Magnetocaloric effect and heat capacity of ferrimagnetic nanosystems: Magnetite-based magnetic liquids and suspensions

The magnetocaloric effect (MCE) and heat capacity of magnetite-based magnetic liquids and suspensions of magnetite in cyclohexane and water were studied calorimetrically at various temperatures and magnetic inductions. It was found that the magnetocaloric effect in the systems under study increases nonlinearly with the magnetic induction. In contrast to monocrystalline magnetite, the inverse temperature dependence was observed for the MCE in the nanosystems studied over the entire temperature range covered; i.e., the effect decreases with increasing temperature. It was found that the dependence of the specific heat on the magnetic induction passes through a maximum for all the systems at all temperatures tested; its height increases with the temperature. The extremal character of the dependence can be explained by the formation of chain structures of magnetite nanoparticles in the presence of a magnetic field.     

Microwave-assisted one-step hydrothermal synthesis of pure iron oxide nanoparticles: magnetite, maghemite and hematite

A simple, rapid, one-step synthesis way of pure iron oxide nanoparticles: magnetite (Fe₃O₄), maghemite (γ-Fe₂O₃) and hematite (α-Fe₂O₃) was investigated. Nanoparticles were prepared by microwave synthesis, from ethanol/water solutions of chloride salts of iron (FeCl₂ and FeCl₃) in the presence of sodium hydroxide NaOH. X-ray powder diffraction (XRD), Transmission Electron Microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize these nanoparticles.     

Thin films of ��-Fe2O3 nanoparticles using as nonmetallic SERS-active nanosensors for submicromolar detection

A new kind of nonmetallic nanosensors based on surface-enhanced Raman spectroscopy (SERS) have been successfully prepared by the assembly of α-Fe₂O₃ nanoparticles (NPs) onto clean quartz surface via the cross-linker of hexamethylene diisocyanate (HDI). The resultant substrates have been characterized by electron micrographs, which show that the α-Fe₂O₃ NPs distribute on the modified surface uniformly with a monolayer or sub-monolayer structure. 4-mercaptopyridine (4-Mpy) and 2-mercaptobenzothiazole (2-MBT) molecules have been used as SERS probes to estimate the detection efficiency of the α-Fe₂O₃ thin films. The SERS experiments show that it is possible to record high quality SERS spectra from probe molecules on the α-Fe₂O₃ thin films at sub-micromolar ( < 10⁻⁶ mol/L) concentration. These results indicate that the highly ordered, uniformly roughed, highly sensitive and low-cost α-Fe₂O₃ thin films are excellent candidates for nonmetallic SERS-active nanosensors.     

Influence of crystallite size on the oxidation kinetics of magnetite

The oxidation of magnetite yields the lacunar phase γ-Fe₂O₃, for sizes less than 5000 Å and the rhombohedral phase, α-Fe₂O₃, for sizes above 10 000 Å. For intermediate sizes, oxidation kinetics and X-ray analysis have confirmed that the γ-Fe₂O₃ phase forms at the beginning of the reaction, followed by phase α-Fe₂O₃ forming from γ-Fe₂O₃ and then directly from the still-unoxidized magnetite. Influence of size could be accounted for in terms of structure and stresses at the crystal lattice level.     

Untersuchung der ferromagnetischen Produkte der explosiven reaktionen zwischen Ammoniumeisencyanid und Kupfernitrat

The wet mixtures of ammonium hexacyanoferrate, (NH₄)₄[Fe(CN)₆], and cupric nitrate, Cu(NO₃)₂, react explosively when heated at 220 ?C. Among the solid products studied by chemical analysis, magnetic measurements and X-ray diffraction there are magnetite (Fe₃O₄), iron nitride (Fe₄N), gamma iron oxide (γ-Fe₂O₃), cuprous oxide (Cu₂O), alpha iron oxide (α-Fe₂O₃), cupric oxide (CuO), cuprous ferrite and metallic copper. Furthermore cupric hexacyanoferrate (Cu₂[Fe(CN)₆]) and ferric ferrocyanide (Fe₄[Fe(CN)₆]₃) have been found in weakly ferromagnetic products. The presence of these phases and their quantitative contribution depend upon the proportion of the initial salts and air supply.     

Influence of iron oxide support preparation method on the properties of Ru/Fe2O3 catalysts for water-gas shift reaction

Studies were undertaken of phase transitions of iron oxide obtained from iron oxide-hydroxides of type α-, β-, γ- and δ-FeOOH, and used as a support of ruthenium catalysts Ru/Fe₂O₃, employed in the water-gas shift reaction. In asprepared pure supports and ruthenium catalysts the main phase was α-Fe₂O₃. After use in the water-gas shift reaction, the support showed the presence of different phases of iron oxide. The most active Ru/Fe₂O₃ catalysts prepared on the basis of α- and δ-FeOOH, after use in the water-gas shift reaction, revealed the presence of Fe₃O₄ or a mixture of phases Fe₃O₄ and γ-Fe₂O₃. The least active catalysts, prepared on the basis of β- and γ-FeOOH, contained a solid solution of Fe₃O₄-γ-Fe₂O₃ with traces of α-Fe₂O₃.     

A general ultra large scale strategy for low temperature sol–gel synthesis of nearly monodispersed metal ions doped γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

A general sol–gel strategy was established for the synthesis of metal ions doped γ-Fe₂O₃ nanoparticles with narrow particle size distribution. The unique chemistry of the route guarantees the simple preparation procedure for the preparation of doped γ-Fe₂O₃ nanoparticles, which includes the boiling of the ethanolic solution of precursor salts after the addition of gelation agent, and the following drying of the obtained sol solution. On the other hand, it guarantees the production of the nanoparticles with nearly monodispersed state and median size of about 5 nm on an ultra large scale of about 60 g in a single reaction. The doping of metal ions in γ-Fe₂O₃ allows the great promotion of phase transformation temperature from γ-Fe₂O₃ to α-Fe₂O₃. Due to the advantages of this strategy over other routes, it is very promising to be applied in the industrial production of undoped and doped γ-Fe₂O₃ nanoparticles as a general route.     

Selective Formation of Spinel Iron Oxide in Thin Films by Complexing Agent-Assisted Sol-Gel Processing

The structure of iron oxide was controlled by regulating the hydrolytic polymerization of aquo iron complexes with organic polydentate ligands such as diols. Iron oxides were prepared by calcining the precursor polymers obtained from iron nitrate nonahydrate and diols. When the diols were 1,2-pentanediol, 1,2-hexanediol and 1,2-octanediol, α-Fe₂O₃ with corundum structure appeared exclusively or as the main crystalline phase, in spite of the amount of diol used and the calcination temperature. In the case of 1,2-decanediol and 1,2-dodecanediol, when five moles of the diols were used to one mole of iron nitrate and the calcination temperatures were below 400°C, ψ-Fe₂O₃ with spinel structure appeared as the main phase and, when less than five moles of the diols were used, α-Fe₂O₃ appeared exclusively or as the main phase, irrespective of the calcination temperature. This tendency was also observed in thin films. Thus, a transparent magnetic film composed of γ-Fe₂O₃ could be prepared by applying a benzene solution of the iron polymer, obtained with 5 equivalents of 1,2-decanediol, on quartz and calcining the gel film at 350°C.     

The oxidation of carbon monoxide on iron oxide

The oxidation of CO on α-Fe₂O₃ was studied in a flow reactor. The conversion was complete at 650–660 K. The catalytic activity of iron oxide was higher than that of the ferrite-containing xMgOyFe₂O₃ catalyst. The adsorption of CO on iron oxide and the kinetics of interaction of carbon monoxide with oxygen atomically adsorbed on the surface of α-Fe₂O₃ were studied. The kinetic parameters of the oxidation of CO are evidence of the participation of adsorbed oxygen atoms, whose binding energy on the surface of α-Fe₂O₃ is lower than that on the surface of the magnesium ferrite-containing catalyst.     

The thermolysis of zinc bis(citrato)ferrate(III) dodecahydrate

The thermolysis of zinc bis(citrato)ferrate(III)dodehydrate has been investigated from ambient temperature to 600 °C using various physico-chemical techniques, i.e., simultaneous TG-DTG-DTA, XRD, Mössbauer and I.R. spectroscopy. After dehydration at 200 °C, the anhydrous complex undergoes oxidative decomposition to yield -Fe₂O₃ and ZnO at 350 °C. Subsequently, the cations remix to yield fine particles of zinc ferrite, ZnFe₂O₄ as a result of solid state reaction between -Fe₂O₃ and ZnO at a temperature (450 °C) much lower than for ceramic method.     

Mössbauer study on thermal decomposition of cesium tris(oxalato) ferrate(III) dihydrate

The thermal decomposition of cesium tris(oxalato) ferrate(III) dihydrate, Cs₃ Fe(ox)₃ 2H₂O has been studied at various temperatures in air, employing Mössbauer and infrared spectroscopies, and thermogravimetric methods. The complex undergoes reduction to an iron(II) intermediate at 473 K. The particle size of -Fe₂O₃ formed during thermolysis increases with increasing decomposition temperature. Finally, a solid state reaction between -Fe₂O₃ and cesium carbonate/oxide occurs, leading to the formation of fine particles of cesium ferrite (CsFeO₂).     

Sol–gel preparation of highly transparent α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> film for the application in red color filter

α-Fe₂O₃ films as inorganic red color filter were synthesized through a simple procedure, epoxide assisted sol–gel route. The sol was prepared through reaction of FeCl₂ in boiling ethanol solution with propylene oxide. The films were formed by the dip-coating of sol on substrate, drying and the following annealing steps. The obtained α-Fe₂O₃ films were composed of homogeneous distributed α-Fe₂O₃ nanoparticles with size of 30–50 nm. The film shows strong absorption to the light below 600 nm and high transparency to the red light (87% at 630 nm). As inorganic red color filter, the optic behavior of this film is nearly as same as the organic color filter made of dye.     

The Ba2LnFeNb4O15 “tetragonal tungsten bronze”: Towards RT composite multiferroics

Several Niobium oxides of formula Ba₂LnFeNb₄O₁₅ (Ln = La, Pr, Nd, Sm, Eu, Gd) with the “tetragonal tungsten bronze” (TTB) structure have been synthesised by conventional solid state methods. The neodymium, samarium and europium compounds are ferroelectric with Curie temperature ranging from 320 to 440 K. The praseodymium and gadolinium compounds behave as relaxors below 170 and 300 K respectively. The praseodymium, neodymium, samarium, europium and gadolinium compounds exhibit magnetic hysteresis loops at room temperature originating from traces of a barium ferrite secondary phase. The presence of both ferroelectric and magnetic hysteresis loops at room temperature allows considering these materials as composites multiferroic. Based on crystal-chemical analysis we propose some relationships between the introduction of Ln³⁺ ions in the TTB framework and the chemical, structural and physical properties of these materials.     

Iron oxide pigmenting powders produced by thermal treatment of iron solid wastes from steel mill pickling lines

Phase changes of iron containing solid wastes from steel mill pickling lines after thermal treatments were investigated aiming the determination of the appropriate conditions for its transformation to be useful for industrial raw materials. Above 275°C, the thermally treated wastes contain a mixture of α-Fe₂O₃ (hematite) and γ-Fe₂O₃ (maghemite) in different proportions, depending on the maximum heating temperature of the thermal treatment. Increasing the maximum temperature the maghemite participation is decreased through its transformation to hematite. Above 850°C hematite is the main constituent, suggesting that thermal treatment of the wastes in this temperature will give a product that could be used as red iron pigment.     

Synthesis of γ-Fe2O3 by Thermal Decomposition of Ferrous Gluconate Dihydrate

Ferrous gluconate dihydrate (FeC₁₂H₂₂O₁₄⋅2H₂O), was prepared and its thermal decomposition was studied by means of simultaneous thermal analysis, supplemented with a two probe d.c. electrical conductivity measurements under the atmospheres of static air, dynamic air and dynamic nitrogen. Under all the atmospheres final product was found to be α-Fe₂O₃ with FeO, γ-Fe₂O₃, Fe₃O₄ etc. as probable intermediates. γ-Fe₂O₃ was formed under the atmosphere of dynamic air containing water vapour. γ-Fe₂O₃ thus synthesised was characterised for its structure, morphology, thermal and magnetic behaviour. This revised version was published online in August 2006 with corrections to the Cover Date.     

Physico-chemical studies on thermal analysis of cobalt hexa(formato)ferrate(III) decahydrate

Thermal decomposition of cobalt hexa(formato)ferrate(III) decahydrate, Co₃[Fe(HCOO)₆]₂. 10H₂O, has been studied up to 973 K in static air atmosphere, employing TG, DTG, DSC, XRD, ESR, Mössbauer and infrared spectroscopic techniques. Dehydration occurs in two stages in the temperature range of 340–430 K. Immediately after the removal of the last water molecule the anhydrous complex undergoes decomposition till -Fe₂O₃ and cobalt carbonate are formed at 588 K. In the final stage of remixing of cations, a solid state reaction between -Fe₂O₃ and cobalt carbonate leads to the formation of CoFe₂O₄ at a temperature (953 K) much lower than for the ceramic method. A saturation magnetization value of 2310 Gauss of ferrite (CoFe₂O₄) shows its potential to function at high frequencies.     

The effect of ball-milling on the thermal behavior of anatase-doped hematite ceramic system

High energy ball-milling methods were employed in the synthesis of anatase-doped hematite xTiO₂(a) · (1−x)α-Fe₂O₃ (x = 0.1, 0.5, and 0.9) ceramic system. The thermal behavior of as obtained ceramic system was characterized by simultaneous DSC–TG. The pure anatase phase was found to be stable below 800 °C, but there is a 10.36% mass loss due to the water content. Two exothermic peaks on DSC curves of pure anatase indicate the different crystallization rates. The pure hematite partially decomposed upon heating under argon atmosphere. Ball-milling has a strong effect on the thermal behaviors of both anatase and hematite phases. For x = 0.1 and 0.5, there is gradual Ti substitution of Fe in hematite lattice, and the decomposition of hematite is enhanced due to the smaller particle size after ball-milling. The crystallization of hematite was suppressed as the enthalpy values decreased due to the anatase-hematite solid–solid interaction. For x = 0.9, most of the anatase phase converted to rutile phase after long milling time. The thermal behavior of xTiO₂(a) · (1−x)α-Fe₂O₃ showed smaller enthalpy value of the hematite transformation to magnetite and anatase crystallization due to the small fraction of hematite phase in the system and hematite–anatase interaction, while the mass loss upon heating increased as a function of milling time due to more water content absorbed by the smaller particle size.     

Rheomagnetic properties of mixed magnetic particle suspensions

Single-domain magnetic particles are the essential ingredient of magnetic tapes, particulate recording disks and magnetic stripes. The particles are single-domain γ-Fe₂O₃, CrO₂ or barium ferrite, and non-magnetic α-Fe₂O₃ mixture. Each of these particles has intrinsic coercivity, which should be matched with the magnetic field strength of the writing element of a particular device. In this study a magnetic inductance measurement with low field strength was employed to obtain the magnetic permeability of suspensions containing two of the particle types mixed together as a function of composition and volume fraction of particles. The bulk magnetic property B is a linear combination of the contributions from each particle type such that the “excess” inductance is L − L_s = Σφ_iB_i where φ_i is the volume fraction and B_i, is the magnetic property of particle type i. For the non-magnetic α-Fe₂O₃, B_i = 0. This allows the formulation of mixed particle suspensions to obtain a desired property for custom-designed magnetic particle coatings. However, mixing magnetic particle types will broaden or produce a bimodal switching field distribution. This may affect the squareness of the magnetic hysteresis loop. These properties should be taken into account for the design of a practical magnetic coating with mixed particle suspension. Another requirement of the magnetic particle suspensions is that they remain well dispersed, even though strong magnetic forces between the particles promote flocculation. An extension of the inductance measurement technique is employed to study the flocculation of a suspension containing magnetic γ-Fe₂O₃ and non-magnetic α-Fe₂O₃. The presence of the α-Fe₂O₃ decreases the flocculation state of the suspension. Thus the suspension stability is enhanced by incorporating a small amount of non-magnetic particles in addition to surfactant.     

Fast degradation of methylene blue with electrospun hierarchical α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanostructured fibers

The α-Fe₂O₃ fibers have been prepared by electrospinning the corresponding sol–gel precursor, then these fibers were characterized by TGA, SEM, XRD, BET and FT-IR respectively, indicating that the hierarchical α-Fe₂O₃ nanostructured fibers came into being. Photocatalytic degradation of methylene blue (MB) in water was carried out under ultraviolet (UV) light, showing that the fibers had better efficiency for removing MB than other catalysts. And several process parameters have also been studied, which showed that the removal effect of MB was influenced by the process parameters, such as the initial dye concentration, catalyst amounts, inorganic anions, and so on.