Phase separation phenomena in solutions of polysulfone in mixtures of a solvent and a nonsolvent: relationship with membrane formation

The phase separation phenomena in ternary solutions of polysulfone (PSf) in mixtures of a solvent and a nonsolvent (N,N-dimethylacetamide (DMAc) and water, in most cases) are investigated. The liquid-liquid demixing gap is determined and it is shown that its location in the ternary phase diagram is mainly determined by the PSf-nonsolvent interaction parameter. The critical point in the PSf/DMAc/water system lies at a high polymer concentration of about 8% by weight. Calorimetric measurements with very concentrated PSf/DMAc/water solutions (prepared through liquid-liquid demixing, polymer concentration of the polymer-rich phase up to 60%) showed no heat effects in the temperature range of ?20°C to 50°C. It is suggested that gelation in PSf systems is completely amorphous. The results are incorporated into a discussion of the formation of polysulfone membranes.     

Structure formation and characterization of EVAL membranes with cosolvent of isopropanol and water

Microporous poly (ethylene-co-vinyl alcohol) (EVAL) membranes can be prepared by the solution casting method in combination of thermally induced phase separation (TIPS) with solvent evaporation. A cosolvent of isopropanol and water (3:2 w/w) is used to prepare the casting solution. EVAL membranes of different bulk or true densities, porosity, flexibility, crystallinity, and structure can be obtained by adjusting the casting temperature. A pseudo-binary temperature-concentration phase diagram of the EVAL-cosolvent system has been proposed, based on the information obtained from SEM, DSC, and light transmittance studies, to account for the membrane formation mechanism. The dense membranes were obtained when the casting temperature was higher than the upper critical solution temperature (UCST) of the system, but they might contain some nonSEM-observable micropores if the casting temperature was below the glass transition temperature (T_g) of EVAL. The porous and the least crystalline membranes with a honeycomb-like morphology were obtained through liquid-liquid demixing and vitrification at a casting temperature between the UCST and the dynamic crystallization temperature (T_c). Highly porous and crystalline membranes were obtained when they were prepared at temperatures near T_c. In this case, the particulate membranes were resulted from solid-liquid demixing mainly via TIPS, and membranes with leafy morphology were created through liquid-liquid demixing and then followed with immediately crystallization.     

Effect of stereoisomerism of poly(lactic acid) during neural guide conduit membrane synthesis

Poly(lactic acid) membranes are being developed as biomaterials for several purposes such as artificial implants for peripheral nerve injury, also known as neural guide conduits (NGC). These membranes need to meet standards of mechanical, degradability, and permeability properties, besides dimensional and structural requirements. Among the stereoisomers of polylactides, poly(l ‐lactic acid), and poly(d ,l ‐lactic acid) are the most used as biomaterials, having significant differences in solubility, crystallinity thermal, and mechanical properties. In this work, PLLA and PDLLA were compared for hollow fiber membrane synthesis by liquid induced phase separation. PLLA samples presented 18% of crystallinity, while PDLLA is amorphous. PDLLA and PLLA polymer solutions on N‐methyl‐pyrrolidone presented values of 3428 and 320.2 cP, respectively. In immersion of PLA‐NMP solutions in water, PLLA solution presented instantaneous demixing, while PDLLA showed a 28 s delay on precipitation. The PLLA–NMP–water has a larger demixing region compared to PDLLA–NMP–water system. Hollow fibers of both polymers presented closed external surface with finger‐like macropores morphology in their cross‐sections. PDLLA presented typical liquid–liquid demixing pores while PLLA presented spherulitical crystalline solid–liquid separation structures, which deeply compromised its mechanical properties. PDLLA presented as a good candidate for hollow fiber NGC material, as presented good mechanical resistance in tensile and suture simulating tests. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46190.     

PVDF-PVP-DMAc-H2O铸膜液体系中浓相固化过程研究

研究了PVDF-PVP-DMAc-H2O体系的聚合物溶液固化的机理和速度.对PVDF聚合物凝胶进行了差示扫描量热实验和粉末衍射实验,表明聚合物溶液转变成凝胶固化是由结晶导致的物理可逆过程,结晶性液固分相按照成核-长大机理发生.通过落球实验测定了聚合物溶液体系从具有流动性的液态转换成凝胶态的过程,实验发现在凝胶点处从流动态转换成凝胶固态的过程大致需要2.5～4 min.光透射曲线法测定了成膜时的相分离速度, 结果表明成膜过程中,在凝胶分相后约1min出现了液液分相. 可见从开始发生液液分相到最后浓相固化、膜形态固定之间大致还有1.5～3 min的时间,这段时间是聚合物浓、稀相间的结构发生变化并最终固化定型的关键阶段.     

Polylactide films formed by immersion precipitation: Effects of additives,nonsolvent, and temperature

The influence of nonsolvent, crystallinity of the polymer film, and addition of dodecane (a poor solvent for the polymer and for the nonsolvent) on the morphology of polylactides films has been investigated and was related to phase separation behavior. Both amorphous poly‐DL ‐lactide (PDLLA) and crystalline poly‐L ‐lactide (PLLA) were dissolved in dichloromethane, and subsequently films were made by immersion in nonsolvent baths. PDLLA gave dense films without any internal structure, since the structure was not solidified by crystallization or glassification. PLLA films show varying structure depending on the nonsolvent. With methanol, asymmetric morphologies were observed as a result from combined liquid‐liquid demixing and crystallization, while with water symmetric spherulitic structures were formed. As a next step, dodecane was added, which is not miscible with the nonsolvent, and we found it to have a strong influence on the morphology of the films. The PDLLA films with dodecane did not collapse: a closed cell structure was obtained. In PLLA films, dodecane speeds up phase separation and induces faster crystallization in the films, and the porosity, size of the pores, and interconnectivity increased. When the PLLA solutions were subjected to a heat pretreatment, crystallization could be postponed, which yielded a cellular structure around dodecane, which did not contain spherulites anymore. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 959–971, 2007     

Phase behavior of poly(N-isopropylacrylamide) in water-methanol cononsolvent mixtures and its relevance to membrane formation

The phase behavior of poly (N-isopropylacrylamide) (PNIPAAm) in solutions composed of water and methanol was studied at 25 °C. The pair of solvents used to dissolve PNIPAAm has been selected for the purpose to perform a cononsolvent system. From the observed phase behavior, PNIPAAm was soluble in either water or methanol individually but liquid-liquid demixing was observed in water/methanol mixtures. Flory-Huggins formalism including three binary interaction parameters and one ternary interaction parameter was used to analyze the phase behavior of the cononsolvent system. The mechanism of cononsolvency and its relation with the ternary interaction parameter were discussed. In addition, the use of two solvents serving as a cononsolvent system, replacing the traditional solvent-nonsolvent pair, for the membrane formation was investigated. Regardless of water or methanol being used as the solvent, it showed a rapidly precipitating system and macrovoid morphology due to liquid-liquid demixing was obtained. Trend expected on the basis of the phase diagram was in reasonable agreement with the observed membrane morphology. Therefore, the principles of membrane formation established for the ternary systems with nonsolvent-solvent-polymer can be extended to a cononsolvent-polymer system.     

Demixing kinetics of phase systems employed for liquid-liquid extraction and correlation with system properties

The kinetics of phase demixing in liquid-liquid extraction for model systems comprising PEG 4000/potassium phosphate and t-butanol/ammonium sulfate was studied. The kinetics of demixing depicts the entire demixing pattern of phases of the phase system during and after extraction and hence the study is essential prior to design of large scale gravity phase separators. With an increase in composition, both the systems showed increase in demixing rate (decrease in demixing time). At high tie line length (TLL) and phase volume ratio <1, with salt rich phase as continuous phase, both PEG 4000/potassium phosphate and t-butanol/ammonium sulfate systems showed reduction in demixing time by 59% and 50%, respectively as compared to that at low TLL. An empirical equation proposed in the literature for rate of phase demixing was used to correlate the experimental data. The agreement was better for t-butanol/ammonium sulfate system when compared to PEG 4000/potassium phosphate system.     

Phase separation,crystallization, and structure formation in immiscible polymer solutions

Morphological and calorimetric studies of phase separation have been carried out in solutions of a crystallizable polymer in poor solvents. Hydrogenated polybutadiene with low branch content was investigated in solutions with diphenyl ether and diphenyl methane, in which the equilibrium phase diagram exhibits both liquid–liquid phase separation and crystallization of the polymer. Emphasis is placed on sample preparation protocols using thermal treatments at low concentrations where it is anticipated that both phase separation mechanisms may influence the resulting morphology. Samples prepared using either ramp cooling or isothermal crystallization exhibit porous structures such as those seen in membrane materials, that predominantly reflect liquid phase separation. However, the interplay between the different kinetics of liquid demixing and crystallization provides a mechanism to control, for instance, pore size. DSC studies during ramp cooling showed evidence of two discrete crystallization processes associated with the two liquid phases expected to be present under these circumstances. Finally, high concentration samples showed morphological evidence of liquid phase separation induced at the growth front of spherulites in otherwise single-phase polymer solutions. © 1995 John Wiley & Sons, Inc.     

Thermally induced phase separation in poly(lactic acid)/dialkyl phthalate systems

Thermally induced phase separation in poly(lactic acid)/dialkyl phthalate systems was investigated. Poly(DL ‐lactic acid) (PDLLA) and poly(L ‐lactic acid) (PLLA) with different molecular weights were used. A series of dialkyl phthalates, with different numbers of carbon atoms in the alkyl chain, were employed as solvents to control the interaction between polymer and solvent. The liquid–liquid phase‐separation temperature of the poly(lactic acid) solutions decreased systematically with a shorter alkyl chain in the phthalate. Based on the interaction between polymer and solvent and the molecular weight of polymer influencing liquid–liquid phase‐separation temperature significantly but crystallization temperature only slightly, proper thermal conditions were employed to investigate competitive phase separation and crystallization in PLLA solutions. Factors that can influence the final morphology of PLLA solutions were examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2224–2232, 2003     

Preparation and Characterization of Poly L-Lactide/Triclosan Nanoparticles for Specific Antibacterial and Medical Applications

This work aims at preparation of poly-L-lactide (PLLA)/triclosan nanoparticles as antibacterial products used in some specific medical applications. PLLA was synthesized by the reaction extrusion via the ring opening polymerization of L-lactide using a continuous single-stage process, which is a fast and easy method. The PLLA triclosan nanoparticles were prepared by the emulsification–diffusion process with few modifications. Chloroform was used for the surface reaction of triclosan without any chemical shifts. The resulting nanoparticles with various triclosan quantities were fully characterized. The release as well as its kinetics was studied using the UV-visible spectroscopy. All the results confirmed the high stability and process efficiency of molecular dispersion and attachment of triclosan to PLLA. The sample containing 30% triclosan showed the best form among the others with the highest encapsulation efficiency. The synthesized nanoparticles with the controlled antibacterial activity could be considered as an appropriate alternative for application as antibacterial agent in the implantable surgical products as well as the drug delivery and wound-dressing applications.     

High-modulus fibres of nylon-6 prepared by a dry-spinning method

Nylon-6 filaments with tensile strengths at break up to 1 GPa and initial moduli in the range of 16 to 19 GPa have been produced by dry-spinning of solutions of nylon-6 in cosolvent mixtures of formic acid and chloroform followed by hot-drawing at 200°C–240°C. Tensile strengths and elastic moduli of the nylon-6 fibres were strongly dependent on the draw ratio, on the molecular weight of the polymer, on the polymer concentration in the spinning solution and on concentration of nonsolvent in the spinning solution. At high concentrations of nonsolvent in the spinning solution, the as-spun fibres of nylon-6 were composed of ball-like structural units, formed possibly due to the liquid-liquid phase separation in the polymer/solvent/nonsolvent ternary system. Formation of ball-like structures reduced the ultimate mechanical properties of hot-drawn fibres of nylon-6.     

Salting-out in Aqueous Solutions of Ionic Liquids and K3PO4: Aqueous Biphasic Systems and Salt Precipitation

The salting-out effect produced by the addition of potassium phosphate, K₃PO₄ to aqueous solutions of water-miscible ionic liquids, viz. 1-ethyl-3-methylimidazolium ethyl sulfate, 1-butyl-3-methylimidazolium methyl sulfate, or 1-alkyl-3-methylimidazolium chloride (alkyl = butyl, octyl or decyl) is investigated. The effects are analyzed using both the corresponding temperature–composition pseudo-binary and composition ternary phase diagrams. Different regions of liquid-liquid and solid-liquid phase demixing are mapped. The phase behavior is interpreted taking into account the complex and competing nature of the interactions between the ionic liquid, the inorganic salt and water. In the case of solutions containing 1-octyl- or 1-decyl-3-methylimidazolium chloride, the smaller magnitude of the salting-out effects is explained in terms of the possibility of self-aggregation of the ionic liquid.     

Preparation of porous poly(L‐lactic acid)‐co‐(trimethylene‐carbonate) structures using supercritical CO2 as antisolvent and as foaming agent

In this work, porous structures of poly(l ‐lactic acid)‐co‐(tri‐methylene‐carbonate) (PLLA‐co‐TMC) were successfully fabricated using two experimental methods, that is, using supercritical CO₂ as antisolvent and as foaming agent through the pressure induced phase separation technique. Considering the phase inversion method, the effect of the initial polymer concentration of the solution, pressure, and temperature on the morphology of the final porous structure (pore size, porosity, and cell density) was investigated. The L–L demixing process was suggested as the dominant mechanism for the phase separation and pore production. The temperature window, for which PLLA‐co‐TMC porous structures are successfully produced using the pressure induced phase separation technique, was determined at 150 and 210 bar. The effect of temperature on the final porous structure was investigated. POLYM. ENG. SCI., 57:1005–1015, 2017. © 2016 Society of Plastics Engineers     

Polymeric scaffolds based on blends of poly-l-lactic acid (PLLA) with poly-d-l-lactic acid (PLA) prepared via thermally induced phase separation (TIPS): demixing conditions and morphology

Porous scaffolds based on blends of high crystalline Poly-l-lactic acid (PLLA) with low crystalline poly-d-l-lactic acid (PLA) were prepared via Thermally Induced Phase Separation (TIPS), with the aim of exploring the possibility to control the degradation behaviour of the PLA-based scaffold, simultaneously preserving the morphological characteristics required for tissue engineering applications. Porous foams with different PLLA/PLA weight ratios (from 95/5 to 60/40) were produced and characterised in terms of pore size, porosity, and thermal properties. The scaffolds present an open porosity, with average pore sizes ranging from 30 to 70 μm. Results showed that, when dealing with a PLLA/PLA blend, some relevant processing conditions of the preparation process (above all demixing temperature and total polymer concentration) must be carefully tuned, in order to attain suitable structures in term of pore size and porosity. In particular, with increasing amounts of PLA in a PLLA/PLA blend, the demixing temperature must be decreased and the overall polymer concentration decreased. Moreover, a preliminary investigation regarding the in vitro biodegradation rate of the blends was attempted, based on the determination of the crystallinity through wide angle X-ray diffractometry.     

Polylactide. II. Discontinuous dry spinning–hot drawing preparation of fibers

The mechanical properties and morphology of poly(L-lactide) fibers, prepared by the dry spinning–hot drawing process using different nonsolvent/chloroform spinning solutions, were studied in relation to fiber in vitro degradability. Acetone, methanol, ethanol, and cyclohexane were used as nonsolvents in the spinning mixture with as-polymerized PLLA, i.e., PLLA containing 10% of residual L-lactide. The tensile strength, structure, and degradability of obtained fibers were mainly governed by the nonsolvent volatility. Generally, the higher the volatility, the higher the strength, and the faster the degradation. The acetone/chloroform spinning system produced fiber with an increased degradation rate in comparison to the pure chloroform spinning system. © 1994 John Wiley & Sons, Inc.     

Effect of different preparation methods on structure and properties of chitosan/poly-lactic acid blend porous membrane

Two kinds of blend solutions were used to prepare chitosan (CS)/poly-l-lactic acid (PLLA) blend membranes by the immersion precipitation phase inversion method. CS/PLLA blend membrane was fabricated by mixing CS-acetic acid solution and PLLA-dioxane solution, chitosan powder (CSP)/PLLA blend membrane was fabricated by mixing CSP and PLLA-dioxane solution. The membrane structure and properties were characterized by Scanning Electron Microscope, Wide Angle X-ray Diffraction, porosity, water vapor transmission rate and swelling property. The results showed that CS content in CSP/PLLA blend membrane was nearly 70 times higher than in CS/PLLA blend membrane. Two types of blend membranes took on an unsymmetrical structure with a skin layer, a microvoid sub-layer and a porous bottom surface. But CSP/PLLA blend membrane exhibited a porous skin layer, while the skin layer of CS/PLLA blend membrane was impact. The WAXD analysis revealed that PLLA and CS were amorphous in CS/PLLA blend membrane, while there were PLLA and CS crystalline in CSP/PLLA membrane, which resulted in the higher initial modulus of CSP/PLLA blend membrane. The porosity, WVTR and equilibrium swelling (Q _eq ) of CSP/PLLA blend membrane were higher than that of CS/PLLA blend membrane, especially Q _eq . The swelling kinetics results showed that in the initial swelling, water molecules diffusion followed Non-Fickian diffusion for CS/PLLA blend membrane swelling, and the swelling of CSP/PLLA blend membrane fitted with the relaxation diffusion model. The swelling kinetics studies for whole swelling revealed that the swelling degree and the initial swelling rate of CSP/PLLA membrane were significantly higher than that of CS/PLLA membrane, although the total swelling rate of CSP/PLLA blend membrane decreased lightly.     

Dynamics of the phase inversion process

An analysis of the dynamics of phase inversion based on mathematical modeling and in situ experimental observations is presented. Calculations based on ternary diffusion models illustrate the effects of casting film composition, evaporation time, and film thickness on the precipitation time and resulting polymer film profiles, which correlate with observed final morphologies. An experimental method based on the use of dark ground optics, interface visualization, and reflected light illumination is used for in situ monitoring of the mass transfer and phase separation dynamics during the quench step. Observations on the systems water—dimethylsulfoxide cellulose acetate and water—dioxane—cellulose acetate show regions in the films corresponding to gel formation and growth, instabilities associated with finger formation, and homogeneous ternary diffusion. Data for the kinetics of the diffusion and gel front motions show that both propagate as the square root of time with rates dependent on the bath—film compositions. Examples of interface structures characteristic of deep quenching and nucleated droplet growth are also shown. Semiquantitative analyses in terms of the ternary models developed earlier and a phenomenological model for diffusion in the growing gel are used to explain the trends seen. © 1992 John Wiley & Sons, Inc.     

液-液水力旋流器分离效率深度提升技术探讨

为解决微小粒径分散相分离效率不高,制约水力旋流器分离效率深度提升的问题,本文以液-液水力旋流器为分析对象,在总结已有理论及研究成果基础上,分别从影响旋流分离效率的关键物理因素,包括分散相在旋流场内的停留时间、分散相粒径、分散相距轴心旋转半径、分散相切向旋转速度以及旋流分离工艺系统五个方面出发,首先对已有提升旋流分离效率的水力旋流器串联工艺、分散相粒径聚结器、小直径旋流分离器及增强切向速度的动态水力旋流器等技术措施进行分析总结,并在此基础上提出了促进旋流分离效率深度提升的新型技术方案,为液-液两相以及固-液、气-液、气-液-固等多相混合介质的高效旋流分离器设计及系统优化提供一定理论及技术支撑。     

PLLA–silver nanoparticles bionanocomposite membranes: Preparation,antibacterial activity,and in vitro hydrolytic degradation assessment

Silver nanoparticles (AgNp) were synthesized in aqueous phase and transferred to chloroform using a fatty amine as phase transfer agent. Poly(l -lactic acid) (PLLA) membranes were prepared using the “functionalized” chloroform. The amount of AgNp in the chloroform was determined by atomic absorption spectroscopy. Thermogravimetric analysis, differential scanning calorimetry, and field emission scanning electron microscopy were used to characterize the membranes. A decrease of the thermal stability of the membranes was observed upon the addition of AgNp; meanwhile, the polymer crystallinity degree increased, making the membranes more fragile and brittle. The in vitro degradation assessments of the membranes in artificial saliva suggested that the time necessary to degrade the PLLA reduced by raising the concentration of the nanostructures. Additionally, the antibacterial assays demonstrated that the addition of only 13 ppm of AgNp were enough to inhibit the formation of biofilm over the bionanocomposite membranes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47998.     

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.