔结构的聚醚砜膜(英文)

Polyethersulfone(PES)film with regular microporous structure was formed using dichloromethane as the solvent via water vapor induced phase separation(VIPS).The effects of solution concentration,atmospheric humidity and temperature,as well as molecular weight of PES on the surface morphology of the polymer film were investigated.The surface morphology characterized by SEM showed that the pore size reduced as the solution concentration increased.There was an optimum range of relative humidity for the formation of regular pore structure, which was from 60%to 90%at concentration of 20 g·L-1 and 20°C.With the atmospheric temperature varied from 20 to 30°C,the pore became larger and the space between pores increased.The pore size in the PES film with low molecular weight was smaller than that with high molecular weight.     

用拟二元方法研究iPP-DBP-DOP三元体系的热致相分离热力学

采用拟二元方法研究等规聚丙烯（iPP）‐邻苯二甲酸二丁酯（DBP）‐邻苯二甲酸二辛酯（DOP）三元聚合物溶液的热致相分离热力学,得出了拟二元相图的数学关联方法.采用光学显微镜法测定浊点温度, 采用差式扫描量热法（DSC）测定熔点、动态结晶温度.利用浊点测定数据回归聚合物-共溶剂的交互作用参数 χ的表达式,χ是共溶剂配比和温度的函数,以此为基础计算的拟二元相图与实验数据吻合较好.发现共溶剂中DBP份数增加,相分离类型由单纯固液分相形式转变为液液分相、固液分相依次发生形式,共溶剂配比能调控拟二元相图结构.研究表明,只需测定一个较低冷却速率下几种共溶剂配比的拟二元溶液的浊点温度、分别测定几个冷却速率下iPP–DOP二元溶液的动态结晶温度即可掌握该三元溶液热致相分离热力学的全部信息.其可用来指导制膜过程,并能准确预测形成的膜结构形貌.     

Effect of the ethylene content of poly(ethylene-co-vinyl alcohol) on the formation of microporous membranes via thermally induced phase separation

Porous poly(ethylene-co-vinyl alcohol) (EVOH) membranes were prepared via thermally induced phase separation. The effect of the EVOH ethylene content on the membrane morphology and solute rejection property was investigated. For EVOHs with ethylene contents of 27–44 mol %, polymer crystallization (solid–liquid phase separation) occurred, and the membrane morphology was the particulate structure. However, the liquid–liquid phase separation occurred before crystallization for EVOH with a 60 mol % ethylene content. Cellular pores were formed in this membrane. For the particulate membranes, higher solute rejection and lower water permeance were obtained for EVOH with a lower ethylene content. The membrane formed by the liquid–liquid phase separation showed a sharper solute rejection change with a change in the solute radius than the particulate membranes did. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2583–2589, 2001     

Porous polyphenylene sulfide membrane with high durability against solvents by the thermally induced phase‐separation method

Porous polyphenylene sulfide membranes were prepared as new solvent‐resistant membranes by the thermally induced phase‐separation (TIPS) method. Porous structures were either formed by solid–liquid phase separation (polymer crystallization) or liquid–liquid phase separation. The effects of solvents, cooling rates, and polymer concentrations on the porous structures were investigated. Various characteristics of pore structure can be obtained with suitable diluents and cooling rates using the TIPS method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2959–2966, 2006     

Comparison of solvent removal methods of microporous polypropylene tubular membranes via thermally induced phase separation using a novel solvent: Camphene

A novel solvent, camphene, was used to prepare microporous polypropylene tubular membranes via thermally induced phase separation (TIPS). In this process, camphene was removed by either sublimation or extraction. The effect of the solvent-removal on the structure and properties of the resulting membrane was studied. Microscopic observation and wide angle X-ray scattering indicate that the morphology and crystalline structure difference is minor. Thermal analysis and tensile tests reveal that the crystallinity and breaking strength of the tubular membrane from the extracting method are slightly higher than those for the sublimating method. Porosity measurements show that the sublimation method can yield membranes with slightly higher porosity than the extraction method. Furthermore, permeation results indicate that membranes from extraction have a smaller permeation rate and higher retention. Therefore solvent-extraction can produce a denser membrane structure than sublimation can.