Phase separation in non-solvent/dimethylformamide/polyethersulphone and non-solvent/dimethylformamide/polysulphone systems

The cloud point curves for the ternary solutions non-solvent/dimethyl-formamide/polyethersulphone and non-solvent/dimethylformamide/polysul-phone were determined by a titration technique, at 303 K. In both systems the following order of increasing non-solvent content at the cloud point was obtained: water < methanol < ethanol < 1-propanol < acetone < carbon tetrachloride. For each non-solvent the cloud point curve for the PES system occurred at higher non-solvent concentrations than for the corresponding PSN system.     

Thermodynamic-based predictions of membrane morphology in water/dimethylsulfoxide/polyethersulfone systems

In this paper, ternary phase diagram was used to predict morphology of the membranes prepared via phase inversion process. Theoretical ternary phase diagrams were calculated based on a compressible regular solution (CRS) model for water/dimethylsulfoxide/polyethersulfone membrane forming system. The CRS model is an alternative for the traditional Flory–Huggins theory. The experimental cloud point data were determined using titration method. The constructed theoretical ternary phase diagrams were consistent with the experimental results. The precipitation rate of the polymeric solution in the non-solvent was obtained by light transmission experiments. The membrane morphology was predicted using the theoretical phase diagram and the phase separation kinetics. To verify this prediction, the light scattering experiments were performed.     

Theoretical phase diagram calculation and membrane morphology evaluation for water/solvent/polyethersulfone systems

Theoretical ternary phase diagrams with very good agreement with experimental cloud point data were constructed for water/N,N-dimethylacetamide (DMAc)/polyethersulfone (PES) and water/N-methyl-2-pyrrolidone (NMP)/polyethersulfone systems. Theoretical phase diagrams were determined based on the extended Flory-Huggins theory of polymer solutions. To construct the theoretical phase diagrams, all binary interaction parameters were determined accurately and thoroughly revisited. Also, the structures of membranes prepared of these systems by phase separation process were investigated. The morphological studies showed that in spite of better miscibility between water and DMAc compared to water and NMP, channel-like structures were observed in membranes prepared of water/NMP/PES systems but tear-like structures with more spongy areas were observed in membranes prepared of water/DMAc/PES system. According to the constructed theoretical ternary phase diagrams of these systems, these unexpected observations were attributed to the higher concentration of polymer in the polymer-rich phase of water/DMAc/PES system, which causes an early vitrification in this system which suppresses the growth of macrovoids.     

Pore morphology control and hydrophilicity of polyacrylonitrile ultrafiltration membranes

The effects of different solvents (dimethyl formamide: DMF and dimethylsulfoxide: DMSO) on the solubility of polyacrylonitrile (PAN) were investigated by the phase diagrams of H₂O/DMF/PAN and H₂O/DMSO/PAN ternary systems through cloud‐point titration method at low polymer concentration. The influences of polymer concentrations and temperatures on the morphologies of PAN ultrafiltration membranes were elucidated. The morphologies of fabricated UF membranes were characterized by scanning electron microscopy (SEM) and atomic force microscope (AFM), and the basic performance of ultrafiltration including pure water flux and rejection of BSA were explored. At 25°C, the pure water flux of ultrafiltration membranes at the lower PAN content (16 wt % PAN in 84 wt % DMSO) reached 213.8 L/m/bar and the rejection of BSA was 100%. Interestingly, the water flux of UF membranes dramatically decreased to 20.6 L/m/bar (20 wt %) and 2.9 L/m/bar (24 wt %) when increasing PAN concentrations in DMSO. On the other hand, the hydrophilicity of membranes can be enhanced by increasing coagulation temperatures and polymer concentrations which were characterized by static contact angle, fitting well with the variation tendency of roughness. Although there are many works concerning on the effects of phase inversion conditions on the performance of PAN UF membranes, to our best knowledge, there is seldom works focusing on investigating the membrane hydrophilicity trend by adjusting phase inversion conditions. To disclose the reason of the enhanced hydrophilicity, the water and glycol contact angles of various membranes were measured and the surface tensions were presented. The results illustrated that the enhanced hydrophilicity of PAN UF membranes fabricated at higher temperatures or higher polymer concentrations was due to the higher polarity on membrane surface. Since the vast majority of ultrafiltration membranes in labs and in industrial scale have been fabricated by immersion phase inversion method, this work can provide a guidance to obtain hydrophilic PAN UF membranes by adjusting the process of phase inversion. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41991.     

Constant rotational rheological behaviors of the PAN/DMSO/nonsolvent systems

The constant rotational rheological behaviors of PAN/DMSO solutions with two kinds of nonsolvent (water and ethanol) have been investigated, respectively, using a cone‐plate rheometer. From viscosity measurements, the flow behavior was described within the shear rate range 0.1–1000 s^?1. The PAN solutions show shear thinning at high shear rates. The viscosities of the solutions decreased with the rising of the temperature at low shear rate. H₂O content has great influence on the viscosity of the solutions, depending on the hydration of H₂O and PAN or desolvent effect, according to different H₂O content. The role of ethanol compared with H₂O was also researched and higher viscosity was found. Non‐Newtonian index, structural viscosity index Δη, and flow activation energy of the PAN/DMSO/H₂O systems were also studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

相转化法聚合物/溶剂/非溶剂铸膜体系的热力学计算

计算了相转化法铸膜体系中常见的典型三元相图,分析了聚合物与溶剂之间、聚合物与非溶剂之间、溶剂与非溶剂之间的相互作用参数对聚合物/溶剂/非溶剂铸膜液体系相图的影响,以及体系温度和聚合物摩尔体积对聚合物/溶剂/非溶剂铸膜液体系相图的影响。根据溶剂-非溶剂汽液平衡数据和溶解度参数得到了溶剂-非溶剂、溶剂与聚合物以及非溶剂与聚合物之间的Flory-Huggins相互作用参数,从而获得了几种常见铸膜液体系的相图。同时,利用聚合物/溶剂/非溶剂铸膜液体系的相图数据对热力学模型的参数进行了优化,取得了与实验结果较一致的计算结果。     

Effects of genistein modification on miscibility and hydrogen bonding interactions in poly(amide)/poly(vinyl pyrrolidone) blends and membrane morphology development during coagulation

Miscibility characteristics of poly(amide):poly(vinyl pyrrolidone) (PA:PVP) blends containing a soybean-derived phytochemical called “genistein” have been investigated using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The occurrence of hydrogen bonding in the binary PA/genistein (PA/G) and PVP/genistein (PVP/G) pairs as well as their ternary blends has been confirmed by Fourier transformed infrared spectroscopy (FTIR). On the basis of DSC and POM data, the morphology phase diagram of PA:PVP/G blends is mapped out, which consisted of various coexistence regions such as isotropic, liquid + liquid, liquid + crystal, liquid + liquid + crystal, and solid crystal regions. Subsequently, PA:PVP membranes modified with genistein were prepared by coagulation via solvent (dimethyl sulfoxide, DMSO) and non-solvent (water) exchange. Addition of genistein reduced the miscibility gap of the PA/DMSO/water system. The actual amounts of genistein in the final membranes have been quantified as a function of the genistein in feed. Of particular interest is the development of the gradient cross-sectional porous channels, showing the progressively larger diameters from the surface to the bottom substrate with the progression of solvent/non-solvent exchange or solvent power. Scanning electron microscopy (SEM) investigation of the morphologies of the modified membranes revealed that genistein crystals were embedded on the membrane surface as well as in the cross-section even at a very low feed concentration of genistein. A schematic of a coagulation pathway was inscribed inside a prism phase diagram in order to comprehensively illustrate the formation of genistein modified PA:PVP membranes through the solvent/non-solvent exchange process followed by drying.     

湿纺工艺纺制PAN中空纤维成形机理研究

利用C型喷丝板进行挤出凝固,采用湿法纺丝工艺制备聚丙烯腈(PAN)中空纤维,从PAN/二甲基亚砜(DMSO)纺丝原液的流变性能和凝固过程的相分离两个方面探讨了PAN中空纤维的成形机理。结果表明:纺丝液随剪切速率(γ)的增加逐渐发生由粘性向弹性的转变是挤出胀大的主要原因,其粘弹转变点随着温度的升高而向高γ移动,在60℃下的纺丝液弧片接触成孔的理论临界γ为212 s~(-1);纺丝液在凝固浴中表层成膜是PAN-DMSO-H_2O三元体系相分离的结果,纺丝液细流表面成膜速度是影响孔结构闭合的重要因素,可以通过凝固浴浓度和凝固浴调节剂来控制。     

聚丙烯腈基碳纤维原丝在干湿法纺丝中非溶剂扩散过程的研究

聚丙烯腈基碳纤维具有高强度、高模量、耐高温、耐腐蚀的优良性能,广泛应用于化工、机械、造船等方面。在聚丙烯腈基碳纤维的干湿法纺丝中,纺丝原液进入凝固浴后发生的非溶剂扩散过程对聚丙烯腈基碳纤维原丝的结构和性能有重要影响。该文通过Fick定律建立了适用于纺丝原液是溶剂、高聚物和非溶剂三组分体系的非溶剂扩散数学模型,指出该模型的适用范围。此外,该文还作出了非溶剂分子的浓度随时间的变化曲线。     

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.     

Activated carbon fibers from electrospinning of polyacrylonitrile/pitch blends

The electrospinnability of pitch was improved by blending in a solution of polyacrylonitrile (PAN) resulting in the reduction of the average fiber diameter from 2000 to 750 nm. The compositions showing good spinnability are proposed within the soluble concentrations in the ternary phase diagram of the PAN-pitch-solvent, which contains lower concentration of the pitch. Activated carbon fibers were derived by stabilization, carbonization and steam activation at 700, 800, 900 and 1000 °C of the PAN/pitch electrospun fibers. The Brunauer, Emmett, Teller (BET) specific surface area ranged from 732 to 1877 m²/g.     

Engkabang Fat Esters for Cosmeceutical Formulation

Engkabang fat esters were synthesized from engkabang fat using an enzyme as catalyst. The main composition of the fat esters were oleyl palmitate, oleyl stearate and oleyl oleate. The percentage yield was 93.67%. Ternary phase diagrams systems containing fat esters/surfactant/water were constructed. Several regions appeared in the ternary phase diagrams such as isotropic, homogenous, liquid crystal, two-phase and three-phase regions. Increasing the hydrophilic-lipophilic balance value of the used surfactants gave a larger homogenous and isotropic region in ternary phase diagrams of engkabang fat esters/nonionic surfactant/deionized water. Isotropic and homogenous regions in the ternary phase diagram of engkabang fat esters: PEG-40 hydrogenated castor oil (2:1)/polyoxyethylene(20) sorbitan tri-oleate/deionized water, was the largest when compared to the other ternary phase diagrams. The isotropic and homogenous region can be used as a medium in formulation of cosmetics and pharmaceutical products such as creams, lotions, balms and lipsticks.     

Rheological study on thermal-induced gelation behavior of polyacrylonitrile solution

Thermal-induced gelation process of different polyacrylonitrile (PAN) solutions was investigated through dynamic rheological measurements. The rheological material parameters characterizing the gelation behavior of the PAN solutions were measured and the effects of such factors as water content, solvent type and concentration on the gelation process were analyzed. It is found that the gel point T _gel of PAN/DMSO (dimethyl sulfoxide)–water solution increases with increased water content in the solution. Also, T _gel becomes higher when the solvent has a lower solvency for PAN. A linear relationship between logG′ and logω, logG″ and logω indicates the beginning of gelation. The PAN concentration of the solution affects T _gel in a way similar to that of the water content. The relaxation exponent n is found to relate to the fractal dimension of the polymer gel. For PAN/DMSO–water solution, this exponent n remains almost constant when the water content differs. The solvent type and concentration respectively influences n value in their own way. The PAN/DMSO–water solution systems in our work exhibit similar characteristics of gel structure, concluded from the n and d _f values of these systems. A logarithmic plot between G′ and G″ can be used to evaluate the structural evolution of the solution, and a comparatively steep slope of the curve is an indication of gelation.     

Liquid–liquid phase separation in polysulfone/polyethersulfone/N‐methyl‐2‐ pyrrolidone/water quaternary system

To construct a phase diagram of the polysulfone (PSF)/polyethersulfone (PES)/N‐methyl‐2‐pyrrolidone (NMP)/water quaternary system, cloud point measurements were carried out by a titration method. The miscible region in the PSF/PES/NMP/water quaternary system was narrow compared to the PSF/NMP/water and PES/NMP/water ternary systems. The binary interaction parameters between PSF and PES were estimated by water sorption experiments. The calculated phase diagram based on the Flory–Huggins theory fit the experimental cloud points well. In addition to the usual polymer–liquid phase separation, polymer–polymer phase separation, which resulted in a PSF‐rich phase and a PES‐rich phase, was observed with the addition of a small amount of nonsolvent. The boundary separating these two modes of phase separation could be well described and predicted from the calculated phase diagrams with the estimated binary interaction parameters of the components. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2113–2123, 1999     

Exploring the effects of non-solvent concentration, jet-stretching and hot-drawing on microstructure formation of poly(acrylonitrile) fibers during wet-spinning

The simultaneous effects of non-solvent concentration in the spinning dope, jet-stretching and hot-drawing on porosity, morphology development and mechanical properties of wet-spun poly(acrylonitrile) fibers were studied. Addition of non-solvent to the spinning dope increased dope viscosity, the entanglement density of the polymeric solution and the number of entanglements per chain. Drawability of the as-spun fiber depended on the number of entanglements per polymer chain. Therefore, addition of non-solvent improved or spoiled drawability of the wet-spun fibers based on the concentration of the initial spinning dope. Hot-drawing and jet-stretching did not affect the fraction of nanovoids but shifted their size distribution towards smaller values. However, hot-drawing was more effective in reducing the overall porosity of the fibers in comparison with jet-stretching. Fiber tenacity increased when overall porosity decreased. Finally, strength-diameter correlation showed good agreement with the Griffith’s theory.     

Thermodynamic study of a water–dimethylformamide–polyacrylonitrile ternary system

Experimental cloud‐point data were obtained by cloud‐point titration. The phase diagram for a ternary system of water–dimethylformamide–polyacrylonitrile was determined by numerical calculation on the basis of the extended Flory–Huggins theory and was found to agree well with the cloud‐point data. To construct the theoretical phase diagram, three binary interaction parameters were obtained with different methods. The ternary phase diagram was used to investigate the mechanism of fiber formation. The skin–core structure and fingerlike pores in polyacrylonitrile fiber may be effectively eliminated if the composition of the spinning solution is properly chosen, and consequently, homogeneous polyacrylonitrile fiber with a bicontinuous structure and good mechanical properties can be obtained through the spinning process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Calculation of the solubility curves in ternary salt systems with compound formation

A new method for the calculation of solubility curves in solubility diagrams of ternary salt systems with compound formation is described. The method is based on the assumption that every physico-chemical process (the formation of a solid phase, formation of complex species in solution) in a given system is characterized by an interaction constant value. The relative magnitudes of these constants determine the type and shape of the diagram. The derivation does not include any empirical or adjustable parameters. The work also contains an explanation for the incongruent solubility of compounds with salt character. The conclusion contains extensive comparison of experimental data with the theoretical results.     

Effect of the solvent type on the formation and physical properties of polyacrylonitrile fibers via a solvent‐free coagulation bath

Polyacrylonitrile (PAN) fibers were fabricated via a dry‐jet wet‐spinning technique, and a solvent‐free coagulation bath system was adopted. The effects of different types of dope solvent on the formation and physical properties of the PAN fibers were investigated. Dimethylformamide and dimethyl sulfoxide (DMSO) were selected as the solvents and were added to a spinning solution consisting of 18 wt % PAN. The PAN fibers were examined with field emission scanning electron microscopy, differential scanning calorimetry, and thermogravimetric analysis. The field emission scanning electron micrographs revealed that the PAN fibers with the DMSO solvent exhibited a more circular shape and a smoother skin. The PAN fibers with the DMSO solvent had their glass‐transition temperature (T_g) at 121°C. This study indicated that the different types of dope solvent used in the dope preparation did not affect T_g of the PAN fibers because of the solvent‐free coagulation bath system; however, they significantly affected the physical formation of the PAN fibers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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).     

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.