Rapid prototyping of a miniaturized Electrospinning setup for the production of polymer nanofibers

Fabrication of polymeric micro/nanofibers with controllable size, density, orientation, and composition is required for their translation into functional devices and materials. Electrospinning (ES) is a frequently used fiber fabrication technique, where ES parameters such as the applied electric field strength, architecture of the setup, and solution composition are manipulated to control the fiber properties. Here, we present a bench‐top method for fabricating miniaturized, integrated, and highly tunable ES setups based on shrinkable polymer substrates. We show that using a combination of numerical modeling and controlling different parameters in the ES setup, including the spinneret to collector distance, and spinneret and collector designs, it is possible to tune the density, alignment, and orientation of electrospun fibers. In this way, we have produced 300–600 nm wide poly(ethylene oxide) fibers arranged as nonwoven mats on planar electrodes, aligned fibers on electrode edges, and individual suspended fibers spanning gaps between collector electrodes. The ability to rapidly prototype ES setups should enable us to study the effects of spinneret–collector configurations on fiber morphology, distribution, and conformation and to aid in the development of miniaturized ES setups designed to serve specific applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40629.     

Sonochemical synthesis and stabilization of concentrated antimicrobial silver‐chitosan nanoparticle dispersions

This work reports on a green synthetic route to produce concentrated aqueous dispersions of silver nanoparticles (AgNP) employing high‐intensity ultrasound (US) and chitosan (CS) as a nontoxic reducing agent for Ag⁺ salts and AgNP stabilizer. The sonication simultaneously boosted the synthesis and improved the stability of the AgNP, capping them with CS. Hybrid AgNP‐CS antimicrobial dispersions, stable for at least 6 months, were synthesized in a simple single step process. The use of US allowed for applying relatively mild processing temperatures (60 °C) and reaction time between 30 min and 3 h to obtain concentrated dispersions of AgNP that otherwise could not be obtained even after 72 h under mechanical stirring at the same reaction conditions. Upon sonication spherical AgNP‐CS with a size between 60 and 100 nm were generated, in contrast to the average diameter of ～200 nm of the particles obtained by stirring. The antibacterial efficiency of the AgNP‐CS hybrids was evaluated against the medically relevant pathogens Staphylococcus aureus and Escherichia coli. The US‐synthesized AgNP‐CS showed more than three fold higher antibacterial activity compared to the particles obtained under stirring, due to their higher concentration and smaller size. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45136.     

Carbonized electrospun polyvinylpyrrolidone/metal hybrid nanofiber composites for electrochemical applications

Electrospinning is a very versatile and efficient method of fabricating nanofibers with the desired properties. Polyvinylpyrrolidone (PVP) in ethanol solution was electrospun into nanofibers and used as a precursor for the preparation of carbon nanofibers. Cobalt chloride was also incorporated with PVP nanofibers to produce carbon nanofiber composites with enhanced electrical conductivity and electrochemical properties. The surface morphology and physical properties of the electrospun nanofibers, carbonized nanofibers, and their composites were observed by scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction. The electrochemical behavior of the carbon nanofiber composites was studied by drop‐casting on a working surface of the screen‐printed carbon electrode and examined by cyclic voltammetry and electrochemical impedance spectroscopy. The results indicated that carbon nanofiber composites were decorated with cobalt nanoparticles and enhanced the charge‐transfer efficiency on the electrode surface. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45639.     

PCL/collagen blends prepared by solution blow spinning as potential materials for skin regeneration

Solution blow spinning (SBS), is used to prepare biocompatible fibrous materials based on poly-ε-caprolactone (PCL), modified with collagen. Materials with different compositions in terms of collagen are prepared. Structure, morphology, topography, wettability behavior, and cytotoxicity are studied in order to investigate the potentiality of these materials for medical applications in the field of tissue repairing and regeneration. Structure is studied by Fourier transformed infrared spectroscopy, morphology by scanning electron microscopy, topography by optical profilometry and wettability behavior by contact angle measurements. The addition of small amounts of collagen to PCL by SBS can induce important variations in the morphology and topography of the materials that, in turns, lead to changes in the wettability behavior and ability of HaCat cells adhesion and proliferation. The analysis of surface characteristics together with the use of a model based on mats constituted by cylinders disposed perpendicularly to each other point out that, under the compositions considered, the main factor leading to higher adhesion and proliferation of cells on the PCL/collagen is the presence of more available surface area.     

Effect of different drying methods on zein-based microcapsules loaded with Artemisia argyis essence obtained by anti-solvent precipitation

Microencapsulation is considered an efficient technique to protect functional materials from oxidization while enabling controlled release. In this study, anti-solvent precipitation was used to prepare zein-based microcapsules loaded with Artemisia argyis essence (AAE@ZMs). The impact of different drying methods, namely vacuum drying, freeze drying, and spray drying on AAE@ZMs was evaluated. Quality of AAE@ZMs was evaluated by the determination of color, moisture content, bulk density, chemical structure, and morphology evaluation. Freeze dried AAE@ZMs (F-AAE@ZMs) and vacuum dried microcapsules (V-AAE@ZMs) respectively showed stronger water and oil absorption capacities. The residual content of Artemisia argyis essence (AAE) in V-AAE@ZMs was higher than those in F-AAE@ZMs and spray dried microcapsules (S-AAE@ZMs) after continuously releasing for 120 h. Meanwhile, heated from 30 to 600°C, the residues of V-AAE@ZMs and F-AAE@ZMs were lower than those of S-AAE@ZMs. Therefore, drying methods greatly affected key quality parameters of AAE@ZMs. This study provides guidance on the use of drying methods in microcapsules delivery systems with zein or other materials.     

Synthesis and properties of magnetite nanoparticles with peroxide-containing polymer shell and nanocomposites based on them

Magnetite nanoparticles (Fe₃O₄ NPs) with peroxide-containing polymer shell have been synthesized using the method of coprecipitation from the mixture solutions of Fe (II) and Fe (III) salts in the presence of peroxide-containing copolymer (PCC). Polymer shell presence has been proved by elemental and complex thermal analysis. Synthesized Fe₃O₄ NPs possess superparamagnetic properties. Their specific saturation magnetization decreases gradually from 65 to 54 A·m²·kg⁻¹ with increasing PCC concentration owing to the surface spin pinning effect caused by a polymer shell. The average sizes of Fe₃O₄ NPs estimated from the data of XRD analysis and magnetic measurements are in the range of 9–12 nm. The NP sizes determined by the DLS method lie in the range of 150–270 nm; this result is significantly larger than the sizes estimated by the two aforementioned methods evidencing a tendency for Fe₃O₄ NPs toward self-association. Cross-linked composite films based on polyvinyl alcohol have been obtained via radical curing initiated by the PCC shell of nanoparticles. The resulting composite films are magnetically sensitive films with rather high physico-mechanical properties (tensile strength reaches 48–67 MPa and relative elongation – 4%–21% depending on cross-linking degree), a priori non-toxic and biocompatible, which makes them promising materials for various applications.     

Electrospun magnetic carbon composite fibers: Synthesis and electromagnetic wave absorption characteristics

Electrospun polyacrylonitrile (PAN)‐based carbon composite fibers embedded with magnetic nanoparticles have been developed as materials for electromagnetic wave absorption. The nanocomposite fibers were prepared by electrospinning from a dispersion of magnetite (Fe₃O₄) nanoparticles stabilized by L ‐glutamic acid in a solution of PAN and N, N‐dimethyl formamide. The Fe₃O₄‐embedded PAN nanofibers were stabilized at 270°C in air and carbonized at 800°C in nitrogen. The Fe₃O₄ nanoparticles were crystalline with a particle size of about 7 nm, most of which was reduced to Fe₃C with agglomerates of up to 50 nm diameter in the carbon fibers. The carbon morphology was mostly disordered, but exhibited a layered graphitic structure in the vicinity of the nanoparticles. The carbon composite fiber exhibited ferromagnetic behavior, and the induced magnetic saturation per unit mass of fibers increased with increasing Fe₃O₄ content in the precursor. The complex relative dielectric permittivity was tuned by adjusting the amount of Fe₃O₄ in the carbon fiber precursor. With increasing Fe₃O₄ content, good electromagnetic wave absorption characteristics were observed below 6 GHz, even for samples with fiber loadings as low as 5 wt %. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Stability and spinnability of modified melamine–formaldehyde resin solution for centrifugal spinning

Melamine microfibers were first prepared by centrifugal spinning. The stability and spinnability of a melamine–formaldehyde (MF) resin solution were improved as expected by adding various modifier combinations. Considering the storage stability of solutions characterized by visual inspection, turbidity tests, and viscosity measurements and combined with the fiber morphology, the optimal modifier combination was obtained. The spun fibers manifested a good morphology and thermal stability as measured by scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Moreover, microfibers prepared by three spinning methods (centrifugal spinning, electrospinning, and centrifugal electrostatic spinning) were compared to choose the suitable spinning method for different fields in the future. This work provides systematic and scientific guidance on the synthesis of MF resin solutions and rapid mass production of melamine microfibers and also demonstrates that centrifugal spinning of melamine microfiber is a promising candidate for flame retardance and CO₂ adsorption at elevated temperature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46072.     

Water-born 3D nanofiber mats using cost-effective centrifugal spinning: comparison with electrospinning process: A complex study

A comparison of the electrostatic and centrifugal spinning of poly(vinyl alcohol) and poly(vinyl pyrrolidone) is shown in terms of the resulting fiber morphology and the process conditions. Specific parameters of centrifugal spinning, such rotational speed of spinneret and the relative humidity, were extensively investigated in details. Morphologies and diameters of resulting fiber mats were investigated by a scanning electron microscopy and compared between the two spinning techniques. The results revealed that formation of fibers is mainly affected by the initial polymer concentrations (and resulting viscosities) of polymeric solutions, which is in line with previous reports. However, the key novel finding of this work is that increasing relative humidity during centrifugal spinning process leads to greatly reduced fiber diameters to the levels typical for electrospinning. The obtained comparison is discussed and clearly shows technological advantages of the centrifugal spinning over electrospinning, enabling quantitative production of fibers with same or similar diameters.     

Synthesis,structure, and thermal properties of new polypropylene nanocomposites prepared by using MgCl2‐mica/TiCl4 based catalyst

Preparation of polypropylene/mica nanocomposites via in situ polymerization is investigated. The nanocomposites were successfully synthesized using a Ziegler‐Natta catalyst based on MgCl₂/modified mica/TiCl₄. Muscovite mica was organically modified with quaternary ammonium salt, and with triethylaluminum. The treatment with triethylaluminum increased the disorder in the stacking of clay layers, producing a more active catalyst for propylene polymerization, although the mica containing catalysts had lower activity than the standard one prepared without clay. The nanostructure of the composites was characterized by X‐ray diffraction. The results showed that part of the mica layers were exfoliated in the polymer matrix, although tactoids were still present. Small‐angle X‐ray scattering analysis was used to determine how mica and its concentration influence the size of the polymer nanocrystals. Differential scanning calorimetry was used to investigate both melting and crystallization temperatures, as well as the crystallinity of the nanocomposite samples. Thermogravimetric analysis showed that polypropylene/mica nanocomposites presented much higher thermal stability than the polypropylene without mica, which means that mica had a barrier effect against heat. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45587.     

Poly(ethylene terephthalate) nanoparticles prepared by CO2 laser supersonic atomization

Poly(ethylene terephthalate) (PET) particles were prepared by the irradiation of PET fibers with a carbon dioxide (CO₂) laser while atomizing them at supersonic velocities. A supersonic jet was generated by blowing air into a vacuum chamber through a fiber injection orifice. The fibers are melted by laser heating and atomized by the supersonic jet at the outlet of the orifice. The PET particles produced by CO₂ laser supersonic atomization conducted at a laser power of 34 W and at a chamber pressure of 10 kPa have an average particle size of 0.619 μm, high circularity, and a smooth surface that is not roughened by laser ablation. The novel CO₂ laser supersonic atomization technique can be used to easily prepare polymeric nanoparticles of various thermoplastic polymers using only CO₂ laser irradiation without the need for solvents and additives. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40909.     

Recycled polyester nanofiber as a reservoir for essential oil release

The importance of creating sustainable alternatives for products that can be easily recyclable, such as, poly (ethylene terephthalate) (PET), is not new, being textile fibers the product of greatest interest. The objective of this work is to propose a recycling alternative for PET bottles for fiber production as a reservoir of essential oils for aromatherapy applications. The fibers were obtained via coaxial and dual-jet electrospinning techniques. The material used in the impregnation and release of peppermint oil was PET originating from disposable bottles. The release of oil from the electrospun fibers was quantified by UV–vis spectroscopy. For the fibers produced by dual-jet electrospinning the cumulative release of peppermint reached around 70% after 30 days. The sample obtained by coaxial electrospinning had a core-shell structure and the amount of oil released was 33% after 30 days. In this investigation, a less aggressive process was introduced, making the electrospinning of PET a viable technique for essential oil impregnation. Dual-jet as well as coaxial electrospinning showed slower release than values reported in the literature. Thus, a procedure with more favorable working conditions was developed, making the process more feasible and serving as an alternative for recycling PET bottles to produce functional textiles.     

Highly scalable nanoparticle–polymer composite fiber via wet spinning

Magnetic nanoparticles have continued to gather the interest of researchers due to the unique physical properties of materials found at this size scale. Herein, the production of composite magnetic fibers composed of iron oxide nanoparticles suspended in alginate is described. These materials were produced via wet spinning of a sodium alginate solution into a bath of an aqueous solution of calcium chloride. The magnetic fibers were found to have similar mechanical properties to normal alginate fibers, and exhibited superparamagnetic behavior when subjected to an external DC magnetic field. In addition, the particle loaded fibers demonstrated the potential to produce significant amounts of heat when exposed to an AC magnetic field, suggesting these new materials could be applicable to a variety of applications including magnetic hyperthermia. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1975–1980, 2013     

Evaluation of hydrophilic cellulose nanofiber dispersions in a hydrophobic isotactic polypropylene composite

An effective approach for the evaluation of dispersed hydrophilic cellulose nanofibers (CNFs) in hydrophobic isotactic polypropylene (iPP) is presented using scattering and microscopic techniques for fiber analysis on nanometer and micrometer scales. iPP composites reinforced with CNF fibrous fillers were characterized by small-angle light scattering, small-angle X-ray scattering, and polarized optical microscopy measurements in the molten state in order to evaluate the shape of CNF fillers and/or larger aggregates formed from these fibers. The best dispersion results in the molten state coincided with low concentrations of CNFs. We observed the effect of CNFs on the acceleration of iPP crystal growth using wide-angle X-ray scattering and differential scanning calorimeter measurements. It was even possible to observe the nucleation morphology around CNF fibrous fillers using transmission electron microscopy.     

Melt spinning and drawing of polyethylene nanocomposite fibers with organically modified hydrotalcite

Fibers of high density polyethylene (HDPE)/organically modified hydrotalcite (LDH) were produced by melt intercalation in a two‐step process consisting of twin‐screw extrusion and hot drawing. The optimum drawing temperature was 125°C at which the draw ratios up to 20 could be achieved. XRD analysis revealed intercalation with a high degree of exfoliation for the composites with 1–2% of LDH. Higher thermal stability of nanofilled fibers was confirmed by TGA analysis. DSC data indicated that dispersed LDH particles act as a nucleating agent. Crystallization kinetics of the HDPE matrix in the composite fibers is characterized by two transition temperatures, that is, for Regimes I/II at 123°C and for Regimes II/III ranging between 114–119°C as a function of the nanocomposite composition. Fibers with 1–2% of LDH show for the drawing ratios up to 15 a higher elastic modulus, 9.0–9.3 GPa (with respect to 8.0 GPa of the neat HDPE), maintain tensile strength of 0.8 GPa and deformation at break of 20–25%. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40277.     

Improved dispersion of carbon nanotubes in poly(vinylidene fluoride) composites by hybrids with core–shell structure

Core–shell structure hybrids of carbon nanotubes (CNTs)/BaTiO₃ (H‐CNT‐BT) and commercial multi‐wall CNTs are respectively incorporated into poly(vinylidene fluoride) (PVDF) for preparing the composites near the percolation thresholds. A comprehensive investigation for CNT's dispersion and composite's conductivity is conducted between H‐CNT‐BT/PVDF and CNT/PVDF at different depths vertical to the injection's direction. Gradual increases of the conductivity in two composites are observed from the out‐layer to the core part which infers an inhomogeneous CNT's dispersion in the interior of composites due to their migration under flow during the injection. However, the use of H‐CNT‐BT fillers with core–shell structure enables to reduce this inhomogeneous dispersion in the composite. Furthermore, the conductive network of CNTs in H‐CNT‐BT/PVDF is less sensitive to the thermal treatment than the one in CNT/PVDF composite, which infers the core–shell structure of hybrids can ameliorate the sensitivity of the conductive network. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45693.     

Facile modification of polysulfone hollow-fiber membranes via the incorporation of well-dispersed iron oxide nanoparticles for protein purification

Protein existence in wastewater is an important issue in wastewater management because proteins are generally present as contaminants and foulants. Hence, in this study, we focused on designing a polysulfone (PSf) hollow-fiber membrane embedded with hydrophilic iron oxide nanoparticles (IONPs) for protein purification by means of ultrafiltration. Before membrane fabrication, the dispersion stability of the IONPs was enhanced by the addition of a stabilizer, namely, citric acid (CA). Next, PSf–IONP–CA nanocomposite hollow-fiber membranes were prepared via a dry–wet spinning process and then characterized in terms of their hydrophilicity and morphology. Ultrafiltration and adsorption experiments were then conducted with bovine serum albumin as a model protein. The results that an IONP/CA weight ratio of 1:20 contributed to the most stable IONP dispersion. It was also revealed that the membrane incorporated with IONP–CA at a weight ratio of 1:20 exhibited the highest pure water permeability (58.6 L m⁻² h⁻¹ bar⁻¹) and protein rejection (98.5%) while maintaining a low protein adsorption (3.3 μg/cm²). The addition of well-dispersed IONPs enhanced the separation features of the PSf hollow-fiber membrane for protein purification. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47502.     

Development of a disposable electrode modified with carbonized,graphene‐loaded nanofiber for the detection of dopamine in human serum

A one‐step electrode surface modification is proposed in which a disposable, screen‐printed carbon electrode is functionalized with carbonized, electrospun polyacrylonitrile (PAN)‐loaded graphene (G) nanoparticles to form a composite, CPAN5G‐4x. The electrochemical behavior of the CPAN5G‐4x electrode was examined by cyclic voltammetry and electrochemical impedance spectroscopy. Scanning electron microscopy and X‐ray diffraction were used to characterize the surface morphology and physical properties of the carbonized composite nanofibers before and after modification. The modified electrode was found to be effective for the detection of dopamine (DA) using square‐wave voltammetry (SWV) in the presence of interfering substances such as ascorbic acid and uric acid. With the addition of sodium dodecyl sulfate (SDS) to an optimized solution of phosphate‐buffered saline (PBS) at a pH of 2, the fabricated electrode exhibited enhanced electrocatalytic activity toward the oxidation of DA relative to PBS without SDS at a pH of 7.4. The SWV current displayed a linear response to DA concentrations ranging from 0.5 to 100 μM, with a limit of detection of 70 nM (S/N = 3) and a sensitivity of 1.4258 μA μM^?1 cm^?2. Finally, the CPAN5G‐4x electrode was used to determine DA levels in human serum. The modified electrode can potentially be harnessed for further electrochemical biosensor applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40858.     

Template process for engineering the photoluminescence of PVK and PPV-based nanowires

Blends or stacking layers of two complementary materials are the dominant methods to get a strong donor-acceptor behavior for in-solution-processed thin film devices. These methods result in different local arrangement of the two species, a central point for tuning the donor-acceptor. In this work, it is proposed to organize a donor (poly[vinylcarbazole], PVK) and an acceptor (poly[para-phenylenevinylene], PPV) in a nanowire geometry. A two-step template process was used to fabricate coaxial nanowires with PPV and PVK alternatively as the core or the shell material, as shown by morphological characterization and micro-Raman spectroscopy study. The differences of the photoluminescence properties of these two types of coaxial nanowires compared with those of PVK-PPV blend nanowires and of pure PPV and PVK nanowires are discussed by considering the local polymer arrangement and the exciton diffusion length. Nano-sources, as well as nanostructured light emitting diodes, could take advantage of this 1D-like morphology for light emission control. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48201.     

Impact of thermal processing or solvent casting upon crystallization of PLA nanocellulose and/or nanoclay composites

Here, we present how processing (solvent casting or isothermal crystallization) impacts crystallinity of poly(lactic acid) (PLA) and its nanocomposites (PLA/1 wt % cellulose nanofibers (CNFs), PLA/1 wt % nanoclay (C30B) or PLA/1 wt % CNF/1 wt % C30B. Polarized optical microscopy demonstrated a heterogeneous nucleation process during isothermal crystallization leading to smaller homogeneously distributed spherulites. With solvent casting, no effect on morphology was observed with respect to the nanoparticles, but an increased spherulite size was observed at higher temperatures. This fact raises significant concerns regarding the suitability of solvent casting as a lab-scale procedure to investigate materials. Additionally, combining the reinforcing agents, CNF, and C30B, did not increase nucleation rate, in contrast with the general tendency, where the incorporation of both particles led to improved properties (e.g., thermomechanical and barrier properties). However, a combination of C30B and CNF did lead to an overall increase in the rigid amorphous fraction and a reduced mobile amorphous fraction. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47486.