Soluble colloidal manganese dioxide: Formation, identification and prospects of application

Soluble colloidal MnO₂ was prepared by the reduction of KMnO₄ by three reducing agents as MnSO₄, Na₂S₂O₃ and HCOOH in neutral aqueous solutions at 25°C. Under suitable conditions, these solutions were dark brown in color and found to remain stable and transparent for several weeks. The obtained colloid was characterized by spectrophotometric and coagulation methods. The spectral behavior of soluble colloidal MnO₂ was studied. The λ_max was 390 nm when MnO₂ was prepared by the reduction of KMnO₄ by MnSO₄. Both the λ_max and the molar extinction coefficient depended on the method of preparation of colloidal MnO₂. The formation of MnO₂ was confirmed by the determination of the oxidation state of Mn-species in MnO₂. The behavior of as-prepared colloidal solution obeys Beer Lambert law, if the concentrations of the colloidal particles are assumed to be equal to [MNO ₄ ^? ]₀. Both spectral analysis and that using Rayleigh’s law confirmed the existence of colloidal MnO₂. The observed coagulating efficiency depends not only on the concentration of electrolyte but also on the charge carried by the cation of the electrolyte. Stability of the colloidal particles in the aqueous solutions is determined by the negative charge on the surface of the colloidal particles.     

Experimental Study on Viscosity of Colloidal Silica in Aqueous Electrolytic Solutions

The relative viscosity of colloidal silica dispersion in aqueous electrolytic solutions as the function of volume fraction of dry particles in the solutions has been experimentally determined in this work, in order to study the effects of pH and electrolytes (Na₂SO₄ and AlCl₃) on the hydration of the silica surfaces in the solutions. The results have shown that the maximum relative viscosity of the silica dispersion and the strongest hydration of the silica in aqueous solutions appeared at neutral pH, while the stronger the acidity and the alkalinity of the aqueous solution, the weaker the hydration. In the presence of the electrolytes (Na₂SO₄ and AlCl₃), the relative viscosity of the silica dispersion reduced and the hydration of the silica in aqueous solutions became weak. The higher the concentration of the electrolytes, the weaker the hydration, indicating that the destabilization of the colloidal silica dispersion in aqueous solutions might be realized through adding the high-valence electrolytes to weaken the hydration of the particle surfaces (hydration forces between the particles). Also, it has been shown that the negative zeta potentials of the colloidal silica in aqueous solutions greatly reduced in the presence of the electrolytes. Therefore, the high-valence electrolytes (Na₂SO₄ and AlCl₃) as the coagulant of colloidal silica in aqueous solutions might be originated from that the presence of the electrolytes simultaneously reduces the electrical double layer repulsive force and the hydration repulsive forces between the particles in aqueous solutions.     

Investigation of iron oxide nanoparticles by capillary zone electrophoresis

The electrophoretic behavior of γ-Fe₂O₃ nanoparticles was studied in aqueous solutions of Na₂SO₄-NaOH (pH 10.8) and of Na₂SO₄-Na₃cit (pH 7.1) as running electrolytes. Two electrophoretic zones (smooth and with spikes) due to colloidal and suspended particles of approximately the same size range were formed during the runs. The suspension stability and size distribution were shown to depend on the composition of electrolyte used for dispersing the solids. The effects of electric field strength, injection time, injection pressure as well as sodium citrate concentration were studied and particle electrophoretic mobilities were calculated. Electron micrographs of particles studied were obtained. Preparation of reference samples based on the colloidal γ-Fe₂O₃ has been discussed.     

Magnetite nanorod thermotropic liquid crystal colloids: Synthesis, optics and theory

We have developed a facile method for preparing magnetic nanoparticles which couple strongly with a liquid crystal (LC) matrix, with the aim of preparing ferronematic liquid crystal colloids for use in magneto-optical devices. Magnetite nanoparticles were prepared by oxidising colloidal Fe(OH)(2) with air in aqueous media, and were then subject to alkaline hydrothermal treatment with 10moldm(-3) NaOH at 100°C, transforming them into a polydisperse set of domain magnetite nanorods with maximal length ～500nm and typical diameter ～20nm. The nanorods were coated with 4-n-octyloxybiphenyl-4-carboxylic acid (OBPh) and suspended in nematic liquid crystal E7. As compared to the conventional oleic acid coating, this coating stabilizes LC-magnetic nanorod suspensions. The suspension acts as a ferronematic system, using the colloidal particles as intermediaries to amplify magnetic field-LC director interactions. The effective Frederiks magnetic threshold field of the magnetite nanorod-liquid crystal composite is reduced by 20% as compared to the undoped liquid crystal. In contrast with some previous work in this field, the magneto-optical effects are reproducible on time scales of months. Prospects for magnetically switched liquid crystal devices using these materials are good, but a method is required to synthesize single magnetic domain nanorods.     

Magneto-Optical Properties of Silica Gel Containing Magnetite Fine Particles

The magnetic composite materials that consist of transparent matrix and magnetic fine particles are expected to have large residual magnetization and coercive force because of their fine magnetic domain structure, and also to show magneto-optical effects. Silica gels containing magnetite (Fe₃O₄) fine particles were prepared by sol-gel method. The magnetic, optical and magneto-optical properties of the composites were investigated by measurements of magnetization curves, UV-visible spectra and Faraday rotation in visible range. The saturation magnetization of the composite was almost as same as that expected from the amount of magnetite fine particles in it. Although the composites had large and broad absorption at around 400 nm, they still maintained their transparency. The origins of decrement of transparency attributed to the optical absorption of magnetite and scattering due to magnetite fine particles. The whole composites showed positive Faraday rotation under external static magnetic field due to the large contribution of diamagnetic silica gel matrix. Magnetite contributed negative Faraday rotation with maximum at around 470–480 nm to the magneto-optical spectra of the composites.     

Water-annealing regulated protein-based magnetic nanofiber materials: tuning silk structure and properties to enhance cell response under magnetic fields

In this study, flexible silk fibroin protein and biocompatible barium hexaferrite (BaM) nanoparticles were combined and electrospun into nanofibers, and their physical properties could be tuned through the mixing ratios and a water annealing process. Structural analysis indicates that the protein structure of the materials is fully controllable by the annealing process. The mechanical properties of the electrospun composites can be significantly improved by annealing, while the magnetic properties of barium hexaferrite are maintained in the composite. Notably, in the absence of a magnetic field, cell growth increased slightly with increasing BaM content. Application of an external magnetic field during in vitro cell biocompatibility study of the materials demonstrated significantly larger cell growth. We propose a mechanism to explain the effects of water annealing and magnetic field on cell growth. This study indicates that these composite electrospun fibers may be widely used in the biomedical field for controllable cell response through applying different external magnetic fields.     

ELECTROCHEMICAL PROPERTIES OF ASPHALTENE PARTICLES IN AQUEOUS SOLUTIONS

The electrical properties of colloidal asphaltene/water solution interface were determined by carrying out the potentiometric titration and electrokinetic measurements. Asphaltenes in aqueous solutions exhibit typical organic colloid properties i.e. surface charge and electrophoretic mobility. It was considered that the surface charge at the asphaltene particles is a result of protonation and dissociation reactions of surface functional groups. On the base of the surface charge density data vs. pH the surface reaction constants were calculated by numerical method. The agreement of these values with calculated ones, on the base of ζ potential data, is noticeable.

The characteristic feature of the investigated systems is the maximum, appearing on the curve ζ potential vs. electrolyte concentration. This behaviour is explained by _”hair layer ” structure of the asphaltene surface     

Synthesis and magnetic properties of the exchange-coupled SrFe10.7Al1.3O19/Co composite

The magnetic composite SrFe_10.7A_l1.3O₁₉/Co was synthesized by ethylene glycol reduction of cobalt ions on the surface of hexaferrite particles dispersed in the solvent. The resulting material contained magnetically hard submicron hexaferrite particles covered by soft magnetic cobalt nanoparticles. The composite demonstrated the exchange-coupling effect between hard and soft magnetic phases.     

A Fluorescence Polarization Study of Polyaromatic Hydrocarbons Adsorbed on Colloidal Kaolin

Abstract

The adsorption of a number of polyaromatic hydrocarbons onto aqueous colloidal kaolin was studied. The fluorescence polarization and hence the fluorescence anistropy of the hydrocarbons was measured as a function of their concentrations in aqueous solutions containing the colloid. The fluorescence anisotropy was found to be highest for dilute solutions of polyaromatic hydrocarbons, with often sharp decreases at higher concentrations. More concentrated solutions gave an isotropies similar to those of plain aqueous solutions of the fluorophores. The concentration versus fluorescence anisotropy curves and BET surface area data were used to calculate surface coverage of the colloid by the adsorbed hydrocarbons. Coverage in the range of 1% to 14% of the colloid surface was found at surface saturation for the compounds studied. This suggested that colloidal clays have the potential of transporting polyaromatic hydrocarbons through environmental waters.     

Improving titanium dioxide dispersion in water through surface functionalization by a dicarboxylic acid

In this work, we show evidence of improving the dispersion of titanium dioxide particles in water. This is observed in the titanium dioxide-water colloid by the shear-thinning flow behavior in rheological measurements induced by the functionalization of a glutaric acid layer on the surface of titanium dioxide particles. The characterization of the layer was achieved by using infrared spectroscopy and ^13?C nuclear magnetic resonance. Rheological measurements corroborated that functionalization of TiO₂ particles decreases the rheological properties such as viscosity measurements at a constant shear rate in two orders of magnitude compared with the pure TiO₂ in suspensions. We present the results as a novel strategy to limit the formation of agglomerates in these colloidal suspensions, and this will be of great use in applications in the paints field and printing technologies.     

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.     

Features of composites prepared by radical graft-polymerization of styrene to a hydrophilic macromer adsorbed on ultrafine colloidal particles

Polymer modifications of ultrafine monodispersed colloidal metal oxide particles, smaller than 80 nm in diameter, by the graft-polymerization of styrene to a hydrophilic macromer adsorbed on the surface were investigated. The polymerization in ethanolic silica and titania colloid solution, which had negatively larger ζ-potentials, ?30 and ?42 mV in neutral aqueous solution respectively, gave poly(styrene)–silica or titania composite, being of nonspherical shape. The modifications of colloidal particles, having lower surface energy, such as Al(OH)₃ and CeO₂–TiO₂–SiO₂ complex, led to the formation of spherical composites, ranging in size from 500 to 3000 nm, of scattered metal oxide or hydroxide particles.     

Preparation of hybrid hollow capsules formed with Fe3O4 and polyelectrolytes via the layer-by-layer assembly and the aqueous solution process

Well-defined magnetic hybrid hollow capsules formed with magnetite (Fe₃O₄) and polyelectrolyte-multilayer films were successfully prepared through colloidal templating with layer-by-layer assembly of polyelectrolytes, followed by aqueous solution deposition of Fe₃O₄. Pd catalyst nanoparticles played an important role in the deposition of Fe₃O₄. Pd nanoparticles favorably adsorbed onto the polyelectrolyte layer with positively charged amino groups. Hollow capsules were obtained by the removal of the melamine–formaldehyde core particles. Although the processes were performed in aqueous solutions at temperatures less than 60 °C, X-ray diffraction patterns revealed that the deposited Fe₃O₄ was highly crystallized. The hollow capsules were stably dispersed in water; however, the capsules rapidly congregated around a locally applied magnet.     

A microfluidics-dispensing-printing strategy for Janus photonic crystal microspheres towards smart patterned displays

From the implementation point of view, the printable magnetic Janus colloidal photonic crystals (CPCs) microspheres are highly desirable. Herein, we developed a dispensing-printing strategy for magnetic Janus CPCs display via a microfluidics-automatic printing system. Monodisperse core/shell colloidal particles and magnetic Fe₃O₄ nanoparticles precursor serve as inks. Based on the equilibrium of three-phase interfacial tensions, Janus structure is successfully formed, followed by UV irradiation and self-assembly of colloid particle to generate magnetic Janus CPCs microspheres. Notably, this method shows distinct superiority with highly uniform Janus CPCs structure, where the TMPTA/Fe₃O₄ hemisphere is in the bottom side while CPCs hemisphere is in the top side. Thus, by using Janus CPCs microspheres with two different structural colors as pixel points, a pattern with red flower and green leaf is achieved. Moreover, 1D linear Janus CPCs pattern encapsulated by hydrogel is also fabricated. Both the color and the shape can be changed under the traction of magnets, showing great potentials in flexible smart displays. We believe this work not only offers a new feasible pathway to construct magnetic Janus CPCs patterns by a dispensing-printable fashion, but also provides new opportunities for flexible and smart displays.     

Precipitation and recrystallization of uniform CuCl particles formed by aggregation of nanosize precursors

Uniform, spherical CuCl particles were obtained by mixing aqueous solutions of CuCl ₂ and ascorbic acid in the presence of polyvinylpyrrolidone (PVP) as dispersing agent. The size and the uniformity of the resulting particles depended on the volume ratio of the reactant solutions, their concentrations, the distribution of the stabilizers, and the mixing method. The single jet precipitation yielded large spheres of broad size distributions, while the particles obtained by the double jet technique were rather uniform in size. The final colloidal CuCl particles were formed by the aggregation of nanocrystals, initially generated in the system. Depending on the pH of the reaction mixture, these particles slowly change to large CuCl crystals on aging in the mother liquor.     

Effects of organic ligands, electrostatic and magnetic interactions in formation of colloidal and interfacial inorganic nanostructures

This paper discusses effects of organic ligands, electrostatic and magnetic interactions involved in morphological control of chemically synthesized inorganic nanostructures including colloid and planar systems. The special attention was concentrated on noble metal (gold and palladium) nanoparticles and nanostructures formed at the gas-liquid interface. The analysis of experimental data showed that electrostatic and ligand-related interactions influence very strongly on the metal nanostructure morphology. The hydrophobicity of ligand, charge and binding affinity to inorganic phase are important factors influencing the morphology of inorganic nanostructures formed in a layer at the gas/liquid interface by the interfacial synthesis method. The important point of this method is the quasi two-dimensional character of reaction area and possibilities to realize ultimately thin and anisotropic dynamic monomolecular reaction system with two-dimensional diffusion and interactions of precursors, intermediates and ligands resulting in planar growth and organization of inorganic nanoparticles and nanostructures in the plain of Langmuir monolayer. The morphology of resulting inorganic nanostructures can be controlled efficiently by variations of growth conditions via changes in state and composition of interfacial planar reaction media with the same precursor, and by variations of composition of adjacent bulk phases. The extreme anisotropy and heterogeneity of two-dimensional interfacial reaction system allows creating conditions when growing inorganic particles floating on the aqueous phase surface interact selectively with hydrophobic water-insoluble ligands in interfacial monolayer or with hydrophilic bulk-phase ligands, or at the same time with ligands of different nature present in monolayer and in aqueous phase. The spatial anisotropy of interfacial reaction system and non-homogeneity of ligand binding to inorganic phase gives possibilities for growth of integrated anisotropic nanostructures with unique morphologies, in particularly those characterized by very high surface/volume ratio, high effective perimeter, and labyrinth-like structure. In a case of magnetic nanoparticles dispersed in colloids specific magnetic dipolar interactions can result in formation of chains, rings and more complex nanoparticulate structures or separated highly anisotropic nanoparticles. Theoretical considerations indicate to the importance of system dimensionality in relation to the energy balance which determines specific features of structure organization in planar charged metallic and magnetic nanostructures. For example, a requirement of Coulomb energy minimum, the possibility of free electron redistribution and strengthened attractive interactions between particles in metallic nanostructures can explain formation of very branchy systems with extremely high "effective perimeter". The obtained experimental and literature data show that system dimensionality, organic ligand nature along with electrostatic and magnetic interactions are most important factors of morphological control of chemically synthesized inorganic nanomaterials. The understanding and appropriate exploitation of these factors can be useful for further developments of efficient nanofabrication techniques based on colloidal and interfacial synthetic methods.     

Dispersibility of Barium Titanate Suspension in the Presence of Polyelectrolytes: A Review

Dispersibility of colloidal barium titanate suspensions is reviewed with an emphasis on the use of various polyelectrolytes as dispersants. The fundamentals of colloidal stability are discussed followed by the colloidal properties of barium titanate powder. Dispersion behavior of BaTiO₃ in both nonaqueous and aqueous media has been reviewed. Several studies on the stabilization of micron and nano‐sized barium titanate using various polymeric dispersants and a rhamnolipid biosurfactant are presented and discussed. The article attempts to provide a comprehensive review of the current state‐of‐the‐art in the area of colloidal processing of barium titanate.     

Structure investigations by P.A.C.

The perturbed angular correlation /P.A.C./ technique is employed to investigate the structures of barium ferrite and barium hexaferrite using radioactive¹³³Ba /10.7 Y/ as a probe. The quadrupole interaction frequencies /W_Q'S/ are found to be 9.68 and 12.02 Mrad sec^–1 for barium ferrite and barium hexaferrite, respectively, showing a drift from usual cubic structure.     

Concentration-Dependent Sedimentation of Stable Magnetic Dispersions

The concentration dependence of the sedimentation coefficient has been studied theoretically for a stable magnetic colloidal system under the influence of an external homogeneous magnetic field. The physical model of the magnetic colloid given by Donselaar et al. (1997, Langmuir 13, 6018) was adopted. It was found that the magnetic interaction accelerated the sedimentation of the particles. The stronger the external magnetic field is, the quicker the sedimentation of the particles. For sterically stabilized particles frequently used in experiments to simulate hard spheres, the combined influence of the magnetic attraction and van der Waals attraction on the sedimentation is also analyzed. Copyright 1999 Academic Press.     

Preparation and characterization of calcium phosphate–albumin colloidal particles by high ultrasonic irradiation

Using high intensity ultrasonic irradiation, we prepared calcium phosphate–albumin colloidal particles from aqueous solutions of Ca(H₂PO₄)₂ and Ca(OH)₂ in the presence of bovine serum albumin (BSA). The effect of concentration of BSA (2–5 g/L) properties of the colloidal particles was studied at constant temperature. The effect of a resting period on the size distribution of the colloidal particles was also investigated. Morphology, phase composition, average diameter, size distribution and zeta potential were obtained by transmission electron microscopy, X-ray diffraction, particle size determination by PCS and electrokinetic measurements.