Preparation of Fe/B powders by mechanical alloying

Steels with a high boron content are valuable as a neutron shield in waste containers and as control absorbers in nuclear reactors. The purpose of this study was to obtain by mechanical alloying an iron powder with 50% boron (by weight) and then powder-metallurgy materials. The elementary powders were mixed in a high-energy mill for 36 h in an inert atmosphere. Samples were withdrawn at intervals, and the powder was characterized by differential thermal analysis, X-ray diffraction and electron microscopy. The Fe/B powders withdrawn at different intervals of milling were diluted with further additions of iron up to a final content of 10% boron. The mixtures were uniaxially compacted at 500 MPa; their green density was verified, and they were sintered in argon at 1150°C. Their physical properties (density and dimensional change) and bending strength were evaluated and microstructural studies and fracture tests were performed.     

Phase and structural transformations of liquid-crystalline polymer systems in the mechanical field

Phase LC transitions and the structure of blends based on cyanoethyl cellulose with DMA and DMF, poly-(γ-benzyl-L-glutamate) with DMF, and hydroxypropyl cellulose with ethanol, acetic acid, DMA, DMF, and water have been studied under static conditions and in a mechanical field. With decreasing molecular mass of the polymer, the boundary curves separating isotropic from anisotropic solutions are shifted to higher concentrations and lower temperatures, in agreement with the Flory theory. When solutions are deformed, the cholesteric type of liquid crystals is transformed into the nematic type; this process is accompanied by the formation of domains in solutions, and the corresponding temperature-concentration boundaries of the LC phases are changed. As the molecular mass of the polymer increases, the ability of macromolecules to orient under the shear field decreases.     

Chemical bonding, electron-phonon coupling, and structural transformations in high-pressure phases of Si

The nature of chemical bonding of the stable phases of Si at high pressure was analyzed. The effect of pressure is to promote sp electrons into the d orbitals, thus increasing the metallic character and reducing the dimensionality of covalent bonding. Localized covalent bonds, however, persist up to approximately 40 GPa (Si-VI, Cmca) and help to stabilize directional framework structures. At high pressures, Si becomes a metal, and the usual dense packed structures prevail. The existence of conducting and localized electrons gives rise to a combination of "steep and flat bands" near the Fermi level in Si-V. This peculiar electron topology in conjunction with low-frequency vibrations contributes to the relatively high superconducting temperature in Si-V and VI.     

Thermodynamic analysis of (Ni,Fe)3Al formation by mechanical alloying

(Ni, Fe)₃Al intermetallic compound was synthesized by mechanical alloying (MA) of Ni, Fe and Al elemental powder mixtures of composition Ni₅₀Fe₂₅Al₂₅. Phase transformation and microstructure characteristics of the alloy powders were investigated by X-ray diffraction (XRD). The results show that mechanical alloying resulted in a Ni (Al, Fe) solid solution. By continued milling, this structure transformed to the disordered (Ni, Fe)₃Al intermetallic compound. A thermodynamic model developed on the basis of extended theory of Miedema is used to calculate the Gibbs free-energy changes. Final product of MA is a phase having minimal Gibbs free energy compared with other competing phases in Ni–Fe–Al system. However in Ni–Fe–Al system, the most stable phase at all compositions is intermetallic compound (not amorphous phase or solid solution). The results of MA were compared with thermodynamic analysis and revealed the leading role of thermodynamic on the formation of MA product prediction.     

Structural,magnetic and thermal characterization of Fe50Se50 powders obtained by mechanical alloying

Journal of Thermal Analysis and Calorimetry - In this paper, Fe50Se50 alloy powders were synthesized from pure elemental powder by mechanical allowing. The structure, microstructure, morphology,...     

Nanostructuration of CoSi by mechanical milling and mechanical alloying

CoSi is an inexpensive thermoelectric material for medium temperature (200–500 °C). Its power factor is as large as the state of the art materials; however, its thermal conductivity is too large. Then, improving its thermoelectric performances implies increasing the scattering of phonons, which can be performed by nanostructuring the material. In this paper we investigate the effect of nanostructuration on the structure, microstructure, lattice dynamics and stability of CoSi. We obtained powders of about 13 nm by mechanical milling bulk CoSi for only four hours or by mechanical alloying pure elements for twelve hours. Nanostructuration induces a 0.1% expansion of the lattice parameter. Raman spectroscopy, associated to ab initio calculations, highlights the effectiveness of nanostructuration on phonon scattering, showing a reduction of the phonon relaxation time by as much as 80%. Powders are stable up to 450 °C; then grains coarsen and a partial degradation of the material occurs, probably due to silicon sublimation. Our results indicate that nanostructuration should be considered when interested to reduce CoSi thermal conductivity.     

Thermal analysis of Fe(Co,Ni) based alloys prepared by mechanical alloying

In this work several Fe(Co,Ni) based nanocrystalline alloys were obtained by mechanical alloying. Thermal study was performed by differential scanning calorimetry and thermogravimetry. After 80 h milling, all DSC scans show several reactions on heating. At low temperature, about 400 K, the exothermal process detected is associated to structural relaxation. In all alloys, the main crystallization process begins over 700 K and has apparent activation energy values between 3.7 and 3.1 eV at^–1. The Co content increases the thermal stability of this process. Furthermore, thermomagnetic measurements confirm the Co solid solution into Fe. The ferromagnetic–paramagnetic transition occurs at about 900 K.     

Effects of structural transformations in magnetic emulsions

Structural transformations and relevant changes in the magnetic and optical properties of magnetosensitive emulsions based on magnetic fluids are experimentally studied. Peculiarities of the changes in the magnetic susceptibility of emulsions associated with the deformation of their microdroplets and the effect of phase inversion (the transformation of dispersions of magnetic droplets in nonmagnetic media into dispersions of nonmagnetic droplets in magnetic fluids) are established. Optical effects occurring in magnetic emulsions under the combined action of a shear flow and a magnetic field are studied. It is concluded that optically active composition media may be developed on the basis of magnetic fluids.     

On the theory of structural transformations in polar colloids

Structural transformations in the ensemble of particles with permanent intrinsic dipole moment are theoretically studied. In addition to dipole-dipole component, interparticle potential includes central attractive interaction. Such systems belong to ferrocolloids (ferrofluids) whose particle central molecular interaction is not completely screened by the protective surface layers, to polar molecular liquids, and other similar media. Main attention is focused on the analysis of chain-dense globule transitions in particle ensembles. The obtained results demonstrate that even weak central interaction between particles can induce such a transition. The performed studies explain why, in most of the known computer experiments with polar particles, the formation of dense bulk phases is observed only at the presence of central interparticle attraction and only dipole-dipole interaction results in the formation of linear chain structures, but not bulk phases.     

Pentanuclear complexes with unusual structural topologies from the initial use of two aliphatic amino-alcohol ligands in Fe chemistry

Five novel pentanuclear Fe(3+) clusters with the aliphatic amino-alcohol ligands 3-amino-1-propanol (Hap) and 2-(hydroxymethyl)piperidine (Hhmpip) [Fe(5)(μ(3)-Ο)(2)(L)(4)(O(2)CR)(7)] [L = ap(-), R = Ph (1); L = ap(-), R = C(CH(3))(3) (2); L = hmpip(-), R = Ph (3); L = hmpip(-), R = C(CH(3))(3) (4)] and [Fe(5)(μ(4)-Ο)(μ(3)-Ο)(O(2)CC(CH(3))(3))(8)(ap)(2)Cl(HO(2)CC(CH(3))(3))] (5) are reported. Compounds 1-4 were prepared from reactions of preformed trinuclear Fe(3+) clusters with the ligands in a molar ratio 1 : 5 in MeCN (1, 3, 4) or DMF (2), whereas compound 5 was prepared from the reaction of FeCl(3) with Hap in the presence of HO(2)CC(CH(3))(3) in a molar ratio 1 : 3 : 2 in MeCN. To the best of our knowledge, 1-5 are the first examples of Fe(3+) complexes with the ligands Hap and Hhmpip. The structures of 1-4 are composed of a quasi-planar [Fe(5)(μ(3)-O)(2)](11+) core which consists of two vertex-sharing [Fe(3)(μ(3)-O)](7+) triangles. The structure of 5 is based on the [Fe(5)(μ(4)-O)(μ(3)-O)](11+) core, in which the five Fe(3+) ions adopt a monocapped trigonal pyramidal topology. Variable-temperature magnetic susceptibility measurements on powdered microcrystalline samples of 1 and 5 revealed the existence of antiferromagnetic interactions which led to an S = 5/2 ground state. M?ssbauer spectroscopy studies on powdered microcrystalline samples of 1 and 5 confirmed that all iron ions of both complexes are in the Fe(3+) (S = 5/2) state. The variation of the ligand environment in the various iron sites was reflected in their different quadruple splitting parameters. At T < 50 K the M?ssbauer spectra indicated the onset of spin relaxation effects in the time scale of the technique (10(-7)-10(-8) s).     

Isomeric structures and structural transformations in small clusters

The temperature dependence of energies of the isomers of a seven-particle system is studied with a view toward understanding ergodicity problems in Monte Carlo simulations. It is found that the phase space of particles in a cluster is not ergodic at lower temperatures.     

Chemical and structural transformations in chitosan films in the course of storage

Changes in the functional composition of chitosan films in the course of storage under ambient conditions were examined by conductometric titration and IR spectroscopy. The deformation-strength and thermal properties of the films were studied, and their supramolecular structure was analyzed by X-ray diffraction.     

Dynamics of structural transformations in the reduction of copper aluminate

The dynamics of structural transformations during copper aluminate reduction in the temperature range used for catalyst activation was studied by high-temperature X-ray analysis under controlled conditions (hydrogen, 2O–4OO‡C). The techniques of neutron diffraction analysis, IR spectroscopy, chemical phase analysis, and electron microscopy were also used at particular stages. In the course of reduction, copper metal is deposited onto the surface of spinel crystals from the bulk. Spinel becomes cation-deficient with respect to copper. An analysis of powder diffraction patterns demonstrated that copper is reduced and released from tetrahedral positions of the spinel structure at temperatures below ~300‡C and from octahedral positions only at temperatures above 300‡C. In this case, a redistribution of aluminum ions was observed simultaneously. It is likely that the electrical neutrality is attained by the formation of OH groups, the appearance of which in reduced samples was detected by IR spectroscopy and confirmed by neutron diffraction analysis. At a reduction temperature of 400‡C, the oxygen framework was partially disintegrated. The structures of reduced copper aluminates and chromites were compared.     

Photoinduced structural transformations in mixed monolayer assemblies

In mixed monolayers with stearic acid at the air-water interface, paranaric acid undergoes photochemical reaction, which, in turn, triggers marked structural change in the monolayer assembly. Changes in the fluid-expanded and fluid-compressed regimes are qualitatively different and are interpreted in terms of a simple model.     

Synthesis,structure, dehydration transformations and ion exchange characteristics of iron-silicate with various Si and Fe contents as mixed oxides

The synthesis of a new series of impregnated metal oxides with different Fe/Si ratios (0.5, 1 and 2) was obtained by the direct precipitation method. Physico-chemical properties and molecular formula of the obtained products were identified with different analytical techniques, such as chemical stability, XRD, IR, elemental and thermal analyses. Thermal kinetic parameters, such as order (n) and activation energy (E_a), of the solid-state phase transformations of the first dehydration process have been studied for the obtained materials from DTA thermograms. The ion exchange applications and the sorption properties of the materials with some radioactive nuclides have been studied, depending on the Fe/Si molar ratios. These investigations indicated that the ion exchange capacities as well as the selectivities of different materials towards the studied nuclides show the order Co²⁺ > Cs⁺ > Na⁺ at a certain pH.     

Physicochemical mechanics of structural transformations in nitrided steel

It is shown that the orientational anisotropy of intergranular cementite precipitates formed in alloyed steels upon nitriding is due to the presence of an internal stress field which affects the rate of cementite precipitation, predominantly at the nucleation stage. The calculation of the formation work of a new phase with account of both the thermodynamic parameters and stress state makes it possible to estimate the probability of the formation of precipitates on grain boundaries depending on their orientation. The results of calculation are in a good agreement with the experimental data.Translated from Kolloidnyi Zhurnal, Vol. 67, No. 1, 2005, pp. 106–112. Original Russian Text Copyright © 2005 by Traskine, Bochenkov, Skvortsova, Barrallier.     

Supramolecular interactions and structural transformations in the metal-organic sorbent-acetone nanoreactor system

By the ¹H NMR and Raman spectroscopy data it is shown that in the porous inclusion compound of Zn₂(C₈H₄O₄)₂[(N₂(CH₂)₆))]·n(CH₃)₂CO (n ≈ 0–4.7) acetone molecules exist in two structural forms: ketonic (CH₃)₂CO, for which the ¹H NMR chemical shift value is δ^ket = 0.8 ppm, and enolic CH₃C(O)=CH₂, for which δ^en(OH) = 11 ppm, δ^en(CH₂) = 8.9 ppm, and δ^en(CH₃) = 1.6 ppm are found, the average value over three proton sites being <δ^en> = 5.6 ppm. A sharp difference in chemical shift values for the keto and enol forms of acetone in the inclusion compounds can be assigned to the effect of structural chemical conditions in two types of adsorption centers.