Nanocomposite particles with core-shell morphology II. An investigation into the affecting parameters on preparation of Fe3O4-poly (butyl acrylate-styrene) particles via miniemulsion polymerization

The encapsulation of inorganic particles with polymers is desirable for many applications in order to improve the stability of the encapsulated products and disperse ability in different media. Colloidal particles with magnetic properties have become increasingly important both technologically and for fundamental studies. This is due to their tunable anisotropic. In the absence of an applied magnetic field, the particles have isotropic sphere dispersion, whereas in an external magnetic field the particles form anisotropic structures. Here, latexes containing nanocomposite particles of styrene-butyl acrylate/Fe₃O₄ with core-shell structure were prepared through miniemulsion polymerization technique. Magnetic composite nanospheres with high magnetic content were synthesized through miniemulsion polymerization using a new process based on a three-steps preparation route including two miniemulsion processes: (1) preparing a dispersion of oleic acid coated magnetite particles in water; (2) mixing of modified magnetite particles with styrene/butyl acrylate in the presence of sodium dodecyl sulfate (SDS), sorbitane mono oleate (Span 80), hexadecane (HD) and (3) miniemulsification of the modified Fe₃O₄ into the monomer droplets to reach to complete encapsulation. Subsequent polymerization generated magnetic nanocomposite spheres. Hence, the copolymerization reaction was performed on the surface of such particles in order to obtain core-shell morphology for these nanoparticles, which were characterized by several techniques such as TEM, SEM, DLS, TGA, VSM and FT-IR. The magnetic copolymer particles with diameter of 120-170 nm were obtained. The effect of several parameters such as magnetite, surfactants and hydrophobe amounts on the stability, particle size and magnetization were investigated and also optimized.     

Magnetic polymer particles: Synthesis and properties

A possibility of preparation of monodisperse magnetic polymer particles containing carboxylic groups by the methid of emulsion (co)polymerization in the presence of a magnetic liquidis considered. Angulation of the magnetite nanoparticles by polymeric spheres of styrene-acroleine copolymer followed by incapsulation to the polystyrene coat is studied. Monodisperse particles with inclusion of the magnetite nanoparticles 30 nm to 1 μm size containing up to 5.6 μmol g^?1 surface carboxylic groups are obtained, their electrosurface and magnetic properties are studied.     

Preparation and properties of monodisperse latex spheres with controlled magnetic moment for field-induced colloidal crystallization and (dipolar) chain formation

We report the preparation and properties of monodisperse magnetic poly(methyl methacrylate) latex spheres that exhibit field-induced colloidal crystallization to exotic morphologies controlled by the geometry of the gradient. The magnetic moment of the novel magnetic spheres is due to an inner core of magnetite particles. These particles, obtained from a conventional ferrofluid, first form a monodisperse emulsion with a silane coupling agent, after which they are directly incorporated in PMMA latex synthesized by standard emulsion polymerization. Scattering from the latex shell dominates over light absorption by the magnetic cores such that visible Bragg reflections of the magnetic crystals can be clearly observed. Concentrated nearly white latex fluids may exhibit near a magnet the warped equilibrium menisci known from the usually dark magnetite ferrofluids. Of the many possible applications, we briefly discuss the subsequent growth and melting of crystals by a slowly oscillating gradient, the formation of radial lattices, and the formation of ordered magnetic dots in PMMA latex films.     

Fabrication of hollow multifunctional spheres containing MCM-41 nanoparticles and magnetite nanoparticles using layer-by-layer method

Macroscopic mesoporous silica spheres have been fabricated by alternatively depositing preformed MCM-41 nanoparticles and polyelectrolytes onto polystyrene lattices. High surface area hollow mesoporous spheres were obtained by removal of the core by solvent or calcination. Further, the versatility of the layer-by-layer (LBL) method was extended to fabricate magnetite-mesoporous silica composites by depositing magnetite and MCM-41 nanoparticles onto polystyrene beads. Such high surface area composites are important since the mesopores can be used for encapsulation of varied materials like enzymes and drugs while the presence of magnetite ensures application in biocatalysis and separation under magnetic field.     

Ferrogel: a new magneto-controlled elastic medium

Magnetic-field-sensitive gels, called ferrogels, have been prepared by introducing monodomain, magnetite particles of colloidal size into chemically crosslinked poly(vinyl alcohol) hydrogels. The influence of a non-uniform external magnetic field on the shape of gel tubes and the possibility to induce elongation and contraction by means of a magnetic field gradient produced by an electromagnet have been demonstrated. It was shown that both the concentration of magnetite particles and the crosslinking density of the ferrogels play an essential role in the magneto-elastic behaviour.     

Preparation of magnetic polystyrene latex via the miniemulsion polymerization technique

Magnetic iron oxide (magnetite, Fe₃O₄) nanoparticles were encapsulated with polystyrene to give a stable water‐based magnetic polymer latex, using the miniemulsion polymerization technique. The resulting magnetic latexes were characterized with transmission electron microscopy (TEM), dynamic light scattering (DLS), vibrating sample magnetometer measurements (VSM), and ⁵⁷Fe Mössbauer spectroscopy measurements. TEM revealed that all magnetite nanoparticles were embedded in the polymer spheres, leaving no empty polystyrene particles. The distribution of magnetite particles within the polystyrene spheres was inhomogeneous, showing an uneven polar appearance. The DLS measurements indicated a bimodal size distribution for the particles in the latexes. According to our magnetometry and Mössbauer spectroscopy data, the encapsulated magnetite particles conserve their superparamagnetic feature when they are separated in the polymer matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4802–4808, 2004     

Influence of a magnetic field on the formation of magnetite particles via two precipitation methods

An experimental investigation is described on the effects of the presence of a magnetic field during the fabrication of magnetite particles. We considered two well-known synthesis methods: that of Massart [IEEE Trans. Magn. 1981, 17, 1247-1248] for the synthesis of nanometer-sized, monodomain particles; and that of Sugimoto and Matijevi? [J. Colloid Interface Sci. 1980, 74, 227-243.] for the fabrication of micrometer-sized multidomain spherical particles. The latter method was studied with two systems of different ionic compositions that lead to two different mechanisms of growth: either growth by aggregation and recrystallization of primary particles or direct crystal growth. When growth was dominated by aggregation of primary units, the magnetic field had a dramatic effect on the morphology, inducing the formation of rodlike particles. Growth dynamics of that system were studied for particles obtained in the presence as well as in the absence of the magnetic field. Particles were also characterized by powder magnetometry, electrophoresis, X-ray diffraction, and optical absorbance techniques. Interestingly, growth dynamics of the rods cross section were comparable to those of the diameter of the spheres. With the exception of the morphology, no other significant difference was found between the rodlike particles and the spheres.     

Physical and Chemical Properties of Magnetite and Magnetite-Polymer Nanoparticles and Their Colloidal Dispersions

The properties of polymer-coated magnetite nanoparticles, which have the potential to be used as effective magnetic resonance contrast agents, have been studied. The magnetite particles were synthesized by using continuous synthesis in an aqueous solution. The polymer-coated magnetite nanoparticles were synthesized by seed precipitation polymerization of methacrylic acid and hydroxyethyl methacrylate in the presence of the magnetite nanoparticles. The particle size was measured by laser light scattering. It was shown that the particle size, variance, magnetic properties, and stability of aqueous magnetite colloidal dispersion strictly depend on the nature of the stabilizing agent. The average hydrodynamic radius of the magnetite particles was found to be 5.7 nm in the stable aqueous colloidal dispersion. An inclusion of the magnetite particle into a hydrophilic polymeric shell increases the stability of the dispersion and decreases the influence of the stabilizing agent on the magnetic and structural properties of the magnetite particles as was shown by X-ray diffraction and M?ssbauer and IR spectroscopy, as well as by vibrating sample magnetometry. The variation in the polymeric shell size and the polymer net density can be useful tools for evaluation of the polymer-coated magnetite particles as effective contrast agents. Copyright 1999 Academic Press.     

Preparation and sedimentation behavior in magnetic fields of magnetite-covered clay particles

This work is devoted to the preparation of magnetite-covered clay particles in aqueous medium. For this purpose, magnetite nanoparticles were synthesized by a coprecipitation method. These magnetic particles are adhered to sodium montmorillonite (NaMt) particles in aqueous suspensions of both materials, by appropriate control of the electrolyte concentrations. The best condition to produce such heteroaggregation corresponds to acid pH and approximately 1 mol/L ionic strength, when the electrokinetic potentials (zeta-potential) of both NaMt and Fe3O4 particles have high enough and opposite sign, as demonstrated from electrophoresis measurements. When a layer of magnetite re-covers the clay particles, the application of an external magnetic field induces a magnetic moment in clay-magnetite particles parallel to the external magnetic flux density. The sedimentation behavior of such magnetic particles is studied in the absence or presence of an external magnetic field in a vertical direction. The whole sedimentation behavior is also strongly affected by the formation of big flocculi in the suspensions under the action of internal colloidal interactions. van der Waals and dipole-dipole magnetic attractions between magnetite-covered clay particles dominate the flocculation processes. The different relative orientation of the clay-magnetite particles (edge-to-edge, face-to-edge, and face-to-face) are discussed in order to predict the most favored flocculi configuration.     

Influence of Magnetic Field and Temperature on the Synthesis and Colloidal and Chemical Properties of Fe3O4

A magnetic field and temperature was shown to affect disperse composition, electrophoretic behavior, and aggregation stability of synthesized magnetite particles. When synthesis proceeds, a process of the nucleation of ultramicroscopic Fe₃O₄ particles prevails over a process of their aggregation. Here an electrostatic factor of stability of magnetite suspension plays an important role. An application of the magnetic field decreases the aggregation stability and increases the sedimentation rate of product particles.     

Magnetite/N-doped carboxylate-rich carbon spheres:Synthesis,characterization and visible-light-induced photocatalytic properties

A novel magnetically separable visible-light-photocatalyst,magnetite/N-doped carboxylate-rich carbon spheres（N-MCRCSs）,was synthesized by a facile ultrasonic method using the magnetite/carboxylaterich carbon spheres（MCRCSs） as precursors.N element has been successfully doped into the MCRCSs in a HNO₃ aqueous solution via an ultrasonic treatment,which were demonstrated by the FT-IR and XPS.NMCRCSs exhibit more intensive absorption over MCRCSs in the entire UV and visible region.N-MCRCSs can not only be easily recycled by applying an external magnetic field,but also exhibit powerful visible light photocatalytic activity.     

Tuning the Colloidal Crystal Structure of Magnetic Particles by External Field

Manipulation of the self‐assembly of magnetic colloidal particles by an externally applied magnetic field paves a way toward developing novel stimuli responsive photonic structures. Using microradian X‐ray scattering technique we have investigated the different crystal structures exhibited by self‐assembly of core–shell magnetite/silica nanoparticles. An external magnetic field was employed to tune the colloidal crystallization. We find that the equilibrium structure in absence of the field is random hexagonal close‐packed (RHCP) one. External field drives the self‐assembly toward a body‐centered tetragonal (BCT) structure. Our findings are in good agreement with simulation results on the assembly of these particles.     

Pre-analysis separation and concentration of actinides in groundwater using a magnetic filtration/sorption method I. Background and concept

A wide variety of iron oxides has been used for the removal of radioactive and toxic metals from aqueous solutions. We have utilized natural magnetite and iron ferrite (FeO·Fe₂O₃) in a batch mode to remove actinides (Pu and Am) from wastewater. Compared to the batch process, enhanced capacity for actinide removal was observed using supported magnetite in a column surrounded by an external magnetic field (0.3 tesla). The enhanced magnetite capacity in the column is primarily due to magnetic filtration of colloidal and submicron actinide particles along with some actinide complex and ion exchange sorption mechanisms. The removal of the magnetic field from around the column and use of a regenerating solution will easily remove the actinides loaded on the magnetite. The magnetic field-enhanced column process is under development for a variety of applications. This paper will review previous work on using ferrites for water treatment and discuss the potential for using the magnetic field-enhanced column process as a pre-analysis separation and concentration method for actinides in groundwater.     

Direct imaging of zero-field dipolar structures in colloidal dispersions of synthetic magnetite

Magnetite (Fe3O4) forms the basis of most dispersions studied in the field of magnetic fluids and magnetic colloids. Despite extensive theory and simulations on chain formation in dipolar fluids in zero field, such structures have not yet been imaged in laboratory-made magnetite dispersions. Here, we present the first direct observation of dipolar chain formation in zero field in a ferrofluid containing the largest synthetic single-domain magnetite particles studied so far. To our knowledge, this is the only ferrofluid system available at present that allows quantifying chain length and ring-size distributions of dipolar structures as a function of concentration and particle size.     

Magnetic and Mössbauer Studies of Magnetite-Loaded Polyvinyl Alcohol Hydrogels

Materials producing strain in a magnetic field are known as magnetoelastic or magnetostrictive materials. A new type of material that is able to produce giant strain in a nonhomogeneous magnetic field has been developed. In these magnetic-field-sensitive gels (ferrogels) fine colloidal particles having superparamagnetic behavior are incorporated into a highly swollen elastic polymer network. Magnetic properties of ferrogels have been investigated using electron microscopy, static magnetization measurements, and M?ssbauer spectroscopy. Analysis of the data yielded information on the superparamagnetic behavior of ferrogels and made it possible to estimate the size distribution of the magnetic cores of magnetite particles made by chemical precipitation and built into a chemically cross-linked polyvinyl alcohol matrix. The results are interpreted on the basis of a core-shell model. Copyright 2000 Academic Press.     

Stimuli‐Responsive Particle‐Based Amphiphiles as Active Colloids Prepared by Anisotropic Click Chemistry

Amphiphiles alter the energy of surfaces, but the extent of this feature is typically constant. Smart systems with amphiphilicity as a function of an external, physical trigger are desirable. As a trigger, the exposure to a magnetic field, in particular, is attractive because it is not shielded in water. Amphiphiles like surfactants are well known, but the magnetic response of molecules is typically weak. Vice‐versa, magnetic particles with strong response to magnetic triggers are fully established in nanoscience, but they are not amphiphilic. In this work colloids with Janus architecture and ultra‐small dimensions (25 nm) have been prepared by spatial control over the thiol‐yne click modification of organosilica‐magnetite core–shell nanoparticles. The amphiphilic properties of these anisotropically modified particles are proven. Finally, a pronounced and reversible change in interfacial stabilization results from the application of a weak (<1 T) magnetic field.     

Demulsification by increasing the gravitational force acting upon the dispersed phase owing to the adsorption/absorption of the magnetite particles

Demulsification using a magnetic demulsifier is commonly used to separate emulsions using an external magnetic field. However, this study presents a new demulsification method based on the increased weight of the dispersed phase due to the adsorption/absorption of the magnetite particles by the droplets. Micron-sized bare magnetite particles were used as the demulsifier in this method which does not necessarily need to apply a surface-active additive and the magnetic field for the demulsification. Magnetic responsivity of the demulsifier can only be used for the recovery of the demulsifier. The demulsification experiments were performed using the oil-in-water and water-in-oil emulsions. The effect of temperature, wettability, demulsifier dosage and activity, sedimentation rate and particles size were investigated. The results showed that the proposed method can remarkably improve the efficiency and speed of the demulsification, and has a great potential to be considered for the commercialization.     

Adsorption of surfactants on superfine magnetite

Superfine magnetite particles were obtained by chemical condensation. Their size can be varied by the magnetic field application and a change in the crystallization temperature. The X-ray diffraction and adsorption data suggested an increase in the crystallite size and a decrease in the value of limiting adsorption and specific area of magnetite with an increase in the temperature and magnetic field intensity. The nature of surfactants and solvents has a substantial effect on the adsorption process. The IR spectroscopic and equilibrium adsorption data showed that oleic acid has the highest affinity to the surface among the surfactants studied (stearic, oleic, and linoleic acids and sodium oleate). On going from carbon tetrachloride to hexane, the value of limiting adsorption of oleic acid decreases.     

Synthesis and characterization of monodisperse, mesoporous, and magnetic sub-micron particles doped with a near-infrared fluorescent dye

Recently, multifunctional silica nanoparticles have been investigated extensively for their potential use in biomedical applications. We have prepared sub-micron monodisperse and stable multifunctional mesoporous silica particles with a high level of magnetization and fluorescence in the near infrared region using an one-pot synthesis technique. Commercial magnetite nanocrystals and a conjugated-NIR-dye were incorporated inside the particles during the silica condensation reaction. The particles were then coated with polyethyleneglycol to stop aggregation. X-ray diffraction, N₂ adsorption analysis, TEM, fluorescence and absorbance measurements were used to structurally characterize the particles. These mesoporous silica spheres have a large surface area (1978 m²/g) with 3.40 nm pore diameter and a high fluorescence in the near infrared region at λ=700 nm. To explore the potential of these particles for drug delivery applications, the pore accessibility to hydrophobic drugs was simulated by successfully trapping a hydrophobic ruthenium dye complex inside the particle with an estimated concentration of 3 wt%. Fluorescence imaging confirmed the presence of both NIR dye and the post-grafted ruthenium dye complex inside the particles. These particles moved at approximately 150 μm/s under the influence of a magnetic field, hence demonstrating the multifunctionality and potential for biomedical applications in targeting and imaging.     

Comparative Study on the Collapse Transition of Poly(N-isopropylacrylamide) Gels and Magnetic Nanoparticles Loaded Poly(N-isopropylacrylamide) Gels

A novel polymer gel exhibiting simultaneous temperature and magnetic field sensitivity has been prepared and studied. Poly(N-isopropylacrylamide) (PNIPA) and magnetic nanoparticles (magnetite, Fe₃O₄) loaded PNIPA gel beads with mm size and monolith gels with cm size were prepared. The dependence of swelling degree on the temperature has been studied. The effects of cross-linking density and the presence of magnetic nanoparticles on the equilibrium swelling degree as well as on the collapse transition have been investigated. Swelling kinetic measurements were also made. By comparing the equilibrium swelling properties of PNIPA and magnetite loaded PNIPA gels it was found that the built in magnetic nanoparticles do not modify the temperature sensitivity of these gels. Within the experimental accuracy the temperature of the collapse transition was not sensitive to the presence of magnetic particles. We have compared the swelling behaviour of mm size gel beads to the cm size monolith gels in order to study the influence of surface skin layer on the swelling equilibrium. It was established that the extent of surface skin formation was decreased by the presence of magnetic particles.