Ultrasonic-assisted synthesis and magnetic studies of iron oxide/MCM-41 nanocomposite

Iron oxide nanoparticles were stabilized within the pores of mesoporous silica MCM-41 amino-functionalized by a sonochemical method. Formation of iron oxide nanoparticles inside the mesoporous channels of amino-functionalized MCM-41 was realized by wet impregnation using iron nitrate, followed by calcinations at 550 °C in air. The effect of functionalization level on structural and magnetic properties of obtained nanocomposites was studied. The resulting materials were characterized by powder X-ray diffraction (XRD), high-resolution transmission electron microscopy and selected area electron diffraction (HRTEM and SAED), vibrating sample and superconducting quantum interface magnetometers (VSM and SQUID) and nitrogen adsorption–desorption isotherms measurements. The HRTEM images reveal that the most of the iron oxide nanoparticles were dispersed inside the mesopores of silica matrix and the pore diameter of the amino-functionalized MCM-41 matrix dictates the particle size of iron oxide nanoparticles. The obtained material possesses mesoporous structure and interesting magnetic properties. Saturation magnetization value of magnetic iron oxide nanopatricles stabilized in MCM-41 amino-functionalized by in situ sonochemical synthesis was 1.84 emu g⁻¹. An important finding is that obtained magnetic nanocomposite materials exhibit enhanced magnetic properties than those of iron oxide/MCM-41 nanocomposite obtained by conventional method. The described method is providing a rather short preparation time and a narrow size distribution of iron oxide nanoparticles.     

Fabrication of nanocomposite particles with superparamagnetic and luminescent functionalities

A new kind of superparamagnetic luminescent nanocomposite particles has been synthesized using a modified Stöber method combined with an electrostatic assembly process. Fe₃O₄ superparamagnetic nanoparticles were coated with uniform silica shell, and then 3-aminopropyltrimethoxysilane was used to terminate the silica surface with amino groups. Finally, negatively charged CdSe quantum dots (QDs) were assembled onto the surface of the amino-terminated SiO₂/Fe₃O₄ nanoparticles through electrostatic interactions. X-ray diffraction (XRD), transmission electron microscopy (TEM), microelectrophoresis, UV-vis absorption and emission spectroscopy and magnetometry were applied to characterize the nanocomposite particles. Dense CdSe QDs were immobilized on the silica surface. The thickness of silica shell was about 35 nm and the particle size of the final products was about 100 nm. The particles exhibited favorable superparamagnetic and photoluminescent properties.     

A magnetic zeolitic nanocomposite from occlusion of silica-coated iron species by crystalline titanosilicate-1

This paper examines the preparation of novel magnetic zeolitic nanocomposites from the occlusion of silica-coated iron species by crystalline titanosilicate-1. The results revealed that well-crystallized TS-1 could be synthesized in the presence of silica-hematite nanoparticles. Each as-made nanocomposite particle exhibited a compact and monolithic ‘brick-like’ morphology with a size of ca. 400 nm × 200 nm × 200 nm. The non-magnetic hematite (iron oxide) in such an as-made nanocomposite can be reduced by hydrogen to produce ferrimagnetic iron oxides and ferromagnetic elemental iron. The resultant nanocomposite consists of TS-1 as outer shell, which occludes a small portion of silica-iron species as the core with a total magnetization value of 3.7 emu/g. The silica coating and size of hematite nanoparticles, the presence of ammonium carbonate as the crystallization-mediating agent for nucleation and growth of TS-1 are critical factors when preparing such nanocomposites.     

Preparation, characterization and microwave absorption properties of polyaniline/Co0.5Zn0.5Fe2O4 nanocomposite

The polyaniline (PAni)/Co_0.5Zn_0.5Fe₂O₄ nanocomposite was prepared by an in situ polymerization in an aqueous solution. The products were characterized by Fourier transform infrared (FT-IR) spectrometer, ultraviolet-visible (UV-vis) spectrometer, X-ray diffraction (XRD) and transmission electron microscope (TEM). The average particle size of the PAni/Co_0.5Zn_0.5Fe₂O₄ was estimated to be about 70 nm by TEM. The reflection loss (dB) of the nanocomposite was measured at different microwave frequencies in X-band (8.2-12.4 GHz), U-band (12.4-18 GHz) and K-band (18-26.5 GHz) by radar cross-section (RCS) method according to the national standard GJB-2038-94. The results showed the reflection loss of the PAni/Co_0.5Zn_0.5Fe₂O₄ nanocomposite was higher than that of the PAni. The maximum reflection loss of the PAni/Co_0.5Zn_0.5Fe₂O₄ nanocomposite was about −39.9 dB at 22.4 GHz with a bandwidth of 5 GHz (full frequency width at about a half of the peak response). In conclusion, this sample is a good microwave shielding and absorbing materials at higher frequency.     

Preparation and properties of UV-cured acrylated silane intercalated polymer/LDH nanocomposite

A novel UV-cured polymer/layered double hydroxide (LDH) nanocomposite was prepared by modifying the LDH with sodium dodecyl sulfate (SDS) and [3-(methyl-acroloxy)propyl]trimethoxysilane (KH570) followed by UV irradiation after blended into a acrylate system. From the XRD analyses, the SDS-modified LDH-DS presented the basal spacing of 2.67 nm, whereas the further KH570-intercalated LDH-KH showed a slight decrease to 2.41 nm. After UV irradiated the exfoliated microstructure was formed, and observed by TEM and HR-TEM, showing the fine dispersion and random orientation of LDH in the polymer matrix. The storage modulus and glass transition temperature of the nanocomposite containing 5% LDH-KH increased to 47.5 MPa and 67.8 °C, respectively, from 39.7 MPa and 66 °C of the pure polymer from DMTA measurements. The tensile strength and Persoz hardness were enhanced to 10.6 MPa and 111 s, respectively, from 7.7 MPa and 85 s of the pure polymer.     

Palladium supported on functionalized mesoporous silica as an efficient catalyst for Heck reaction

Pd nanoparticles supported in functionalized mesoporous silica were prepared. Mesoporous silica support was modified with [3-(2-aminoethyl aminopropyl)] trimethoxysilane. Palladium ions were grafted onto the functionalized mesoporous silica and reduced with hydrazine hydrate to obtain the Pd nanoparticles supported on functionalized mesoporous silica. The Pd loading in the nanocomposite of Pd supported on the functionalized mesoporous silica is 4.30 wt%. CO chemisorption analysis on the nanocomposite shows a Pd dispersion as high as 35% and a Pd surface area of 156 m²/g. The surface area, pore size, and pore volume decrease slightly with the incorporation of the Pd nanoparticles into the functionalized mesoporous silica. Pd supported on the functionalized mesoporous silica with controlled molar ratio of amino groups to palladium exhibits an excellent catalytic activity and low Pd leaching for the Heck carbon-carbon coupling reaction. The catalyst can be reused for at least six recycles in air with only a minor loss of activity.     

Preparation of polymer/LDH nanocomposite by UV-initiated photopolymerization of acrylate through photoinitiator-modified LDH precursor

The exfoliated polymer/layered double hydroxide (LDH) nanocomposite by UV-initiated photopolymerization of acrylate systems through an Irgacure 2959-modified LDH precursor (LDH-2959) as a photoinitiator complex was prepared. The LDH-2959 was obtained by the esterification of 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959) with thioglycolic acid, following by the addition reaction with 3-(2,3-epoxypropoxy)propyltrimethoxysilane (KH-560), finally intercalation into the sodium dodecyl sulfate-modified LDH. For comparison, the intercalated polymer/LDH nanocomposite was obtained with additive Irgacure 2959 addition. From the X-ray diffraction (XRD) measurements and HR-TEM observations, the LDH lost the ordered stacking-structure and well dispersed in the polymer matrix at 5 wt% LDH-2959 loading. The glass transition temperature of UV-cured exfoliated nanocomposites increased to 64 °C from 55 °C of pure polymer without LDH addition. The tensile strength was improved from 10.1 MPa to 25.2 MPa, as well the Persoz hardness enhanced greatly, while the elongation at break remained an acceptable level.     

Silica-[Fe(bpy)3] composite particles with photo-responsive change of color and magnetic property

Photo-induced complex formation of tris-2,2′-bipyridine iron(II) complex ([Fe(bpy)₃]²⁺) from the mixture of FeCl₃ and 2,2′-bipyridine was achieved in silica gel containing 150-300 μm silica particles, derived from a complex emulsion with HCl aqueous solution and tetraethyl orthosilicate (TEOS). More than 95% of Fe(III) and 2,2′-bipyridine were incorporated in silica particles. Yellow-red color change, due to [Fe(bpy)₃]²⁺, was observed by irradiation with 365 nm UV beam at 0.3 mW cm⁻² for 120 s. The complex formation accompanies simultaneous spin transition from the high-spin state of Fe(III) to the low-spin state of Fe(II).     

Synthesis of PbS/poly (vinyl-pyrrolidone) nanocomposite

A simple solution growth method for synthesis of nanocomposite of PbS nanoparticles in poly(vinyl-pyrrolidone) (PVP) polymer is described. The nanocomposite is prepared from methanolic solution of lead acetate (PbAc), thiourea (TU) and PVP at room temperature (∼27 °C). Optical absorption spectrum of PbS/PVP nanocomposite solution shows strong absorption from 300 to 650 nm with significant bands at 400 and 590 nm which is characteristic of nanoscale PbS. Spin-coated nanocomposite films on glass have an absorption edge at ∼650 nm with band gap of 2.55 eV. Fourier transform infrared (FTIR) spectroscopy of PbS/PVP nanocomposite and PVP shows strong chemical bond between PbS nanoparticles and host PVP polymer. The transmission electron microscope (TEM) images reveal that 5-10 nm PbS particles are evenly embedded in PVP polymer. The formation of PbS is confirmed by selective area electron diffraction (SAED) of a typical nanoparticle.     

Templated synthesis of nanosized mesoporous carbons

Mesoporous carbon materials formed by nanosized particles have been synthesized by means of a nanocasting technique based on the use of mesostructured silica materials as templates. We found that the modification of the chemical characteristics of the surfactant employed allows mesostructured silica materials with particle sizes <100 nm to be synthesised. The mesoporous carbons obtained from these silica materials retain the structural properties of the silica used as template and consequently they have a particle size in the 20-100 nm range. These carbons exhibit large BET surfaces areas (up to 1300 m² g⁻¹) and high pore volumes (up to 2.5 cm³ g⁻¹), a framework confined porosity made up of uniform mesopores (3.6 nm) and an additional textural porosity arising from the interparticle voids between the sub-micrometric particles. The main advantage of nanometer-sized mesoporous carbons in relation to the micrometer-sized carbons is that they have enhanced mass transfer rates, which is important for processes such as adsorption or catalysis.     

The tensile fatigue behaviour of a silica nanoparticle-modified glass fibre reinforced epoxy composite

An anhydride-cured thermosetting epoxy polymer was modified by incorporating 10 wt.% of well-dispersed silica nanoparticles. The stress-controlled tensile fatigue behaviour at a stress ratio of R = 0.1 was investigated for bulk specimens of the neat and the nanoparticle-modified epoxy. The addition of the silica nanoparticles increased the fatigue life by about three to four times. The neat and the nanoparticle-modified epoxy resins were used to fabricate glass fibre reinforced plastic (GFRP) composite laminates by resin infusion under flexible tooling (RIFT) technique. Tensile fatigue tests were performed on these composites, during which the matrix cracking and stiffness degradation was monitored. The fatigue life of the GFRP composite was increased by about three to four times due to the silica nanoparticles. Suppressed matrix cracking and reduced crack propagation rate in the nanoparticle-modified matrix were observed to contribute towards the enhanced fatigue life of the GFRP composite employing silica nanoparticle-modified epoxy matrix.     

Sonochemical synthesis of (3-aminopropyl)triethoxysilane-modified monodispersed silica nanoparticles for protein immobilization

3-Aminopropyltriethoxysilane modified monodispersed silica nanoparticles were synthesized by a rapid sonochemical co-condensation synthesis procedure. The chemical nature of surface organic modifier on the obtained modified silica nanoparticle was characterized by ¹³C and ²⁹Si MAS Nuclear Magnetic Resonance (NMR) spectroscopies, Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA)- differential scanning calorimetry (DSC). Due to the strengthened positive surface charge of the silica nanoparticles by the modification with aminopropyl groups, the capability for bovine serum albumin (BSA) adsorption was significantly increased as compared with bare silica nanoparticles. 80 mg/g BSA was adsorbed on modified silica nanoparticles, whereas only 20 mg/g BSA could be loaded on pure silica nanoparticles. The enhanced positive surface charge repelled proteins with net positive charge and the modified silica nanoparticles exhibited negligible adsorption of lysozyme, thus a selective adsorption of proteins could be achieved.     

Preparation of gold-silica heterogeneous nanocomposite particles by alcohol-reduction method

Au-silica heterogeneous nanocomposite particles were prepared by novel preparation strategy involving alcohol-reduction method using 3-aminopropyltrimethoxysilane (APTMS) as a binder between silica surface and Au nanoparticles, and using PVP as a stabilizer for Au nanoparticles. The evolution of morphology of composite particles was investigated with increasing reaction time at different Au precursor concentrations of 100 ppm and 250 ppm using UV-vis spectrophotometer and TEM. It is shown that the size of immobilized Au particles on silica surface can be controlled with the variation of reaction rate via adjusting Au precursor concentration and reaction time, but the high concentration of Au precursor hinders the immobilization of well-defined Au nanoparticles due to the slow reduction rate of Au precursor. On the basis of experimental results, the role of APTMS and PVP on the formation of composite particles and the effect of Au precursor concentration on the morphological evolution of composite particles are briefly discussed.     

A novel magnetic nanocomposite involving anatase titania coating on silica-modified cobalt ferrite via lower temperature hydrolysis of a water-soluble titania precursor

A high surface area magnetic nanocomposite titania/silica/cobalt ferrite photocatalyst was synthesized via controlled hydrolysis and condensation of water-soluble titanium bis-ammonium lactato dihydroxide at relatively lower temperature (<97 °C) and characterized by XRD, FTIR, HRTEM, BET, XPS and magnetism analysis. The results reveal that as-prepared photocatalyst possesses a core/shell structure involving ferrite particles sequentially coated with coherent silica layer and anatase nanocrystallites via a heterogeneous nucleation and growth mechanism. The photodegradation of the photocatalyst for methyl orange is comparative to Degussa P25 and higher than the heated samples, being tentatively attributed to the proper microstructure and isolation/immobilization functions by silica intermediate phase as well as the surface-bond hydroxyl groups.     

Preparation of nanocomposite of polyaniline and gamma-zirconium phosphate (γ-ZrP) by power ultrasonic irradiation

The high-intensity ultrasound was applied to the preparation of nanocomposite of polyaniline (PANI) and gamma-zirconium phosphate (γ-ZrP) by intercalation of aniline into γ-ZrP. The intercalation rate was enhanced greatly and the interlayer distance of aniline-intercalated γ-ZrP was determined to be 16.0 Å. The intercalated aniline polymerized at low pH during the sonication by initiator (NH₄)₂S₂O₈ and nanocomposite of exfoliation of γ-ZrP in PANI bulk was obtained. The intercalated or exfoliated compounds were characterized by XRD, FTIR, TEM, UV-Vis spectrum, and TG-DTA.     

Structure and biological response of polymer/silica nanocomposites prepared by sol–gel technique

Structure of P(EMA-co-HEA)/SiO₂ nanocomposites with silica content in the range from 0 to 30 wt.% was correlated with cell behavior on substrates of those compositions by making use of two different populations of primary human cells: articular cartilage chondrocytes and dental pulp cells. Substrates were prepared by the simultaneous copolymerization of the organic monomers and the sol–gel reaction of the silica precursor in different proportions, which led to weight fractions of the silica phase in the materials closely matching the stoichiometric ratios employed during the preparation, both in the bulk and at the material surface. The silica nanophase increases surface wettability and improves the mechanical properties of the base materials. Both chondrocytes and dental pulp cells were cultured on serum-coated nanocomposite substrates in the same conditions, but very different cellular responses were obtained. While chondrocytes adhered and proliferated, dental pulp cells formed viable aggregates weakly adhered on the sample that were viable up to 11 days. The results suggest that these sol–gel derived nancomposites may be used as culture surfaces maintaining the dental pulp cell phenotype in vitro.     

Preparation and magnetic properties of SrFe12O19/Ni0.5Zn0.5Fe2O4 nanocomposite ferrite microfibers via sol–gel process

SrFe₁₂O₁₉/Ni_0.5Zn_0.5Fe₂O₄ nanocomposite ferrite microfibers with diameters of 1–2 μm have been prepared by the sol–gel process. The SrFe₁₂O₁₉/Ni_0.5Zn_0.5Fe₂O₄ nanocomposite ferrites are formed after the precursor calcined at 850 °C for 2 h, fabricating from nanosized particles with a uniform phase distribution. The ferrite grain size increases with the calcination temperature. The magnetic properties for the nanocomposite ferrite microfibers are mainly influenced by the chemical composition and grain size. The nanocomposite ferrite microfibers obtained at 900 °C show the enhanced specific saturation magnetization (M_sh) of 64.8 Am² kg⁻¹, coercivity (H_c) of 146.5 kA m⁻¹ and remanence (M_r) of 33.6 Am² kg⁻¹ owing to the exchange–coupling interaction. This exchange–coupling interaction in the SrFe₁₂O₁₉/Ni_0.5Zn_0.5Fe₂O₄ nanocomposite ferrite microfibers has been discussed.     

Ultrafine magnetic particles dispersed in silica: Characterization of cobalt iron citrate precursor and magnetic properties

Ultrafine magnetic particles dispersed in a silica matrix were successfully obtained by treatment of a cross-linked cobalt iron citrate precursor, synthesized by a modified Pechini route, with 0.001 M K₂Cr₂O₇ at 130 °C. The IR and NMR spectroscopic characterization of the precursor gel containing Co²⁺ and Fe³⁺ shows that the citric acid reacts with the metallic ions by coordination, the ethylene glycol by esterification and the tetraethylorthosilicate by substitution. SQUID measurements of the composite indicate superparamagnetic behavior. The blocking temperature, from the peak of the zero-field-cooled measurements, was 3 K at 1000 Oe. The magnetic diameter calculated using Langevin's equation was 4 nm.     

Influence of SiO2 fillers on microwave absorption properties of carbonyl iron/carbon black double-layer coatings

Epoxy resin (ER) based double-layer composite coatings were prepared with the thickness of 1.2 mm, employing carbonyl iron (CI) and carbon black (CB) as absorbents in the matching layer and absorption layer respectively. Especially, SiO₂ was introduced into the matching layer as wave-transmission material to improve the matching impendence. The complex permittivity, complex permeability and absorption properties were investigated in 2–18 GHz. With increasing SiO₂ content in the matching layer, the reflection loss (RL) was enhanced in the range 2–18 GHz. When the coating with the optimized SiO₂ and CI weight concentration (SiO₂:CI:ER) of 2:5:1, the optimal RL got to −17.3 dB and the effective absorption band (RL better than −4 dB) reached 5.7 GHz. In comparison, the minimum RL value was only −5.9 dB and the bandwidth (RL better than −4 dB) was just 4.1 GHz for the SiO₂-free composite coating.