Facile fabrication of nanocomposite microspheres with polymer cores and magnetic shells by Pickering suspension polymerization

Pickering suspension polymerization was used to prepare magnetic polymer microspheres that have polymer cores enveloped by shells of magnetic nanoparticles. Styrene was emulsified in an aqueous dispersion of Fe₃O₄ nanoparticles using a high shear. The resultant Pickering oil-in-water (o/w) emulsion stabilized solely by magnetic nanoparticles was easily polymerized at 70 °C without stirring. Fe₃O₄ nanoparticles act as effective stabilizers during polymerization and as building blocks for creating the organic–inorganic hybrid nanocomposite after polymerization. The fabricated magnetic nanocomposites were characterized by FTIR, XRD, TGA, DSC, GPC, XPS and SEM. The structures of the polymer core and the nanoparticle shell were analyzed. We investigated the effects on the products of the weight of Fe₃O₄ nanoparticles used to stabilize the original Pickering emulsions. Pickering suspension polymerization provides a new route for the synthesis of a variety of hybrid nanocomposite microspheres with supracolloidal structures.     

Synthesis of pH-sensitive hollow polymer microspheres with movable magnetic core

The pH-sensitive hollow poly(N,N′-methylenebisacrylamide-co-methacrylic acid) (P(MBAAm-co-MAA)) microspheres with movable magnetic/silica (Fe₃O₄/SiO₂) cores were prepared by the selective removal of poly(methacrylic acid) (PMAA) layer in ethanol/water from the corresponding Fe₃O₄/SiO₂/PMAA/P(MBAAm-co-MAA) tetra-layer microspheres, which were synthesized by the distillation precipitation copolymerization of N,N′-methylenebisacrylamide (MBAAm) and methacrylic acid (MAA) in the presence of Fe₃O₄/SiO₂/PMAA tri-layer microspheres as seeds in acetonitrile with 2,2′-azobisisobutyronitrile (AIBN) as the initiator. The Fe₃O₄/SiO₂/PMAA tri-layer microspheres were afforded by the distillation precipitation polymerization of MAA with 3-(methacryloxy)propyl trimethoxysilane (MPS)-modified Fe₃O₄/SiO₂ core-shell particles as the seeds. The functional multi-layer inorganic/polymer microspheres and the corresponding hollow polymer microspheres with movable magnetic cores were characterized with transmission electron microscopy (TEM), Fourier-transform infrared (FT-IR) spectra, dynamic light scattering (DLS), and vibrating sample magnetometer (VSM).     

Preparation and characterization of magnetic composite microspheres using a free radical polymerization system consisting of DPE

In this paper, a free radical polymerization system consisting of DPE was used to prepare magnetic composite microspheres. Fe₃O₄/P(AA-MMA-St) core-shell magnetic composite microspheres have been synthesized by copolymerization of acrylic acid, methyl methacrylate and styrene using DPE as radical control agent in the presence of Fe₃O₄ nanoparticles. The structure and properties of the magnetic composite microspheres were analyzed by FTIR, ¹H NMR, SEC-MALLS, TEM, TGA, VSM and other instruments, and the formation mechanism of composite microspheres was supposed by those results. It was found that the Fe₃O₄/P(AA-MMA-St) microspheres were nano-size with relatively homogeneous particle size distribution, perfect sphere-shaped morphologies, superparamagnetism with a saturation magnetization of 18.430 emu/g, and high magnetic content with a value of 40%. ¹H NMR and TEM analysis indicated that at the first stage of polymerization, a DPE-containing copolymer of acrylic acid, methyl methacrylate formed and was then absorbed on the surface of Fe₃O₄ nanoparticles. Contact angle analysis indicated that the DPE-containing copolymer improved hydrophobicity of Fe₃O₄ nanoparticles through chemical absorption. In the second step polymerization, certain amount of monomers of styrene and residue methacrylate were initiated by the DPE-containing copolymer on the Fe₃O₄ nanoparticles' surface and resulted in the formation of Fe₃O₄/P(AA-MMA-St) composite microspheres.     

Multihollow nanocomposite microspheres with tunable pore structures by templating Pickering double emulsions

Micrometer-sized dual nanocomposite polymer microspheres with tunable pore structures were fabricated using a simple and straightforward method based on Pickering double emulsions. First, a primary water-in-styrene (oil) emulsion (w₁/o) was prepared using the hydrophobic silica nanoparticles as a particulate emulsifier without any molecular surfactants. Then, a water-in-styrene-in-water (w₁/o/w₂) Pickering emulsion was produced by the emulsification of the primary w₁/o emulsion into water using Fe₃O₄ nanoparticles as external emulsifier. The big styrene droplets containing small water droplets were polymerized after the formation of the double emulsions. Nanocomposite polystyrene microspheres with a multihollow structure were obtained and their morphological structures were studied by scanning electron microscopy (SEM). The pore structure of the microspheres could be tuned by the volume ratio of the internal water phase to the medium oil phase (w₁:o) of the primary emulsions. With increasing w₁:o from 1:8 to 4:1, the amount of the pores in one microsphere increased gradually and the pore structures changed from close to interconnected. The resulting multihollow microspheres had a responsive ability to magnetic stimulus due to the existence of Fe₃O₄ nanoparticles. This kind of multihollow hybrid polymer microspheres is expected to have a wide potential application in materials science and biotechnology.     

Controlled release of protein from magnetite–chitosan nanoparticles exposed to an alternating magnetic field

In this research, the controlled release of proteins from magnetite (Fe₃O₄)–chitosan (CS) nanoparticles exposed to an alternating magnetic field is reported. Fe₃O₄–CS nanoparticles were synthesized with sodium tripolyphosphate (TPP) molecules as a crosslinking reagent. Bovine serum albumin (BSA) was used as a model protein, and its controlled release studied through the variation of the frequency of an alternating magnetic field. The results show the successful coating of CS and BSA on the Fe₃O₄ nanoparticles with an average diameter of 50 nm. Intermolecular interactions of TPP with CS and BSA were confirmed by Fourier transform infrared spectroscopy. The application of low‐frequency alternating magnetic fields to such magnetic CS nanoparticles enhanced the protein release properties, in which the external magnetic fields could switch on the unloading of these nanoparticles. We concluded that enhanced BSA release from nanoparticles exposed to an alternating magnetic field is a promising method for achieving both the targeted delivery and controlled release of proteins. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43335.     

Hybrid nanocomposites based on superparamagnetic and ferromagnetic particles: A comparison of their magnetic and dielectric properties

Nanocomposites of magnetic nanoparticles and polymer matrices combine the properties of their components, and as such are good examples of functional nanomaterials with excellent application potential. Against this background, experimental and theoretical studies of such composites are of great interest. In this study we aim to provide insight into the static and dynamic magnetic response, as well as the dielectric response, of magnetic nanocomposites subjected to external magnetic and electric fields. We directly compare the behavior of polyurethane films doped with superparamagnetic Fe₃O₄, and blocked ferromagnetic CoFe₂O₄ nanoparticles. While a reversible, Langevin magnetization curve is observed for Fe₃O₄@PU films, hysteretic magnetic behavior is found in case of CoFe₂O₄@PU films. The hysteresis observed for CoFe₂O₄ nanoparticles can be explained by interactions at the interface between particles and polymer matrix in conjunction with its ferromagnetic nature. The results of dielectric spectroscopy experiments revealed different effects of Fe₃O₄ and CoFe₂O₄ nanoparticles on polymer dynamics.     

Enhanced photocatalytic degradation of tri-chlorophenol by Fe3O4@TiO2@Au photocatalyst under visible-light

Heterogeneous Fe₃O₄@TiO₂@Au core-shell microspheres, a facile and highly efficient catalyst have been fabricated by a simple surface modification. The fabrication process involved the coating of TiO₂ nanoshell onto the magnetic core using by sol-gel process, and then the anchoring of Au nanoparticles onto the surface of the Fe₃O₄@TiO₂ microspheres through the wet chemical reaction of 3-aminopropyltriethoxysilane (APTES). The as-synthesized Fe₃O₄@TiO₂ microspheres exhibited a narrow size distribution, with a typical size of 350 nm and shell thickness of 25 nm. The Fe₃O₄@TiO₂@Au microspheres can be easily collected by applying external magnetic field due to the magnetic property of core Fe₃O₄ particles. Compared to unmodified Fe₃O₄@TiO₂ microspheres, the Fe₃O₄@TiO₂@Au microspheres showed higher photocatalytic activity for 2, 4, 6-trichlorophenol (TCP). The photocatalytic efficiency of the Fe₃O₄@TiO₂ microspheres was 28% after 40 min irradiation while, the efficiency of Fe₃O₄@TiO₂@Au microspheres was 98% at the same condition.     

New Magnetic Polymer Nanocomposites on the Basis of Isotactic Polypropylene and Magnetite Nanoparticles for Adsorption of Ultrahigh Frequency Electromagnetic Waves

In this study, we report about the preparation of magnetic polymer nanocomposites on the basis of isotactic polypropylene and magnetite Fe₃O₄ nanoparticles. The structure and composition of polymer nanocomposite materials have been studied by scanning electron microscopy, atomic force microscopy, and X-ray dispersive analysis. The magnetic properties of polymer nanocomposites based on PP+Fe₃O₄have been investigated. It is found that not significant adhesion and agglomeration of nanoparticles occur, by increasing the nanoparticle content in polymer matrix up to 40%, and therefore they act as single-domain nanoparticles. The samples of nanocomposites based on PP+Fe₃O₄, with up to 40% content of Fe₃O₄, exhibit superparamagnetic properties. It was also found out that the magnetic polymer nanocomposite material based on PP+Fe₃O₄ is able to absorb ultrahigh frequency electromagnetic waves in the frequencies range from 0.1 to 30?GHz. The increase in Fe₃O₄ concentration from 5 to 40% at the 400?µm thicknesses of the films leads to an increase in absorption of electromagnetic waves of high frequency from 15 to 22.7%.     

Controlled preparation of Fe3O4/P (St-MA) magnetic composite microspheres by DPE method

In this work, controlled radical polymerization based on 1, 1-diphenylethylene (DPE method) was used to prepare magnetic composite microspheres. By this method, Fe₃O₄/P (St-MA) magnetic composite microspheres were prepared via copolymerization of styrene (St) and maleic anhydride (MA) using DPE as radical control agent in the presence of Fe₃O₄ nanoparticles. The structure and properties of the magnetic composite microspheres obtained were characterized by IR, ¹H-NMR, SEC-MALLS, TEM, TGA, VSM, DLS and other instruments. It was found that the DPE method allows the controlled preparation of magnetic composite microspheres, and Fe₃O₄/ P(St-MA) microspheres possess perfect sphere-shaped morphology, homogeneous particle size, carboxylic surface, superparamagnetism with a saturation magnetization of 14.704 emu/g, and magnetic content with a value of 25%.     

Preparation and sedimentation behavior of conductive polymeric nanoparticles

A facile route to prepare Fe₃O₄/polypyrrole (PPY) core-shell magnetic nanoparticles was developed. Fe₃O₄ nanoparticles were first prepared by a chemical co-precipitation method, and then Fe₃O₄/PPY coreshell magnetic composite nanoparticles were prepared by in-situ polymerization of pyrrole in the presence of Fe₃O₄ nanoparticles. The obtained nanoparticles were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM) and laser particle size analyzer. The images indicate that the size of Fe₃O₄ particles is about 10 nanometers, and the particles are completely covered by PPY. The Fe₃O₄/PPY core-shell magnetic composite nanoparticles are about 100 nanometers and there are several Fe₃O₄ particles in one composite nanoparticle. The yield of the composite nanoparticles was about 50%. The sedimentation behavior of Fe₃O₄/PPY core-shell magnetic nanoparticles in electrolyte and soluble polymer solutions was characterized. The experimental results indicate that the sedimentation of particles can be controlled by adjusting electrolyte concentration, solvable polymers and by applying a foreign field. This result is useful in preparing gradient materials and improving the stability of suspensions.     

Preparation and characterization of magnetic poly(styrene–glycidyl methacrylate) microspheres for highly efficient protein adsorption by two‐stage dispersion polymerization

Micrometer‐sized superparamagnetic poly(styrene–glycidyl methacrylate)/Fe₃O₄ spheres were synthesized by two‐stage dispersion polymerization with modified hydrophobic Fe₃O₄ nanoparticles, styrene (St), and glycidyl methacrylate (GMA). The morphology and properties of the magnetic Fe₃O₄–P (St‐GMA) microspheres were examined by scanning electron microscopy, transmission electron microscopy, vibrating sample magnetometry, thermogravimetric analysis, and attenuated total reflectance. The average size of the obtained magnetic microspheres was 1.50 μm in diameter with a narrow size distribution, and the saturation magnetization of the magnetic microspheres was 8.23 emu/g. The magnetic Fe₃O₄–P (St‐GMA) microspheres with immobilized iminodiacetic acid–Cu²⁺ groups were used to investigate the adsorption capacity and selectivity of the model proteins, bovine hemoglobin (BHb) and bovine serum albumin (BSA). We found that the adsorption capacity of BHb was as high as 190.66 mg/g of microspheres, which was 3.20 times greater than that of BSA, which was only 59.64 mg/g of microspheres as determined by high‐performance liquid chromatography. With a rather low nonspecific adsorption, these microspheres have great potential for protein separation and purification applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43005.     

Adsorption of reactive yellow 145 onto chitosan coated magnetite nanoparticles

Removal of dyes from the industrial discharge water is an important issue for safety of the environment. In this study, magnetic (magnetite, Fe₃O₄) nanoparticles were coated with chitosan (CS) and the efficiency of these chitosan coated magnetic nanoparticles (Fe₃O₄‐CS) for the adsorption of a reactive textile dye (Reactive Yellow 145, RY145) was examined first time in literature. TEM, XRD, and EPR results revealed that the thickness of the coat was about 2–5 nm, no phase change in the spinel structure of magnetic particles existed after coating, and particles had paramagnetic property, respectively. Adsorption of RY145 on Fe₃O₄‐CS nanoparticles occurs according to Langmuir model in the temperature range 25°C–45°C with a maximum adsorption capacity of 47.62 mg g^?1 at 25°C, in aqueous media. Thermodynamic parameters demonstrated that the adsorption process was endothermic and spontaneous, and the maximum desorption of the dye was 80% over a single adsorption/desorption cycle. In this study, the high efficiency of the CS coated magnetic nanoparticles in the adsorption and removal of reactive dyes from water was shown on model RY145. This type of nanoparticles can be good candidates in industrial applications for the decolorization of waste waters. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of Fe3O4@SiO2@Ption–TiO2 hybrid composites with high efficient UV–visible light photoactivity

Platinum ion doped magnetic TiO₂ (Fe₃O₄@SiO₂@Pt_ion–TiO₂) hybrid microspheres with uniform magnetic cores were synthesized and characterized in this work. The results indicate that the photoactivity of Fe₃O₄@SiO₂@Pt_ion–TiO₂ is much higher than Fe₃O₄@SiO₂@TiO₂ for the decolorization of acid orange 20 under UV–visible light irradiation. The trend for the final degradation ratio with Fe₃O₄@SiO₂@Pt_ion–TiO₂ is quite small, even after seven repetitive experiments. These data indicate that the magnetic microspheres possess the potential to be effective and stable catalysts. The results demonstrate that the Pt ion doped magnetic catalyst meets the needs for both immobilization and high photoactivity.     

Electrospun polyacrylonitrile nanocomposite fibers reinforced with Fe3O4 nanoparticles: Fabrication and property analysis

The manufacturing of pure polyacrylonitrile (PAN) fibers and magnetic PAN/Fe₃O₄ nanocomposite fibers is explored by an electrospinning process. A uniform, bead-free fiber production process is developed by optimizing electrospinning conditions: polymer concentration, applied electric voltage, feedrate, and distance between needle tip to collector. The experiments demonstrate that slight changes in operating parameters may result in significant variations in the fiber morphology. The fiber formation mechanism for both pure PAN and the Fe₃O₄ nanoparticles suspended in PAN solutions is explained from the rheologial behavior of the solution. The nanocomposite fibers were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectrophotometer, and X-ray diffraction (XRD). FT-IR and XRD results indicate that the introduction of Fe₃O₄ nanoparticles into the polymer matrix has a significant effect on the crystallinity of PAN and a strong interaction between PAN and Fe₃O₄ nanoparticles. The magnetic properties of the nanoparticles in the polymer nanocomposite fibers are different from those of the dried as-received nanoparticles.     

Preparation of chitosan‐coated magnetite nanoparticles and application for immobilization of laccase

In this study, immobilization of laccase (L) enzyme on magnetite (Fe₃O₄) nanoparticles was achieved, so that the immobilized enzyme could be used repeatedly. For this purpose, Fe₃O₄ nanoparticles were coated and functionalized with chitosan (CS) and laccase from Trametes versicolor was immobilized onto chitosan‐coated magnetic nanoparticles (Fe₃O₄‐CS) by adsorption or covalent binding after activating the hydroxyl groups of chitosan with carbodiimide (EDAC) or cyanuric chloride (CC). For chitosan‐coated magnetic nanoparticles, the thickness of CS layer was estimated as 1.0–4.8 nm by TEM, isoelectric point was detected as 6.86 by zeta (ζ)‐potential measurements, and the saturation magnetization was determined as 25.2 emu g^?1 by VSM, indicating that these nanoparticles were almost superparamagnetic. For free laccase and immobilized laccase systems, the optimum pH, temperature, and kinetic parameters were investigated; and the change of the activity against repeated use of the immobilized systems were examined. The results indicated that all immobilized systems retained more than 71% of their initial activity at the end of 30 batch uses. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization of stabilized porous magnetite core–shell nanogel composites based on crosslinked acrylamide/sodium acrylate copolymers

Stabilized and dispersed superparamagnetic porous nanogels based on sodium acrylate (AA‐Na) and acrylamide (AM) in a surfactant‐free aqueous system were synthesized via solution polymerization at room temperature. The formation of magnetite nanoparticles was confirmed and their properties characterized using Fourier transform infrared spectroscopy. Extensive characterization of the magnetic polymer particles using transmission electron microscopy (TEM), dynamic light scattering and zeta potential measurements revealed that Fe₃O₄ nanoparticles were incorporated into the shells of poly(AM/AA‐Na). The average particle size was 5–8 nm as determined from TEM. AM/AA‐Na nanoparticles with a diameter of about 11 nm were effectively assembled onto the negatively charged surface of the as‐synthesized Fe₃O₄ nanoparticles via electrostatic interaction. Crosslinked magnetite nanocomposites were prepared by in situ development of surface‐modified magnetite nanoparticles in an AM/AA‐Na hydrogel. Scanning electron microscopy was used to study the surface morphology of the prepared composites. The morphology, phase composition and crystallinity of the prepared nanocomposites were characterized. Atomic force microscopy and argon adsorption–desorption measurements of Fe₃O₄.AM/AA indicated that the architecture of the polymer network can be a hollow porous sphere or a solid phase, depending on the AA‐Na content. © 2013 Society of Chemical Industry     

Preparation and characterization of micron‐sized non‐porous magnetic polymer microspheres with immobilized metal affinity ligands by modified suspension polymerization

A novel preparation method of micron‐sized non‐porous magnetic polymer microspheres with immobilized metal affinity ligands was developed. A modified suspension polymerization of methacrylate (MA) and divinylbenzene (DVB) was performed in the presence of oleic acid‐coated magnetic Fe₃O₄ nanoparticles to obtain magnetic poly (methacrylate‐divinylbenzene) (mPMA‐DVB) microspheres. Through ammonolysis using ethylenediamine (EDA) and subsequent carboxymethylation with chloroacetic acid, magnetic polymer microspheres with chelate ligands of iminodiacetic acid (IDA) were obtained. Charging with copper ions resulted in magnetic polymer microspheres capable of binding proteins that display metal affinity. The morphology, magnetic properties, and composition of magnetic polymer microspheres were characterized with scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), and Fourier transform infrared spectroscopy (FTIR), respectively. Bovine hemoglobin (BHb) was adopted as a model protein to investigate their affinity adsorption capacity. It was found that the adsorption capacity was as high as 168.2 mg/g microspheres and with rather low non‐specific adsorption. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2174–2180, 2005     

Chitosan- and dehydroascorbic acid-coated Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles: preparation,characterization and their potential as draw solute in forward osmosis process

Forward osmosis (FO) is a natural osmosis process that has attracted a significant attention due to its many advantages. However, the development of FO process depends on the development of proper draw solutions. In this work, chitosan (CS)-coated Fe₃O₄ nanoparticles and dehydroascorbic acid (DHAA)-coated Fe₃O₄ nanoparticles were successfully synthesized by co-precipitation method and their performance as draw solutes was investigated for application in FO systems. CS and DHAA could improve the surface hydrophilicity of the Fe₃O₄ nanoparticles. The synthesized nanoparticles were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometry (VSM) which the results presented a small size, crystalline morphology and high magnetization value for their structure as well as a good dispersion in water. Cellulose triacetate/cellulose acetate (CTA/CA)-based membranes were also prepared by immersion precipitation and used as FO membranes. The synthesized FO membranes were characterized by FESEM. The performance evaluation of synthesized nanoparticles revealed that the water flux of Fe₃O₄ nanoparticles capped with DHAA was higher than that of the chitosan-coated Fe₃O₄ nanoparticles. At the end of the process, the Fe₃O₄ nanoparticles were easily separated from the diluted draw solution by applying the magnetic field.     

Porous Fe3O4/C microspheres for efficient broadband electromagnetic wave absorption

Porous Fe₃O₄/C microspheres, which were Fe₃O₄ nanocrystals (～8?nm) embedded in an open nanostructured carbon network, were successfully synthesized via a facile hydrothermal process. The porous Fe₃O₄/C microspheres possessed many distinct attributes that facilitate efficient broadband electromagnetic wave absorption (EMWA). EMWs were attenuated through multiple reflections and absorption in the 3D interconnected porous structure of the microspheres; these processes collectively improved the interaction between the EMWs and the absorber. Additionally, the carbon network and embedded Fe₃O₄ nanoparticles caused significant dielectric losses and magnetic losses, respectively, which also enhanced EMWA. The EMWA characteristics of the microspheres could be precisely tuned via changing the carbon content to achieve optimized impedance matching. Porous Fe₃O₄/C microspheres with a 71.5?wt% carbon content displayed particularly impressive EMWA properties: a maximum reflection loss (RL) value of ??31.75 across broad band frequencies in the range of 7.76–12.88?GHz (RL < ?10?dB) at an absorber thickness of 3.0?mm. These excellent EMWA properties may be attributed to both dielectric loss (carbon) and magnetic loss (Fe₃O₄). Additionally, the 3D interconnected porous structure of the Fe₃O₄/C microspheres is especially favorable for impedance matching.     

Thermoresponsive hollow magnetic microspheres with hyperthermia and controlled release properties

Thermoresponsive hollow magnetic microspheres consisting of a hollow magnetic core, a carbon shell, and a smart polymer layer are presented in this article. A carbon nanomaterial was used as a steric stabilizer for Fe₃O₄ nanoparticles and a supporter for polymer. The thermoresponsive monomer, N‐isopropyl acrylamide, was grafted on the carbon‐encapsulate hollows by surface radical polymerization. The experimental results indicate that the composites had a phase‐transition temperature around 43°C and a saturation magnetization of 56.9 emu/g; this showed apparent thermosensitivity and magnetism. The performances in hyperthermia evaluated by an inductive magnetic field showed that the hybrid microspheres had a specific absorption rate of 240 W/g. The model drug, 5‐fluorouracil, was loaded in and released from the microspheres with different release rates at 35 and 50°C. This demonstrated that the as‐synthesized microspheres had a thermotriggered release ability and would be a good drug carrier in the biomedical field. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42617.