Aluminum – general characteristics of the element, chemical properties. Adapter plates MA and AP for connecting aluminum busbars to copper terminals of electrical devices. Aluminum and copper-aluminum plates Aluminum easily dissolves in salt and water

Ceramic materials based on double aluminum nitrides and group IV elements are widely used in various fields of industry and technology. In microelectronics, it is generally accepted to use substrates made of aluminum nitride, which has a unique combination of high properties: heat resistance, electrical resistance and thermal conductivity. Due to its resistance to metal melts, titanium nitride is promising for metallurgy. Zirconium nitride is an important component of nitride nuclear fuel in fast breeder reactors.

Currently, significant interest is being paid to the development of various composite materials based on aluminum nitride in combination with nitrides of transition metals of groups IV - V. In particular, an important role in the development of microelectronics is assigned to multilayer materials consisting of A1N and NbN layers. No less promising for creating wear-resistant and protective coatings, diffusion barriers in microelectronics, high-temperature ceramic, metal-ceramic, and composite materials are Ti - Al - N and Zr - Al - N alloys. Determination of the phase composition of such materials showed the presence of only double nitride phases. However, recent, thorough studies of M - Al - N alloys (hereinafter M = Ti, Zr, Hf, Nb) have revealed the existence of complex nitrides: Ti3AlN, TÎ2A1N, Ti3Al2N2; Zr3AlN, ZrsAbNj.x; Hf3AlN, Hf5Al3N; Nb3Al2N. Their properties have been practically unstudied, although there is good reason to believe that they may be unique. This is evidenced by the fact that composite materials based on a combination of double nitrides A1 and M have the maximum level of physical characteristics precisely in the areas of triple phase compositions. For example, the abrasive properties of Ti - Al - N ternary compounds are twice as high as those of corundum and even than those of tungsten carbide.

An equally important role is played by compounds of A1 and elements of groups IV - V with nitrogen in the design and production of a wide range of grades of steels and alloys, especially with increased content nitrogen. Naturally, the physical, physicochemical and mechanical properties of the listed materials are directly related to the type and quantities of nitrogen-containing phases formed. Accurate data on the composition and conditions of existence of complex compounds are also of fundamental theoretical importance for understanding the nature of the chemical bond and other key characteristics that determine the degree of their stability. To predict the synthesis conditions and stability of nitrides, reliable information about phase equilibria is required. Constructing multicomponent phase diagrams with the participation of nitrogen is a very difficult task due to the low thermodynamic incentives for the formation of mixed compounds from double phases adjacent in the phase diagram, the low diffusion rates of components in them, as well as the complexity and low accuracy of determining the true nitrogen content. Therefore, the currently available information is fragmentary and extremely contradictory both regarding the composition of ternary nitrides and the position of the phase equilibrium lines. It was mainly obtained by one group of researchers by annealing powder compacts, in which achieving an equilibrium state of the alloy is difficult.

PURPOSE OF THE WORK:

Development of a new approach to the study of phase diagrams of multicomponent nitride systems, based on the use of a complex of modern experimental techniques of physicochemical analysis, methods of thermodynamic analysis and calculation, which makes it possible to determine with high accuracy the conditions for the coexistence of phases and obtain comprehensive evidence of their compliance with equilibrium. Study of phase equilibria in the solid-phase region of ternary systems aluminum - nitrogen - metal of IV - V groups at a temperature of 1273 K.

SCIENTIFIC NOVELTY:

Methods of thermodynamic analysis and calculations have been used to show the inconsistency of the available experimental data on the conditions of phase equilibrium in T1-Al-Ligg-Al-K systems;

A methodology has been developed for studying the phase diagrams of nitride systems, which is based on a set of modern methods of physical and chemical analysis and the implementation of different ways to achieve the same final state of the alloy, which allows obtaining comprehensive evidence of compliance with its equilibrium;

Thermodynamic modeling, analysis and calculation of phase equilibria in the systems Bx - A1 - N and NG - A1 - N were carried out. The thermodynamic functions of ternary compounds formed in these systems were found for the first time;

The solid-phase regions of the state diagrams of the P - A1 - N systems are constructed.

A1-S and NG-A1-S at 1273 K; The nature of phase equilibria in the Lib - Al - N system at a temperature of 1273 K has been established.

SCIENTIFIC AND PRACTICAL SIGNIFICANCE OF THE WORK:

The information obtained about the equilibrium conditions and thermodynamic functions phases in the systems M - A1 - N (M = T1, bx, H £ bb), are the fundamental scientific basis for the development of coatings, ceramic and metal-ceramic, composite materials, important for microelectronics, energy, and mechanical engineering. They make it possible to determine the technological parameters for the production and processing of such materials, and are also of fundamental importance for predicting the phase composition and properties of a wide range of steels and alloys with a high nitrogen content.

RELIABILITY AND VALIDITY:

Data obtained by various methods of physicochemical analysis on samples of alloys synthesized by various methods (nitriding of binary alloys, long-term homogenizing annealing, diffusion pairs), using modern experimental approaches and equipment, such as electron probe microanalysis, scanning electron microscopy, X-ray phase analysis, in all cases were in excellent agreement both with each other and with the results of thermodynamic calculations.

THE FOLLOWING PROVISIONS ARE MADE FOR DEFENSE:

1. A technique for constructing phase diagrams of multicomponent nitride systems, based on a combination of a set of modern methods of physical and chemical analysis with various ways to achieve the same equilibria, thermodynamic modeling and calculation of phase equilibria.

2. Structure of the solid-phase region of the isothermal section of the phase diagram “L - A1 - N at a temperature of 1273 K.

3. Results of thermodynamic analysis and calculation of phase equilibria in the Tl - A1 - N system at 1273 and 1573 K.

4. Structure of the solid-phase regions of the state diagrams of the systems Zg - A1 - N. NG- A1 - N. N1) - A1 - N at 1273 K.

II. LITERATURE REVIEW

VI. conclusions.

1. A technique has been developed for studying the state diagrams of multicomponent nitride systems, based on a combination of methods of nitriding of binary alloys, long-term homogenizing annealing of three-component compositions, diffusion pairs, thermodynamic calculations and modeling of phase equilibria. It allows you to implement different ways to achieve the same final state of the alloy and obtain comprehensive evidence of compliance with its equilibrium. It has been established that when studying areas of state diagrams with high nitrogen concentrations, the most reliable and informative method is the nitriding method of binary alloys. At low nitrogen concentrations, the best results are obtained by the diffusion pair method.

2. Using modern approaches thermodynamic calculation and modeling of phase equilibrium conditions, an analysis of existing data on state diagrams of M-A1-I systems was carried out. Their inconsistency has been revealed and ways of optimal experimental research have been determined.

3. Using a complex of modern methods of physicochemical analysis, the patterns of interaction of elements in 85 samples of binary and ternary alloys of the M-A1-N systems were studied.

4. A solid-phase state diagram of the T1-A1-K system at 1273 K has been constructed. It has been established that aluminum nitride is in equilibrium with the phases IA13, "PgASH and TO^.*. The ternary compound TS3AIA forms three-phase regions with the phases TSgASH, T1A1, T13A1, a(P) and The parameters of the crystal lattices of the ternary phases T12ASh (a=2.986(9)A, c=13.622(5)A), T13ASh (a=4.1127(17)A), and the Gibbs energy of their formation from modifications of elements stable at this temperature: -360.0 kJ/mol and -323.3 kJ/mol, respectively.

5. Phase equilibria in crystalline alloys at 1273 K were studied. The position of all regions of three-phase equilibria was reliably established. Aluminum nitride is in equilibrium with the 2gAl3, ZmA\2 and ZgN phases. The triple phase rzANYA forms fields of three-phase equilibria with phases

ZrsAbNi.x and a(Zr)-based solid solution. The lattice parameters of the complex nitride Z^AIN are d=3.366(6)А, ¿»=11.472(10)В, c=8.966(9)В, Gibbs energy of formation А/3 = -380.0 kJ/mol.

6. It has been established that in solid compositions of the Hf-Al-N system at 1273 K, almost all double phases of the Hf-Al system are in equilibrium with hafnium nitride HfN. The ternary compound Hf^AlN forms regions of three-phase equilibrium with the HfsAh, HfN phases and the a(Hf)-based solid solution. Double phases Hf2Al, ^N2 occur only in limited compositional regions of the ternary system. Aluminum nitride is in equilibrium with HgAl3 and HfN.

7. For the first time, an isothermal T=1273 K cross section of the solid-phase part of the state diagram of the Nb-Al-N system was constructed. The ternary compound Nl^AhN is in equilibrium with the phases AIN, NbAb, NbAb and Nb2N. The Nb3Al-based phase and the niobium-based solid solution form a three-phase field with Nb2N. Niobium nitride NbN is in equilibrium with aluminum nitride and Nb2N.

V. CONCLUSION.

General pattern in the structure of the phase diagrams of the studied M - Al - N systems is a decrease in the number and stability of complex nitride phases as the difference between the thermodynamic stability of the double phases MN and A1N increases, which is characterized by the Gibbs energy of formation Zl/7(A1N) = -180.0 kJ/ mol, Zl/7(TiN)=-217.8 kJ/mol, 4G(ZrN)=-246.4 kJ/mol, ZlyG(HfN)-251.0 kJ/mol, zl/7(NbN)=- 110.7 kJ/mol. Thus, in the systems Ti - Al - N and Zr - Al - N at 1273 K there are two complex nitrides TijAIN, Ti2AlN and Z^AIN, ZrsAbNi-x, respectively. Moreover, at high temperatures in Ti - Al - N alloys, the TÎ4A1N3.X phase is stable, and the ZrsAbNi-* compound cannot be considered ternary, since it is isostructural with the ZrsAb intermetallic compound. In the phase diagrams of Hf - Al - N and Nb - Al - N, there is only one complex compound Hf3AlN and Nb3Al2N, respectively.

In the Ti - Al - N and Nb - Al - N systems, aluminum nitride is in equilibrium with the corresponding complex nitride, titanium or niobium nitrides and titanium or niobium aluminides with the maximum concentration of aluminum. In systems with zirconium and hafnium, the AIN - M3AIN equilibrium disappears. This is caused by an increase in the thermodynamic stability of the double nitride phases ZrN and HfN. Thus, predicting the possibility of obtaining three-component nitride phases, including in steels and alloys, can be carried out by comparing the values ​​of the Gibbs energy of formation of A1N and MN.

The research carried out made it possible to develop a technique for adequately constructing state diagrams of multicomponent nitrogen-containing systems and to establish the following patterns. At high concentrations of nitrogen and aluminum, the most informative method is the nitriding of powders of binary metal alloys at elevated nitrogen pressure. It was found that the optimal pressure is several tens of atmospheres.

In alloys based on transition metals and with low nitrogen content, the best results are obtained by methods of long-term homogenizing annealing and diffusion pairs. A distinctive feature of the latter is the possibility of obtaining a large amount of data on the conditions of phase equilibrium when studying one sample. The commonly used technique for annealing powder compacts requires long-term isothermal exposure and at temperatures below 1473 - 1573 K, in many cases, does not allow achieving an equilibrium state of the alloy.

Experimental study phase equilibria in alloys with low nitrogen content is in many cases difficult or even impossible due to the low accuracy of determining its concentration by existing methods. For such sections of phase diagrams, it is effective to use methods of thermodynamic modeling and calculation of phase equilibria. They, based on data on phase equilibrium conditions found for more experimentally accessible sections of the phase diagram and available information on thermodynamic functions, make it possible to unambiguously establish the missing information. When solving a given problem, the corresponding system of equations, as a rule, turns out to be overdetermined, so the calculation not only makes it possible to establish the position of the equilibrium lines, but also to obtain comprehensive evidence of the adequacy of the solution. Thus, when carrying out thermodynamic calculations for all studied systems, the result did not depend on which experimentally found phase fields were used as initial data.

Another important area of ​​using thermodynamic modeling and calculation is predicting experimental conditions and choosing original compositions samples in such a way as to achieve the same final state of the alloy in different ways and prove its compliance with equilibrium.

In this work, using a complex of modern methods of physicochemical analysis, four isothermal sections of the state diagrams of ternary systems T1 - A1 - N. bm - A1 - N. W - A1 - N and N> - A1 - N at 1273 K are constructed. For this An approach based on the implementation of different paths to achieve the same final state of the alloy is consistently applied. The data found using various techniques are in good agreement both with each other and with the results of thermodynamic analysis, and therefore can be recommended for predicting phase equilibria in these systems and compositions based on them.

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