High flux ultrafiltration membranes based on electrospun nanofibrous PAN scaffolds and chitosan coating

Conventional ultrafiltration (UF) or nanofiltration (NF) filters for water treatments are based on porous membranes, typically manufactured by the phase immersion method. The torturous porosity in these membranes usually results in a relatively low flux rate. In this study, we demonstrated a new type of high flux UF/NF medium based on an electrospun nanofibrous scaffold (e.g. polyacrylonitrile, PAN) coupled with a thin top layer of hydrophilic, water-resistant, but water-permeable coating (e.g. chitosan). Such nanofibrous composite membranes can replace the conventional porous membranes and exhibit a much higher flux rate for water filtration. The interconnected porosity of the non-woven nanofibrous scaffold can be controlled partially by varying the fiber diameter (from about 100 nm to a few micrometers) through the electrospinning processing. The example membrane, containing an electrospun PAN scaffold with an average diameter from 124 to 720 nm and a porosity of about 70%, together with a chitosan top layer having a thickness of about 1 μm, although not yet fully optimized, exhibited a flux rate that is an order magnitude higher than commercial NF membranes in 24 h of operation, while maintaining the same rejection efficiency (>99.9%) for oily waste-water filtration.     

Application of nanofibers to improve the filtration efficiency of the most penetrating aerosol particles in fibrous filters

Conventional, mechanical fibrous filters made of microfibers exhibit a local minimum of fractional collection efficiency in the aerosol particle size-range between 100 and 500 nm, which is called the most penetrating particle size (MPPS). Simple theoretical calculations predict that this efficiency may be significantly increased using nanofibrous media. The main objective of this paper is an experimental verification of these expectations and simultaneously checking whether this anticipated gain in the filtration efficiency is not overpaid with an excessive pressure drop. For this purpose we developed a modified melt-blown technology, which allowed us to produce filters composed of micrometer as well as nanometer sized fibers. One conventional microfibrous filter and five nanofibrous filters were examined. The complete structural characteristics, pressure drop and efficiency of removal of aerosol particles with diameters 10-500 nm were determined for all media. The results of the experiments confirmed that using nanofibrous filters a significant growth of filtration efficiency for the MPPS range can be achieved and the pressure drop rises moderately. Simultaneously, we noticed a shift of the MPPS towards smaller particles. Consequently, the quality factor for bilayer systems composed of a microfibrous support and a nanofibrous facial layer was considerably higher than this one for a conventional microfibrous filter alone. Additionally, it was found that utilization of many-layer nanofibrous filters combined with a single microfibrous backing layer is even more profitable from the quality factor standpoint. Comparing experimental results with theoretical calculations based on the single-fiber theory we concluded that for microfibrous filters a fairly good agreement can be obtained if the resistance-equivalent fiber diameter is used in calculations instead of the mean count diameter determined from the SEM images analysis; in the latter case, filtration efficiency computed theoretically is slightly overestimated. This is even more evident for nanofibrous media, suggesting that in such case a structural filter inhomogeneity has a strong influence on the filter efficiency and its resistance and one should strive for minimization of this effect manufacturing nanofibrous filters as homogeneous as possible. We can finally conclude that fibrous filters containing nanofibers, which are produced using the melt-blown technique, are very promising and economic tools to enhance filtration of the most penetrating aerosol particles.     

A study of the electrophoretic deposition of bioactive glass-chitosan composite coating

Bioactive glass is coated on implant's surface to improve corrosion resistance and osseointegration, when placed in the body. Bioactive glass particles were synthesized through a sol-gel process and deposited along with chitosan to form a composite coating on a stainless steel substrate using electrophoretic deposition technique. Stable suspensions of chitosan-bioactive glass were prepared using bioactive glass particles (<1 μm) and 0.5 g/l chitosan solution. The influence of ethanol-water ratio on deposition yield was investigated. For all process conditions, best results were achieved with suspension of 30 vol% water in ethanol-water containing 2 g/l bioactive glass. FTIR studies showed that chitosan was absorbed on ceramic particle surface via hydroxyl and amid bonds. In order to evaluate the coating, its structure and electrochemical properties were studied. It was concluded that increasing the process voltage led to an increase in particle size and porosity, but induced cracks in the coating. In the presence of the polymer-bioactive glass coating, current density in artificial saliva was decreased by 52% and corrosion potential shifted toward more noble values.     

3-D simulation of particle filtration in electrospun nanofibrous filters

Virtual 3-D geometries resembling the internal microstructure of electrospun fibrous materials are generated in this work to simulate the pressure drop and collection efficiency of nanofibrous media when challenged with aerosol particles in the size range of 25 to 1000 nm. In particular, we solved the air flow field in the void space between the fibers in a series of 3-D fibrous geometries with a fiber diameter in the range of 100 to 1000 nm and a Solid Volume Fraction (SVF) in the range of 2.5 to 7.5%, using the Fluent CFD code, and simulated the flow of large and fine particles through these media using Lagrangian and Eulerian methods, respectively. Particle collection due to interception and Brownian diffusion, as well as the slip effect at the surface of nanofibers, has been incorporated in the CFD calculations by developing customized C++ subroutines that run in the Fluent environment. Particle collection efficiency and pressure drop of the above fibrous media are calculated and compared with analytical/empirical results from the literature. The numerical simulations presented here are believed to be the most complete and realistic filter modeling published to date. Our simulation technique, unlike previous studies based on oversimplified 2-D geometries, does not need any empirical correction factors, and can be used to directly simulate pressure drop and efficiency of any fibrous media.     

The sorption of acid dye onto chitosan nanoparticles

The behavior of chitosan nanoparticles as an adsorbent to remove Acid Green 27 (AG27), an acid dye, from an aqueous solution has been investigated with nanochitosan (particle size = 180 nm; degree of deacetylation = 74%). The dye concentration at equilibrium (Q_e, mg/g) was calculated using the weight of the nanoparticles in the mixed solution (Q_es) and the weight of chitosan in the nanoparticles (Q_ep). The experimental isotherm data were analyzed using the Langmuir equation for each chitosan sample; the Langmuir monolayer adsorption capacity (Q₀) was calculated with Q_es and Q_ep and the results were 1051.8 mg/g and 2103.6 mg/g, respectively, which were significantly higher than that of the micron-sized chitosan.     

Removal of hexavalent chromium from aqueous solution by adsorption on treated sugarcane bagasse using response surface methodological approach

In the present study, effect of adsorbent dose, pH and agitation speed on the removal of chromium from aqueous medium using an agricultural waste biomass (sugarcane bagasse treated with succinic acid) has been investigated. Batch mode experiments were carried out to assess the adsorption equilibrium. The influence of three parameters on the removal of chromium was examined using a response surface methodological approach. The Central Composite Face-Centered Experimental Design in Response Surface Methodology (RSM) by Design Expert Version 6.0.10 (Stat Ease, USA) was used for designing the experiments as well as for full response surface estimation and 20 trials as per the model were run. The optimum conditions for maximum removal of chromium from an aqueous solution of 50 mg/L were as follows: adsorbent dose (20 g/L), pH (2.0) and stirring speed (250 rpm). This was evidenced by the higher value of coefficient of determination (r² = 0.9873).     

Removal of Cr(III) in the fixed bed column and batch reactors using as adsorbent zeolite NaX

In this work, the uptake capacity of Cr(III) ions in NaX zeolite was investigated. The experiments were carried out in continuous and batch systems at . The batch isotherm evidenced an irreversible shape with a maximum chromium uptake of 3.61 meq/g. The column experiments were carried out at pH=3.5, with a flow rate of 9 ml/min and an average particle size of 0.180 mm. The dynamic system provided a distinct ion-exchange mechanism, which generated a favorable isotherm with a chromium uptake of 3.27 meq/g. A mathematical model was also applied to represent the dynamics of the sorption of the column. The model considered the axial dispersion in the column and the intraparticle diffusion as the rate-controlling step. The dynamic isotherm was successfully modeled by the Freundlich equation and the mathematical model described well the experimental dynamic data for the feed concentrations from 0.3 up to 3.0 meq/g.     

Evaluation of a novel low-cost culture medium containing exclusively milk,potato and glycerol for microbial transglutaminase production by Streptomyces mobaraensis

The aim of this work was to evaluate the production of microbial transglutaminase (MTG) by Streptomyces mobaraensis in a reduced nutritional medium based on non-commercial potatoes. Initially, the production was studied comparing 3 culture media based on potato: (i) media based on acid hydrolysed potato, (ii) media based on gelified non-hydrolysed potato and (iii) media based on gelified non-hydrolysed potato supplemented with glucose (20 g/L). All media were supplemented with nutrients and inductors of MTG production (yeast extract, peptone, sodium caseinate, glycerol and mineral salts such as sodium phosphate, potassium phosphate, magnesium sulphate). The best medium was gelified non-hydrolysed potato allowed to obtain up to 2.72 U/mL at 96 h. In a second study, it was proposed the substitution of all the nutrients and inductors by exclusively skim milk and glycerol. An experimental design was performed to optimize the composition of milk, potato and glycerol. The economical yield of the process was also evaluated. Fermentations were carried out and samples were taken at 72 h and 96 h. Results showed that the maximum MTG activity was obtained at 72 h. A significant effect of potato and milk on MTG activity was observed, including an effect of interaction between both compounds. Optimal conditions selected were: 600 g/L of skim milk, 40 g/L of potato and 5 g/L of glycerol, yielding a maximum activity of 3.2 U/mL and an economic yield of 8.11 € of MTG/€ of nutrients. The results showed that the medium milk–potato–glycerol was feasible for the production of transglutaminase, obtaining a high MTG activity in a simple natural medium.     

Synthesis of high magnetization hydrophilic magnetite (Fe3O4) nanoparticles in single reaction—Surfactantless polyol process

High magnetization hydrophilic magnetite nanoparticles have been synthesized in two different batches with mean particle sizes of 32.3 and 9.2 nm by inexpensive and surfactant-free facile one-pot modified polyol method. In the synthesis, polyethylene glycol was used as a solvent media and it has been found to play a key role to act as a reducing agent as well as a stabilizer simultaneously. It was shown that the size of the nanoparticles can be effectively controlled by modifying the reaction parameters such as reaction temperature, time and polyol/metal precursor ratio. X-ray diffraction and energy dispersive spectroscopy studies confirm the formation of a pure magnetite phase without the presence of any other phases. Transmission electron microscopy and the Fourier transform infrared spectroscopy results reveal that the particle size and surface adsorption properties are very much dependent on reaction parameters. The magnetic properties of the samples measured by physical property measurement system have shown that the as-synthesized magnetite nanoparticles possess a high magnetization of 85.87 emu/g at 300 K and 91.7 emu/g at 5 K with negligible coercivities. The structural and magnetic characterizations of these polyol coated, hydrophilic, monodisperse, superparamagnetic nanoparticles clearly indicate that they are suitable for biomedical applications.     

Structural, morphological, magnetic and optical properties of chromium substituted strontium ferrites, SrCrxFe12 − xO19 (x = 0.5, 1.0, 1.5, 2.0 and 2.5) annealed with potassium halides

Chromium substituted strontium ferrites SrCr_xFe_12 − xO₁₉ (x = 0.5, 1.0, 1.5, 2.0 and 2.5) have been synthesized via sol gel method and the dry gels obtained have been annealed with various inorganic template agents (KCl, KBr and KI). The powder X ray diffraction studies reveal a crystallite size of ~ 40-45 nm. The use of KCl as inorganic template agent leads to an increase in the crystallite size. This may be attributed to the fact that the coordination ability of Cl⁻ is maximum due to its larger charge to size ratio, which promotes crystal growth in one dimension leading to needle-like morphology. On the other hand, KI undergoes sublimation to form I₂ which gets entrapped in the strontium ferrite crystal leading to a bubble-like morphology. A systematic change in the lattice constants, a and c, is not observed because the radius of Cr³⁺ ion (0.63 Å) is similar to that of Fe³⁺ ion (0.64 Å). The saturation magnetization decreases with increase in the chromium concentration from 43.03 emu/g to 17.40 emu/g due to the substitution of Fe³⁺ ions by less magnetic Cr³⁺ ions in 2a and 12k sites of the lattice. The coercivity decreases with increase in the chromium concentration due to decrease in magnetocrystalline anisotropy. In the presence of KCl and KBr, both saturation magnetization and coercivity increase and the saturation magnetization has the maximum value in case of samples annealed with KBr. However, with KI, the values of both saturation magnetization and coercivity decrease sharply which may be due to lower crystallinity due to bubble-like morphology because of the decomposition of KI to I₂. The energy band gap for all the ferrite compositions is found to be ~ 2.2 eV and its value increases in the samples annealed with KI.     

High saturation capacity of activated carbons prepared from mesophase pitch in the removal of volatile organic compounds

A series of binderless activated carbon monoliths (ACMs) have been prepared from petroleum pitch and using KOH as activating agent. Characterization shows that these activated carbons combine a large “apparent” surface area (up to S_BET ∼ 3000 m²/g) together with a well-developed narrow micropore size distribution. Dynamic column adsorption experiments using different volatile organic compounds (VOCs), ethanol and benzene, show that these activated carbons prepared from mesophase-based materials exhibit a superior saturation capacity compared to conventional carbon materials. The total amount adsorbed reaches values as high as 18 g/100 g AC and 40 g/100 g AC, for ethanol and benzene, respectively. These are the best results reported in the literature. The total amount adsorbed for both molecules correlates with the total volume of narrow micropores, thus confirming the pore size specificity required for the adsorption of VOC molecules. Regeneration studies show that ethanol can be easily desorbed at room temperature by flowing clean air through the adsorbent whereas benzene requires a further heating for complete desorption/regeneration.     

Thiol-modified cellulose nanofibrous composite membranes for chromium (VI) and lead (II) adsorption

Oxidized cellulose nanofibers (CNF), embedded in an electrospun polyacrylonitrile (PAN) nanofibrous scaffold, were grafted with cysteine to increase the adsorption capability for chromium (VI) and lead (II). Thiol-modified cellulose nanofibers (m-CNF) were characterized by titration, FT-IR, energy dispersive spectroscopy (EDS) and SEM techniques. Static and dynamic Cr(VI) and Pb(II) adsorption studies of m-CNF nanofibrous composite membranes were carried out as a function of pH and of contact time. The results indicated these membranes exhibited high adsorption capacities for both Cr(VI) (87.5 mg/g) and Pb(II) (137.7 mg/g) due to the large surface area and high concentration of thiol groups (0.9 mmol of –SH/gram m-CNF). The morphology and property of m-CNF nanofibrous composite membranes was found to be stable, and they could be used and regenerated multiple times with high recovery efficiency.     

Microstructure and electrochemical characterization of trivalent chromium based conversion coating on zinc

A trivalent chromium based conversion coating (CCC), based on chromium nitrate solution with Co(II) ions, was developed on Zn substrate. The corrosion resistance of the trivalent CCC, measured in deaerated pH 8.0 borate buffer + 0.01 M NaCl solution using anodic polarization and electrochemical impedance spectroscopy (EIS), was very sensitive to both immersion time and bath pH. Micro-cracks were found on the surface of the CCC. Besides, the density of micro-crack and the coating thickness also depended on immersion time and bath pH. With increasing the coating thickness its pitting potential increased and passive current density decreased. The trivalent CCC formed on Zn for 40 s in pH 1.7 bath showed the best corrosion resistance, and the pitting potential increased significantly from −355 mV_SCE for Zn to 975 mV_SCE for the trivalent CCC on Zn. To explain the corrosion behavior of the trivalent CCC using EIS analysis, a modified equivalent circuit, which considered the micro-cracks in the coating and chromium corrosion product (CCP) deposited in the micro-cracks, was designed and the variation of each electrical parameter was examined. Especially, its corrosion behavior was well described by the variation of the resistance of CCP (R_ccp).     

Preparation of activated carbon derived from Jatropha curcas fruit shell by simple thermo-chemical activation and characterization of their physico-chemical properties

High surface area activated carbons were prepared by simple thermo-chemical activation of Jatropha curcas fruit shell with NaOH as a chemical activating agent. The effects of the preparation variables, which were impregnation ratio (NaOH:char), activation temperature and activation time, on the adsorption capacity of iodine and methylene blue solution were investigated. The activated carbon which had the highest iodine and methylene blue numbers was obtained by these conditions as follows: 4:1 (w/w) NaOH to char ratio, 800 °C activation temperature and 120 min activation time. Characterization of the activated carbon obtained was performed by using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and nitrogen adsorption isotherm as BET. The results present that the activated carbon possesses a large apparent surface area (S_BET = 1873 m²/g) and high total pore volume (1.312 cm³/g) with average pore size diameter of 28.0 Å.     

Aerosol filtration performance of nanofibrous mats produced via electrically assisted industrial-scale solution blowing

Highly efficient polyamide 6 (PA6)-based nanofibrous air filter media was developed for particulate matter (PM) removal in the ambient atmosphere. The PA6 nanofibrous mats exhibited 85% PM0.3 capture performance at a cost of 164 Pa pressure drop when the multiple-nozzle solution blowing system was set to 8 m/h fabric winding speed. However, an increase in the winding speed at a constant feeding rate lowered the filtration efficiency to 62% due to the less amount of nanofibrous mats collected on the substrate. The application of electrical field at the same parameters allowed us to produce a filter media having FFP3-level filtration performance, which means 99% PM0.3 capture performance. This was attributed to a fine fiber diameter (116 nm), higher solidity value (0.149), and lower average pore size (2.28 μm). These results show that the electrically assisted solution blowing provides a feasible route for the production of high-quality nanofibrous filter media.     

Amphiphilic chitosan nanospheres: Factors to control nanosphere formation and its consequent pH responsive performance

Chitosan grafted with hydrophobic and hydrophilic groups initiates the formation of amphiphilic chitosan nanospheres. The molecular weight of mPEG plays an important role to control the particle size. As compared to mPEG 2000, which gives a bimodal nanosphere (∼200, and ∼300 nm), mPEG 5000 initiates a monodispersed nanosphere with the smaller size (150 nm). In aqueous solution, the nanosphere surface is negatively charged resulting in a well dispersion in neutral to high pH but a significant precipitation in low pH. A model drug incorporation using lidocaine is successful when amphiphilic chitosan nanospheres were dissolved in good solvent followed by allowing mixing with drug solution before dialysis. The particle size of the drug incorporated chitosan is significantly increased, that is, from 100-150 nm to approximately 400-500 nm when the amount of incorporated lidocaine was about 0.68 mg per mg of lidocaine-loaded nanosphere.     

Supercritical fluid extraction of flavonoids from Maydis stigma and its nitrite-scavenging ability

Supercritical fluid carbon dioxide (SF-CO₂) extraction (SFE) of flavonoids from Maydis stigma and its nitrite-scavenging ability were investigated. The effects of extraction time, particle size and co-solvent composition in terms of water content in ethanol were first optimized. Then, a Box-Behnken design combined with response surface methodology (RSM) was employed to study the effects of three independent variables (temperature, pressure and co-solvent amount) on the extraction yield of flavonoids. A maximal extraction yield of flavonoids of approximately 4.24 mg/g of M. stigma by SFE was obtained under optimal conditions (a temperature of 50.88 °C, a pressure of 41.80 MPa, a co-solvent amount of 2.488 mL/g and an extraction time of 120 min with 0.4-mm particle sizes and 20% aqueous ethanol as the co-solvent). Furthermore, the nitrite-scavenging ability of the flavonoid-enriched SFE extracts was assessed using the Griess reagent. The flavonoid-enriched SFE extracts exhibited the highest scavenging ability on nitrite (88.1 ± 3.04%) at the concentration of 500 μg/mL and at pH 3.0. The nitrite-scavenging ability of the extracts appeared to be concentration dependent but negatively correlated with the pH.     

Diffusional mass transfer model for the adsorption of food dyes on chitosan films

The adsorption kinetics of erythrosine B and indigo carmine on chitosan films was studied by a diffusional mass transfer model. The experimental curves were obtained in batch system under different conditions of stirring rate (80–200 rpm) and initial dye concentration (20–100 mg L⁻¹). For the model development, external mass transfer and intraparticle diffusion steps were considered and the specific simplifications were based on the system characteristics. The proposed diffusional mass transfer model agreed very well with the experimental curves, indicating that the surface diffusion was the rate limiting step. The external mass transfer coefficient (k_f) was dependent of the operating conditions and ranged from 1.32 × 10⁻⁴ to 2.17 × 10⁻⁴ m s⁻¹. The values of surface diffusion coefficient (D_s) increased with the initial dye concentration and were in the range from 0.41 × 10⁻¹⁴ to 22.90 × 10⁻¹⁴ m² s⁻¹. The Biot number ranged from 17.0 to 478.5, confirming that the intraparticle diffusion due to surface diffusion was the rate limiting step in the adsorption of erythrosine B and indigo carmine on chitosan films.     

Experimental study of cake formation on heat treated and membrane coated needle felts in a pilot scale pulse jet bag filter using optical in-situ cake height measurement

Pulse-jet bag filters are frequently employed for particle removal from off gases. Separated solids form a layer on the permeable filter media called filter cake. The cake is responsible for increasing pressure drop. Therefore, the cake has to be detached at a predefined upper pressure drop limit or at predefined time intervals. Thus the process is intrinsically semi-continuous. The cake formation and cake detachment are interdependent and may influence the performance of the filter. Therefore, understanding formation and detachment of filter cake is important. In this regard, the filter media is the key component in the system. Needle felts are the most commonly used media in bag filters. Cake formation studies with heat treated and membrane coated needle felts in pilot scale pulse jet bag filter were carried out. The data is processed according to the procedures that were published already [Powder Technology, Volume 173, Issue 2, 19 April 2007, Pages 93-106]. Pressure drop evolution, cake height distribution evolution, cake patches area distribution and their characterization using fractal analysis on different needle felts are presented here. It is observed that concavity of pressure drop curve for membrane coated needle felt is principally caused by presence of inhomogeneous cake area load whereas it is inherent for heat treated media. Presence of residual cake enhances the concavity of pressure drop at the start of filtration cycle. Patchy cleaning is observed only when jet pulse pressure is too low and unable to provide the necessary force to detach the cake. The border line is very sharp. Based on experiments with limestone dust and three types of needle felts, for the jet pulse pressure above 4 bar and filtration velocity below 50 mm/s, cake is detached completely except a thin residual layer (100-200 μm). Uniformity and smoothness of residual cake depends on the surface characteristics of the filter media. Cake height distribution of residual cake and newly formed cake during filtration prevails. The patch size analysis and fractal analysis reveal that residual cake grow in size (latterly) following regeneration initially on the base with edges smearing out, however, the cake heights are not leveled off. Fractal dimension of cake patches boundary falls in the range of 1-1.4 and depends on vertical position as well as time of filtration. Cake height measurements with Polyimide (PI) needle felts were hampered on account of its photosensitive nature.     

Determination of the adhesion force between particles and a flat surface, using the centrifuge technique

By using a centrifuge technique, the influence of powdery material particle size on the adhesion force particle-surface was determined. In order to achieve this, the adhesion of phosphatic rock (ρ_p = 3.090 kg m^− 3) and of manioc starch particles (ρ_p = 1.480 kg m^− 3) on a steel surface were studied. A microcentrifuge that reached a maximum speed rotation of 14000 rpm and which contained specially designed centrifuge tubes was used. There tubes contained the flat surface where the test particles were deposited. The powder particles were dispersed on these disks and the particles detachment were performed using diverse centrifugal speeds. The graphics of particle percentages still adhering on the surface of the disks as a function of the applied detachment force showed that the profile of adhesion force followed a log-normal distribution. The adhesion force increased with particle size. The manioc starch particles presented adhesion forces greater than those for the phosphatic rock particles for all particle sizes studied. The results obtained were compared with the theory proposed by Derjaguin, Muller and Toporov whose theoretical adhesion presented values close to the experimental data for the phosphatic rock particles adhesion on the stainless steel surface. On the contrary, the theoretical values were lower than the experimental ones for the manioc starch particles maybe due to the small roughness of these particles, their physical properties (softer and deformable material) and/or specific chemical interactions since the organic composition of the manioc starch particles that can dominate the adhesion force. Finally, the separation distance among the surfaces in contact (Z₀) was estimated in approximately 1.0 × 10^− 9 m for the phosphatic rock and 5.0 × 10^− 10 m for the manioc starch. These results were weakly dependent on the particle size range.