Synthesis and encapsulation of magnetite nanoparticles in PLGA: effect of amount of PLGA on characteristics of encapsulated nanoparticles

Oleic acid-coated superparamagnetic iron oxide nanoparticles (Fe₃O₄) encapsulated within poly(d,l-lactide-co-glycolide) (PLGA) particles were prepared by the w/o/w emulsion technique using poly(vinyl alcohol) as a dispersant. The concentration of PLGA in the oil phase was varied (5, 15, 30, 45, and 60?mg/ml) at constant magnetite concentration in the oil phase (5?mg/ml) to study the properties of composite Fe₃O₄–PLGA nanoparticles. Even though PLGA concentration varied widely in the oil phase, the weight percent of 7–16?nm diameter magnetite in the particles varied only from 56 to 62?% (23–28?vol.%). The obtained composite nanoparticles were essentially spherical with magnetite spatially uniformly dispersed in individual PLGA particles, as measured by transmission electron microscopy (TEM). Also, the magnetite concentration in each particle did not vary widely as determined qualitatively via microscopy. Hydrodynamic diameters of the composite nanoparticles as measured by dynamic light scattering increased by approximately 10?% with added magnetite, with a smaller relative increase in diameter measured by TEM. The zeta potential of the particles was about ?26?mV, independent of Fe₃O₄ loading. Relatively high saturation magnetizations (36–45?emu/g) were measured for these highly loaded particles, with the latter value only 7?emu/g lower than the value measured for the oleic acid-coated particles alone.     

包覆油酸的Fe_3O_4纳米粒子的制备

用FeSO4和FeCl3在氨水和油酸作用下,共沉淀制备了包覆油酸的Fe3O4纳米粒子,考察了沉淀温度、油酸加入前反应时间及总铁离子浓度对其粒径的影响。结果显示,沉淀温度的升高和油酸加入前反应时间的延长,均可使Fe3O4粒径增大。沉淀温度从20℃增加到80℃,粒径从大约5 nm增加到8 nm;油酸加入前反应时间从10 min延长到30 min,粒径从大约3 nm增加到8 nm。c(总铁离子)=0.1~1.1 mol/L时对粒径没有显著影响,Fe3O4粒径均为8 nm左右,c(总铁离子)>1.1 mol/L时,粒径明显减小。     

Fe3O4水基磁流体的制备及其分散性能研究

采用共沉淀法制备了纯Fe3O4纳米粒子,分别用高氯酸、四甲基羟胺和油酸/十二烷基苯磺酸钠为表面活性剂对其进行表面处理后分散在水中,得到了3种水基磁流体,对这3种磁流体的浓度及稳定性进行了测定。实验结果显示:酸性、碱性和中性水基磁流体中Fe3O4的浓度分别为4.8%、5.8%和8.1%,其中中性水基磁流体中粒子的分散性能最佳;经过离心后,3种水基磁流体中的粒子均产生了沉降,且酸性和碱性磁流体中的粒子比中性磁流体中的粒子沉降的多。在此基础上,对影响粒子分散稳定性的机理进行了初步探讨。     

Composite magnetic particles: 2. Encapsulation of iron oxide by surfactant-free emulsion polymerization

This is a second paper in the series concerning the synthesis and characterization of composite polymeric particles with encapsulated magnetic iron oxide and bearing reactive β-diketone groups on the surface. Composite particles have been prepared by two-step method in which first step requires preparation of the iron oxide nano-particles and during second step iron oxide was encapsulated into formed poly(styrene/acetoacetoxyethyl methacrylate) (PS-AAEM) particles directly during polymerization process. It has been found that the modification of the iron oxide nano-particle surface with sodium oleate improves significantly the encapsulation during polymerization process. This procedure gives a possibility to obtain composite particles with raspberry morphology and both the particle size and iron oxide content can be varied. Change of monomer to iron oxide ratio gives a possibility to change effectively the morphology of hybrid particles, however, polydispersity of composite particles increases at higher content of magnetic particles in the system. Variation of AAEM concentration in reaction mixture at constant iron oxide particles concentration gives a possibility to control the particle size of formed hybrid microspheres. Composite particles were characterized by dynamic light scattering and electron microscopy (SEM) with respect to their particle size and morphology of the surface layer. X-ray diffraction (XRD) and magnetization measurements indicate presence of maghemite (γ-Fe₂O₃) in composite particles.     

Composite magnetic particles: 1. Deposition of magnetite by heterocoagulation method

In this paper we report synthesis and characterization of composite polymeric particles bearing magnetite inclusions and reactive β-diketone groups on the surface. Composites were prepared by two-step method in which first step requires preparation of the functionalized polystyrene core and during second step magnetite was deposited onto core particle surface. This procedure gives a possibility to obtain composite particles with core-shell morphology and both the core size and magnetite shell thickness can be varied. Highly monodisperse PS/AAEM microspheres were synthesized by surfactant-free emulsion polymerization. Change of monomer fleet-ratio gives a possibility to change effectively the final particle size of dispersions without strong changes in particle size distribution. PS/AAEM particles were characterized by light scattering techniques (DLS, SLS) and electron microscopy (SEM) with respect to their particle size and morphology of the surface layer. Magnetite was deposited in form of nano-crystals onto PS-AAEM particle surface by heterocoagulation process. It has been established that more uniform magnetite coating was obtained at lower base amounts used for synthesis of magnetite. Amount of the magnetite on the polymeric particle surface can be effectively controlled by changing the initial FeCl₂ and FeCl₃ concentrations and/or variation of the PS/AAEM core dimensions. It has been confirmed by separation centrifugation technique, that stepwise increase of the magnetite content on the particle surface decrease gradually the stability of colloidal system. Magnetization curves for composite particles indicate that deposited magnetite content is high enough to achieve considerable magnetic response to external magnetic field.     

Preparation of aluminum oxide coating on carbon/carbon composites using a new detonation sprayer

A new multi-chamber cumulative detonation sprayer (MCDS) was applied to fabricate an aluminum oxide coating on carbon/carbon composites. MCDS provides heating and acceleration of ceramic micropowders by means of combustible gas mixture detonation products with a frequency of 20 Hz and above. The ceramic aluminum oxide particle kinetic energy ensures the destruction of the weakened areas on the carbon-carbon composite material surface and the incorporation of these particles into the surface layer. The following powder particles decelerate on the already fixed particles and form a ceramic coating. The formed aluminum oxide coating is characterized by high hardness and low porosity (<1%). MCDS provides the formation of a high-quality ceramic layer, which can also serve as the basis for the formation of protective heat-resistant coatings.     

Enhanced Dielectric Properties of Ba0.5Sr0.5TiO3/MgO Composites Prepared by Coprecipitation Derived Core–Shell Powders

Ba_0.5Sr_0.5TiO₃/MgO (BST/MgO) composite ceramics have been prepared in situ by using an oxalate precipitation process. SEM and TEM images show that oleic acid modified BST/MgO nanocomposite exhibits helminth‐like particles consisting of BST core and MgO shell. Results reveal that oleic acid modification is chemisorbed on MgO particles as a carboxylate to form MgO shell, which connects to interparticles. Accordingly, the BST particles are well surrounded naturally by a thin MgO layer in the composite ceramics. As a result, the oleic acid modified BST/MgO composite ceramics shows better dielectric properties, with permittivity of 203, loss tangent of 0.0025 (at 2.4 GHz), and tunability of 10.2%.     

Oxidation protective multilayer coatings for carbon-carbon composites

An oxidation protective double layered coating was deposited on a carbon-carbon composite (C/C) using a simple and low cost method. A surface modification of the C/C was obtained by direct reaction of liquid silicon with the C/C, promoting the formation of a 5-10 μm β-SiC layer on the composite surface. The inner layer, in contact with the C/C, is a composite made with a barium borosilicate glass matrix (SABB) and boron carbide particles; the outer layer is another composite layer formed by a SABB glass matrix and yttrium oxide particles. The layers are deposited by a slurry technique. Oxidation tests were carried out in a furnace in air, in order to verify the coating stability and its effectiveness. No mass loss of the C/C composite was observed after 100 h at 1200°C, while after 150 h at 1300°C the C/C mass loss did not exceed 1%.     

Magnetic Characteristics of Ferrimagnetic Microspheres Prepared by Dispersion Polymerization

Summary: A magnetite‐based colloid was obtained by chemical co‐precipitation of iron(II) and iron(III) salts in alkaline medium and stabilized with oleic acid. Magnetic micron‐size poly(2‐hydroxyethyl methacrylate) (PHEMA)‐based latex particles of narrow size distribution were prepared by dispersion polymerization in toluene/2‐methylpropan‐1‐ol in the presence of three kinds of ferrimagnetic nanoparticles: chromium dioxide, maghemite, and magnetite. Cellulose acetate butyrate and dibenzoyl peroxide were used as the stabilizer and the initiator, respectively. The magnetic characteristics were examined with respect to behavior in the magnetic field and thermal stability. Our results show that chromium dioxide and derived PHEMA particles are magnetically stable in moderate temperatures up to about 100 °C. Maghemite particles are thermally stable up to 500 °C. Measurements of the hysteresis loops and remanent magnetization showed that embedment of magnetic particles in organic polymer has practically no effect on their magnetic hysteresis. All the samples reached magnetic saturation in fields below 0.3 T (saturation of magnetite). Regarding separation by the magnetic field, ultrafine, superparamagnetic magnetite particles show the best performance because of their magnetic susceptibility, the highest measured here, and the absence of coercive force.

Scanning electron micrograph of magnetite‐containing P(HEMA‐co‐25% GMA) microspheres.     

磷酸铝包覆氧化铁黄颜料的制备及其耐温性能研究

氧化铁黄颜料受热易脱水变色,限制了其在温度较高环境下的应用。提高氧化铁黄的热稳定性具有很重要的意义。通过液相水解沉积的方法对氧化铁黄表面进行磷酸铝表面包覆,研究了磷酸铝包膜的工艺条件（pH、包膜量、温度）对氧化铁黄包覆的表面形貌和微观结构的影响。结果表明：在pH为7、磷酸铝的包膜量为13%、包覆温度为65 ℃时,在氧化铁黄表面的包覆效果最佳。采用色差法研究了在最佳条件下进行磷酸铝包覆的氧化铁黄颜料,结果表明其耐温性得到显著提高。     

Influence of two structural phases of Fe3O4 and γ‐Fe2O3 on the properties of polyimide/iron oxide composites

Partially aliphatic polyimide/iron oxide composites based on the poly(amic acid) from 5‐(2,5‐dioxotetrahydro‐3‐furyl)‐3‐methyl‐3‐cyclohexene‐1,2‐dicarboxylic acid anhydride and 4,4′‐oxydianiline with iron oxide in different weight percentages were obtained. The structural phases of the transition of magnetite to maghemite occurring in these composites, at different temperatures, are discussed. The physical characteristics, including magnetic, thermal, structural and morphological properties, evaluated using X‐ray diffraction, scanning electron microscopy and thermal analysis, are influenced by the interplay of the filler content and the structural changes of the composite. The X‐ray diffraction patterns of all samples show a cubic structure indexed as magnetite (Fe₃O₄) or maghemite (γ‐Fe₂O₃). Quantification of these two phases was evidenced by the Rietveld method. The electrical properties analysed under different humidity conditions evidence the potential applicability of these polyimide/iron oxide materials as humidity sensors. © 2015 Society of Chemical Industry     

油酸、聚甲基丙烯酸甲酯修饰可磁化颗粒的磁流变液的流变行为

主要研究了拥有相同极性基团不同长度的非极性基团的表面活性剂对磁流变液流变行为的影响。分别以油酸、聚甲基丙烯酸甲酯修饰后的羰基铁粉为可磁化颗粒,硅油为载液,经过超声分散制备磁流变液。黏度测试表明,低速剪切时,颗粒表面表面活性剂层的空间位阻作用（熵斥力）起主导作用,黏度降低;高速剪切时,表面活性剂层又会增大颗粒的内摩擦,使黏度增加。通过流变模型的定量分析也印证了上述结论。磁流变测试表明,油酸为表面活性剂的磁流变液对磁场有更强烈的响应,形成更强的链束结构,屈服应力增大,而聚甲基丙烯酸甲酯的作用相反。两种表面活性剂都明显改善磁流变液的沉降稳定性能,降低了沉降速率与最终沉降量。本研究为磁流变液表面活性剂的选用提供了参考。     

Permalloy/alumina soft magnetic composite compacts obtained by reaction of Al-permalloy with Fe2O3 nanoparticles upon spark plasma sintering

Composite sintered soft magnetic materials of permalloy/alumina type have been obtained by reactive spark plasma sintering. The composite compacts have been obtained by sintering of Ni71.25Fe23.75Al5 alloy with 3 and 5% (wt.) Fe₂O₃ nanoparticles. The Ni based alloy with large particles (up to hundreds of μm) have been covered by a thin layer of iron ferric oxide nanoparticles (20–40 nm). The as obtained composite particles have been subjected to sintering process using a homemade installation at 900 °C for 10 min. Upon sintering process several reactions between Ni-based alloy and iron oxide are induced, the main phase resulting from reaction is alumina-Al₂O₃ as it results by X-ray diffraction investigations. According to the scanning electron microscopy and energy dispersive X-ray spectroscopy investigations, alumina forms a matrix embedding the Ni-based particles. The alumina matrix is continuous, but the layer has large variation in width, and offers a high electrical resistivity. A mechanism of formation is proposed for the alumina matrix composite compacts when using Al-permalloy powder and iron oxide. The compacts have been tested in DC and AC for magnetic characteristics.     

Double‐miniemulsion preparation of Fe3O4/poly(methyl methacrylate) magnetic latex

Magnetic poly(methyl methacrylate) (PMMA) microspheres were prepared by double‐miniemulsion polymerization. First, oleic acid coated magnetite particles synthesized by means of coprecipitation were dispersed into octane to obtain a ferrofluid. The ferrofluid and MMA were emulsified to form O/W emulsion, respectively. Subsequently two miniemulsions were mixed together for polymerization. The obtained magnetic polymer particles were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, X‐ray powder diffraction, and thermogravimetry. The results showed that oleic acid coated magnetite particles were well encapsulated in PMMA. The effects of initiator dosage and monomer concentration on the conversion of MMA were also investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis by in situ chemical oxidative polymerization and characterization of polyaniline/iron oxide nanoparticle composite

Polyaniline (PANI) is a well‐studied material and is the pre‐eminent electrically conducting organic polymer with the potential for a variety of applications such as in batteries, microelectronics displays, antistatic coatings, electromagnetic shielding materials, sensors and actuators. Its good environmental as well as thermal stability and electrical conductivity tunable by appropriate doping make PANI an ideal active material for several applications. In this paper, we report the synthesis of water‐dispersible colloidal PANI/iron oxide composite nanoparticles using an in situ chemical oxidation polymerization method in a micellar medium of sodium dodecylsulfate, where the cores (iron oxide) are embedded in a PANI matrix layer. Transmission electron micrographs showed evidence of the formation of an iron oxide core/PANI shell composite with a thin layer of PANI over the iron oxide cores. The results of thermogravimetric, Fourier transform infrared and UV‐visible analysis indicated that the iron oxide nanoparticles could improve the composite thermal stability possibly due to the interaction between iron oxide particles and PANI backbone. We believe that the synthetic route described can also be adapted for the assembly of hierarchical structures of other metal oxides or hydroxides onto various cores. Copyright © 2010 Society of Chemical Industry     

A simple synthesis of magnetically modified zeolite

A composite of zeolite with magnetite was prepared by urethane coating. Formation of magnetic modified zeolite (MMZ) was confirmed by magnetization measurements and X-ray diffraction (XRD) pattern analysis. Also, scanning electron microscopic (SEM) analysis reveals the presence of zeolite and magnetite particles. It is thought that approximately 16% urethane polymer is retained in composite particle as a result of thermogravimetric analysis (TGA).     

Alkaline Corrosion Resistance of Anodized Aluminum Coated with Zirconium Oxide by a Sol-Gel Process

To improve the alkaline corrosion resistance of aluminum, composite films were prepared that consisted of a porous layer of anodically grown aluminum oxide filled with zirconium oxide, with a zirconium oxide coating layer that was deposited thereon via the sol—gel process, using a dip-coating technique. The alkaline corrosion resistance of these composite films was extremely improved when this coating layer was placed on an anodic oxide film. Comparisons of the composite film and conventional anodic oxide film showed that the alkaline corrosion resistance of the composite film was increased by a factor of 24–50. Because these composite films, which have high corrosion resistance, indicated a vibration phenomenon of voltage in the duration time curve of the electromotive force measurement, the composite film had a self-repairing action for alkaline corrosion.     

Synthesis of nanosized biogenic magnetite and comparison of its catalytic activity in ozonation

Nanosized biogenic iron oxide was synthesized by dissimilatory iron-reducing bacterium, Shewanella sp. This biogenic iron oxide was evaluated as a catalyst in the heterogeneous catalytic ozonation of para-chlorobenzoic acid (pCBA). XRD and TEM analyses showed that the biogenic iron oxide was magnetite phase (Fe₃O₄) and was composed of nanosized irregular particles in the range of 10.0 ± 4.0 nm in diameter. Catalytic ozonation was carried out at acidic pH levels (2.5) in the presence of the biogenic magnetite. It was clearly shown that the biogenic magnetite enhanced the degradation of pCBA by the production of OH resulting from the catalytic decomposition of ozone on the surface of the particles. Functional groups on the surface of the biogenic magnetite played a role of catalytic active sites, and this was confirmed by FT-IR and titration analyses. However, the biogenic magnetite showed a lower catalytic efficiency than the commercial nanosized magnetite, resulted from the formation of 4 times bigger aggregates of the biogenic magnetite than the commercial one in aqueous solutions. The R_ct values representing the ratio of hydroxyl radicals and ozone were found to be divided into two regions during reaction. The R_ct values during first period (1 min) were much greater than those during second period, and this was caused by initial rapid decrease of pCBA.     

Interpolyelectrolyte complexes of maleic acid copolymers and chitosan for stabilization and functionalization of magnetite nano‐ and microparticles

A facile method of preparation of stabilized and functionalized nano‐ and microparticles of magnetite by successive application of oppositely charged polymers with a regular structure of macromolecular chains (chitosan and maleic acid copolymers) onto Fe₃O₄ core are developed. This approach makes it possible to create two types of magnetite interpolyelectrolyte shells, containing carboxylic or amino groups in outer layer of shell. Composition and magnetic properties of composite particles depend on nature of the copolymer of maleic acid, reaction conditions and size of obtained particles. The carboxylic groups of copolymer in outer layer of interpolyelectrolyte shell were converted into reactive anhydride groups by heating. Thermal treatment also leads to covalent crosslinking of shell and improves stability of composites both in acidic and alkaline media. Horseradish peroxidase was successfully immobilized onto covalently crosslinked and activated microparticles of Fe₃O₄ in aqueous medium without of condensing agents. The proposed reproducible and low‐cost technique does not use toxic reagents or solvents at all stages, including preparation of Fe₃O₄, formation, activation and crosslinking, of magnetite shell, modification of activated surface of composite particles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39663.     

Magnetite nanoparticles stabilized with polymeric bilayer of poly(ethylene glycol) methyl ether-poly(?-caprolactone) copolymers

In this work, we report a synthetic method of water dispersible magnetite nanoparticles having oleic acid and poly(ethylene glycol) methyl ether-poly(?-caprolactone) (mPEG-PCL) amphiphilic block copolymer as polymeric stabilizers. The particles were prepared by coprecipitation of Fe(II) and Fe(III) in NH₄OH and had bilayer surface with hydrophobic inner layer and hydrophilic corona. mPEG-PCL copolymer was synthesized by a ring-opening polymerization of ?-caprolactone using mPEG as a macroinitiator in the presence of stannous octoate catalyst. FTIR and thermogravimetric analysis (TGA) indicated the presence of the copolymer on the particle surface. Roles of reaction parameters, such as stabilizer concentrations and time of ultrasonicating treatment, on percent of magnetite in the complex and its magnetic properties were investigated. Transmission electron microscopy (TEM) showed the average particle size about 9.0 ± 1.1 nm in diameter. Vibrating sample magnetometry (VSM) measurement indicated that the magnetite nanoparticles were superparamagnetic at room temperature. Approximately 6.8 ± 0.5% of indomethacin model drug (68 μg/mg of magnetite) was effectively entrapped on the particles.