Characterization of Prussian blue and its thermal decomposition products

The mixed-valence state of Prussian blue and its thermal decomposition products has been studied by Mössbauer and infrared spectra, and X-ray powder diffraction and conductivity measurements. The⁵⁷Fe Mössbauer spectra have revealed that the coordination environment of Prussian blue is not changed by the heat-treatment at lower than 200°C while the flipping of the cyano ligands takes place when the heat-treatment temperature exceeds 250°C. The electrical conductivity of the Prussian blue samples heat-treated in vacuo at 300 and 350°C is higher than that of the samples heat-treated at lower temperatures. All the spectral measurements have demonstrated that a new mixed-valence state is produced in Prussian blue by thermally flipping the cyano ligand and quenching the flipped cyano ligand to liquid nitrogen temperature.     

Susceptibility and Inverted Hysteresis Loop of Prussian Blue Analogs with Orthorhombic Structure

The magnetic susceptibility of ternary metal Prussian blue analogues with orthorhombic structure is studied using Ising model. Within the frame work of effective-field theory with correlations, the roles of the mole fraction y, uniaxial magnetic anisotropy, transverse and longitudinal magnetic field are discussed in details. The temperature dependence of the magnetic susceptibility is also investigated. The interesting phenomenon of the inverted magnetic hysteresis loop has been found. The results can help to understand the experimental work of the molecule-based ferriferrimagnet.     

Susceptibility and Inverted Hysteresis Loop of Prussian Blue Analogs with Orthorhombic Structure

The magnetic susceptibility of ternary metal Prussian blue analogues with orthorhombic structure is studied using Ising model. Within the frame work of effective-field theory with correlations, the roles of the mole fraction y, uniaxial magnetic anisotropy, transverse and longitudinal magnetic field are discussed in details. The temperature dependence of the magnetic susceptibility is also investigated. The interesting phenomenon of the inverted magnetic hysteresis loop has been found. The results can help to understand the experimental work of the molecule-based ferri-ferrimagnet.     

Spin-glass state and ferromagnetic order in Cu(II)－Fe(III) cyanides

The static and dynamic magnetic properties of a Prussian blue analogue, molecular magnet Cu^Ⅱ_{3}[Fe^Ⅲ(CN)_6]_2·3NH_3·6H_2O were investigated in detail. The H dependence of the linear AC susceptibility, the irreversibility in the field-cooled (FC)/zero-field-cooled (ZFC) magnetization (M_{FC}/M_{ZFC}) and the relaxation of M_{ZFC} suggest that the magnetic system can be visualized as containing a ferromagnetic cluster of spin below T_C, mixed with small spin-glass clusters formed below temperature T_g less than T_C. The observed magnetic properties are explained with a ferromagnetic-spin-glass phase model. The magnetic ordering of the sample occurs below 19.8K.     

Magnetic Metastability of the Photo-Induced State of CI x Co[Fe(CN)6] y Prussian Blue Analogues (CI=Rb, Cs)

A generic feature of photo-induced magnetic structures is reported, on the example of the photo-magnetic Prussian Blue analogues C _x Co[Fe(CN)₆] _y , zH₂O (C=Rb, Cs): the magnetic metastability of the “raw photo induced” (RPI) state obtained at low temperatures (below T _C) and in low magnetic fields (below H _C). The RPI state is characterised by a non-relaxed domain structure, due to the lack of thermal fluctuations during the building process of the ferrimagnetic domains. It evolves irreversibly under the effect of temperature or magnetic field. Some insight is given into the building mechanism of the RPI state, by consideration of the progressive increase of the Curie temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Exchange-coupled nanoscale SmCo/NdFeB hybrid magnets

Nanoscale hybrid magnets containing SmCo₅ and Nd₂Fe₁₄B hard magnetic phases have been produced via a novel “in-one-pot” processing route. The grain size of the processed bulk composite materials is controlled below 20 nm. The refinement of the nanoscale morphology leads to effective inter-phase exchange coupling that results in single-phase like magnetic properties. Energy product of 14 MGOe was obtained in the isotropic nanocomposite magnets at room temperature. At elevated temperatures, the hybrid magnets have greatly improved thermal stability compared to the Nd₂Fe₁₄B single-phase counterpart and have substantially increased magnetization and energy products compared to the single-phase SmCo₅ counterpart.     

The hyperfine magnetic field in Fe-Hf amorphous alloys at low temperatures

The time-differential perturbed angular correlation (TDPAC) technique was applied to study the hyperfine magnetic field in amorphous Fe-Hf alloys with different Hf contents at low temperatures. The Hf content was changed from 20 to 40 at% andthe TDPAC measurements were carried out in the temperature range from room temperature down to 18 K. Very strong perturbations were observed for the specimen of low Hf content at low temperatures due to a strong hyperfine magnetic field. The characteristic feature observed by the present study is that the temperature dependence of the perturbation for the Fe-30 at% Hf source is quite different from that for other sources, indicating a maximum around 80 K. Discussions have been given on the explanation of the experimental results in the light of magnetic properties of these alloys.     

Monte Carlo simulation of Prussian blue analogs described by Heisenberg ternary alloy model

Within the framework of Monte Carlo simulation technique, we simulate magnetic behavior of Prussian blue analogs based on Heisenberg ternary alloy model. We present phase diagrams in various parameter spaces, and we compare some of our results with those based on Ising counterparts. We clarify the variations of transition temperature and compensation phenomenon with mixing ratio of magnetic ions, exchange interactions, and exchange anisotropy in the present ferro-ferrimagnetic Heisenberg system. According to our results, thermal variation of the total magnetization curves may exhibit N, L, P, Q, R type behaviors based on the Néel classification scheme.     

Preparation, characterization, and property of polyaniline/Prussian blue micro-composites in a low-temperature hydrothermal process

Polyaniline/Prussian blue micro-composites have been synthesized by a low-temperature hydrothermal process. Prussian blue is obtained using the single iron-source precursor K₃[Fe(CN)₆] in acidic aqueous solution. The composite was characterized by field-emission scanning electron microscopy (FE-SEM), Fourier transmission infrared spectroscopy (FT-IR), and X-ray diffractometer (XRD). The magnetic behavior of polyaniline/Prussian blue composites and the effect of the concentration of K₃[Fe(CN)₆] on the morphology of polyaniline/Prussian blue micro-composites have been investigated.     

Individual-collective crossover driven by particle size in dense assemblies of superparamagnetic nanoparticles

Prussian blue analogues (PBA) ferromagnetic nanoparticles Cs ^I _x Ni ^II [Cr ^III (CN)₆ ] _z ·3(H₂O) embedded in CTA⁺ (cetyltrimethylammonium) matrix have been investigated by magnetometry and magnetic small-angle neutron scattering (SANS). Choosing particle sizes (diameter D = 4.8 and 8.6 nm) well below the single-domain radius and comparable volume fraction of particle, we show that the expected superparamagnetic regime for weakly anisotropic isolated magnetic particles is drastically affected due to the interplay of surface/volume anisotropies and dipolar interactions. For the smallest particles (D = 4.8 nm), magnetocrystalline anisotropy is enhanced by surface spins and drives the system into a regime of ferromagnetically correlated clusters characterized by a temperature-dependent magnetic correlation length L _mag which is experimentally accessible using magnetic SANS. For D = 8.6 nm particles, a superparamagnetic regime is recovered in a wide temperature range. We propose a model of interacting single-domain particles with axial anisotropy that accounts quantitatively for the observed behaviors in both magnetic regimes.     

多晶Ba2FeMoO6的溶胶-凝胶制备及其结构、磁性和磁电阻效应研究

采用一种特殊的溶胶－凝胶方法制备出具有纳米尺寸晶粒的双钙钛矿结构Ba2FeMoO6多晶材料，样品的晶粒尺寸和相纯度可以通过改变烧结温度和不同的混合流动气体Ar/H2比例加以控制，对样品的电磁输运性质测量表明，在约316K处出现顺磁到铁磁的转变，并且样品从室温到低温的一个很宽的温区出现了低场磁电阻效应。     

Spin-glass behavior of the polyvinyl pyrrolidone-protected Prussian blue analog K1.14Mn[Fe(CN)6]0.88 nanocubes

Prussian Blue analog K_1.14Mn[Fe(CN)₆]_0.88 nanocubes were synthesized by using polyvinyl pyrrolidone (PVP) as a protective matrix. The PVP-protected MnFe PBA nanocubes with face centered cubic structure are well dispersed with a narrow size distribution of around 50 nm. A spin-glass behavior (including hysteresis, a peak in the zero-field-cooled magnetization and frequency-dependent AC magnetic susceptibility) is observed in the nanoparticles. A possible origin of this spin-glass freezing is discussed. Spin disorder due to the structural defects may be the reason that causes the spin-glass freezing in the MnFe PBA nanoparticles.     

Optical properties of InAs quantum dots in a Si matrix

We report on the optical properties of nanoscale InAs quantum dots in a Si matrix. At a growth temperature of 400°C, the deposition of 7 ML InAs leads to the formation of coherent islands with dimensions in the 2–4 nm range with a high sheet density. Samples with such InAs quantum dots show a luminescence band in the 1.3 μm region for temperatures up to 170 K. The PL shows a pronounced blue shift with increasing excitation density and decays with a time constant of 440 ns. The optical properties suggest an indirect type II transition for the InAs/Si quantum dots. The electronic structure of InAs/Si QDs is discussed in view of available band offset information.     

Magnetic transitions in delafossite CuFeO2: A magnetocaloric effect study

CuFeO₂ was synthetized by a solid-state reaction and its low temperature magnetic properties were investigated using the magnetocaloric effect. Magnetic susceptibility measurements show that there are two magnetic transition temperatures at about 16 and 11 K. Measurement of isothermal magnetization curves for different applied magnetic fields near these temperatures show a reversal in the magnetization trend around 16 K, and Arrott plots indicate they are accompanied by second- and first-order magnetic phase transitions, respectively. Both normal and inverse magnetocaloric effects are observed, and the maximum magnetic entropy change is obtained at 11 K.     

Low-frequency and high-power ultrasound-assisted production of natural blue colorant from the milk and unripe Genipa americana L.

This study presents the production of a novel natural blue colorant obtained from the cross-linking between milk proteins and genipin assisted by low-frequency and high-power ultrasound technology. Genipin was extracted from unripe Genipa americana L. using milk as a solvent. Also, milk colloidal system was used as a reaction medium and carrier for the blue color compounds. The effects of ultrasound nominal power (100, 200, 300, and 400 W) on the blue color formation kinetics in milk samples were evaluated at 2, 24, and 48 h of cold storage in relation to their free-genipin content and color parameters. In addition, Fourier transform infrared (FTIR) spectrum, droplet size distribution, microstructure, and kinetic stability of the blue colorant-loaded milk samples were assessed. Our results have demonstrated that the ultrasound technology was a promising and efficient technique to obtain blue colorant-loaded milk samples. One-step acoustic cavitation assisted the genipin extraction and its diffusion into the milk colloidal system favoring its cross-linking with milk proteins. Ultrasound process intensification by increasing the nominal power promoted higher genipin recovery resulting in bluer milk samples. However, the application of high temperatures associated with intensified acoustic cavitation processing favored the occurrence of non-enzymatic browning due to the formation of complex melanin substances from the Maillard reaction. Also, the blue milk samples were chemically stable since their functional groups were not modified after ultrasound processing. Likewise, all blue colorant-loaded milk samples were kinetically stable during their cold storage. Therefore, a novel natural blue colorant with high-potential application in food products like ice creams, dairy beverages, bakery products, and candies was produced.     

Temperature Dependence of the Mössbauer Effect on Prussian Blue Nanowires

Highly ordered Prussian blue nanowires with diameter of about 50 nm and length up to 4 m have been fabricated by an electrodepositing technology with two-step anodizing anodic aluminum oxide films. The Mössbauer spectra taken between 15 and 300 K indicate that the hyperfine parameters decrease as the temperature increases. The temperature dependence of the quadrupole splitting, the isomer shift and the spectra area are discussed. A decrease of Debye temperature for Prussian blue nanowires was found with respect to that of Prussian blue bulk.     

Mechanism of reversible photo-induced magnetization in prussian blue analogues

Photo-induced magnetic phase transitions observed in Co—Fe Prussian blue analogues are discussed from a theoretical point of view. In this material a magnetization is induced by visible light, and the induced magnetization can be completely diminished not only by thermal annealing but also by irradiation of infra red light. After a brief survey of relevant experiments, we present an overview of our theoretical approaches to clarify the underlying mechanism of this interesting phenomenon. The ligand field at the Co site is shown to be the most relevant variable controlling spin states. The presence of Fe vacancies and the resultant ligand substitution by water molecules turns to be an essential prerequisite for the photoinduced magnetization.     

Hierarchical ZnO microrods: synthesis,structure, optical and photocatalytic properties

Hierarchical ZnO microrods have been prepared by cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process at low temperature. Sheetlike or fluffy ZnO nanostructures have been developed in a large density on the surface of the microrods. The ZnO cores grow preferentially along [001]; the nanosheets are single crystalline and grow in two dimensions along the [001] and [120] directions. The formation of hierarchical structures has been attributed to the presence of CTAB in the solution, which facilitates the secondary nucleation and growth. The nanosheet-covered hierarchical microrods have been analyzed by Raman and photoluminescence spectroscopy, and they exhibit a blue emission at 465 nm and a strong orange emission at 640 nm. Photocatalytic activities of the products have been examined, and the nanosheet-covered hierarchical microrods display the best activity in photodegradation of phenol due to their unique surface features and high surface area.     

Physical properties of nanofluid suspension of ferromagnetic graphite with high Zeta potential

We report on the magnetic properties and stability of nanofluid ferromagnetic graphite (NFMG) studied through the measurements of its magnetization hysteresis curves, Raman spectrum and the so-called Zeta potential. The obtained results suggest a robust ferromagnetic behavior of NFMG even at room temperature along with a good stability of the dispersed solution (with Zeta potential around 41.3 mV) and a good reactivity between magnetic graphite and CTAB type cationic surfactant.     

Low temperature magnetic structure of MnSe

In this paper we report low temperature neutron diffraction studies on MnSe in order to understand the anomalous behaviour of their magnetic and transport properties. Our study indicates that at low temperatures MnSe has two coexisting crystal structures, high temperature NaCl and hexagonal NiAs. NiAs phase appears below 266 K and is antiferromagnetically ordered at all temperatures while the NaCl phase orders antiferromagnetically at 130 K.