Preparation and performances of poly(phthalazinone ether sulfone ketone) hollow fiber membranes with excellent thermotolerance

The cloud points of PPESK/NMP/H₂O ternary system at different temperatures were measured by titrimetric method. The binodal lines in the ternary phase diagram of the poly(phthalazinone ether sulfone ketone (PPESK) dope system was determined, on the basis of the cloud point experimental data being linearly fitted with the semiempirical linear cloud point correlation. Furthermore, phase separation behavior during the phase inversion of PPESK membrane‐forming system was discussed in terms of the phase diagram. Then, dry–wet spinning technique was employed in manufacturing PPESK hollow fiber membranes by immersion precipitation method. The cross‐section morphologies of hollow fibers were observed by scanning electronic microscopy. Also, the effects of dope solution composition and spinning parameters, including the coagulant composition and the spinning temperature on the separation performances of fibers, were evaluated by permeability measurements. The thermotolerance of the PPESK hollow fiber membranes prepared in the work was examined for the permeation operation at different temperatures and pressure differences. The experimental results showed that pure water flux increases several fold along with the temperature increases from 20 to 80°C at different operation pressures, while the solute rejection only decreases slightly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 878–884, 2006     

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     

Effect of diluent on poly(ethylene‐co‐vinyl alcohol) hollow‐fiber membrane formation via thermally induced phase separation

Poly(ethylene‐co‐vinyl alcohol) hollow‐fiber membranes with a 44 mol % ethylene content were prepared by thermally induced phase separation. A mixture of 1,3‐propanediol and glycerol was used as the diluent. The effects of the ratio of 1,3‐propanediol to glycerol in the diluent mixture on the phase diagram, membrane structure, and membrane performance were investigated. As the ratio increased, the cloud point shifted to lower temperatures, and the membrane structure changed from a cellular structure due to liquid–liquid phase separation to a particulate structure due to polymer crystallization. Better pore connectivity was obtained in the hollow‐fiber membrane when the ratio of 1,3‐propanediol to glycerol was 50:50, and the membrane showed about 100 times higher water permeability than the membrane prepared with pure glycerol. For the prepared hollow‐fiber membrane, the solute 20 nm in diameter was almost rejected. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 219–225, 2005     

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.     

Thermodynamic study of non-solvent/dimethyl sulfoxide/polyacrylonitrile ternary systems: effects of the non-solvent species

In order to investigate the effects of the non-solvent species on the formation mechanism of polyacrylonitrile (PAN) fiber in wet spinning, theoretical ternary phase diagrams of water/DMSO/PAN and ethanol/DMSO/PAN systems were constructed based on the extended Flory–Huggins theory. The cloud-points of dilute PAN solutions of the two systems were determined by titration method and those of concentrated PAN solutions from Boom’s linearized cloud-point correlation. Binary interaction parameters were calculated and optimized to construct the theoretical phase diagram. The obtained diagrams were used to investigate the effects of the non-solvent species on the formation of PAN fibers. If the non-solvent water is replaced with ethanol, the meta-stable two-phase region in the ternary phase diagram increases. This favors the de-mixing of the filament via nucleation and growth mechanism during the coagulation process, resulting in homogenous dense PAN fibers with low porosity.     

Use of MWNTs‐COOH to improve thermal energy storage and release rates of capric–palmitic–stearic acid ternary eutectic/polyacrylonitrile form‐stable phase change composite fibrous membranes

A series of novel capric–palmitic–stearic acid ternary eutectic/polyacrylonitrile/carboxyl purified multi‐walled carbon nanotubes (CA–PA–SA/PAN/MWNTs‐COOH) form‐stable phase change composite fibrous membranes (PCCFMs) were fabricated by electrospinning and physical absorption methods. In these form‐stable PCCFMs, the CA–PA–SA ternary eutectic was served as phase change material for thermal energy storage, and the loaded MWNTs‐COOH was acted as thermal conductivity enhancement filler to improve heat transfer rates, as well as electrospun PAN/MWNTs‐COOH fibrous membranes with different weight fractions of MWNTs‐COOH (i.e., 5, 10, and 20 wt%) were used as supporting materials to provide structural strength and prevent liquid leakage of melted CA–PA–SA ternary eutectic. The morphological structure and thermal performances were investigated and analyzed. The images of scanning electron microscopy showed that the CA–PA–SA ternary eutectic was uniformly embedded and dispersed into the three‐dimensional porous network structure of electrospun PAN/MWNTs‐COOH fibrous membranes. Thermal performance tests suggested that the melting and freezing times of the CA–PA–SA/PAN/MWNTs‐COOH form‐stable PCCFMs with the addition of 10 wt% MWNTs‐COOH were significantly shorten by about 52% and 56% in comparison with those of the CA–PA–SA/PAN form‐stable PCCFMs. Their phase change temperatures and enthalpies were about 7°C–32°C and 130–138 kJ/kg, respectively. POLYM. ENG. SCI., 59:E403–E411, 2019. © 2018 Society of Plastics Engineers     

PEEKWC ultrafiltration hollow‐fiber membranes: Preparation,morphology, and transport properties

A series of hollow‐fiber membranes was produced by the dry–wet spinning method from PEEKWC, a modified poly(ether ether ketone) with good mechanical, thermal, and chemical resistance. The fibers were prepared under different spinning conditions, varying the following spinning parameters: polymer concentration in the spinning solution, height of the air gap, and bore fluid composition. The effect of these parameters on the water permeability, the rejection of macromolecules (using dextrane with an average molecular weight of 68,800 g/mol), and the morphology of the membranes was studied. The results were also correlated to the viscosity of the spinning solution and to the ternary polymer/solvent/nonsolvent phase diagram. The morphology of the cross section and internal and external surfaces of the hollow fibers were analyzed using scanning electron microscopy (SEM). All membranes were shown to have a fingerlike void structure and a skin layer, depending on the spinning conditions, varying from (apparently) dense to porous. Pore size measurements by the bubble‐point method showed maximum pore sizes ranging from 0.3 to 2 μm. Permeability varied from 300 to 1000 L/(h^?1 m^?2 bar) and rejection to the dextrane from 10 to 78%. The viscosity of polymer solutions was in the range of 0.2 to 3.5 Pa s. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 841–853, 2004     

Raman spectroscopy for spinline crystallinity measurements. II. Validation of fundamental fiber‐spinning models

The original Doufas–McHugh two‐phase microstructural/constitutive model for stress‐induced crystallization is expanded to polyolefin systems and validated for its predictive capability of online Raman crystallinity and spinline tension data for two Dow homopolymer polypropylene resins. The material parameters—inputs to the model—are obtained from laboratory‐scale material characterization data, that is, oscillatory dynamic shear, rheotens (melt extensional rheology), and differential scanning calorimetry data. The same set of two stress‐induced crystallization material/molecular parameters are capable of predicting the crystallinity profiles along the spinline and fiber tension very well overall for a variety of industrial fabrication conditions. The model is capable of predicting the freeze point, which is shown, for the first time, to correlate very well with the measured stick point (i.e., the point in the spinline at which the fiber bundle converts from a solid‐like state to a liquid‐like state and sticks to a solid object such as a glass rod). The model quantitatively captures the effects of the take‐up speed, throughput, and melt flow rate on the crystallization rate of polypropylene due to stress‐induced crystallization effects. This validated modeling approach has been used to guide fiber spinning for rapid product development. The original Doufas–McHugh stress‐induced crystallization model is shown to be numerically robust for the simulation of steady polypropylene melt spinning over a wide range of processing conditions without issues of discontinuities due to the onset of the two‐phase constitutive formulation downstream of the die face, at which crystallization more realistically begins. Because of the capturing of the physics of polypropylene fiber spinning and the very good model predictive power, the approximations of the original Doufas–McHugh model are asserted to be reasonable. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effects of spinning temperature on morphologies and properties of polyethersulfone hollow fiber membranes

Polyethersulfone (PES) hollow fiber membranes were prepared by traditional dry‐wet spinning technique. Scanning electronic microscopy (SEM) was used to characterize membrane morphologies, and the membrane properties were evaluated via bubble point measurements and ultrafiltration experiments. The effects of spinning temperature on the morphologies and properties of PES fibers were investigated in detail. At a high spinning temperature, the obtained membrane structure consisting of a thin skin‐layer and loose sponge‐like sublayer endows PES membrane with not only good permeability, but also high solute rejection. Based on the determination of ternary phase diagrams and light transmittance curves, the relationship of membrane morphologies with thermodynamics and precipitation kinetics of membrane‐forming system was discussed. It was concluded that the morphologies and properties of PES hollow fiber membrane could be conveniently tuned by the adjustment of the spinning temperature and air gap. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of kinetics coefficients on ternary phase separation during the wet spinning process

A new Monte Carlo diffusion model is employed to simulate the phase separation of the ternary system during wet spinning process. Our results illustrate the thermodynamics parameters are the primary factors in morphology determination during the phase separation process. Meanwhile by varying kinetic parameters different fiber structures ranging from dust-like, finger-like to sponge-like morphologies are obtained. The morphological patterns are discussed in relation to the rate of particle exchange and the phase diagram. On the basis of the systematical simulation experiments we propose how the competition between segment–solvent and solvent–nonsolvent exchange determines the ultimate fiber morphologies in spinning solution.© 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Rheological behavior of polyester blend and mechanical properties of the polypropylene–polyester blend fibers

The article deals with method of preparation, rheological properties, phase structure, and morphology of binary blend of poly(ethylene terephthalate) (PET)/poly(butylene terephthalate) (PBT) and ternary blends of polypropylene (PP)/(PET/PBT). The ternary blend of PET/PBT (PES) containing 30 wt % of PP is used as a final polymer additive (FPA) for blending with PP and subsequent spinning. In addition commercial montane (polyester) wax Licowax E (LiE) was used as a compatibilizer for spinning process enhancement. The PP/PES blend fibers containing 8 wt % of polyester as dispersed phase were prepared in a two‐step procedure: preparation of FPA using laboratory twin‐screw extruder and spinning of the PP/PES blend fibers after blending PP and FPA, using a laboratory spinning equipment. DSC analysis was used for investigation of the phase structure of the PES components and selected blends. Finally, the mechanical properties of the blend fibers were analyzed. It has been found that viscosity of the PET/PBT blends is strongly influenced by the presence of the major component. In addition, the major component suppresses crystallinity of the minor component phase up to a concentration of 30 wt %. PBT as major component in dispersed PES phase increases viscosity of the PET/PBT blend melts and increases the tensile strength of the PP/PES blend fibers. The impact of the compatibilizer on the uniformity of phase dispersion of PP/PES blend fibers was demonstrated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4222–4227, 2006     

The effect of molecular weight and temperature on phase separation in the ternary system polystyrene/polybutadiene/tetralin

The phase diagram and cloud point surface for the ternary system polystyrene/polybutadiene/tetralin were determined at 29°, 87°, and 143°C. Polystyrenes and polybutadienes of narrow molecular weight distribution were used to study the effect of molecular weight on the cloud point concentration. The phase diagram obtained was bimodal. This unusual shape was more pronounced at higher molecular weights. A model describing the molecular weight dependence of the cloud point concentration was tested and found to hold over a wide composition and temperature range.     

Toughening of recycled poly(ethylene terephthalate)/glass fiber blends with ethylene–butyl acrylate–glycidyl methacrylate copolymer and maleic anhydride grafted polyethylene–octene rubber

The aim of this study was to improve the toughness of recycled poly(ethylene terephthalate) (PET)/glass fiber (GF) blends through the addition of ethylene–butyl acrylate–glycidyl methacrylate copolymer (EBAGMA) and maleic anhydride grafted polyethylene–octene (POE‐g‐MAH) individually. The morphology and mechanical properties of the ternary blend were also examined in this study. EBAGMA was more effective in toughening recycled PET/GF blends than POE‐g‐MAH; this resulted from its better compatibility with PET and stronger fiber/matrix bonding, as indicated by scanning electron microscopy images. The PET/GF/EBAGMA ternary blend had improved impact strength and well‐balanced mechanical properties at a loading of 8 wt % EBAGMA. The addition of POE‐g‐MAH weakened the fiber/matrix bonding due to more POE‐g‐MAH coated on the GF, which led to weakened impact strength, tensile strength, and flexural modulus. According to dynamic rheometer testing, the use of both EBAGMA and POE‐g‐MAH remarkably increased the melt storage modulus and dynamic viscosity. Differential scanning calorimetry analysis showed that the addition of EBAGMA lowered the crystallization rate of the PET/GF blend, whereas POE‐g‐MAH increased it. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

聚丙烯腈/聚乙烯醇/石蜡储能纤维的制备及表征

以聚丙烯腈(PAN)和聚乙烯醇(PVA)共混作为纤维材料,石蜡为相变材料,通过湿法复合纺丝制得相变储能纤维;采用红外光谱(IR)、广角X射线衍射仪(WAXD)、差示扫描量热仪(DSC)表征了纤维的结构以及相变储能性能;分析了纤维的力学性能及相变潜热与纤维中聚乙烯醇含量之间的关系。结果表明:PVA的加入对储能纤维的断裂伸长率和断裂强度影响不大;随着PVA含量的增加,纤维的初生模量由49.1cN/dtex提高到100.5cN/dtex,热焓呈现先增加后减小的趋势,储能纤维中各组分化学结构基本稳定,在水中软化点由93℃增加到110℃。     

Influence of the amount of ferromagnetic addition on the rheological properties of spinning solutions,the structure,the strength,and thermal properties of polyacrylonitrile fibres

The rheological properties of spinning solutions of polyacrylonitrile in dimethyl formamide (DMF) containing various amounts of a ferromagnetic nanoaddition were investigated. The porous structure, the strength and thermal properties of fibers obtained from these solutions were assessed, as well as the uniformity of the nanoaddition distribution on the fiber surface was estimated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of poly(lactic acid) fiber by dry–jet–wet spinning. II. Effect of process parameters on fiber properties

The dry–jet–wet spinning process was employed to spin poly(lactic acid)(PLA) fiber by the phase inversion technique using chloroform and methanol as solvent and nonsolvent, respectively, for PLA. The as spun fiber was subjected to two‐stage hot drawing to study the effect of various process parameters, such as take‐up speed, drawing temperature, and heat‐setting temperature on the fiber structural properties. The take‐up speed had a pronounced influence on the maximum draw ratio of the fiber. The optimum drawing temperature was observed to be 90°C to get a fiber with the tenacity of 0.6 GPa for the draw ratio of 8. The heat‐setting temperature had a pronounced effect on fiber properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3774–3780, 2006     

Structure and properties of partially cyclized polyacrylonitrile‐based carbon fiber—precursor fiber prepared by melt‐spun with ionic liquid as the medium of processing

Carbon fiber has many excellent properties. Currently, the precursor fiber of polyacrylonitrile (PAN)‐based carbon fiber is made from solution by wet or dry spinning process that requires expensive solvents and costly solvent recovery. To solve this problem, we developed a melt‐spun process with ionic liquid as the medium of processing. The melt‐spun precursor fiber exhibited partially cyclized structure. The structure and properties of the melt‐spun PAN precursor fiber were analyzed by combination of scanning electron microscope, Fourier transform infrared spectroscopy, differential scanning calorimetry, X‐ray diffraction, thermogravimetry, ultraviolet spectroscopy, flotation technique, sound velocity orientation test, linear density, and tensile strength tests. The results showed that the tensile strength of melt‐spun PAN precursor fiber was fairly high reached up to 7.0 cN/dtex. The reason was the low imperfect morphology and a cyclized structure formed by in situ chemical reaction during melt‐spun process. Due to the existence of partially cyclized structure in the melt‐spun PAN precursor fiber, exothermic process was mitigated and the heat evolved decreased during thermal stabilization stage in comparison with commercial precursor fibers produced by solution‐spun, which could shorten the residence time of thermal stabilization and reduce the cost of final carbon fiber. POLYM. ENG. SCI., 55:2722–2728, 2015. © 2015 Society of Plastics Engineers     

Subsolidus Phase Relationship in the CaO–CuO–TiO2 Ternary System at 950°C in Air

The subsolidus phase relationship in the CaO–CuO–TiO₂ ternary system at 950°C in air was investigated. Total 26 samples having various nominal compositions were prepared by the solid‐state reaction at 950°C in air, and their equilibrium phases were analyzed by powder X‐ray diffraction (XRD). The CaCu₃Ti₄O₁₂ phase exhibits variable stoichiometry and forms as the Ca_1?xCu_3+xTi₄O₁₂‐type (?0.019 ≤x ≤0.048) solid solution at 950°C in air. On the basis of our results and previous reports on the binary phase diagrams, the subsolidus phase diagram of the CaO–CuO–TiO₂ ternary system could be constructed at 950°C in air.     

Correlation between inhomogeneity in polyacrylonitrile spinning dopes and carbon fiber tensile strength

The nano‐scale and micro‐scale inhomogeneity of polyacrylonitrile (PAN) spinning dopes obtained from dynamic light scattering (DLS) experiment is correlated with the tensile strength of the resulting carbon fiber. The nanoscale inhomogeneity was estimated by calculating the diffusion coefficients from the slow relaxation mode of polymer solutions in DLS. The nanoscale inhomogeneity in the spinning dopes was found to be in the range of 1–45 nm. We also demonstrate mean of the count rate (MCR) obtained from DLS of PAN solution as a tool to detect the microscale inhomogeneity in the spinning dope for the first time. The MCR of spinning dopes varied from ~10.0 to 77.5 kcps (kilo‐counts per second). The tensile strength of carbon fibers from the precursor fiber spun from the spinning dopes in this study varied from 3 to 5.2 GPa. Correlation studies show that the microscale inhomogeneity in the spinning dope was a major contributor to the decrease in the tensile strength of carbon fibers in the range of 3–4.5 GPa. Contaminants causing microscale inhomogeneity in PAN powder were removed by using micelles, reverse micelles and frothing. The surfactant treated PAN polymer was characterized using a fourier transform infrared spectroscope, differential scanning calorimeter, and thermal gravimetic analyzer to demonstrate complete removal of surfactants. POLYM. ENG. SCI., 59:478–482, 2019. © 2018 Society of Plastics Engineers     

Cloud‐point measurements for salt + poly(ethylene glycol) + water systems by viscometry and laser beam scattering methods

The phase separation of salt + poly(ethylene glycol) + water systems was studied by cloud‐point measurements using viscometry and laser beam scattering methods. The Flory–Huggins model was applied to determinate the condition for salt‐induced liquid–liquid phase separation in the system. A temperature‐ and concentration‐dependent interaction parameter was employed to fit the phase diagrams for the systems. The temperature and concentration functionality of the interaction parameter was determined and used to predict cloud‐point curves for the systems. The cloud‐point curves were found to be in quantitative agreement with experimental data. Also, the effect of various salts on the measured cloud points was studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1983–1990, 2003