Microwave‐Assisted Synthesis of Magnetic Hydroxyapatite for Removal of Heavy Metals from Groundwater

A simple, fast, and economic methodology to fabricate a highly efficient superparamagnetic Fe₃O₄/hydroxyapatite nanocomposite (MHAP) was successfully developed. Hydroxyapatite was functionalized with magnetite nanoparticles through coprecipitation‐assisted microwave processes to improve the magnetic properties. The synthesized magnetic hybrid adsorbent matrix was investigated by different methods. Transmission electron microscopy demonstrated a good impregnation of Fe₃O₄ on the hydroxyapatite matrix with uniform morphology. Magnetic hysteresis measurement revealed that MHAP nanocomposites exhibit excellent strong, soft‐magnetic properties. The synergistic effect was an evidence for iron and manganese ion removal, enlightening their potentialities in treatment of polluted ground water.     

Room temperature in situ chemical synthesis of Fe3O4/graphene

A simple, cost-effective, efficient, and green approach to synthesize iron oxide/graphene (Fe₃O₄/rGO) nanocomposite using in situ deposition of Fe₃O₄ nanoparticles on reduced graphene oxide (rGO) sheets is reported. In the redox reaction, the oxidation state of iron(II) is increased to iron(III) while the graphene oxide (GO) is reduced to rGO. The GO peak is not observed in the X-ray diffraction (XRD) pattern of the nanocomposite, thus providing evidence for the reduction of the GO. The XRD spectra do have peaks that can be attributed to cubic Fe₃O_4. The field emission scanning electron microscopy (FESEM) images show Fe₃O₄ nanoparticles uniformly decorating rGO sheets. At a low concentration of Fe²⁺, there is a significant increase in the intensity of the FESEM images of the resulting rGO sheets. Elemental mapping using energy dispersive X-ray (EDX) analysis shows that these areas have a significant Fe concentration, but no morphological structure could be identified in the image. When the concentration of Fe²⁺ is increased, the Fe₃O₄ nanoparticles are formed on the rGO sheets. Separation of the Fe₃O₄/rGO nanocomposite from the solution could be achieved by applying an external magnetic field, thus demonstrating the magnetic properties of the nanocomposite. The Fe₃O₄ particle size, magnetic properties, and dispersibility of the nanocomposite could be altered by adjusting the weight ratio of GO to Fe²⁺ in the starting material.     

Biodegradable magnetic‐sensitive shape memory poly(ɛ‐caprolactone)/Fe3O4 nanocomposites

A novel biodegradable magnetic‐sensitive shape memory poly(?‐caprolactone) nanocomposites, which were crosslinked with functionalized Fe₃O₄ magnetic nanoparticles (MNPs), were synthesized via in situ polymerization method. Fe₃O₄ MNPs pretreated with γ‐(methacryloyloxy) propyl trimethoxy silane (KH570) were used as crosslinking agents. Because of the crosslinking of functionalized Fe₃O₄ MNPs with poly(?‐caprolactone) prepolymer, the properties of the nanocomposites with different content of functionalized Fe₃O₄ MNPs, especially the mechanical properties, were significantly improved. The nanocomposites also showed excellent shape memory properties in both 60 °C hot water and alternating magnetic field (f = 60, 90 kHz, H = 38.7, 59.8 kA m^?1). In hot water bath, all the samples had shape recovery rate (R_r) higher than 98% and shape fixed rate (R_f) nearly 100%. In alternating magnetic field, the R_r of composites was over 85% with the highest at 95.3%. In addition, the nanocomposites also have good biodegradability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45652.     

Removal of heavy metal ions from aqueous solutions by radiation‐induced chitosan/(acrylamidoglycolic acid‐co‐acrylic acid) magnetic nanopolymer

An effective method was developed to isolate toxic heavy metal ions from the aqueous solution by the magnetic nanopolymers. The magnetic sorbent was prepared with radiation‐induced crosslinking polymerization of chitosan (CS), 2‐acrylamido‐glycolic acid (AMGA), and acrylic acid (AAc), which stabilized by magnetite (Fe₃O₄) as nanoparticles. The formation of magnetic nanoparticles (MNPs) into the hydrogel networks was confirmed by Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy, and Scanning electron microscopy, which revealed the formation of MNPs throughout the hydrogel networks. The swelling behavior of the hydrogels and magnetic ones was evaluated at different pH values. The adsorption activity for heavy metals such as Cu²⁺ and Co²⁺ by nonmagnetic and magnetic hydrogels, Fe₃O₄/CS/(AMGA‐co‐AAc), in terms of adsorption amount was studied. It was revealed that hydrogel networks with magnetic properties can effectively be used in the removal of heavy metal ions pollutants and provide advantageous over conventional ones. POLYM. ENG. SCI., 55:1441–1449, 2015. © 2015 Society of Plastics Engineers     

Magnetic nanoparticles embedded in pectin‐based hydrogel for the sustained release of diclofenac sodium

A supermagnetic polysaccharide‐based nanocomposite gel has been developed as a potential drug delivery system. The gel was made via graft copolymerization of 2‐acrylamido‐2‐methylpropanesulfonic acid on pectin using ammonium peroxodisulfate as an initiator and N,N‐methylenebisacrylamide as a crosslinker under microwave irradiation. The magnetic nanoparticles (MNPs) were incorporated within the gel network via an in situ method of diffusion of Fe²⁺/Fe³⁺ followed by reduction with ammonia solution. The graft copolymer gel and its nanocomposite were characterized using attenuated total reflection Fourier transform infrared spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, field‐emission scanning electron microscopy, energy‐dispersive X‐ray spectroscopy and transmission electron microscopy. The magnetic properties of the nanocomposite were measured using a vibrating sample magnetometer and mechanical properties using a tensile compressive tester. The gel was evaluated for adsorption and release of the drug diclofenac sodium. The presence of MNPs is observed to enhance significantly the mechanical properties, swelling capacity, drug loading and release ability of the graft polymer gel. The increased porosity of the gel network and higher surface area of MNPs allowed for 20% higher adsorption of diclofenac sodium molecules compared to the parent nonmagnetic gel. About 95% of the loaded drug was released from the MNP‐containing gel. The drug release pattern followed first‐order kinetic model and the Higuchi square root model, indicating swelling‐controlled diffusion to be the mode of drug release. © 2018 Society of Chemical Industry     

Synthesis of Magnetic Fe3O4 Modified Graphene Nanocomposite and its Application on the Adsorption of some Dyes from Aqueous Solution

A novel magnetic Fe₃O₄ modified reduced graphene oxide nanocomposite (Fe₃O₄@SiO₂-rGO) was prepared by a covalent bonding method. The morphology and properties of the Fe₃O₄@SiO₂-rGO were characterized by transmission electron microscopy and X-ray diffraction. The prepared Fe₃O₄@SiO₂-rGO was tested as an efficient adsorbent for the removal of some dyes from aqueous solution for the first time. The performance of Fe₃O₄@SiO₂-rGO was evaluated using methylene blue and neutral red as model compounds. Experiments were carried out to investigate the adsorption kinetics and adsorption capacity of the adsorbent and the effect of the adsorbent dosage and sample solution pH on the removal of the dyes. Kinetic data were well fitted by pseudo second-order model. The Langmuir model and the Freundlich model were used to study the adsorption isotherms. The Fe₃O₄@SiO₂-rGO nanocomposite showed to be a highly efficient adsorbent with the advantage of separation convenience. The thermodynamic parameters indicated that the adsorption of the dyes onto the Fe₃O₄@SiO₂-rGO was a spontaneous process.     

Efficient removal of Cu(II) using amino‐functionalized superparamagnetic nanoparticles prepared via SI‐ATRP

An amino‐functionalized nano‐adsorbent (DETA‐MNPs) was prepared by a process involving: (1) synthesis of superparamagnetic Fe₃O₄ nanoparticles; (2) introduction of amino groups after which ATRP initiator was anchored; (3) grafting of glycidyl methacrylate (GMA) via SI‐ATRP; and (4) ring‐opening reaction of epoxy groups with diethylenetriamine (DETA). The nano‐adsorbent was characterized by Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), transmission electron microscope (TEM), and vibrating sample magnetometer (VSM) and applied to remove Cu(II) in batch experiments. The effects of pH, Cu(II) concentrations, solution ionic strength, and contact time were investigated. The results show that the DETA‐MNPs are spherical with cubic spine structure, high saturation magnetization (41.9 emu g^?1), and an average diameter of 10 nm. The maximum Cu(II) adsorption capacity achieves 83.33 mg g^?1 at pH 5.0 by Langmuir model. The adsorption process is highly pH‐dependent and reaches equilibrium within 20 min. Furthermore, the DETA‐MNPs exhibit excellent dispersibility and reusability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42859.     

Magnetic removal of crystal violet from aqueous solutions using polysaccharide‐based magnetic nanocomposite hydrogels

Magnetic Fe₃O₄@SiO₂ starch‐graft‐poly(acrylic acid) (SPAA) nanocomposite hydrogels were prepared and used as absorbents for removal of crystal violet from aqueous solutions. Dynamic swelling, effect of contact time, absorption kinetics and nanocomposite hydrogel mass for removal of crystal violet dyes from aqueous solutions were studied. Fourier transform infrared spectroscopy, scanning electron microscopy and vibrating sample magnetometer measurements were used for the characterization of the nanocomposite hydrogels. The nanocomposite hydrogels had high magnetic sensitivity under an external magnetic field, which allowed their magnetic separation from water, thus avoiding secondary pollution. The results obtained are very promising since: (i) high levels of colour removal (>85%) were achieved with low magnetic SPAA nanocomposite mass and (ii) the magnetic SPAA nanocomposites can be successfully used several times as absorbents of crystal violet in aqueous solution without needing filtration. © 2012 Society of Chemical Industry     

Novel carboxyl functional spherical electromagnetic polypyrrole nanocomposite polymer particles with good magnetic and conducting properties

Magnetic conducting nanoparticles with reactive functional groups are attractive materials for applications in electromagnetic interference shielding, magneto‐optical storage, biomedical sensing, gas and humidity sensors, flexible electronics etc. The objective of this work was to prepare carboxyl functionalized polypyrrole (PPy) nanocomposite particles having good magnetic properties. Electromagnetic PPy nanostructures, abbreviated as PPy/γ‐Fe₂O₃, were first prepared by a chemical one‐step method. In this reaction process FeCl₃ is used as an oxidant for the polymerization of pyrrole and as a source of Fe³⁺ for the formation of γ‐Fe₂O₃. The formation of γ‐Fe₂O₃ is also aided by the initial presence of Fe²⁺, and p‐toluenesulfonic acid (p‐TSA) acted as a dopant. The effects of different stabilizers on the stability and morphology of PPy/γ‐Fe₂O₃ particles were evaluated. The presence of citric acid/sodium dodecyl sulfate during chemical oxidative polymerization produced a relatively stable PPy/γ‐Fe₂O₃ colloidal emulsion. PPy/γ‐Fe₂O₃/poly(methylmethacrylate‐methacrylic acid) (PPy/γ‐Fe₂O₃/P(MMA‐MAA)) nanocomposite polymer particles were then prepared by the seeded copolymerization of MMA and MAA in the presence of magnetic PPy/γ‐Fe₂O₃ nanocomposite seed particles. The structure and morphology of the prepared nanocomposites were confirmed by different instrumental techniques such as Fourier transform IR spectroscopy, UV?visible spectroscopy, electron micrographs, XRD and X‐ray photoelectron spectroscopy. The electrical and magnetic properties were also investigated. The carboxyl functional electromagnetic PPy nanocomposite polymer particles should be useful for the immobilization of drugs or biomolecules to design electrically stimulated drug delivery systems for modulating the activities of nerve, cardiac, skeletal muscle and bone cells. © 2016 Society of Chemical Industry     

Ag/αFe2O3-rGO novel ternary nanocomposites: Synthesis,characterization, and photocatalytic activity

In this research, novel ternary Ag/αFe₂O₃-rGO nanocomposites with various contents of GO were synthesized via a facile one-pot hydrothermal method. Ag/αFe₂O₃-rGO nanocomposites were characterized by X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectrometer (EDX), photoluminescence (PL) spectroscopy, and Fourier transform infrared (FTIR). The results showed that hematite nanoparticles and Ag nanoparticles were well decorated on the graphene surface. Photocatalytic activity of Ag/αFe₂O₃-rGO ternary nanocomposites and pure Ag/αFe₂O₃ was investigated for photodegradation of Congo red dye solution as a model pollutant under UV light irradiation. The ternary nanocomposite with 1.8?mg/ml GO aqueous solution concentration shows higher degradation efficiency under UV light irradiation than the pure Ag/αFe₂O₃ and the nanocomposites with other GO aqueous solution concentrations. It was observed that the adsorption of the dyes on the nanocomposites surface is dependent on the graphene content due to a decrease in the recombination rate, particles size, and increase charge carrier transfer. The results show that the Ag/αFe₂O₃-rGO nanocomposite can be used as an excellent photocatalytic material for degradation of Congo red dye in wastewater. A possible photocatalytic mechanism was proposed for degradation of Congo red dye.     

Synthesis and characterization of polyimide‐γ‐Fe2O3 nanocomposites

Novel polyimide‐γ‐Fe₂O₃ hybrid nanocomposite films (PI/γ‐Fe₂O₃) has been developed from the poly(amic acid) salt of oxydianiline with different weight percentages (5, 10, 15 wt %) of γ‐Fe₂O₃ using tetrahydrofuran (THF) and N,N‐dimethylacetamide (DMAc) as aprotic solvents. The prepared polyimide‐γ‐Fe₂O₃ nanocomposite films were characterized for their structure, morphology, and thermal behavior employing Fourier transform infrared spectroscopy (FTIR), scanning electron micrograph (SEM), transmission electron micrograph (TEM), X‐ray diffraction (XRD), ¹³C‐NMR, and thermal analysis (TGA/DSC) techniques. These studies showed the homogenous dispersion of γ‐Fe₂O₃ in the polyimide matrix with an increase in the thermal stability of the composite films on γ‐Fe₂O₃ loadings. Magnetization measurements (magnetic hysteresis traces) have shown very high values of coercive force indicating their possible use in memory devices and in other related applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 834–840, 2007     

Novel polyurethane rigid foam/organically modified iron oxide nanocomposites

Magnetic polyurethane rigid foam nanocomposites were synthesized by incorporation of surface functionalized iron oxide nanoparticles with 3‐aminopropyltriethoxysilane (APTS). Magnetite nanoparticles (MNPs) and Fe₃O₄@APTS were synthesized via co‐precipitation and sol–gel methods, respectively. The main purpose of the surface modification of MNPs was the formation of hydrogen bond between amino groups of Fe₃O₄@APTS with the urethane groups to improve magnetic and thermal properties of the nanocomposites. The effect of different amounts of Fe₃O₄@APTS on the thermal and magnetic behavior of resultant nanocomposite was investigated and the optimum percentage of nanostructure in foam formulation was defined. POLYM. COMPOS., 38:877–883, 2017. © 2015 Society of Plastics Engineers     

Separation of Arsenic from Aqueous Solutions by Amino-Functionalized γ-Fe2O3-β-Zeolite

In this research, γ-Fe₂O₃-β-zeolite nanocomposite was synthesized and functionalized by 3-amino propyl trimethoxysilane. The magnetic functionalized adsorbent was characterized by FTIR, X-ray diffraction, thermal analysis, vibrating sample magnetometry, scattering electron microscopy, and N₂ adsorption-desorption techniques. The adsorbent was then used for adsorption of arsenic from aqueous solutions. At optimized conditions the adsorption capacity of 30 mg.g^?1 was obtained, which was higher than the previously reported values. The loaded adsorbent was easily separated from the solution by applying an external magnetic field. Regeneration of the adsorbent by NaOH solution indicated that 97% of the initial capacity was remained after four adsorption-regeneration cycles.     

A recyclable β‐cyclodextrins‐based supramolecular adsorbent for removal of organic dyes

In this article, a novel recyclable β‐cyclodextrins (β‐CDs)‐based supramolecular adsorbent had been fabricated. With Fe₃O₄ magnetic nanoparticles as core, the adsorbent could be separated from water conveniently. Moreover, the hydrophobic β‐CDs caving had strong host‐guest interaction with organic compounds to form complexes. With the pH value changing, the stable complexes would disassemble to recover the adsorbent. Fourier transform infrared analysis, X‐ray diffraction measurement, transmission electron microscopy measurements, thermogravimetric analysis, and vibrating sample magnetometer analysis had been explored to confirm the structure and properties of supramolecular adsorbent. Congo red and Rhodamine B were used to characterize the adsorption capacity of adsorbent. By changing the parameters such as temperature, time, adsorbent dosage, and pH value indicated that the designed adsorbent could rapidly remove organic dyes from water with satisfactory removal effects and adsorbent recycling capacity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45084.     

Preparation and investigation of structural,magnetic, and microwave absorption properties of aluminum‐doped strontium ferrite/MWCNT/polyaniline nanocomposite at KU‐band frequency

Aluminum‐doped strontium hexaferrite nanoparticle SrAl_1.3Fe_10.7O₁₉ was prepared by sol–gel method and polyaniline (PANi) multiphase magnetic nanocomposite SrAl_1.3Fe_10.7O₁₉/MWCNT/PANi was synthesized through a sonochemical method by in situ polymerization. The morphology, structure, and magnetic properties of the nanocomposites are investigated by field emission scanning electron microscopy, X‐ray powder diffraction, Fourier transform infrared spectroscopy, and vibrating sample magnetometer. The electromagnetic interference shielding efficiency was evaluated in the KU‐band (12.4–18 GHz). The reflection loss (RL) value showed that the composites have an excellent absorbing property in the KU‐band, minimum ?24.93 dB at 16.40 GHz with a bandwidth of 2.81 GHz (shielding effectiveness up to 10 dB) at a matching thickness 6.5 mm. The RL value of the SrAl_1.3Fe_10.7O₁₉/MWCNT nanocomposite was ?15.92 dB at 15.84 GHz with a bandwidth of 1.66 GHz (with a shielding effectiveness up to 10 dB). These results disclose the remarkable microwave shielding ability of SrAl_1.3Fe_10.7O₁₉/MWCNT/PANi in KU‐band due to the interactive effect of the three components. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45135.     

Cr(III)‐containing Fe3O4/mercaptopropanoic acid‐poly(2‐hydroxyethyl acrylate) nanocomposite: Highly active magnetic catalyst for direct hydroxylation of benzene

In this study, polymer‐grafted magnetic nanoparticles containing chromium(III) ions incorporated onto Fe₃O₄/mercaptopropanoic acid‐poly(2‐hydroxyethyl acrylate) was prepared via a simple and in situ method. The obtained magnetic nanocomposite exhibited high catalytic activity and excellent selectivity in direct hydroxylation of benzene in the presence of hydrogen peroxide under solvent‐free condition. The magnetic catalyst could be also separated by an external magnet and reused seven times without any significant loss of activity/selectivity. Due to the Lewis acidity of the Fe³⁺ groups in the structure of magnetic nanoparticles, the high efficiency of this catalyst is possibly due to the synergetic effect of Cr³⁺ and Fe³⁺ groups in the structure of magnetic nanocomposite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40383.     

One-pot method fabrication of superparamagnetic sulfonated polystyrene/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/graphene oxide micro-nano composites

In this work, using monodispersed sulfonated polystyrene (SPS) microspheres as carriers, FeCl₃·6H₂O and FeSO₄·7H₂O as precursors, NaOH as precipitant in the presence of graphene oxide (GO), SPS/Fe₃O₄/GO micro-nano composites were fabricated by a simple one-pot method employing an inverse coprecipitation in-situ compound technology. The SPS/Fe₃O₄/GO micro-nano composites were characterized by scanning electron microscopy, transmission electron microscopy, X-ray powder diffractometer, Fourier transform infrared spectroscopy, nitrogen adsorption/desorption isotherms and vibrating sample magnetometer. The results show that the SPS/Fe₃O₄/GO micro-nano composites were fabricated with SPS as core, GO and Fe₃O₄ nanoparticles as shell. The SPS/Fe₃O₄/GO micro-nano composites had larger BET specific surface area, average pore width and micropore volume than the pure SPS microspheres. Meanwhile, the SPS/Fe₃O₄/GO micro-nano composites had superparamagnetism and hydrophilic property. The saturation magnetization (M_s) of the SPS/Fe₃O₄/GO micro-nano composites was 10.86 emu/g, which was enough to ensure the convenient magnetic separation of solid and liquid phase.     

Synthesis and characterization of carboxyl‐functionalized magnetic nanogel via “green” photochemical method

Carboxyl‐functionalized magnetic nanogel was synthesized by facile “green” photochemical method. A possible mechanism of photochemical synthesis was proposed. Effects of irradiation time and volume of monomer dropped on the hydrodynamic diameter of the magnetic nanogel were investigated by photo correlation spectroscopy. The image of atomic force microscopy presented that the magnetic nanogel was with loosed structure. X‐ray diffraction analysis showed that UV irradiation did not induce phase change of Fe₃O₄. Superparamagnetic behaviors were retained for Fe₃O₄ while slightly reducing the value of saturation magnetization for surface coating. High magnetic content of (as high as 85%) and strong magnetization of Fe₃O₄ guaranteed that the magnetic nanogel was susceptive to external applied magnetic field. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

In situ development of bio‐based polyurethane‐blend‐epoxy hybrid materials and their nanocomposites with modified graphene oxide via non‐isocyanate route

We developed a series of sunflower oil‐based non‐isocyanate polyurethane (NIPU)‐blend‐epoxy hybrid materials (HNIPUs) and their nanocomposites with amine‐functionalized graphene oxide (AF‐GO). Firstly, carbonated sunflower oil (CSFO) containing five‐membered cyclocarbonate groups was synthesized by the reaction of epoxidized sunflower oil with carbon dioxide (CO₂) at a pressure of 50 bar and temperature of 110 °C. Then, a series of HNIPUs were synthesized using a mixture of CSFO and a commercially available epoxy resin in various amounts (10, 20 and 30 wt% with respect to CSFO) using isophorone diamine as the curing agent. The HNIPU with 30 wt% epoxy showed the best mechanical properties. Finally, nanocomposites of 30 wt% HNIPU‐based composition were prepared with various amounts of AF‐GO (0.3, 0.6 and 1.0 wt%) and were characterized using Fourier transform infrared and ¹H NMR spectroscopies, X‐ray diffraction and scanning electron microscopy. These results emphasize the potentiality of this environmentally friendly approach for preparing renewable HNIPU and nanocomposite materials of high performances. © 2018 Society of Chemical Industry     

Preparation of electrospun magnetic polyvinyl butyral/Fe2O3 nanofibrous membranes for effective removal of iron ions from groundwater

Removing iron ions from groundwater to purify, it is a challenge faced by countries across the globe, which is why developing polymeric microfiltration membranes has garnered much attention. The authors of this study set out to develop nanofibrous membranes by embedding magnetic Fe₂O₃ nanoparticles (MNPs) into polyvinylbutyral (PVB) nanofibers via the electrospinning process. Investigation was made into the effects of the concentration of the PVB and MNPs on the morphology of the nanofibers, their magnetic properties, and capacity for filtration to remove iron ions. The fabrication and presence of well-incorporated MNPs in the PVB nanofibers were confirmed by scanning electron microscopy and transmission electron microscopy. Depending on the concentration of the MNPs, the membranes exhibited magnetization to the extent of 45.5 emu g⁻¹; hence, they exceeded the performance of related nanofibrous membranes in the literature. The magnetic membranes possessed significantly higher efficiency for filtration compared to their nonmagnetic analogues, revealing their potential for groundwater treatment applications.