Morphologies and crystalline forms of polyvinylidene fluoride membranes prepared in different diluents by thermally induced phase separation

We have studied the morphologies and crystalline forms of polyvinylidene fluoride (PVDF) membranes separately prepared in four different diluents bearing >C?O groups, namely 1,2‐propylene glycol carbonate (PGC), dimethyl phthalate (DMP), diphenyl ketone (DPK), and dibutyl phthalate (DBP), by the thermally induced phase separation (TIPS) method. The permittivities of the diluents and PVDF were measured to compare the different PVDF–diluent systems. The results showed the permittivity of PGC to be much greater than that of PVDF, and those of DMP and DBP to be lower than that of PVDF. The permittivity difference between DPK and PVDF was not apparent above 120 °C. On cooling mixtures with a PVDF concentration of 10 wt %, PVDF crystallization was observed in the PVDF–DMP, PVDF–DBP, and PVDF–PGC systems, while liquid–liquid phase separation occurred in the PVDF–DPK system. A cross‐section of the PVDF–PGC membrane presented smooth PVDF particles in the β‐phase crystalline form. Those of the PVDF–DMP and PVDF–DBP membranes presented PVDF particles consisting of a fibrillar network in the α‐phase. The PVDF–DPK membrane preferentially adopted an α‐phase bicontinuous channel structure. When the concentration of PVDF was 60 wt %, the cross‐sections of the above four membranes revealed PVDF polyhedra, among which the PVDF–DMP, PVDF–DBP, and PVDF–DPK membranes retained the α‐phase crystalline form, and the diffraction peak of the α‐phase became visible in the X‐ray diffraction (XRD) spectrum of the PVDF–PGC membrane. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Slippery liquid-infused porous surface via thermally induced phase separation for enhanced corrosion protection

Slippery liquid-infused porous surface (SLIPS) is a rising star in corrosion protection owing to its outstanding corrosive medium resistance and self-healing property. The large-area and facile fabrication of SLIPS remains a challenge lying on the way of its practical application. Herein, we develop a novel SLIPS based on a porous polyvinylidene fluoride (PVDF) substrate fabricated by thermally induced phase separation. A sphere-packing structure can be easily obtained by blade-coating followed by cooling. The SLIPS exhibits an extremely low sliding angle of 5.8° so that it can resist the fouling of even the Chinese ink, ascribing to its slippery dynamic surface with low surface energy. We also evaluated the anti-corrosion performance of the SLIPS and superhydrophobic PVDF coating by electrochemical impedance spectroscopy (EIS) and scanning Kelvin probe technique (SKP), both of which exhibited enhanced corrosion resistance in 3.5 wt% NaCl solution due to the physical oil and air barriers against the corrosive medium penetration. Nevertheless, the SLIPS coatings performed outstanding self-healing properties because of the high fluidity of infused oil to recover the surface damages, and the self-healing process was recorded by the SKP.     

Critical parameters controlling the properties of monolithic poly(lactic acid) foams prepared by thermally induced phase separation

Monolithic poly(lactic acid) (PLA) foams were produced by thermally induced phase separation. PLA solutions with concentrations 8–22 wt % were prepared in tetrahydrofuran/methanol (THF/MeOH) solvent/nonsolvent mixtures at 55 °C. Homogenous solutions were quenched at ?20 °C to induce phase separation and gelation. Resulting gels were mechanically stabilized by solvent exchange. Subsequent supercritical CO₂ drying yielded monolithic PLA foams. Crystal structure and degree of crystallinity of the foams were obtained by x‐ray diffractometry and differential scanning calorimetry. Morphologies were determined by scanning electron microscopy. Tuning the PLA concentration and THF/MeOH ratio enabled preparation of monolithic PLA foams. Depending on the experimental conditions various morphologies, such as: interconnected networks, thin platelets, lamellar stacks, axialites, and spherulites were formed. Monoliths obtained were highly crystalline. By changing the PLA concentration monoliths with controlled average pore sizes (170–1440 nm) and porosities (80–90%) were produced. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 98–108     

Effect of cooling baths on EVOH microporous membrane structures in thermally induced phase separation

The purpose of this work is to investigate the effect of cooling bath on the membrane preparation of crystalline polymer/diluent system via thermally induced phase separation (TIPS), when the cooling bath is compatible with the diluent. In this work, poly(ethylene-co-vinyl alcohol) (EVOH)/PEG300 system with water and methanol as the cooling baths was proposed. Results showed that when water was used as the cooling bath, the membrane presented an asymmetric structure consisting of a porous skin, macrovoids near the top and lacy structures near the bottom. In contrast, when cooled in the bath of methanol, it showed particulate morphology on the top surface and cellular pores near the bottom. The lacy and cellular structures were the typical structures resulted from liquid–liquid thermally induced phase separation, the novel macrovoids and particulate morphology were then supposed to be induced by the mutual diffusion between the diluent and the cooling bath. In the case of water, the diluent's outflow was comparative with the water's inflow into the membrane, so the penetrated water acted as a strong nonsolvent and induced macrovoids near the top. In the bath of methanol, the diluent's outflow was much faster than the methanol's inflow, which changed the solution composition from a liquid–liquid phase separation region to a solid–liquid phase separation region and resulted in particulate morphology near the top.     

Hydrophilic modification of polyvinylidene fluoride membrane by blending amphiphilic copolymer via thermally induced phase separation

A new amphiphilic copolymer TD‐A is melt‐blended with polyvinylidene fluoride to fabricate hollow fiber membranes in order to improve the hydrophilicity and anti‐fouling property. Membrane samples with different blending ratios are prepared via thermally induced phase separation method. An optimum blending ratio of TD‐A (10 wt%) is determined by a series of characterizations to evaluate the effects of TD‐A contents on membrane properties. The hydrophilicity of the blended membrane samples increases with the increasing blending ratio, but excessive content of TD‐A in blended membranes can lead to structural defects and reduction of mechanical properties. TD‐A blended hollow fiber membrane with optimum blending ratio shows excellent bi‐continuous structure and high water flux. Membrane fouling is remarkably reduced due to the incorporation of TD‐A by static absorption and cyclic filtration tests of bovine serum albumin. Moreover, constant surface chemical compositions and stable flux during long‐term chemical cleaning demonstrate the hydrophilic stability of the blended membrane.     

Morphology changes of polyvinylidene fluoride membrane under different phase separation mechanisms

In this study, the strong morphology changes of polyvinylidene fluoride (PVDF) membrane were demonstrated by changing phase separation process from a diffusion induced phase separation (DIPS) to its combination with a thermally induced phase separation (TIPS) which can be attained via changing the diluent – dibutyl phthalate (DBP) content in solvent – N,N-dimethylacetamide (DMAc). The solvent became poor when it mixed with DBP, so TIPS could occur in the quenching process which resulted in a rapid crystallization process. In this process, the porous skin and interlocked small crystallite particle (or bi-continuous) morphologies were formed, while the porous skin and leaf-like network morphology came from the rapidly crystallizing in TIPS, the large spherulite and dense skin could be attributed to the relaxed crystallization in DIPS, the finger-like macro-void and dense skin resulted from the liquid–liquid phase separation in DIPS. Simply speaking, the different membrane morphologies can be obtained by changing the DBP content in DMAc and the coagulation bath temperature.     

Structure and performance of polyamide-6 membranes prepared by thermally induced phase separation

<正>The asymmetric polyamide-6(PA6) membranes were prepared by thermally induced phase separation.From the scanning electron microscopy(SEM) images,it is observed that with the increase of silicon dioxide(SiO_2) content the structure of obtained membranes gradually varied from cellular structure to large ball-shaped cluster aggregates. Subsequently,with the addition of SiO_2,pure water flux increased first and then decreased,while rejection showed the opposite trend.Besides,raising the coagulation bath temperature was favorable to increase pure water flux.Consequently, different membrane morphologies and performance were obtained by changing SiO_2 content and coagulation bath temperature.     

Evidence of mechanisms occurring in thermally induced phase separation of polymeric systems

Thermally induced phase separation is a fabrication technique for porous polymeric structures. By means of easy‐to‐tune processing parameters, such as system composition and demixing temperature, a vast latitude of average pore dimensions, pore size distributions, and morphologies can be obtained. The relation between demixing temperature and morphology was demonstrated via cloud point curve measurement and foams fabrication with controlled thermal protocols, for the model system poly‐l ‐lactide–dioxane–water. The morphologies obtained at a temperature lower than cloud point showed a closed‐pore architecture, suggesting a “nucleation‐and‐growth” separation mechanism, which produced larger pores at higher holding times. Conversely, the porous structures attained when holding the sample above the cloud point exhibited open pores with dimensions independent of time, denoting a phase separation occurring during sample freezing. Finally, the influence of the cooling rate on final morphology was investigated, showing a clear correlation with microstructure and pore size. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 979–983     

Effect of TiO2 nanoparticles on structure and properties of high density polyethylene membranes prepared by thermally induced phase separation method

Polyethylene/TiO₂ membranes were fabricated via thermally induced phase separation (TIPS) method. A set of characterization tests including FE‐SEM, EDX, XRD, DSC, TGA, DMA, mechanical test and relative pure water flux for characterization of membranes were carried out to investigate the effect of TiO₂ nanoparticles on membrane properties. The results of EDX, XRD and TGA analyses confirmed the presence of TiO₂ nanoparticles in the polymer matrix. The results of DSC analysis revealed that the melting point as well as the crystallinity of the membranes increased slightly with increasing TiO₂ content. However, the glass transition temperature of the membranes was not affected by the presence of particles. Addition of nanoparticles also increased storage modulus, loss modulus and tensile strength at break of the membranes due to the stiffness improvement effect of inorganic TiO₂. Finally, it was observed that incorporation of the nanoparticles improved pure water flux of the membranes. Copyright © 2015 John Wiley & Sons, Ltd.     

Thermally induced phase separation of poly(vinylidene fluoride)/diluent systems: Optical microscope and infrared spectroscopy studies

Thermally induced phase separation (TIPS) has been developed to prepare porous membranes. The porous structures are mainly dependent on diluents adopted in the TIPS process. We obtained two typical morphologies of poly(vinylidene fluoride) (PVDF) membranes using cyclohexanone (CO) and propylene carbonate (PC) as diluents, respectively. SEM observation displays that porous spherulites are formed from PVDF/CO system, whereas smooth particles result from PVDF/PC system. The TIPS processes of these two systems have been investigated in detail by optical microscope observation and temperature‐dependent FTIR combined with two‐dimensional infrared correlation analysis. Rapid crystallization of PVDF can be seen around 110 °C in the PVDF/CO system, which is consistent with the results of temperature‐dependent FTIR spectra. The spectral evolution indicates a transform of PVDF from amorphous to α‐phase after 110 °C. The ν_s(C?O) band at 1712 cm^?1 narrows and the ν_s(C? F) band at 1188 cm^?1 shifts to 1192 cm^?1 before crystallization, which implies the destruction of interaction between PVDF and CO. In contrast, the PVDF/PC system shows slow crystallization with all‐trans conformation assigned to β‐phase and γ‐phase below 60 °C but no obvious change of polymer?diluent interaction. We propose two mechanisms for the different phase behaviors of PVDF/CO and PVDF/PC systems: a solid?liquid phase separation after destruction of polymer?diluent interaction in the former, and a liquid?liquid phase separation process coupled with rich‐phase crystallization in the later. This work may provide new insight into the relationship among morphologies, crystal forms, and phase separation processes, which will be helpful to adjust membrane structure. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1438–1447     

Control of droplet size of polymer–diluent blends through thermally induced phase separation

The effects of process conditions and molecular structure of polymer and diluent on the droplet size of membranes formed by thermally induced phase separatiom (TIPS) process were examined. The observed upper critical solution temperature–type phase boundaries of nylon‐12 blended with poly(ethylene glycol) (PEG) and nylon 12 diluted with poly(ethylene glycol) dimethyl ether (PEGDE) and their interaction energy densities calculated using the Flory–Huggins theory suggest that the nylon‐12/PEGDE blends are less stable than the nylon‐12–PEG blends. Infrared spectra confirmed that the difference in phase stability might come from specific interactions of the hydroxyl terminal groups of PEG with the amide groups from nylon‐12, which are not be feasible in the nylon‐12–PEGDE blends. The phase stability of diluent PEG blended with various nylons that are different in the number of methyl groups in the repeat unit was ranked in the order of: nylon‐6–PEG blend < nylon‐12–PEG blend < nylon‐11–PEG blend. We also noted that the phase‐separated droplets grew by both coalescence and the Oswald ripening process after the onset of phase separation. As a result, the cubic exponent of average droplet radius (R³) plotted against time satisfied the linear relationship. As the blends became less stable, the droplet growth rate increased and larger equilibrium droplets formed at a constant quenching depth. The TIPS membranes with desired pore structure could be prepared by controlling the molecular structure of components as well as by varying processing conditions such as quenching depth and annealing time. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3042–3052, 2000     

Free poly(l‐lactic acid) spherulites grown from thermally induced phase separation and crystallization kinetics

Free poly(L‐lactic acid) (PLLA) sheaves and spherulites were prepared by thermally induced phase separation method from its tetrahydrofuran solution without the assistance of other additives. The effects of variables such as polymer concentration, quenching temperature and time on the morphology of PLLA spherulites were studied. The morphology, size, degree of crystallinity, and crystal structure of spherulites were characterized by SEM, DSC and XRD, and so forth. No obvious sheaves or spherulites were observed at quenching temperature of 8 and 0 °C, whereas sheaves composed of fluffy nanofibers with diameter of about 250 nm were formed at quenching temperature range of ?10 to ?40 °C. With increasing quenching time, the PLLA morphology changed from small sheaves to big sheaves (cauliflower‐like) to spherulites. Low concentration (3 and 5 wt %) solutions were favorable for the formation of sheaves, whereas high concentration (7 wt %) solution as good for the formation of spherulites. The mechanism for the formation of PLLA sheaves or spherulites was examined by the isothermal and nonisothermal crystallization of PLLA/tetrahydrofuran solutions using DSC. The Avrami equation was used to analyze the data and good linear double‐logarithmic plots were obtained. The Avrami exponent n and rate constant K indicated the crystal growth mechanism was intermediate between completely instantaneous and completely sporadic types of nucleation and growth, and the spherulites were there dimensional. Compared to the spherulites embedded in the bulky film obtained from the melt processing, this study provided a feasible technique for the fabrication of free PLLA spherulites. The PLLA spherulites composed of fluffy nanofibers with a high porosity (≥90%) may be potentially applied as functional materials such as catalyst support, adsorption and biomedical materials, and so forth. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1476–1489     

Morphology and crystallization behavior of poly(vinylidene fluoride)/poly(methyl methacrylate)/methyl salicylate,and benzophenone systems via thermally induced phase separation

Poly(vinylidene fluoride) (PVDF) blend microporous membranes were prepared by PVDF/poly(methyl methacrylate) blend (with mass ratio = 70/30) via thermally induced phase separation. Benzophenone (BP) and methyl salicylate (MS) were used as diluents. The phase diagram calculations were carried out in terms of a pseudobinary system, considering the PVDF blend to be one component. The crytallization behaviors of PVDF in the dilutions were detected by differential scanning calorimetry measurement. In these two systems, the melting and crystallization temperatures leveled off in the low polymer concentration (<40 wt %), but shifted to a higher temperature when the polymer concentration >40 wt %. The calculated crystallinity of PVDF for samples with low polymer concentrations was greater than those with high polymer concentrations, because of the limited mobility of polymer chains at a high polymer concentration. The membrane structure as determined by scanning electron microscopy depended on the phase separation mechanism. The quenched samples mainly illustrated the occurrence of crystallization on the same time scale as the liquid–liquid phase separated, resulting in the obvious spherulitic structure with small pores in the spherulites. As the polymer concentration increased, the size of the spherulites and pores within the spherulite was decreased. The evaluated porosity for BP diluted system was higher than that for MS diluted system, and decreased with the increased polymer concentration. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 248–260, 2009     

High density polyethylene-grafted-maleic anhydride low-k porous films prepared via thermally induced phase separation

Low dielectric constant (low-k) porous films of high density polyethylene-grafted-maleic anhydride were prepared via thermally induced phase separation (TIPS) using di-n-octyl phthalate as the solvent and methanol as the extractant. The results show that, for the process of TIPS, cellular structures of spherical pores were obtained. Lower polymer concentration and lower cooling rate induced larger pores and higher porosity. For the dielectric constant, the introduction of pores considerably reduced the dielectric constant from 2.60 to 1.56 at most. Pore size showed little effect on dielectric constant in our experiment, but porosity was found to be the key influential factor. The relationship between dielectric constant and porosity was found to be best fit to Rayleigh model.     

Phase separation and polymer crystallization in a poly(4‐methyl‐1‐pentene)–dioctylsebacate–dimethylphthalate system via thermally induced phase separation

The effects of the polymer concentration and quenching temperature on the phase separation, the membrane morphology and polymer crystallization behavior in a poly(4‐methyl‐1‐pentene) (TPX)‐dioctylsebacate (DOS)‐dimethylphthalate (DMP) system via thermally induced phase separation were studied with a pseudobinary phase diagram, with the weight ratio of DOS:DMP = 1:1. SEM was used to observe the membrane morphology and structure, whereas the TPX crystallization behavior was studied with DSC and WAXD. Liquid‐liquid phase separation occurred, although quenching under the crystallization temperature. As the quenching temperature decreased, the pore size decreased, with better connected pore structure formed. The membranes quenched at 333 and 363 K showed good cellular structures, with an average pore size of about 2.3μm, whereas the pores of the membranes quenched at 393 and 423 K were not well formed, with some lamellar crystals on the inner side. The diluent assisted the mobility of the polymer chain, which improved the polymer crystallization. Dual‐melting‐peak behavior occurred for all the samples studied here. As the quenching temperature increased, the first peak of the melting trace moved to a higher temperature, whereas the second one stayed almost the same. The flexibility of the TPX main chain was restricted by the side groups, which allowed liquid‐liquid phase separation to occur first when quenched below the equilibrium crystallization temperature. This allowed primary and secondary crystallization, which was responsible for the dual‐melting‐peak behavior. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 153–161, 2007     

Preparation of PVDF/PEO-PPO-PEO blend microporous membranes for lithium ion batteries via thermally induced phase separation process

Microporous poly(vinylidene fluoride)/polyethylene oxide-co-polypropylene oxide-co-polyethylene oxide (PVDF/PEO-PPO-PEO, or PVDF/F127) blend membranes were prepared via thermally induced phase separation (TIPS) process using sulfolane as the diluent. Then they were soaked in a liquid electrolyte to form polymer electrolytes. The effects of F127 weight fraction on the morphology, crystallinity and porosity of the blend membranes were studied. It was found that both electrolyte uptake of blend membranes and ionic conductivity of corresponding polymer electrolytes increased with the increase of F127 weight fraction. The maximum ionic conductivity was found to reach 2.94 ± 0.02 × 10⁻³ S/cm at 20 °C. Electrochemical stability window was stable up to 4.7 V (vs. Li⁺/Li). The testing results indicated that the PVDF/F127 blend membranes prepared via TIPS process can be used as the polymer microporous matrices of polymer electrolytes for lithium ion batteries.     

Polymerization of Acrylamide Initiated by the Redox System Potassium Persulfate/Lactic Acid,Catalyzed by Silver Ions

The aqueous polymerization of acrylamide initiated by the potassium persulfate/lactic acid system catalyzed by Ag⁺ ions has been studied iodometrically over the temperature range from 35 to 50 ± 0.2°C. The rate of polymerization is governed by the expression R_p ∞ [M]^0.8[K₂S₂O₈]^1.0[Ag]^1.0 The deviation from normal kinetics has been studied. A tentative mechanism of initiation is suggested. The overall energy of activation is 5.52 kcal/mol.     

Hollow spheres of aromatic polyamide prepared by reaction‐induced phase separation

Hollow spheres of aromatic polyamide are obtained by the reaction‐induced phase separation during polymerization of 5‐hydroxyisophthalic acid and 1,4‐phenylene diamine in an aromatic solvent at a concentration of 1–2% at 320 °C without stirring. The hollow sphere has a dimple hole and the diameters of the hollow spheres are 3–4 μm. The droplets are initially generated via liquid–liquid phase separation and then rigid cross‐linked network structure formed the rigid skin layer on the surface of the droplets. The solidification of the droplets occurred owing to the further polymerization in them with maintaining the morphology to form the hollow spheres. The hollow spheres exhibit outstanding thermal stability. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Self-Reguiating Poiycondensations. II. A Study of the Order Present in Polyamide-Hydrazides Derived from Terephthaloyl Chloride and p-Aminobenzhydrazide

The problem of chemical order of polyamide-hydrazides prepared from terephthaloyl chloride with an unsymmetrical monomer, p-aminobenzhydrazide, is discussed. An NMR method for identifying the molecular structure of species formed in the early stages of poly condensation has enabled the course of a polymerization to be followed during this time and the final degree of order to be predicted qualitatively. These studies have provided a demonstration that the structure of these polymers can be controlled to a significant degree by appropriate variations in experimental conditions. But even under the most adverse conditions usually employed, poly amide-hydrazides are found to be at least “partially ordered” copolymers. The techniques developed for this study may find application in the study of other polymer forming reactions with monomers having two functional groups with dissimilar reactivities.     

Effect of cellulose nanofiber on the dynamically asymmetric phase separation in epoxy/polysulfone blends

Significant effect of cellulose nanofibers (CNFs) on cure‐induced phase separation in dynamically asymmetric system is reported. An epoxy/polysulfone blends with typical layered structure formation was chosen as the polymer matrix, and morphology evolution and rheological behavior of systems with different nano‐size fiber loadings upon curing reaction were investigated using optical microscopy and rheological measurement. CNF distributed uniformly in the polymer matrix and had good interaction with polymer chains. Curing reaction of epoxy was promoted by CNF, making the system gel and phase separate earlier. Meanwhile, system viscosity was increased with CNF addition, and the movement of polymer chains and component diffusion were constrained, as a result, the structure evolution process was slowed down. The CNF altered the final morphologies, resulting in refined structures with smaller characteristic length scales or even completely change the morphologies from the layered structures to a bicontinuous structure when the CNF concentration reached to a relatively high level. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1357–1366