Yuri N. Starodubtsev

Melting, solidification, and viscosity properties of multicomponent Fe-Cu-Nb-Mo-Si-B alloys with low aluminum addition (up to 0.42 at.% Al) were studied using an oscillating cup viscometer. It is shown that melting and solidification are divided into two stages with a knee point at 1461 K. The temperature dependences of the liquid fraction between the liquidus and solidus temperatures during melting and solidification are calculated. It has been proven that aluminum accelerates the processes of melting and solidification and leads to an increase in liquidus and solidus temperatures. In the liquid state at temperatures above 1700 K in an alloy with a low aluminum content, the activation energy of viscous flow increases. This growth was associated with the liquid–liquid structure transition, caused by the formation of large clusters based on the metastable Fe₂₃B₆ phase. Aluminum atoms attract iron and boron atoms and contribute to the formation of clusters based on the Fe₂AlB₂ phase and metastable phases of a higher order.

Melting, solidification and viscosity properties of a multicomponent Fe-Cu-Nb-Mo-Si-B alloys with low aluminum addition up to 0.42 at.% Al were studied using an oscillating cup viscometer. It is shown that melting and solidification are divided into two stages with a knee point at 1461 K. The temperature dependences of the liquid fraction between the liquidus and solidus temperatures during melting and solidification are calculated. It has been proven that aluminum accelerates the processes of melting and solidification and leads to an increase in liquidus and solidus temperatures. In the liquid state at temperatures above 1700 K in an alloy with a low aluminum content, the activation energy of viscous flow increases. This growth was associated with the liquid – liquid structure transition caused by the formation of large clusters based on the metastable Fe23B6 phase. Aluminum atoms attract iron and boron atoms and contribute to the formation of clusters based on the Fe2AlB2 phase and metastable phases of a higher order.

The temperature dependences of the kinematic viscosity during heating and cooling have been investigated in Co-B melts with a boron content of up to 30.8 at. A liquid–liquid structural transition was found, which is accompanied by an increase in the activation energy and cluster size, as well as a significant decrease in the density of the melt. The liquid–liquid structural transition was associated with the formation of clusters with a short-range order of Co₂₃B₆ in the intermediate temperature region. At low and high temperatures, clusters of the order of an atomic size are active participants in the viscous flow. It was shown that with an increase in the cluster size, the activation energy increases and the viscosity of melts decreases. The formation of large Co₂₃B₆ clusters during the cooling of melt with low boron content leads to undercooling and the appearance of the transition temperature region with high activation energy, although this region does not exist during the heating stage.

The relationship between the volumetric thermodynamic coefficients of liquid metals at the melting point and interatomic bond energy was studied. Using dimensional analysis, we obtained equations that connect cohesive energy with thermodynamic coefficients. The relationships were confirmed by experimental data for alkali, alkaline earth, rare earth, and transition metals. Cohesive energy is proportional to the square root of the ratio of melting point T_m divided by thermal expansivity α_p. Thermal expansivity does not depend on the atomic size and atomic vibration amplitude. Bulk compressibility β_T and internal pressure p_i are related to the atomic vibration amplitude by an exponential dependence. Thermal pressure p_th decreases with an increasing atomic size. Fcc and hcp metals with high packing density, as well as alkali metals, have the relationships with the highest coefficient of determination. The contribution of electrons and atomic vibrations to the Grüneisen parameter can be calculated for liquid metals at their melting point.

The temperature dependences of the kinematic viscosity and surface tension of liquid pipe steel with different modes of melt preparation were investigated. A transition zone was found on the temperature dependences of the thermophysical properties, which separates the regions with different activation energies of viscous flow and surface tension. At the heating stage in the transition zone, the thermal decomposition of clusters based on cementite Fe₃C occurs. As a result of the decomposition, free carbon atoms appear which tend to give a uniform distribution in liquid iron with increasing temperature. At a low content of alloying elements and impurities, a high-temperature melt should have a large-scale cluster structure, which provides a more uniform distribution of chemical elements. The melt after vacuum degassing has a narrow transition zone near 1920 K, in contrast to the wide transition zone of the melt without vacuum degassing. The wider transition zone is shifted to high-temperature and this shift is associated with the thermal decomposition of carbides and oxides. Studies have shown that heating liquid pipe steel above the temperature of the liquid–liquid structural transition makes it possible to obtain a more homogeneous structure with a more uniform distribution of alloying and impurity elements in the melt. The sharp drop in surface tension at temperatures above 1920 K in the melt without vacuum degassing is associated with the diffusion of free S and O atoms, which are released after thermal decomposition of sulfides and oxides.

The work investigated the temperature dependences of the kinematic viscosity for multicomponent melts of nanocrystalline soft magnetic alloys. It is shown that there is a linear relationship between the reduced activation energy of viscous flow E_a·(RT)⁻¹ and the pre-exponential factor ν₀. This ratio is universal for all quantities, the temperature dependence of which is expressed by the Arrhenius equation. It is shown that the activation energy of a viscous flow is linearly related to the cluster size on a natural logarithmic scale, and the melt viscosity increases with decreasing cluster size. The change in the Arrhenius plot in the anomalous zone on the temperature dependence of viscosity can be interpreted as a liquid–liquid structure transition, which begins with the disintegration of clusters and ends with the formation of a new cluster structure.

The influences of the atomic size and mass on the kinematic viscosity and self-diffusion coefficient of metal liquids have been studied. The analysis was performed with experimental data on the kinetic properties of metals at the melting temperature. Regression analysis shows that the kinematic viscosity and self-diffusion coefficient increase with an increase in the size of atoms and a decrease in their mass. Note that the atomic mass is more closely related to the kinetic properties of a metal liquid in comparison with the atomic size. It is proposed to use the size–mass factor (which is equal to the ratio of the size of an atom to a square root of its mass) to analyze the kinetic properties of a liquid. The relationship between the kinetic properties and the size–mass factor is characterized by a adjusted determination coefficient, the value of which is above 0.90. It is shown that the kinematic viscosity of a liquid and the self-diffusion coefficient decrease with an increase in the cluster size. It was determined from the dimensionless kinetic parameters that the dimensionless excess entropy at the melting temperature is close to the calculated values for the solidification point of a simple liquid.

The review is devoted to the analysis of physical processes occurring at different stages of production and application of nanocrystalline soft magnetic materials based on Fe–Si–B doped with various chemical elements. The temperature dependences of the kinematic viscosity showed that above a critical temperature, the viscosity of multicomponent melts at the cooling stage does not coincide with the viscosity at the heating stage. Above the critical temperature, the structure of the melt is more homogeneous, the amorphous precursor from such a melt has greater plasticity and enthalpy of crystallization and, after nanocrystallization, the material has a higher permeability. The most effective inhibitor elements are insoluble in α-Fe and form a smoothed peak of heat release during crystallization. On the other hand, the finest nanograins and the highest permeability are achieved at a narrow high-temperature peak of heat release. The cluster magnetic structure of a nanocrystalline material is the cause of magnetic inhomogeneity, which affects the shape of the magnetic hysteresis loop and core losses.