Role of thermodynamic and kinetic interaction of poly(vinylidene fluoride) with various solvents for tuning phase inversion membranes

An extensive study of thermodynamics and kinetics of non‐solvent induced phase separation was carried out for poly(vinylidene fluoride)/solvent/water system for four different solvents. Literature available on semicrystalline polymers was mostly based on experimental cloud points, obtained to a narrow range of polymer concentration (<10 wt%), much less than the working range for membrane preparation (20–25 wt%). Aim of this work was to model the thermodynamic phase diagram using extended Flory–Huggins theory which was used as a tool, along with the kinetic data to obtain tailor‐made membranes with desired morphology and properties. Interaction parameters involving solvent, nonsolvent, and polymer played an important role to tune the porosity of the membrane. Thermodynamic calculation showed solvent N,N‐dimethyl acetamide resulted in the most porous membrane (permeability 5.4 × 10^?11 m Pa^?1 s^?1) followed by N,N‐dimethyl formamide (permeability 4.2 × 10^?11 m Pa^?1 s^?1), N‐methyl pyrrolidone (permeability 3.8 × 10^?11 m Pa^?1 s^?1), and acetone (impermeable to water even at 1380 kPa), which was the densest one. Prepared membranes were characterized in terms of surface morphology, molecular weight cut‐off, tensile strength, pore volume distribution, crystallinity, and surface roughness, which were correlated to inferences based on thermodynamic and kinetic calculations. POLYM. ENG. SCI., 58:1062–1073, 2018. © 2017 Society of Plastics Engineers     

Morphology and performance of poly(vinylidene fluoride) flat sheet membranes: Thermodynamic and kinetic aspects

In this study, poly(vinylidene fluoride) (PVDF) membranes were prepared using two different solvents with various polymer concentrations to investigate the predominant kinetic or thermodynamic aspects of membrane preparation in a phase separation process. For this purpose, dimethyl sulfoxide (DMSO) as a weak solvent and N‐2‐methylpyrrolidone (NMP) as a strong solvent were used with polymer concentrations between 8 and 15 wt %. Scanning electron microscopy and water content, contact angle, and pore size measurements were used to assess the factors affecting the physicochemical properties of the prepared membranes. The results showed that in the case of NMP, the membrane structure is mainly controlled by thermodynamic parameters, while when using DMSO, kinetic parameters are predominant. According to the results, the prepared PVDF‐based membranes with DMSO exhibited a relatively denser top layer and less permeation compared to the NMP/PVDF membranes. The difference between the viscosities of the casting solutions with equal polymer concentrations in DMSO and NMP was considered to be the main effective factor in solvent/nonsolvent exchange, resulting in denser top layers in the DMSO/PVDF membranes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46419.     

The influence of solvent properties on the performance of polysulfone/β‐cyclodextrin polyurethane mixed‐matrix membranes

This study investigates the effect of solvent properties on the structural morphology and permeation properties of polysulfone/β‐cyclodextrin polyurethane (PSf/β‐CDPU) mixed‐matrix membranes (MMMs). The membranes were prepared by a modified phase‐inversion route using four different casting solvents [dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), dimethyl acetamide (DMA), and N‐methyl‐2‐pyrrolidone (NMP)]. While DMSO‐based membranes demonstrated particularly high permeability (ca 147 L/m²h.bar), their crystallinity was low compared to MMMs prepared using DMA, DMF and NMP due to the formation of thin active layers on their surfaces. Cross‐sectional morphology revealed that the MMMs have a dense top skin with finger‐like inner pore structures. Membranes prepared using NMP displayed the highest hydrophilicity, porosity, and crystallinity due to the low volatility of NMP; DMF membranes exhibited superior mechanical and thermal stability due to its (DMF) high hydrogen bonding (δH) values. Thus, the morphological parameters, bulk porosity, and flux performance of MMMs have a significant inter‐relationship with the solubility properties of each solvent (i.e., δH, density, volatility, solubility parameter). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2005–2014, 2013     

Porosity control in silicon nitride-based support materials toward enhanced gas permeability

Porous Si₃N₄ materials in tubular geometry are prepared by slip casting before partial sintering. A variety of material- and process-specific variables and their respective effects on densification and resulting pore morphology are systematically evaluated, focusing on starting powder type, amount of sintering additives, and sintering parameters including temperature and time. An increased β-Si₃N₄ content in the starting powder was found to promote the formation of a network of elongated grains exhibiting increased pore diameters, as opposed to a more finely featured pore network obtained from starting materials consisting of α-Si₃N₄. Following an iterative evaluation of processing variables, materials exhibiting a characteristic diametral compression strength (C-ring test) of 163 MPa and a Darcian permeability of 4.7 ⋅ 10⁻¹⁵ m² at a total porosity of 41% were obtained, corresponding to an increase of over 40% in strength and of over 600% in permeability in comparison to materials obtained by α-Si₃N₄ powders at comparable porosities. These results demonstrate that the composition of Si₃N₄ powders significantly affects the resulting pore structure, and by combining the respective selection of starting materials with finely tuned sintering parameters, materials with superior performance in terms of mechanical properties as well as permeability characteristics are accessible.     

Preparation of hydrophilic polysulfone membrane using polyacrylic acid with polyvinyl pyrrolidone

This study examined the consequences of the addition of polyvinyl pyrrolidone (PVP) of different molecular weights with constant molecular weight of polyacrylic acid (PAA) on the morphology and permeation properties of polysulfone (PSF) membranes. The asymmetric polymeric membranes were prepared by phase inversion process using PSF in N‐methyl‐2‐pyrrolidone (NMP) as a solvent. The surface structure and morphology of the prepared membranes were analyzed by field‐emission scanning electron microscope (FESEM) and atomic force microscopy (AFM). The pore number, average pore size and area of pores for all the membranes were determined by permeability method. These ultrafiltration membranes were subjected to characterizations such as measurement of pure water flux (PWF), compaction factor (CF), bovine serum albumin (BSA) rejection for finding the permeability performance, whereas equilibrium water content, contact angle, porosity, hydraulic resistance, and ion exchange capacity (IEC) are measured for evaluating the hydrophilicity. Results demonstrate that the flux performance of the membranes and morphological parameters own a crucial inter‐relationship with the molecular weight of PVP. The membrane pore area and pore number were found to be increased by increasing molecular weight of PVP with constant molecular weight of PAA. A detailed comparative study was done with Chakrabarty et al. (J. Membr. Sci. 2008, 309, 209) and found better in almost all the aspects. All the resulting parameters were compared and concluded with the fact that addition of small amount of PAA in PSF/PVP/NMP casting solution can be better than addition of PVP alone. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41964.     

Influences of the chain structure of PE‐b‐PEG on the properties of PE/PE‐b‐PEG blend membranes prepared by TIPS

In this article, a series of diblock copolymer polyethylene‐b‐ poly(ethylene glycol)s (PE‐b‐PEGs) with various molecular weight of polyethylene segment was blended with linear low‐density PE. The PE/PE‐b‐PEG blend porous membranes with high porosity were obtained by thermally induced phase separation (TIPS) process. The isothermal crystallization kinetics of PE/LP/PE‐b‐PEG blends indicated that the introduction of PE‐b‐PEG could inhibit the growth rate of polyethylene crystals which could increase the pore size and porosity of the membranes. The PE/PE‐b‐PEG blend membranes with PE₁₃₀₀‐b‐PEG₂₂₀₀ showed the largest pore size and porosity due to its crystallization behavior during TIPS. The surface of the membranes became smoother and the morphology of the membranes could be effectively tuned by introducing PE‐b‐PEG. Compared with the PE membrane, the PE/PE‐b‐PEG blend membranes exhibited higher hydrophilicity (the water contact angle decreased from 112° to 84°), water permeability (the permeation flux increased from 80 to 440 L/m² h under 0.1 MPa), rejection performance (completely reject carbon particles in the filtration of carbon ink solution), and fouling resistance (the value of protein adsorption dropped from 0.25 to 0.05 mg/cm²). The hydrophilicity and fouling resistance of PE/PE‐b‐PEG blend membranes increased as the length of PE segment in PE‐b‐PEGs decreased. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46499.     

Effect of PEG additives on properties and morphologies of polyetherimide membranes prepared by phase inversion

This study investigated the effect of poly (ethylene glycol) (PEG) additive as a pore-former on the structure formation of membranes and their permeation properties connected with the changes in thermodynamic and kinetic properties in the phase inversion process. The membranes were prepared by using polyetherimide/N-methyl-2-pyrrolidone/PEG (PEI/NMP/PEG) casting solution and water coagulant. The resulting membranes, prepared by changing the ratio of PEG to PEI, were characterized by scanning electron microscope (SEM) observations, measurements of water flux and γ-globin rejection. The thermodynamic and kinetic properties of the membrane-forming system were studied through viscosity. The pore radius distribution curves were especially obtained by differential scanning calorimetry (DSC). Furthermore, the membranes were characterized for pure water flux and rejection of solute and by SEM observation. The filtration results agreed well with the SEM observations. As expected, PEG with a fixed molecular weight (PEG 600) acted as a pore forming agent, and membrane porosity increased as the PEG content of the casting solution increased.     

Effect of PEG additives on properties and morphologies of membranes prepared from poly(2,6‐dimethyl‐1,4‐phenylene oxide) by benzyl bromination and in situ amination

This study investigated the effect of PEG additive on the structure formation and permeation properties of membranes. The membranes were prepared from a bromomethylated poly(2,6‐dimethyl‐1,4‐phenylene oxide)/chlorobenzene/ethanol system using the phase inversion method with PEG as an additive. As expected, PEG with a fixed molecular weight (e.g., PEG 600) acted as a pore‐forming agent, and membrane porosity increased as the PEG content of the casting solution increased. However, when the PEG content was fixed, the effect of PEG on the membrane properties and morphology was largely dependent on its molecular weight. It was found that when the molecular weight of PEG was less than 800, it acted as a pore former, but when the molecular weight of PEG was more than 1000, the pore size and porosity of the resulting membrane decreased. These results can be explained by the membrane‐forming system's thermodynamic and kinetic properties, which can be assessed by coagulation value and viscosity. Furthermore, the membranes were characterized for pure water flux and rejection of solute and by SEM observation. The filtration results agreed well with the SEM observations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2414–2421, 2005     

Chemical modification of controlled‐pore silica with N‐propylsalicylaldimine

Two controlled‐pore silica phases were prepared with a sol–gel precursor from a sodium silicate solution. N‐Propylsalicylaldimine was immobilized on these silica species to be used as chelating ion exchangers (IE11 and IE2). The monomer phase was also prepared for comparison. The N‐propylsalicylaldimine moiety was detected by Fourier transform infrared and ultraviolet in both the ion exchangers and the monomer phases. 1H‐NMR and mass spectrometry of the monomer also confirmed the structure. The capacity (C) of the ion exchangers was dependent on the porosity of the ion exchanger (C_IE11 = 0.36 mmol of Cu/g and C_IE2 = 0.026 mmol of Cu/g). The uptake behavior of IE11 toward some metal ions was studied, and log distribution coefficient (k_d) was within the range of 2.19–5.16. Also, thermogravimetric and differential thermogravimetric analysis data were used to study the kinetics of the thermal decomposition process of IE11. Some thermodynamic parameters for the ion exchanger were calculated by the application of the rate theory of the first‐order reaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3159–3167, 2003     

Porosity effect on microstructure,mechanical, and fluid dynamic properties of Ti2AlC by direct foaming and gel‐casting

In this study, Ti₂AlC foams were fabricated by direct foaming and gel‐casting using agarose as gelling agent. Slurry viscosity, determined by the agarose content (at a fixed solids loading), as well as surfactant concentration and foaming time were the key parameters employed for controlling the foaming yield, and hence the foam porosity after sintering process. Fabricated foams having total porosity in the 62.5‐84.4 vol% range were systematically characterized to determine their pore size and morphology. The effect of the foam porosity on the room‐temperature compression strength and elastic modulus was also determined. Depending on the amount of porosity, the compression strength and Young's modulus were found to be in the range of 9‐91 MPa and 7‐52 GPa, respectively. Permeability to air flow at temperatures up to 700°C was investigated. Darcian (k₁) and non‐Darcian (k₂) permeability coefficients displayed values in the range 0.30‐93.44 × 10^?11 m² and 0.39‐345.54 × 10^?7 m, respectively. The amount of porosity is therefore a very useful microstructural parameter for tuning the mechanical and fluid dynamic properties of Ti₂AlC foams.     

Effect of additives concentration on the surface properties and performance of PVDF ultrafiltration membranes for refinery produced wastewater treatment

The aim of this study was to investigate the effect of pore-forming hydrophilic additives on the porous asymmetric polyvinylideneflouride (PVDF) ultrafiltration (UF) membrane morphology and transport properties for refinery produced wastewater treatment. PVDF ultrafiltration membranes were prepared via a phase inversion method by dispersing lithium chloride monohydrate (LiCl·H₂O) and titanium dioxide (TiO₂) nanoparticles in the spinning dope. The morphological and performance tests were conducted on PVDF ultrafiltration membranes prepared from a different additive content. The top surface and cross-sectional area of the membranes were observed using a field emission scanning electron microscope (FESEM) and energy dispersive X-ray (EDX) analysis. The surface wettability of porous membranes was determined by the measurement of a contact angle. The mean pore size and surface porosity were calculated based on the permeate flux. The results indicated that the PVDF/LiCl/TiO₂ membranes with lower TiO₂ nanoparticles loading possessed smaller mean pore size, more apertures inside the membrane with enhanced membrane hydrophilicity. LiCl·H₂O has been employed particularly to reduce the thermodynamic miscibility of dope which resulted in increasing the rate of liquid–liquid demixing process. The maximum flux and rejection of refinery wastewater using PVDF ultrafiltration membrane achieved were 82.50 L/m² h and 98.83% respectively at 1.95 wt.% TiO₂ concentration.     

Study on the preparation and thermal shrinkage properties of nano‐SiO2/UHMWPE/HDPE blend microporous membranes

Nano‐SiO₂/UHMWPE/HDPE blend microporous membranes (NBMs) with different content of nano‐SiO₂ particles were prepared via thermally induced phase separation process. Thermogravimetric analysis was used to investigation of the amount of nano‐SiO₂ particles reserved in NBMs. This approach showed that about 59% of total content of nano‐SiO₂ particles reserved in NBMs. The formation and development of the interface pores were studied by scanning electron microscopy. NBMs performance was characterized by a variety of metrics including thermal shrinkage, melting and crystallization behavior, porosity and pore diameter, and permeability. The results indicated that nano‐SiO₂ particles served as nucleating agent increasing the crystalline of NBMs. The comprehensive properties of NBMs were optimum when the content of nano‐SiO₂ particles was 1%. Compared with pure HDPE separators, NBMs exhibit higher porosity and lower thermal shrinkage due to its high crystalline and the enrichment of UHMWPE chains. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41321.     

Study on the tribological properties of modified polyurethane material for water‐lubricated stern bearing

Polyurethane (PU) has been studied as alternative bearing material for marine water‐lubricated stern tube due to its excellent wear resistance, remarkable mechanical properties and so on. In this study, nine types of PU samples which are composed of different additives were prepared and tested in order to investigate their tribological properties under various working conditions. A pin‐on‐disc tribo‐tester was used to conduct tests. Then comparison analyses were conducted from three aspects, including the friction coefficient, wear mass loss, and the wear surface topography. The analysis results showed that: (1) the different additives as well as the mass fraction of these additives lead to significant difference in terms of tribological properties of PU; (2) the lubricating grease, as one of additives, improved the wear resistance and friction performance effectively; (3) modified PU is eligible to work as matrix because of satisfied mechanical properties and specific internal morphology. It is believed that understandings in this study are beneficial to the improvement of the tribological properties of PU and also provide the real practical basis for the studies of polymer materials which applied on water‐lubricated marine stern tube bearing. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46305.     

A fractal model for real gas transport in porous shale

A model for real gas flow in shale gas matrices is proposed and consists of two main steps: (a) developing a microscopic (single pore) model for a real gas flow by generalizing our previously reported Extended Navier‐Stokes Equations (ENSE) method and (b) by using fractal theory concepts, up‐scaling the single pore model to the macroscopic scale. A prominent feature of the up‐scaled model is a predictor for the apparent permeability (AP). Both models are successfully validated with experimental data. The impact of the deviation of the gas behavior from ideality (real gas effect) on the gas transport mechanisms is investigated. The effect of the structural parameters (porosity Ф, the maximum pore diameter D_max, and the minimum pore diameter D_min) of the shale matrix on the apparent permeability is studied and a sensitivity analysis is performed to evaluate the significance of the parameters for gas transport. We find that (1) the real gas transport models for a single pore and porous shale matrix are both reliable and reasonable; (2) the real gas effect affects the thermodynamic parameters of the free gas and the adsorption and transport capacity of the adsorbed gas; (3) the real gas effect decreases the effective permeability for convective flow and surface diffusion; i.e., the derivation degree of the effective permeability for bulk diffusion and Knudsen diffusion increases with increasing pressure but presents a bathtub shape when the pore diameter is smaller than 10 nm; and (4) the apparent permeability increases with Ф, D_max, and D_min. It is more sensitive to D_max, followed by the porosity. D_min has a minor impact. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1430–1440, 2017     

A biaxial stretched β‐isotactic polypropylene microporous membrane for lithium‐ion batteries

In this article, microporous polypropylene (PP) membranes were produced with TMB‐5 as β‐crystal nucleating agent by biaxial stretching. Influences of different concentration of TMB‐5 were studied using differential scanning calorimetry and X‐ray diffraction. It was found that the highest crystallinity was reached when the nucleating agent content was 0.5 wt %. The effect of stretching temperature and stretching ratio on pore size distribution and porosity of the membranes were investigated by scanning electron microscopy and mercury porosimeter, respectively. And physical properties, such as tensile strength, permeability, and puncture resistance of the microporous membrane prepared at the optimized conditions, were evaluated. Compared with commercial PP separator membrane, the as‐prepared microporous membrane shows similar uniform pore size distribution and exhibits slightly higher porosity and ionic conductivities. When used as lithium‐ion separator, the experimental film shows more stable cycling performance than the commercial one. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45825.     

Dynamic Young's modulus of open-porosity titanium measured by the electromagnetic acoustic resonance method

As biological implants, porous titanium with adjustable mechanical properties can solve the stress-shielding effect. In this paper, porous titanium was prepared by the powder metallurgy method, where urea powders as the second phase were removed by heat treatment. Pore morphology (such as pore size and character) was controlled by the character of urea powders. The dynamic Young's moduli of such porous titanium with different morphology was measured by the electromagnetic acoustic resonance method. From the semi-log plots of Young's modulus versus the porosity, it was found that with increased porosity this modulus firstly decreases linearly, then decreases rapidly and goes to zero at certain porosity. However, the Young's modulus was independent of pore size. The relationship between Young's modulus and the porosity was explained by a parallel model based on the Minimum Solid Area method. The value of linear slop `b' and the percolation limit `P_C' were used for predicting the trend of Young's modulus varied with the porosity and pore size. So porous titanium with appropriate Young's modulus can be chosen as a candidate for bone substitutes.     

Experimental study of CO2 absorption/stripping via PVDF hollow fiber membrane contactor

Gas–liquid hollow fiber membrane contactor can be a promising alternative for the CO₂ absorption/stripping due to the advantages over traditional contacting devices. In this study, the structurally developed hydrophobic polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared via a wet spinning method. The membranes were characterized in terms of morphology, permeability, wetting resistance, overall porosity and mass transfer resistance. From the morphology analysis, the membranes demonstrated a thin outer finger-like layer with ultra thin skin and a thick inner sponge-like layer without skin. The characterization results indicated that the membranes possess a mean pore size of 9.6 nm with high permeability and wetting resistance and low mass transfer resistance (1.2 × 10⁴ s/m). Physical CO₂ absorption/stripping were conducted through the fabricated gas–liquid membrane contactor modules, where distilled water was used as the liquid absorbent. The liquid phase resistance was dominant due to significant change in the absorption/stripping flux with the liquid velocity. The CO₂ absorption flux was approximately 10 times higher than the CO₂ stripping flux at the same operating condition due to high solubility of CO₂ in water as confirmed with the effect of liquid phase pressure and temperature on the absorption/stripping flux.     

Thermally induced phase separation and electrospinning methods for emerging membrane applications: A review

In this review, thermally induced phase separation (TIPS) and electrospinning methods for preparation of fluoropolymer membranes are assessed, particularly for the polyvinylidene fluoride (PVDF) and polyethylene chlorotrifluoroethylene membranes. This review focuses on controlling the membrane morphology from the thermodynamic and kinetic perspectives to understand the relationship between the membrane morphology and fabrication parameters. In addition, the current status of the nonsolvent induced phase separation (NIPS) method and the combined NIPS‐TIPS (N‐TIPS) method, which is a new emerging fabrication method, are discussed. The past literature data are compiled and an upperbound curve (permeability vs. tensile strength) is proposed for the TIPS‐prepared PVDF membranes. Furthermore, the key parameters that control and determine the membrane morphology when using the electrospinning method are reviewed. Exploiting the unique advantages of the electrospinning method, our current understanding in controlling and fine‐tuning the PVDF crystal polymorphism (i.e., β‐phase) is critically assessed. © 2015 American Institute of Chemical Engineers AIChE J, 62: 461–490, 2016     

Influence of Co‐Solvent Concentration on the Properties of Dope Solution and Performance of Polyethersulfone Membranes

Polyethersulfone (PES) dope solutions were prepared from mixtures of two solvents containing N,N‐dimethylformamide (DMF) as core solvent and acetone as co‐solvent (CS) in a closed heating system. PES asymmetric membranes were cast by a dry/wet phase inversion process. Complete miscibility of PES with the fixed mixture of acetone and DMF under atmospheric pressure could be achieved. The kinetic and thermodynamic properties indicated that interaction of DMF and acetone is strongest when their mole ratio is unity, pointing to the phenomenon of true co‐solvency for PES dissolution. These results were supported by determination of the water uptake, contact angle measurement, and SEM analyses. Membrane performance, pore volume, and total pore volume on the membrane surface were also investigated.     

Microporous anisotropic phase inversion membranes from bisphenol A polycarbonate: Effect of additives to the polymer solution

Phase inversion is a very flexible technique to obtain membranes with a large sort of morphologies. Membrane properties can vary greatly depending on the kind of polymer system used. Bisphenol A polycarbonate (PC) could be used as a phase inversion membrane base polymer, and presents very good properties. Nevertheless, very little information on membrane preparation using PC and the phase inversion process can be found in the literature. In this work flat‐sheet microporous membranes were obtained by the phase inversion process using the immersion precipitation technique. A new polymer system was studied, consisting of polycarbonate, N‐methyl‐2‐pyrrolidone as solvent, water as the nonsolvent, and an additive. The influence of some parameters on membrane morphology, such as polymer solution composition, exposition time before immersion into the precipitation bath, and the kind of additive was investigated. Precipitation was followed using light transmission experiments and membrane morphology was observed through Scanning Electron Microscopy (SEM). The viscosity and cloud points of all polymer solutions were also determined. The results were related to the studied synthesis parameters, using the basic principles of membrane formation by the phase inversion technique, looking forward to establishing criteria to control the morphology of flat‐sheet membranes using polycarbonate as the base polymer. The results showed that both additives were able to increase pore interconnectivity and even suppress macrovoid formation. The decrease in the miscibility region of the polymer system and increase in mass transfer resistance are found to be the determining factors during polymer solution precipitation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3085–3096, 2002