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 of bilayer oleic acid-coated Fe3O4 nanoparticles and their application in pH-responsive Pickering emulsions

Fe(3)O(4) nanoparticles coated with oleic acid bilayer (a diameter about 12 nm) were synthesized. The structure and composition of the particles were analyzed by TEM, FTIR and TGA. The TGA experiments of the bilayer-coated particles show a distinct two-stage mass loss. Partition experiments show that the modified Fe(3)O(4) nanoparticles are affected by aqueous dispersion pH and ion strength. Accordingly, the Pickering emulsions stabilized by modified Fe(3)O(4) particles are also sensitive to pH and ion strength. The phase inversion of the emulsions occurs when 1.0013.50. The phase inversion of emulsions also can be adjusted by the ion strength. In interfacial adsorption experiments, the hydrophobic Fe(3)O(4) nanoparticles form particle clusters, while the hydrophilic particles form uniform multilayers.     

多元醇还原法制备片状六边形Fe3O4纳米颗粒

在表面活性剂油酸和油胺,液相环境二苄醚体系中,利用多元醇还原法,采用1,2-十二烷二醇还原前驱体乙酰丙酮铁Fe(acac)3,通过表面活性剂、金属前驱体以及液相环境的共同作用,制备出了单分散片状六边形Fe3O4纳米颗粒。分析了表面活性剂以及还原剂多元醇对纳米颗粒尺寸及形貌的影响。TEM表征结果显示：与未使用表面活性剂的情况相比,油酸和油胺的加入抑制了颗粒的生长,使颗粒尺寸从24.2 nm降低到10.7 nm;颗粒形貌多样化,出现了片状六边形形貌的Fe3O4纳米颗粒。磁性能检测表明： Fe3O4纳米颗粒具有高饱和磁化强度（Ms=88 emu/g）和零剩磁的特点,有望作为磁标记材料应用在生物检测上     

Highly stable,active and recyclable solid acid catalyst based on polymer-coated magnetic composite particles

A facile approach has been adopted for coating cross-linked polystyrene(PS) shells on the surface of Fe304 magnetic clusters using reflux-precipitation polymerization(RPP).Treating the PS shell with chlorosulfonic acid yields magnetic composite particles with acid functionality.By adjusting the amount and proportion of monomers(styrene and divinylbenzene),the obtained magnetic composite particle solid acid(MPM-5 S) exhibits a saturation magnetization value of 18 emu/g,a specific surface area of 243 m~2/g and an acid density of 2.113 mmol/g.The MPM-5 S magnetic solid acid catalyst was evaluated for esterification of oleic acid with methanol to prepare biodiesel.Under mild conditions,the conversion of oleic acid reached 91%,which was much higher than the catalytic activity of Amberlyst-15 and close to the catalytic activity of concentrated H_2 SO_4.The solid acid catalyst can be recovered by magnetic separation and reused three times maintaining over 95% of its initial catalytic activity.Additionally,the solid acid can be used to catalyze the dehydration of fructose to 5-hydroxymethylfurfural.     

Preparation and properties of colloidal iron dispersions

We systematically study the properties of dispersions of iron-based colloids synthesized in a broad size range by thermal decomposition of ironcarbonyl using different stabilizing surfactants. The synthesis results in stable dispersions of monodomain magnetic colloids. Our particles appear to consist of an amorphous Fe(0.75)C(0.25) alloy. Sizes of particles coated with modified polyisobutene or oleic acid can be easily controlled in the 2-10 nm range by varying the amounts of reactants. Extensive characterization with various techniques gives particle sizes that agree well with each other. In contrast to dispersions of small particles, which consist of single colloids, dynamic aggregates are present in dispersions of larger particles. On exposure to air, an oxide layer forms on the particle surface, consisting of a disordered Fe(III) oxide.     

New insight into mesoporous silica for nano metal-organic framework

In this paper the particle volume fraction and temperature dependence of the dynamic viscosity of highly concentrated transformer oil based magnetic nanofluids was investigated in the absence of an external magnetic field. The solid particle volume fraction dependence of the relative viscosity was found to be very well fitted by the Krieger-Dougherty formula, whence the mean ellipticity of the colloidal particles and the effective surfactant layer thickness were obtained. Using the information on the particles' size and shape statistics obtained from TEM, DLS and magnetogranulometry investigations, it was concluded that the magnetite nanoparticles agglomerate in small clusters of about 1.3 particles/cluster, due to the van der Waals interactions. The effective thickness of the oleic acid surfactant layer was estimated as about 1.4 nm, in very good agreement with the value resulted from previous SANS investigations.     

α-Fe粉体浓悬浮体系的制备及磁流变效应

报道使用价格低廉的还原铁粉制备磁性粒子浓悬浮体系,对体系磁流变效应进行研究,并研究了磁性颗粒尺寸和氧化物对悬浮体系力学性质及沉降稳定性的影响.     

Air stable Fe and Fe?Co magnetic fluids—synthesis and characterization

Thermolysis of Fe(CO)₅ and Co₂(CO)₈, dissolved in tetrahydronaphthalene, in the presence of aluminum trialkyl leads to uniform‐sized Fe or Fe? Co nanoparticles, respectively. Subsequent treatment with very dilute oxygen forms a shell which protects the metallic or alloyed core of the particles against further oxidation. With the help of surfactants, for instance oleic acid or cashew nut shell liquid, the particles can be peptized in organic solvents like toluene or kerosene, resulting in magnetic fluids with extraordinary magnetic properties. The saturation of magnetization, M_s, of the fluids was determined by specific magnetization. The sizes and structure of the particles were investigated by transmission electron microscopy, and Moessbauer analysis showed that the core of the particles was metallic or alloyed, respectively. The particle surface termination was studied by X‐ray photoelectron spectroscopy and Auger electron spectroscopy. Copyright © 2005 John Wiley & Sons, Ltd.     

New Oleic Acid-Capped Mesoporous Silica Particles as Surfactant-Responsive Delivery Systems

A new delivery microdevice, based on hydrophobic oleic acid-capped mesoporous silica particles and able to payload release in the presence of surfactants, has been developed. The oleic acid functionalization confers to the system a high hydrophobic character, which avoids cargo release unless surfactant molecules are present. The performance of this oleic-acid capped microdevice in the presence of different surfactants is presented and its zero-release operation in the absence of surfactants is demonstrated.     

Colloidal stability of magnetite/poly(lactic acid) core/shell nanoparticles

In this work, we describe an experimental investigation on the colloidal stability of suspensions of three kinds of particles, including magnetite, poly(lactic acid) (PLA), and composite core/shell colloids formed by a magnetite core surrounded by a PLA shell. The experiments were performed with dilute suspensions, so that recording the optical absorbance with time gives a suitable indication of the aggregation and sedimentation of the suspensions. The method allowed us to distinguish very accurately between the different surface and magnetic forces responsible for the structures acquired by particle aggregates. Thus, the pure PLA suspensions are very sensitive to ionic strength and almost unaffected by pH changes. On the contrary, the stability of magnetite systems is mainly controlled by pH. The effect of vertical magnetic fields on the stability of magnetite and magnetite/PLA suspensions is also investigated. The PLA shell reduces the magnetic responsiveness of magnetite, but it is demonstrated that the mixed particles can also form structures induced by the field, despite their lower magnetization, and they can be considered in magnetically targeted biomedical applications.     

Synthesis of magnetic chelator for high-capacity immobilized metal affinity adsorption of protein by cerium initiated graft polymerization

A novel magnetic chelator with high adsorption capacity of protein by immobilized metal affinity adsorption was prepared by cerium (IV) initiated graft polymerization of tentacle-type polymer chains with iminodiacetic acid (IDA) chelating group on magnetic particles with hydroxyl groups. The micron-sized magnetic poly(vinyl acetate-divinylbenzene) (PVAc-DVB) particles were prepared by a modified suspension polymerization in the presence of oleic acid-coated magnetite nanoparticles and subsequently modified by ester exchange reaction to introduce functional hydroxyl groups. Bovine hemoglobin (BHb) was selected as a model protein to investigate the adsorption capacity of these magnetic particles. The magnetic particles were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), superconducting quantum interference device (SQUID) magnetometry, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and X-ray diffraction (XRD). The results showed that the magnetic particles had an average size of 5 microm and superparamagnetism with saturation magnetization of 20.0 emu/g at room temperature. The protein adsorption indicated that the graft polymerization of tentacle type polymer chains on the magnetic particles could produce magnetic adsorbents with high adsorption capacity (1428.21 mg/g) and low nonspecific adsorption of protein. The magnetic particles with grafted tentacle polymer chains have potential application in large-scale affinity separation of proteins.     

Effect of oil soluble surfactant in emulsions stabilised by clay particles

Although surfactants and particles are often mixed together in emulsions, the contribution of each species to the stabilisation of the oil-water interface is poorly understood. We report the results of investigations into the formation of emulsions from solutions of surfactant in oil and aqueous suspensions of laponite. Depending on the salt concentration in the aqueous suspensions, the laponite dispersed as individual disc-shaped particles, 30 nm in diameter, or flocculated into aggregates tens of micrometres in diameter. At the concentrations studied, the flocculated particles alone stabilized oil-in-water emulsions. Synergistic interactions between the particles and octadecylamine at the oil-water interface reduced the average emulsion drop size, while antagonistic interactions with octadecanoic acid enhanced coalescence processes in the emulsions. The state of particle dispersion had dramatic effects on the emulsions formed. Measurements of the oil-water interfacial tension revealed the origins of the interactions between the surfactants and particles.     

Mechanism for defoaming by oils and calcium soap in aqueous systems

The effect of oils, hardness, and calcium soap on foam stability of aqueous solutions of commercial surfactants was investigated. For conditions where negligible calcium soap was formed, stability of foams made with 0.1 wt% solutions of a seven-EO alcohol ethoxylate containing dispersed drops of n-hexadecane, triolein, or mixtures of these oils with small amounts of oleic acid could be understood in terms of entry, spreading, and bridging coefficients, i.e., ESB analysis. However, foams made from solutions containing 0.01 wt% of three-EO alcohol ethoxysulfate sodium salt and the same dispersed oils were frequently more stable than expected based on ESB analysis, reflecting that repulsion due to overlap of electrical double layers in the asymmetric oil-water-air film made oil entry into the air-water interface more difficult than the theory predicts. When calcium soap was formed in situ by the reaction of fatty acids in the oil with calcium, solid soap particles were observed at the surfaces of the oil drops. The combination of oil and calcium soap produced a synergistic effect facilitating the well-known bridging instability of foam films or Plateau borders and producing a substantial defoaming effect. A possible mechanism of instability involving increases in disjoining pressure at locations where small soap particles approach the air-water interface is discussed. For both surfactants with the triolein-oleic acid mixtures, calculated entry and bridging coefficients for conditions when calcium soap formed were positive shortly after foam generation but negative at equilibrium. These results are consistent with the experimental observation that most defoaming action occurred shortly after foam generation rather than at later times.     

Synthesis and real-time magnetic manipulation of a biaxial superparamagnetic colloid

Superparamagnetic colloidal plates were synthesized from tetrabutylammonium stabilized Ca(2)Nb(3)O(10) nanosheets and oleic acid-stabilized Fe(3)O(4) nanoparticles. Modification with 3-aminopropyltrimethoxysilane produces amine-terminated Ca(2)Nb(3)O(10) with an amine concentration of 0.43 +/- 0.06 groups per Ca(2)Nb(3)O(10) unit as follows from spectroscopic quantification with trinitrobenzenesulfonic acid as a dye. Treatment of the modified sheets in THF/ethanol with 5.3 nm oleic acid-stabilized magnetite nanoparticles yields pseudo-2D assemblies that consist of 2 nm thick nanosheets decorated on both sides with a dense collection (9.3 +/- 0.5 x 10(3) particles per square micrometer per side) of magnetite particles. In noncoordinating or weakly coordinating solvents, these composite particles further aggregate into stacked aggregates with a mean edge length of 1.6 +/- 0.7 microm and a thickness of 79 +/- 30 nm. The colloidal plates were characterized by elemental analysis, X-ray powder diffraction, and infrared and UV/vis spectroscopy. SQUID measurements show that films of the aligned particles are superparamagnetic at room temperature. The magnetic hysteresis that is observed at 5 K reveals that the plates have a magnetic anisotropy with the easy axis in the plane of the plates and the hard axis perpendicular to it. Calculations show that the magnetic anisotropy is a direct consequence of the two-dimensional distribution of the magnetic nanoparticles on the sheets. Optical microscopy reveals that when suspended in ethanol or THF, the colloidal plates can be rotated in real time with a variable external magnetic field (200 Oe). Magnetic alignment of the particles in suspensions also produces asymmetric light scattering patterns and magnetic birefringence. These effects and the observed magneto-orientational properties make the biaxial colloids interesting as components in displays and as magnetic actuators.     

Porous magnetic manganese oxide nanostructures: synthesis and their application in water treatment

Magnetic manganese oxide nanostructures are fabricated at room temperature by mixing a KMnO(4) solution and oleic acid capped Fe(3)O(4) particles. Oleic acid molecules capped Fe(3)O(4) particles are oxidized by potassium permanganate (KMnO(4)) in an aqueous solution to produce porous magnetic manganese oxide nanostructures. The synthesis technique can be extended to other MnO(x) structures with composition of different nanocrystals, such as quantum dots, noble metal crystals which may have important applications as catalysts, adsorbents, electrodes and advanced materials in many scientific disciplines. Transmission electron microscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, and nitrogen adsorption-desorption measurements are employed to characterize the structures. As an adsorbent in water treatment, the nanostructures possess a large adsorption capability and high organic pollutant removal rates due to the large surface area and pore volume. The nanostructures are recyclable as their adsorption capability can be recovered by combustion. Furthermore, the strong magnetism exhibited by the structures provides an easy and efficient separation means in wastewater treatment under an external magnetic field.     

Highly stable,active and recyclable solid acid catalyst based on polymer-coated magnetic composite particles

Sulfonic acid-functionalized polymer-coated magnetic composite particles were prepared and applied as highly stable, active and recyclable magnetic solid acid catalyst for biodiesel preparation and biomass transformation.     

Understanding mercapto ligand exchange on the surface of FePt nanoparticles

Tailoring the surface of nanoparticles is essential for biological applications of magnetic nanoparticles. FePt nanoparticles are interesting candidates owing to their high magnetic moment. Established procedures to make FePt nanoparticles use oleic acid and oleylamine as the surfactants, which make them dispersed in nonpolar solvents such as hexane. As a model study to demonstrate the modification of the surface chemistry, stable aqueous dispersions of FePt nanoparticles were synthesized after ligand exchange with mercaptoalkanoic acids. This report focuses on understanding the surface chemistry of FePt upon ligand exchange with mercapto compounds by conducting X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) studies. It was found that the mercapto end displaces oleylamine on the Pt atoms and the carboxylic acid end displaces the oleic acid on the Fe atoms, thus exposing carboxylate and thiolate groups on the surface that provide the necessary electrostatic repulsion to form stable aqueous dispersions of FePt nanoparticles.     

The effect of oligomeric electrolytes on the aggregative stability and rheological properties of aqueous mineral suspensions

Oligomeric electrolytes of benzene and naphthalene series are synthesized, and the effects of chain length and hydrophilic group position in their molecules on not only the aggregative stability but also rheological and electrokinetic properties of concentrated mineral suspensions are studied. On the basis of the data of adsorption experiments, a parallel orientation of oligomer molecules on the surface of dispersed phase particles is revealed. By the sedimentation and electron microscopy techniques, it is established that, at the optimal concentration of oligomers, systems display aggregative stability. It is shown that the plasticizing effect of oligo-electrolytes is due to the combined action of electrostatic and adsorption-solvation factors.     

Water-Based Oil Spill Dispersants Based on Rosin Formaldehyde Resins

Water-soluble surfactants based on rosin acids were synthesized from condensed rosin acid-formaldehyde. This was completed by esterification of series of rosin acid formaldehyde resins with poly(ethylene glycol) having different molecular weights to produce series of rosin esters. The structure of the produced resins was determined by infrared and ¹HNMR analysis. The molecular weight of the produced surfactants was determined by gel permeation chromatography (GPC) technique. The surface properties of the prepared surfactants were determined by measuring the surface tension at different temperatures. The surface tension, critical micelle concentration (CMC), and surface activities were determined at different temperatures. Surface parameters such as surface excess concentration (Γmax), the area per molecule at interface (A_min), and the effectiveness of surface tension reduction (πCMC) were determined from the adsorption isotherms of the prepared surfactants. Some thermodynamic data for the adsorption process were calculated and are discussed. The dispersion efficiency of the prepared surfactants as petroleum oil spill dispersants was determined and correlated with the surface activity, concentrations of the prepared surfactants and type of petroleum crude oil.     

Effect of Polymer on Dynamic Interfacial Tensions of Anionic–nonionic Surfactant Solutions

The dynamic interfacial tensions (IFTs) of enhanced oil recovery (EOR) surfactant/polymer systems against n-decane have been investigated using a spinning drop interfacial tensiometer in this paper. Two anionic–nonionic surfactants with different hydrophilic groups, C₈PO₆EO₃S (6-3) and C₈PO₆EO₆S (6-6), were selected as model surfactants. Partially hydrolyzed polyacrylamide (HPAM) and hydrophobically modified polyacrylamide (HMPAM) were employed. The influences of surfactant concentration, temperature, polymer concentration, and oleic acid in the oil on IFTs have been studied. The experimental results show that anionic–nonionic surfactants can form compact adsorption films and reach ultralow IFT (10^?3 mN/m) under optimum conditions. The addition of polymer has great influence on dynamic IFTs between surfactant solutions and n-decane mainly by the formation of looser mixed films resulting from the penetration of polymer chains into the interface. The compact surfactant film will also be weakened by the competitive adsorption of oleic acid, which results in the increase of IFT. Moreover, the penetration of polymer chains will be further destroyed surfactant/polymer mixed layer and lead to the obvious increase of IFT. On the other hand, polymers show little effect on the IFTs of 6-6 systems than those of 6-3 because of the hindrance of longer EO chain of 6-6 at the interface.