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.     

MWCNTs-TiO<Subscript>2</Subscript> core-shell nanoassemblies for fabrication of poly(vinylidene fluoride) based composites with high breakdown strength and discharged energy density

Dielectric polymer composites with high breakdown strength and discharged energy density have potential applications in modern electric power systems. In this study, composites comprising MWCNTs-TiO₂ core-shell nanoparticles and poly(vinylidene fluoride) (PVDF) were fabricated by a solution casting method, followed by a melting and quenching process. The obtained composites are γ-phase PVDF dominated and present a dense structure. By the incorporation of MWCNTs-TiO₂ core-shell nanoparticles, the dielectric constant of composites can be significantly enhanced while the dielectric loss of composites remains low. Because of the core-shell structure of well-dispersed MWCNTs-TiO₂ and their strong interactions with matrix, high breakdown strength above 175 V/μm can be achieved in the composites. Additionally, the composites exhibit enhanced discharged energy density, which can be as high as 6.4 J/cm³ at 250 V/μm, while the maximum discharged energy density obtained in pure PVDF is only 2.6 J/cm³ (270 V/μm).     

Microwave Absorption Studies on Superparamagnetic Conducting Nanocomposites as Signal Coating Materials

In this paper, preparation and characterization of superparamagnetic nanoparticles and their polymer composites prepared by varing doping level of conducting polymer and their microwave absorption studies at radar system in 8–12 GHz frequency range have been discussed. These composites are conducting polymers have been widely used because of their lower density as well their good environmental stability as in the case of polyaniline (PAN). In the present work, in situ polymerization of aniline was carried out in the presence of 30 mole% Fe₃O₄ nanoparticles to synthesize polyaniline/Fe₃O₄(PAN/Fe₃O₄) composites in epoxy resin matrix. The composites, thus synthesized have been characterized by infrared (IR) spectroscopy and X-ray diffraction. The morphology of these composites was studied by scanning electron microscopy. The measurement of % absorption was carried out in X and K band microwave region.     

Acid Functionalized Multiwall Carbon Nanotube/Magnetite (MWCNT)-COOH/Fe3O4 Hybrid: Synthesis, Characterization and Conductivity Evaluation

A functionalized multiwall carbon nanotube (MWCNT)–COOH/Fe₃O₄ hybrid was fabricated by co-precipitation method. Fe₃O₄ nanoparticles were stably attached to the surface of carboxyl groups (COOH). The presence of Fe₃O₄ nanoparticles and their surface conjugation to MWCNT have been confirmed by XRD, TEM and FT-IR techniques. Magnetic evaluation revealed a superparamagnetic character of the hybrid and therefore the attached Fe₃O₄ nanoparticles. The crystallite size (9 ± 3 nm), particle size (9 ± 2 nm) and magnetic domain size estimated for Fe₃O₄ are consistent with each other, which reveal the single crystalline character of the nanoparticles. Electrical conductivity and dielectric behavior have also been characterized by utilizing impedance spectroscopy up to 3 MHz for an isotherm line varying from 293 to 393 K by 10 K steps. Electrical characteristics and its complex dielectric approaches might be elucidated with the existence of a conventional tunneling conduction mechanism of temperature-independency. The AC conductivity of MWCNT–COOH/Fe₃O₄ hybrid could also be a consequence of the estimations of the universal dynamic response.     

Graphene non-covalently tethered with magnetic nanoparticles

We describe a novel approach for coupling pristine graphene with superparamagnetic iron oxide nanoparticles to create dispersed, magnetically responsive hybrids. The magnetic iron oxide (Fe₃O₄) nanoparticles are synthesized by a co-precipitation method using ferric (Fe³⁺) and ferrous (Fe²⁺) salts and then grafted with polyvinylpyrrolidone (PVP). These PVP-grafted Fe₃O₄ nanoparticles are then used to stabilize colloidal graphene in water. The PVP branches non-covalently attach to the surface of the pristine graphene sheets without functionalization or defect creation. These Fe₃O₄–graphene hybrids are stable against aggregation and are highly responsive to external magnetic fields. These hybrids can be freeze-dried to a powder or magnetically separated from solution and still easily redisperse while retaining magnetic functionality. At all stages of synthesis, the Fe₃O₄–graphene hybrids display no coercivity after being brought to magnetic saturation, confirming superparamagnetic properties. Microscopy and light scattering data confirm the presence of pristine graphene sheets decorated with Fe₃O₄ nanoparticles. These materials show promise for multifunctional polymer composites as well as biomedical applications and environmental remediation.     

Improved dielectric properties and energy density of PVDF composites using PVP engineered BaTiO<Subscript>3</Subscript> nanoparticles

This work systematically investigates the effect of modifier polyvinylpyrrolidone (PVP) on the microstructure, dielectric and energy storage properties of BaTiO₃/PVDF composites. The results demonstrate that the BaTiO₃ nanoparticles modified by PVP are uniformly dispersed in the composites, and the defects including cracks and voids are obviously decreased in contrast to the composites with unmodified BaTiO₃ nanoparticles. Due to the enhanced interfacial polarization, the composites with BaTiO₃@PVP show improved dielectric properties compared with the composites with unmodified BaTiO₃ nanoparticles. For instance, at 1 kHz, the dielectric constant and dielectric loss of the composite with 50 vol% of BaTiO₃@PVP nanoparticles are 80.4 and 0.085, while of which the BaTiO₃/PVDF are 35 and 0.265, respectively. The discharge energy density of the composites is largely improved with PVP engineered BaTiO₃ nanoparticles. The composite with 30 vol% BaTiO₃@PVP achieves a discharged energy density of 4.06 J/cc at 240 kV/mm, which is 116% larger than that of pure PVDF (1.88 J/cc). This research provides an effect modifier to prepare high performance dielectric materials.     

Novel high dielectric constant nanocomposites of polyaniline dispersed with γ‐Fe2O3 nanoparticles

Novel nanocomposites of polyaniline dispersed with γ‐Fe₂O₃ nanoparticles were prepared by the in situ polymerization of aniline in the presence of ammonium peroxysulfate as an oxidizing agent. Dielectric constants of the derived composites varied with the composition of γ‐Fe₂O₃ present in the matrix. A maximum dielectric constant of ～5500 was achieved when 10 mass % γ‐Fe₂O₃ nanoparticles were present. Nanocomposites were characterized by X‐ray diffraction, Fourier transform infrared, scanning electron microscopy, and thermal analytical techniques. Conductivity increased marginally by increasing the amount of γ‐Fe₂O₃ in the matrix. Dielectric constants increased 100–150 times compared to plain polyaniline matrix and were 20–40 times higher than that of γ‐Fe₂O₃ nanoparticles. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1868–1874, 2005     

Hollow polyaniline/Fe3O4 microsphere composites: Preparation,characterization, and applications in microwave absorption

Hollow polyaniline/Fe₃O₄ microsphere composites with electromagnetic properties were successfully prepared by decorating the surface of hollow polyaniline/sulfonated polystyrene microspheres with various amounts of Fe₃O₄ magnetic nanoparticles using sulfonated polystyrene (SPS) as hard templates and then removing the templates with tetrahydrofuran (THF). The synthesized hollow microsphere composites were characterized by FT-IR, UV/Vis spectrophotometry, SEM, XRD, elemental analysis, TGA, and measurement of their magnetic parameters. Experimental results indicated that the microspheres were well-defined in size (1.50–1.80 μm) and shape, and that they were superparamagnetic with maximum saturation magnetization values of 3.88 emu/g with a 12.37 wt% content of Fe₃O₄ magnetic nanoparticles. Measurements of the electromagnetic parameters of the samples showed that the maximum bandwidth was 8.0 GHz over ?10 dB of reflection loss in the 2–18 GHz range when the Fe₃O₄ content in the hollow polyaniline/Fe₃O₄ microsphere composites was 7.33 wt%.     

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%.     

Enhanced energy storage property of plate-like Na0.5Bi4.5Ti4O15/poly(vinylidene fluoride) composites through texture arrangement

The plate-like Na_0.5Bi_4.5Ti₄O₁₅ (P-NBT4) particles were synthesized by molten salt method and dispersed in a poly (vinylindene fluoride) (PVDF) matrix. The alignment of P-NBT4 particles in PVDF matrix perpendicular to the direction of applied electric field could bring to impressive dielectric performance and breakdown strength to the composites. On the one hand, the excellent dielectric property of the P-NBT4/PVDF composites is ascribed to the high capacitance that is consist of P-NBT4 particles micro-capacitances. On the other hand, a higher breakdown strength of the P-NBT4/PVDF composites is owing to that strong barrier layer was formed in the composites by P-NBT4 particles alignment, which bring difficulty to form a conductive pathway. Moreover, the textured P-NBT4/PVDF composites exhibit a high energy density (9.45 J/cm³) and energy efficiency (η) of 52.28% under the critical electric field of 300 kV/mm.     

Fabrication of graphene nanosheet (GNS)–Fe3O4 hybrids and GNS–Fe3O4/syndiotactic polystyrene composites with high dielectric permittivity

Graphene nanosheet–Fe₃O₄ (GNS–Fe₃O₄) hybrids were obtained by a one-step solvothermal reduction of iron (III) acetylacetonate [Fe(acac)₃] and graphene oxide (GO) simultaneously, which had several advantages: (1) the Fe₃O₄ nanoparticles were firmly anchored on GNS surface even after mild ultrasonication; (2) the loading amount of Fe₃O₄ nanoparticles could be effectively controlled by changing the initial feeding weight ratio of Fe(acac)₃ to GO; (3) the Fe₃O₄ nanoparticles were homogeneously distributed on the GNS surface without much aggregation. Composites based on syndiotactic polystyrene (sPS) and GNS–Fe₃O₄ were prepared by a solution-blending method and the electric and dielectric properties of the resultant GNS–Fe₃O₄/sPS composites were investigated. The percolation threshold of GNS–Fe₃O₄ in the sPS matrix was determined to be 9.41 vol.%. Slightly above the percolation threshold with 9.59 vol.% of GNS–Fe₃O₄, the GNS–Fe₃O₄/sPS composite showed a high dielectric permittivity of 123 at 1000 Hz, which was 42 times higher than that of pure sPS. The AC electrical conductivity at 1000 Hz increased from 3.6 × 10⁻¹⁰ S/m for pure sPS to 2.82 × 10⁻⁴ S/m for GNS–Fe₃O₄/sPS composite containing 10.69 vol.% of GNS–Fe₃O₄, showing an obvious insulator-semiconductor transition.     

Facile preparation of poly(ε-caprolactone)/Fe3O4@graphene oxide superparamagnetic nanocomposites

The main goal in this work was to prepare and characterize a kind of novel superparamagnetic poly(ε-caprolactone)/Fe₃O₄@graphene oxide (PCL/Fe₃O₄@GO) nanocomposites via facile in situ polymerization. Fabrication procedure included two steps: (1) GO nanosheets were decorated with Fe₃O₄ nanoparticles by an inverse co-precipitation method, which resulted in the production of the magnetite/GO hybrid nanoparticles (Fe₃O₄@GO); (2) incorporation of Fe₃O₄@GO into PCL matrix through in situ polymerization afforded the magnetic nanocomposites (PCL/Fe₃O₄@GO). The microstructure, morphology, crystallization properties, thermal stability and magnetization properties of nanocomposites were investigated with various techniques in detail. Results of wide-angle X-ray diffraction showed that the incorporation of the Fe₃O₄@GO nanoparticles did not affect the crystal structure of PCL. Images of field emission scanning electron microscope and transmission electron microscopy showed Fe₃O₄@GO nanoparticles evenly spread over PCL/Fe₃O₄@GO nanocomposites. Differential scanning calorimeter and polar optical microscopy showed that the crystallization temperature increased and the spherulites size decreased by the presence of Fe₃O₄@GO nanoparticles in the nanocomposites due to the heterogeneous nucleation effect. Thermogravimetric analysis indicated that the addition of Fe₃O₄@GO nanoparticles reduced the thermal stability of PCL in the nanocomposites. The superparamagnetic behavior of the PCL/Fe₃O₄@GO nanocomposites was testified by the superconducting quantum interference device magnetometer analysis. The obtained superparamagnetic nanocomposites present potential applications in tissue engineering and targeted drug delivery.     

Study on Maximum Specific Loss Power in Fe3O4 Nanoparticles Decorated with Biocompatible Gamma-Cyclodextrins for Cancer Therapy with Superparamagnetic Hyperthermia

Different chemical agents are used for the biocompatibility and/or functionality of the nanoparticles used in magnetic hyperthermia to reduce or even eliminate cellular toxicity and to limit the interaction between them (van der Waals and magnetic dipolar interactions), with highly beneficial effects on the efficiency of magnetic hyperthermia in cancer therapy. In this paper we propose an innovative strategy for the biocompatibility of these nanoparticles using gamma-cyclodextrins (γ-CDs) to decorate the surface of magnetite (Fe₃O₄) nanoparticles. The influence of the biocompatible organic layer of cyclodextrins, from the surface of Fe₃O₄ ferrimagnetic nanoparticles, on the maximum specific loss power in superparamagnetic hyperthermia, is presented and analyzed in detail in this paper. Furthermore, our study shows the optimum conditions in which the magnetic nanoparticles covered with gamma-cyclodextrin (Fe₃O₄–γ-CDs) can be utilized in superparamagnetic hyperthermia for an alternative cancer therapy with higher efficiency in destroying tumoral cells and eliminating cellular toxicity.     

High-strength superparamagnetic composite fibers

The polymer composites of magnetic nanoparticles can be possibly used in a bulk form by preserving all the novel characteristics of magnetic nanoparticles such as superparamagnetic behavior. By introducing magnetic properties of Fe₃O₄ nanoparticles into polymer fibers, novel magnetic properties combine with the advantages of composite fibers such as light-weight and ease-of-use. Using dry-jet-wet fiber spinning technology, we have successfully fabricated iron oxide/polyacrylonitrile (Fe₃O₄/PAN) composite fibers with 10 wt% nanoparticle in the polymer matrix. Composite fiber with a diameter as small as 15 μm can achieve tensile strength and tensile modulus values as high as 630 MPa and 16 GPa, respectively. Superparamagnetic properties of Fe₃O₄ nanoparticles were preserved in the composite fibers with saturation magnetization at 80 emu/g and coercivity of 165 G.     

COOH?MWCNTs‐induced BiFeO3‐poly(vinylidene fluoride) (PVDF) composites with enhanced dielectric and ferroelectric properties

In this work, flexible three phase composite films were prepared with surface functionalized multi‐walled carbon nanotubes (f‐MWCNTs) and bismuth ferrite (BiFeO₃;BFO) particles embedded into the poly(vinylidene fluoride) (PVDF) matrix via solution casting technique. The properties and the microstructure of prepared composites were investigated using an impedance analyzer and field emission scanning electron microscope. The micro‐structural study showed that the f‐MWCNTs and BFO particles were dispersed homogeneously within the PVDF matrix, nicely seated on the floor of the f‐MWCNTs separately. The dielectric measurement result shows that the resultant composites with excellent dielectric constant (≈96) and relatively lower dielectric loss (<0.23 at 100 Hz). Furthermore, the percolation theory is explored to explain the dielectric properties of the resultant composites. It says that the percolation threshold of f_MWCNTs = 0.9 wt % and the enhancement of the dielectric constant of the composite was also discussed. In addition, the remnant polarization of the un‐poled PVDF‐BFO‐f‐MWCNTs composites (2P_r ～1.34 µC/cm² for 1.1 wt % of f‐MWCNTs) is also improved. These three phase composites provide a new insight to fabricate flexible and enhanced dielectric properties as a promising application in modern electrical and electronic devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46002.     

COOHMWCNTs‐induced BiFeO3‐poly(vinylidene fluoride) (PVDF) composites with enhanced dielectric and ferroelectric properties

In this work, flexible three phase composite films were prepared with surface functionalized multi‐walled carbon nanotubes (f‐MWCNTs) and bismuth ferrite (BiFeO₃;BFO) particles embedded into the poly(vinylidene fluoride) (PVDF) matrix via solution casting technique. The properties and the microstructure of prepared composites were investigated using an impedance analyzer and field emission scanning electron microscope. The micro‐structural study showed that the f‐MWCNTs and BFO particles were dispersed homogeneously within the PVDF matrix, nicely seated on the floor of the f‐MWCNTs separately. The dielectric measurement result shows that the resultant composites with excellent dielectric constant (≈96) and relatively lower dielectric loss (<0.23 at 100 Hz). Furthermore, the percolation theory is explored to explain the dielectric properties of the resultant composites. It says that the percolation threshold of f_MWCNTs = 0.9 wt % and the enhancement of the dielectric constant of the composite was also discussed. In addition, the remnant polarization of the un‐poled PVDF‐BFO‐f‐MWCNTs composites (2P_r ～1.34 µC/cm² for 1.1 wt % of f‐MWCNTs) is also improved. These three phase composites provide a new insight to fabricate flexible and enhanced dielectric properties as a promising application in modern electrical and electronic devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46002.     

Investigation of polymer dynamics in chitosan-maghemite nanocomposites: a potential green superparamagnetic material

Magnetic composites with superparamagnetic properties have attracted great scientific interest recently. In this article we have investigated chitosan-maghemite (γ-Fe₂O₃) nanocomposite. We have analyzed the effect of temperature and the concentration of maghemite nanoparticles upon the relaxation behaviour of the nanocomposite using Broad band dielectric spectroscopy (BDS). Additionally, various characterization techniques such as X-ray diffraction (XRD), Fourier transform infra red spectra (FTIR), Scanning electron microscopy (SEM), Transmission electron spectroscopy (TEM), Thermo gravimetric Analysis (TGA), Vibrating Sample Magnetometer (VSM), Atomic Force Microscopy (AFM) and Raman spectroscopy have been used for our investigation. Our investigation shows that maghemite nanoparticles interact with chitosan leading to morphological changes in the films and results in modifications in the dielectric and electrical characteristics of the nanocomposite. New relaxations have been identified and their modifications due to maghemite nanoparticles have been investigated. The nanocomposites exhibit superparamagnetic behaviour. This research will benefit research in battery technology and super capacitors.     

Effect of iron oxide on the vulcanization and electrical properties of conductive butyl rubber composites

Rubber ceramic composite, negative temperature coefficient of conductivity (NTCC) thermistors, are widely used in industry because of the high dependence of their electrical conductivity on temperature. The effect of iron oxide (Fe₃O₄) on the vulcanization process, DC conductivity, thermoelectric power, dielectric constant and I–V characteristics have been measured. Also the conduction mechanism is discussed. A hot‐pressing technique has been used to enhance the microstructure core of rubber composites. It has been found that Fe₃O₄ acts as a catalyst during vulcanization process and the characteristic time constant during vulcanization decreases as the content of Fe₃O₄ increases. © 2000 Society of Chemical Industry     

Graphene/acid assisted facile synthesis of structure-tuned Fe3O4 and graphene composites as anode materials for lithium ion batteries

Structure-tuned Fe₃O₄ and graphene composites were prepared using a facile graphene/acid assisted facile one-pot hydrothermal method. The structural characteristics of Fe₃O₄ can be tuned by adjusting the initial molar ratio between iron acetylacetonate and citric acid. The citric acid serves dual function as a reducing agent during the production of Fe₃O₄ nanoparticles (NPs), and as a bridging agent which under optimized conditions can result in mesoporous Fe₃O₄ nanospheres (NSs) self-assembled by numerous Fe₃O₄ NPs. The fabricated mesoporous Fe₃O₄ NSs and graphene composites were evaluated as potential anode materials for lithium ion batteries. These composites exhibit better electrochemical performance with high reversible capacity, good rate capability and cyclic stability derived from their unique mesoporous structural features.     

Crystallinity,conductivity, and magnetic properties of PVDF‐Fe3O4 composite films

The formation of Fe₃O₄ nanoparticles by hydrothermal process has been studied. X‐ray Diffraction measurements were carried out to distinguish between the phases formed during the synthesis. Using the synthesized Fe₃O₄ nanoparticles, poly(vinyledene fluoride)‐Fe₃O₄ composite films were prepared by spin coating method. Scanning electron microscopy of the composite films showed the presence of Fe₃O₄ nanoparticles in the form of aggregates on the surface and inside of the porous polymer matrix. Differential Scanning calorimetry revealed that the crystallinity of PVDF decreased with the addition of Fe₃O₄. The conductitivity of the composite films was strongly influenced by the Fe₃O₄ content; conductivity increased with increase in Fe₃O₄ content. Vibration sample magnetometry results revealed the ferromagnetic behavior of the synthesized iron oxide nanoparticles with a Ms value of 74.50 emu/g. Also the presence of Fe₃O₄ nanoparticles rendered the composite films magnetic. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011