Chemical equilibrium calculations for multicomponent aqueous systems involving the reductive dissolution of magnetite (Fe3O4) with oxalic acid (H2C2O4) were performed using the HSC Chemistry® version 9. They were conducted with an aqueous solution model based on the Pitzer’s approach of one molality aqueous solution. The change in the amounts and activity coefficients of species and ions involved in the reactions as well as the solution pH at equilibrium was calculated while changing the amounts of raw materials (Fe3O4 and H2C2O4) and the system temperature from 25°C to 125°C. In particular, the conditions under which Fe3O4 is completely dissolved at high temperatures were determined by varying the raw amount of H2C2O4 and the temperature for a given raw amount of Fe3O4 fed into the aqueous solution. When the raw amount of H2C2O4 added was small for a given raw amount of Fe3O4, no undissolved Fe3O4 was present in the solution and the pH of the solution increased significantly. The formation of ferrous oxalate complex (FeC2O4) was observed. The equilibrium amount of FeC2O4 decreased as the raw amount of H2C2O4 increased.

We report the crystallization and magnetic properties of non-equilibrium alloy powders produced by rod-milling as well as by new chemical leaching. X-ray diffractometry, transmission electron microscopy, differential scanning calorimetry and vibrating sample magnetometry were used to characterize the as-milled and leached specimens. After 400 h or 500 h milling, only the broad peaks of nano bcc crystalline phases were detected in the XRD patterns. The crystallite size, the peak and the crystallization temperatures increased with increasing Fe. After being annealed at for 1 h for as-milled alloy powders, the peaks of bcc are observed. After being annealed at for 1 h for leached specimens, these non-equi-librium phases transformed into fcc Cu and phases for the x=0.25 specimen, and into bcc phases for both the x=0.50 and the x=0.75 specimens. The saturation magnetization decreased with increasing milling time for alloy powders. On cooling the leached specimens from ,\;the magnetization first sharply increase at about for x=0.25, x=0.50, and x=0.75 specimens, repectively.

We report on the formation and chemical leaching of non-equilibrium alloy produced by rod milling. X-ray diffractometry, transmission electron microscopy, differential scanning calorimetry, scanning electron microscopy, and vibrating sample magnetometry were used to characterize the as-milled and leached specimens. After 400 h, only the peak of the body-centered cubic type was present in the XRD pattern. The entire rod milling process could be divided into three different stages of milling: agglomeration, disintegration, and homogenization. The saturation magnetization, decreased with increased milling time, the of the powders before milling was about 113.8 emu/g, the after milling for 400 h was about 11.55 emu/g. Leaching of the Al in KOH of the Al at room temperature from the as-milled powders did not induce any significant change in the diffraction pattern. After the leached specimen had been annealed at for 1 hour, the nanoscale crystalline phases were transformed into the bcc Fe, cubic Co, and phases. On cooling the specimen from 85, the degree of magnetization increased slightly, then increased sharply at approximately 364.8, indicating that the bcc phase had been transformed to the Fe and Co phases.

We report the structure, thermal and magnetic properties of a non-equilibrium alloy powder produced by rod milling and chemical leaching. An X-ray diffractometry(XRD), a transmission electron microscope(TEM), a differential scanning calorimeter(DSC), a vibrating sample magnetometer(VSM), and superconducting quantum interference device(SQUID) were utilized to characterize the as-milled and leaching specimens. The crystallite size reached a value of about 8.82 nm. In the DSC experiment, the peak temperatures and crystallization temperatures decreased with increasing milling time. The activation energy of crystallization is 200.5 kJ/mole for as-milled alloy powder. The intensities of the XRD peaks of as-milled powders associated with the bcc type structure formative at sharply increase with increasing annealing temperature. Above , peaks alloted to and are observed. After annealing at for 1h, the leached Ll specimen transformed into bcc -Fe and fcc Cu phases, accompanied by a change in the structural and magnetic properties. The saturation magnetization decreased with increasing milling time, and a value of about 8.42 emu/g was reached at 500 h of milling. The coercivity reached a maximum value of about 142.7 Oe after 500 h of milling. The magnetization of leached specimens as function of fields were higher at 5 K, and increased more sharply at 5 K than at 100 K.

The Principal deficiency of the existing notion about the sintering-mixtures consists in the fact that almost no attention is focused on the Phenomenon of alloy formation during sintering, its connection with dimensional changes of powder bodies, and no correct ideas on the driving force for the sintering process in the stage of establishing chemical equilibrium in a system are available as well. Another disadvantage of the classical sintering theory is an erroneous conception on the dissolution mechanism of solid in liquid. The two-particle model widely used in the literature to describe the sintering phenomenon in solid state disregards the nature of the neighbouring surrounding particles, the presence of pores between them, and the rise of so called arch effect. In this presentation, new basic scientific principles of the driving forces for the sintering process of a two-component powder body, of a diffusion mechanism of the interaction between solid and liquid phases, of stresses and deformation arising in the diffusion zone have been developed. The major driving force for sintering the mixture from components capable of forming solid solutions and intermetallic compounds is attributed to the alloy formation rather than the reduction of the free surface area until the chemical equilibrium is achieved in a system. The lecture considers a multiparticle model of the mixed powder-body and the nature of its volume changes during solid-state and liquid-phase sintering. It explains the discovered S-and V-type concentration dependencies of the change in the compact volume during solid-state sintering. It is supposed in the literature that the dissolution of solid in liquid is realised due to the removal of atoms from the surface of the solid phase into the melt and then their diffusicn transfer from the solid-liquid interface into the bulk of liquid. It has been shown in our experimental studies that the mechanism of the interaction between two components, one of them being liquid, consist in diffusion of the solvent atoms from the liquid into the solid phase until the concentration of solid solutions or an intermetallic compound in the surface layer enables them to pass into the liquid by means of melting. The lecture discusses peculimities of liquid phase formation in systems with intermediate compounds and the role of the liquid phase in bringing about the exothermic effect. At the frist stage of liquid phase sintering the diffusion of atoms from the melt into the solid causes the powder body to grow. At the second stage the diminution of particles in size as a result of their dissolution in the liquid draws their centres closer to each other and makes the compact to shrink Analytical equations were derived to describe quantitatively the porosity and volume changes of compacts as a result of alloy formation during liquid phase sinteIing. Selection criteria for an additive, its concentration and the temperature regime of sintering to control the density the structure of sintered alloys are given.

Cu(hfac)2,(Cu(II) hexafluoroacetylacetonate)를 프리커서로 하는 구리 화학증착에 대해 자유에너지 최소화법으로 열역학적 평형조성 계산을 수행하였다. Cu(hfac)2-Ar계의 경우Cu(hfac)2 프리커서 자체의 열분해로부터 모든 공정조건에서 증착박막내로의 탄소 출입이 관찰되었다. Cu(hfac)2-H2,계에서는 Cu(hfac)2-Ar계보다 낮은 온도에서 구리박막이 증착되며, H2입력비 및 반응온도의 증가에 따라 응축상의 석출형태는 C(s)+CuF(s)로부터 C(s)+CuF(s)+Cu(s), C(s)+Cu(s), Cu(s), C(s)의 순으로 변화되는 것으로 나타났다.