home Biology Changeover from aluminum to copper. Aluminum - general characteristics of the element, chemical properties

Changeover from aluminum to copper. Aluminum - general characteristics of the element, chemical properties

/ Copper-aluminum adapter plate MA

Copper-aluminum adapter plates GOST 19357-81 are used for connecting aluminum busbars to copper terminals of electrical devices and copper busbars. The connection with aluminum busbars is welded, the connection with copper terminals of electrical devices and copper busbars is either collapsible (bolted) or welded.

Type of climatic version of the plate MA - UHL1i T1 according to GOST 19357-81. The connection of the aluminum part of the MA plate with the copper part is performed by cold pressure welding.

We will produce adapter plates MA in any quantity and in the shortest possible time

Example symbol transitional copper-aluminum plate UHL1 version:

Adapter plate MA 40x4 UHL1 GOST 19357-81
Adapter plate MA 50x6 UHL1 GOST 19357-81
Adapter plate MA 60x8 UHL1 GOST 19357-81
Adapter plate MA 80x8 UHL1 GOST 19357-81
Adapter plate MA 100x10 UHL1 GOST 19357-81
Adapter plate MA 120x10 UHL1 GOST 19357-81

The plates are manufactured in accordance with the requirements of this standard according to working drawings approved in the prescribed manner. The surface of MA platinum has no burrs, cracks, scuffs, metal peeling and other mechanical damage. Checking the quality of the weld, the surface of the MA plate is carried out visually.

Specifications - adapter plate copper-aluminum MA

plates MA 40x4, MA 50x6, M 60x8, M 80x8, MA100x10, MA120x10

Insert type	MA plate dimensions, mm			Weight, no more than, kg
Insert type		copper part, I	thickness, S	Weight, no more than, kg
Adapter plate MA 40 x 4
Adapter plate MA 50 x 6
Adapter plate MA 60 x 8
Adapter plate MA 80 x 8
Adapter plate MA 100 x 10
Adapter plate MA 120 x 10

Copper-aluminum adapter plates are designed for connecting aluminum busbars to copper terminals of various electrical devices, as well as to copper busbars.

Copper-aluminum adapter plates have welded connections with an aluminum bus, as well as collapsible (bolted) connections with copper leads. The plates themselves are manufactured using the so-called contact welding or cold pressure welding.

Copper-aluminum adapter plates are standardized in full compliance with the state standard, namely the standard 19357-81. According to him, such plates are divided into the following types:

with an equal section with a welded joint for CIP tires;
plated and equal in terms of their electrical conductivity for collapsible tires.

As for the connecting seam of the adapter plate, which takes place when connecting a copper plate to an aluminum one, it must be cleaned of sludge and burrs. Moreover, it must be made without any cracks and fistulas. Copper-aluminum transition plates should not have any mechanical damage on their surface, for example, burrs, scuffs, peeling, cracks.

In accordance with the state standard, namely the standard 10434-82, protective metal coatings must be on the copper area of \u200b\u200bthe plate. Although, if the adapter plates are made in accordance with certain climatic conditions according to the state standard 15150-69 version "T", then they just do not have such coatings.

According to special technical requirements, copper-aluminum transition plates must be aligned to their original position when bent at eighteen degrees. As for the welded connection of the adapter plate, it must fully comply with the state standard 10434-82. The service life of such a product as copper-aluminum transition plates can in no case be less than similar indicators for the entire electrical device where they are used.

Checking such plates for compliance with the state standard 19357-81 is carried out upon acceptance by the manufacturer, delivery, as well as according to type and periodic tests. Such tests are carried out on a random sample. If the results of the tests carried out are unsatisfactory, take twice the number of plates from the same lot and test again. If the result is repeated, then the entire batch, as a rule, is recognized as unsuitable.

Adapter plates for connecting aluminum busbars to copper terminals of electrical devices. Plates are aluminum and copper-aluminum.

Adapter plates MA (copper-aluminum)

Plates are intended for connection of aluminum busbars to copper terminals of electrical devices and copper busbars.

The plates are made by applying copper to an aluminum billet.

Due to the absence of a welded seam, the plate heats up less, unlike welded plates.

The connection with aluminum busbars is welded, the connection with copper terminals of electrical devices and copper busbars is collapsible (bolted).

Adapter plates AP

(from aluminum alloy AD31T TU 36-931-82

The plates are made of aluminum alloy AD31T1 (AD31T).

Serve for connection of aluminum tires to copper conclusions of electrotechnical devices and copper tires in the atmosphere of types I and II in accordance with GOST 15150-69.

The connection with aluminum busbars is welded, the connection with copper terminals of electrical devices and copper busbars is bolted.

The M1 grade copper strip bar is used for the manufacture of busbars, busbar assemblies, current ducts and switchgears, as well as for connecting any stationary powerful equipment. Copper busbars are quite easy to install and provide high reliability.

The copper bars supplied by us are manufactured in accordance with GOST 434-78 from copper grade not lower than M1 (chemical composition in accordance with GOST 859-78). The tire can be soft (SMM) and hard (ShMT)

We supply a tire with a width of 16 to 120 mm, a thickness of 3 to 30 mm and a length of 2 to 6 m (standard version 4 m), rectangular and with a radius.

The flexible insulated busbar is made of several layers of thin electrolytic copper conductor and PVC insulation with high electrical resistance.

Copper insulated bar used for distribution and transmission of electricity in all types of low voltage installations for all types of connections in cases where increased flexibility, cabinet aesthetics are needed, as well as when working in corrosive conditions.

Especially flexible bus comfortablefor installation directly on sitewithout the use of tire benders and use as tire expansion joints for connecting busbars and transformer leads (busbar compensators).

Easily take the desired shape. They speed up assembly and dismantling processes and improve the appearance of circuits assembled in switch cabinets. Increase system reliability and security.

Flexible insulated copper bar

The flexible insulated busbar is made of several layers of thin electrolytic copper conductor and high electrical resistance PVC insulation.

Transfer plates MA, AP. bimetallic plates.

Transitional and bimetallic plates are designed for high-quality connection of copper and aluminum conductors.

Copper bus M1T, M1M

The M1 grade copper strip bar is used for the manufacture of busbars, busbar assemblies, current ducts and switchgears, as well as for connecting any stationary powerful equipment.

Tire holders ShPPA, ShPPB, ShPRSH, etc.

Designed for mounting conductive tires on insulators.

Copper busbar SMT (hard) and SMM (soft)

Copper profiles of any section.

Aluminum adapter plate AP

Plates AP 40x4, AP 50x6, AP 60x8, AP80x8, AP100x10, AP120x10

Transitional aluminum plates AP are used for connecting aluminum busbars to terminals of electrical devices and busbars. Type of climatic version of the plate AP - UHL1 according to TU 36-931-82. Material of plates AP - aluminum AD31T.

An example of a symbol for a transitional aluminum plate of UHL1 version:

Adapter plate AP 40x4 UHL1 TU 36-931-82

Adapter plate AP 50x6 UHL1 TU 36-931-82

Adapter plate AP 60x8 UHL1 TU 36-931-82

Adapter plate AP 80x8 UHL1 TU 36-931-82

Adapter plate AP 100x10 UHL1 TU 36-931-82

Adapter plate AP 120x10 UHL1 TU 36-931-82

Adapter plates

Adapter plates are used to connect aluminum busbars to copper terminals of electrical devices. Plates are aluminum and copper-aluminum.

Our company will produce adapter plates in the shortest possible time, according to the drawings provided by the customer and the dimensions required by him. These parts are indispensable, therefore, the highest demands must be made on them, and one of these requirements is reliable quality.

Aluminum plates are produced in various types, they can be from 160 to 330mm long, 40-120mm wide and 4-10mm thick. The weight of such plates can be from 70 to 1070 grams.

They are made from the highest quality material. This is aluminum ad31t in UHL1 climatic design. Thanks to the skill of the specialists of our company, the customer will receive adapter plates of impeccable quality at the lowest prices.

Copper-aluminum plates, which are also produced by our company, allow you to join aluminum, copper busbars with copper terminals of electrical devices. These plates are produced by cold pressure welding. These plates can be connected to aluminum busbars by welding, and to copper busbars and leads with bolts, which is called a collapsible connection.

Our company guarantees that copper-aluminum adapter plates will be manufactured in strict compliance with all technical requirements. These plates are made from a copper strip (tire), an aluminum profile according to the standards of GOST 19357-81 and strictly according to the drawings. The plates are clad with a double-sided copper strip, which is joined by cold welding. The copper-aluminum plate in our company is produced without any roughness, fistulas, cracks and creeping of copper on aluminum. The copper part of the plate is protected by a metal coating.

Adapter plates, both aluminum and copper-aluminum, are tested by our company's specialists using the following methods:

bend test;

checking the dimensions of compliance with GOST and the submitted drawings;

checking for mass and correct marking;

checking for compliance with the type of metal and the applied metal coating;

Adapter plates have the same service life as the electrical device in which they are used.

Copper-aluminum adapter plate MA

Type of climatic version of the plate MA - UHL1i T1 according to GOST 19357-81. The connection of the aluminum part of the MA plate with the copper part is performed by cold pressure welding.

An example of a symbol for a transitional copper-aluminum plate of UHL1 version:

Adapter plate MA 40x4 UHL1 GOST 19357-81

Adapter plate MA 50x6 UHL1 GOST 19357-81

Adapter plate MA 60x8 UHL1 GOST 19357-81

Adapter plate MA 80x8 UHL1 GOST 19357-81

Adapter plate MA 100x10 UHL1 GOST 19357-81

Adapter plate MA 120x10 UHL1 GOST 19357-81

Specifications - adapter plate copper-aluminum MA

plates MA 40x4, MA 50x6, M 60x8, M 80x8, MA100x10, MA120x10

Copper-aluminum adapter plates are designed for connecting aluminum busbars to copper terminals of various electrical devices, as well as to copper busbars.

Copper-aluminum adapter plates are standardized in full compliance with the state standard, namely the standard 19357-81. According to him, such plates are divided into the following types:

with an equal section with a welded joint for CIP tires;

plated and equal in terms of their electrical conductivity for collapsible tires.

According to special technical requirements, copper-aluminum transition plates must be aligned to their original position when bent at eighteen degrees. As for the welded connection of the adapter plate, it must fully comply with the state standard 10434-82. The service life of such a product as copper-aluminum transition plates can in no case be less than the same indicators for the entire electrical device where they are used.

Aluminum is an element of the main subgroup of group III, of the third period, with atomic number 13. Aluminum is a p-element. The outer energy level of an aluminum atom contains 3 electrons, which have an electronic configuration 3s 2 3p 1. Aluminum exhibits an oxidation state of +3.

Belongs to the group of light metals. Most common metal and third most common chemical element in earth's crust(after oxygen and silicon).

A simple substance aluminum is a light, paramagnetic silver-white metal, easily molded, cast, and machined. Aluminum has high thermal and electrical conductivity, resistance to corrosion due to the rapid formation of strong oxide films that protect the surface from further interaction.

Chemical properties of aluminum

Under normal conditions, aluminum is covered with a thin and strong oxide film and therefore does not react with classical oxidizing agents: with H 2 O (t °); O 2, HNO 3 (without heating). Due to this, aluminum is practically not subject to corrosion and therefore is widely demanded by modern industry. When the oxide film is destroyed, aluminum acts as an active reducing metal.

1. Aluminum easily reacts with simple non-metal substances:

4Al + 3O 2 \u003d 2Al 2 O 3

2Al + 3Cl 2 \u003d 2AlCl 3,

2Al + 3Br 2 = 2AlBr 3

2Al + N 2 = 2AlN

2Al + 3S = Al 2 S 3

4Al + 3C \u003d Al 4 C 3

Aluminum sulfide and aluminum carbide are completely hydrolyzed:

Al 2 S 3 + 6H 2 O \u003d 2Al (OH) 3 + 3H 2 S

Al 4 C 3 + 12H 2 O \u003d 4Al (OH) 3 + 3CH 4

2. Aluminum reacts with water

(after removing the protective oxide film):

2Al + 6H 2 O \u003d 2Al (OH) 3 + 3H 2

3. Aluminum reacts with alkalis

2Al + 2NaOH + 6H 2 O = 2Na + 3H 2

2(NaOH H 2 O) + 2Al \u003d 2NaAlO 2 + 3H 2

First, the protective oxide film dissolves: Al 2 O 3 + 2NaOH + 3H 2 O = 2Na.

Then the reactions proceed: 2Al + 6H 2 O \u003d 2Al (OH) 3 + 3H 2, NaOH + Al (OH) 3 \u003d Na,

or in total: 2Al + 6H 2 O + 2NaOH \u003d Na + 3H 2,

and as a result, aluminates are formed: Na - sodium tetrahydroxoaluminate Since the aluminum atom in these compounds is characterized by a coordination number of 6, and not 4, the actual formula of tetrahydroxo compounds is as follows: Na

4. Aluminum dissolves easily in hydrochloric and dilute sulfuric acids:

2Al + 6HCl = 2AlCl 3 + 3H 2

2Al + 3H 2 SO 4 (razb) \u003d Al 2 (SO 4) 3 + 3H 2

When heated, it dissolves in acids - oxidizing agents, forming soluble aluminum salts:

8Al + 15H 2 SO 4 (conc) = 4Al 2 (SO 4) 3 + 3H 2 S + 12H 2 O

Al + 6HNO 3 (conc) = Al(NO 3) 3 + 3NO 2 + 3H 2 O

5. Aluminum restores metals from their oxides (aluminothermy):

8Al + 3Fe 3 O 4 = 4Al 2 O 3 + 9Fe

2Al + Cr 2 O 3 \u003d Al 2 O 3 + 2Cr

Lesson Objectives: consider the distribution of aluminum in nature, its physical and chemical properties, as well as the properties of the compounds it forms.

Progress

2. Learning new material. Aluminum

The main subgroup of group III of the periodic system is boron (B), aluminum (Al), gallium (Ga), indium (In) and thallium (Tl).

As can be seen from the above data, all these elements were discovered in the 19th century.

Discovery of metals of the main subgroup III groups


1806	1825	1875	1863	1861
G. Lussac,	G.H. Oersted	L. de Boisbaudran	F. Reich,	W. Crooks
L. Tenard	(Denmark)	(France)	I. Richter	(England)
(France)			(Germany)

Boron is a nonmetal. Aluminum is a transition metal, while gallium, indium and thallium are full metals. Thus, with an increase in the atomic radii of the elements of each group of the periodic system, the metallic properties of simple substances increase.

In this lecture, we will take a closer look at the properties of aluminum.

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MUNICIPAL BUDGET EDUCATIONAL INSTITUTION

GENERAL EDUCATIONAL SCHOOL № 81

Aluminum. The position of aluminum in the periodic system and the structure of its atom. Finding in nature. Physical and chemical properties of aluminum.

chemistry teacher

MBOU secondary school №81

2013

Lesson topic: Aluminum. The position of aluminum in the periodic system and the structure of its atom. Finding in nature. Physical and chemical properties of aluminum.

Lesson Objectives: consider the distribution of aluminum in nature, its physical and chemical properties, as well as the properties of the compounds it forms.

Progress

1. Organizational moment of the lesson.

2. Learning new material. Aluminum

The main subgroup of group III of the periodic system is boron (B),aluminum (Al), gallium (Ga), indium (In) and thallium (Tl).

As can be seen from the above data, all these elements were discovered in the 19th century.

Discovery of metals of the main subgroup of group III


1806	1825	1875	1863	1861
G. Lussac,	G.H. Oersted	L. de Boisbaudran	F. Reich,	W. Crooks
L. Tenard	(Denmark)	(France)	I. Richter	(England)
(France)			(Germany)

In this lecture, we will take a closer look at the properties of aluminum.

1. The position of aluminum in the table of D. I. Mendeleev. The structure of the atom, the oxidation states shown.

The element aluminum is located in group III, main “A” subgroup, 3rd period of the periodic system, serial number No. 13, relative atomic mass Ar (Al) \u003d 27. Its neighbor on the left in the table is magnesium - a typical metal, and on the right - silicon - already a non-metal . Therefore, aluminum must exhibit properties of some intermediate nature and its compounds are amphoteric.

Al +13) 2 ) 8 ) 3 , p is an element,

Basic state

1s 2 2s 2 2p 6 3s 2 3p 1

excited state

1s 2 2s 2 2p 6 3s 1 3p 2

Aluminum exhibits an oxidation state of +3 in compounds:

Al 0 - 3 e - → Al +3

2. Physical properties

Free form aluminum is a silvery-white metal with high thermal and electrical conductivity. Melting point 650 about C. Aluminum has a low density (2.7 g/cm 3 ) - about three times less than that of iron or copper, and at the same time it is a durable metal.

3. Being in nature

In terms of prevalence in nature, it occupies1st among metals and 3rd among elementssecond only to oxygen and silicon. The percentage of aluminum content in the earth's crust, according to various researchers, ranges from 7.45 to 8.14% of the mass of the earth's crust.

In nature, aluminum occurs only in compounds(minerals).

Some of them:

Bauxites - Al 2 O 3 H 2 O (with impurities SiO 2, Fe 2 O 3, CaCO 3)

Nephelines - KNa 3 4

Alunites - KAl(SO 4 ) 2 2Al(OH) 3

Alumina (mixtures of kaolins with sand SiO 2 , limestone CaCO 3 , magnesite MgCO 3 )

Corundum - Al 2 O 3

Feldspar (orthoclase) - K 2 O × Al 2 O 3 × 6 SiO 2

Kaolinite - Al 2 O 3 ×2SiO 2 × 2H 2 O

Alunite - (Na,K) 2 SO 4 × Al 2 (SO 4 ) 3 × 4Al (OH) 3

Beryl - 3BeO Al 2 O 3 6SiO 2

Bauxite
Al2O3	Corundum
	Ruby
	Sapphire

4. Chemical properties aluminum and its compounds

Aluminum easily interacts with oxygen under normal conditions and is covered with an oxide film (it gives a matte appearance).

Its thickness is 0.00001 mm, but thanks to it, aluminum does not corrode. To study the chemical properties of aluminum, the oxide film is removed. (Using sandpaper, or chemically: first by dipping into an alkali solution to remove the oxide film, and then into a solution of mercury salts to form an aluminum-mercury alloy - an amalgam).

I. Interaction with simple substances

Aluminum already at room temperature actively reacts with all halogens, forming halides. When heated, it interacts with sulfur (200 °C), nitrogen (800 °C), phosphorus (500 °C) and carbon (2000 °C), with iodine in the presence of a catalyst - water:

2Al + 3S \u003d Al 2 S 3 (aluminum sulfide),

2Al + N 2 = 2AlN (aluminum nitride),

Al + P = AlP (aluminum phosphide),

4Al + 3C \u003d Al 4 C 3 (aluminum carbide).

2 Al + 3 I 2 = 2 AlI 3 (aluminum iodide)

All these compounds are completely hydrolyzed with the formation of aluminum hydroxide and, accordingly, hydrogen sulfide, ammonia, phosphine and methane:

Al 2 S 3 + 6H 2 O \u003d 2Al (OH) 3 + 3H 2 S

Al 4 C 3 + 12H 2 O \u003d 4Al (OH) 3 + 3CH 4

In the form of shavings or powder, it burns brightly in air, releasing a large amount of heat:

4Al + 3O 2 = 2Al 2 O 3 + 1676 kJ.

II. Interaction with complex substances

Interaction with water:

2 Al + 6 H 2 O \u003d 2 Al (OH) 3 + 3 H 2

without oxide film

Interaction with metal oxides:

Aluminum is a good reducing agent, as it is one of the active metals. It is in the activity series right after the alkaline earth metals. That's whyrestores metals from their oxides. Such a reaction - aluminothermy - is used to obtain pure rare metals, such as tungsten, vanadium, etc.

3 Fe 3 O 4 + 8 Al \u003d 4 Al 2 O 3 + 9 Fe + Q

Thermite mixture Fe 3 O 4 and Al (powder) - also used in thermite welding.

Cr 2 O 3 + 2Al \u003d 2Cr + Al 2 O 3

Interaction with acids:

With sulfuric acid solution: 2 Al + 3 H 2 SO 4 \u003d Al 2 (SO 4) 3 + 3 H 2

It does not react with cold concentrated sulfuric and nitrogenous (passivates). Therefore, nitric acid is transported in aluminum tanks. When heated, aluminum is able to reduce these acids without releasing hydrogen:

2Al + 6H 2 SO 4 (conc) \u003d Al 2 (SO 4) 3 + 3SO 2 + 6H 2 O,

Al + 6HNO 3 (conc) \u003d Al (NO 3) 3 + 3NO 2 + 3H 2 O.

Interaction with alkalis.

2 Al + 2 NaOH + 6 H 2 O \u003d 2 NaAl (OH) 4 + 3 H 2

Na [Al (OH) 4] - sodium tetrahydroxoaluminate

At the suggestion of the chemist Gorbov, in Russo-Japanese War this reaction was used to produce hydrogen for balloons.

With salt solutions:

2Al + 3CuSO 4 \u003d Al 2 (SO 4) 3 + 3Cu

If the surface of aluminum is rubbed with mercury salt, then the following reaction occurs:

2Al + 3HgCl 2 = 2AlCl 3 + 3Hg

The released mercury dissolves the aluminum, forming an amalgam.

5. Application of aluminum and its compounds

The physical and chemical properties of aluminum have led to its widespread use in technology.The aviation industry is a major consumer of aluminum.: 2/3 aircraft is made of aluminum and its alloys. An aircraft made of steel would be too heavy and could carry far fewer passengers.Therefore, aluminum is called the winged metal.Cables and wires are made from aluminum: with the same electrical conductivity, their mass is 2 times less than the corresponding copper products.

Considering the corrosion resistance of aluminum, itmanufacture parts of apparatuses and containers for nitric acid . Aluminum powder is the basis for the manufacture of silver paint to protect iron products from corrosion, as well as to reflect heat rays, such paint is used to cover oil storage facilities and firefighters' suits.

Aluminum oxide is used to produce aluminum and also as a refractory material.

Aluminum hydroxide is the main component of the well-known drugs Maalox, Almagel, which lower the acidity of gastric juice.

Aluminum salts are highly hydrolyzed. This property is used in the process of water purification. Aluminum sulfate and a small amount of slaked lime are added to the water to be purified to neutralize the resulting acid. As a result, a volumetric precipitate of aluminum hydroxide is released, which, settling, takes with it suspended particles of turbidity and bacteria.

Thus, aluminum sulfate is a coagulant.

6. Obtaining aluminum

1) The modern cost-effective method for producing aluminum was invented by the American Hall and the Frenchman Héroux in 1886. It consists in the electrolysis of a solution of aluminum oxide in molten cryolite. Molten cryolite Na 3 AlF 6 dissolves Al 2 O 3, how water dissolves sugar. The electrolysis of a "solution" of aluminum oxide in molten cryolite proceeds as if cryolite were only a solvent, and aluminum oxide was an electrolyte.

2Al 2 O 3 electric current → 4Al + 3O 2

In the English Encyclopedia for Boys and Girls, an article about aluminum begins with the following words: “On February 23, 1886, a new metal age began in the history of civilization - the age of aluminum. On this day, Charles Hall, a 22-year-old chemist, showed up in his first teacher's laboratory with a dozen small balls of silvery-white aluminum in his hand, and with the news that he had found a way to manufacture this metal cheaply and in large quantities. So Hall became the founder of the American aluminum industry and an Anglo-Saxon national hero, as a man who made a great business out of science.

2) 2Al 2 O 3 + 3 C \u003d 4 Al + 3 CO 2

IT IS INTERESTING:

Metallic aluminum was first isolated in 1825 by the Danish physicist Hans Christian Oersted. By passing gaseous chlorine through a layer of hot alumina mixed with coal, Oersted isolated aluminum chloride without the slightest trace of moisture. To restore metallic aluminum, Oersted needed to treat aluminum chloride with potassium amalgam. After 2 years, the German chemist Friedrich Wöller. He improved the method by replacing potassium amalgam with pure potassium.
In the 18th and 19th centuries, aluminum was the main jewelry metal. In 1889, in London, D.I. Mendeleev was awarded a valuable gift for his services to the development of chemistry - scales made of gold and aluminum.
By 1855, the French scientist Saint-Clair Deville had developed a process for producing aluminum metal on an industrial scale. But the method was very expensive. Deville enjoyed the special patronage of Napoleon III, Emperor of France. As a sign of his devotion and gratitude, Deville made for Napoleon's son, the newborn prince, an elegantly engraved rattle - the first "consumer product" made of aluminum. Napoleon even intended to equip his guardsmen with aluminum cuirasses, but the price was prohibitive. At that time, 1 kg of aluminum cost 1000 marks, i.e. 5 times more expensive than silver. It wasn't until the invention of the electrolytic process that aluminum became as valuable as conventional metals.
Did you know that aluminum, entering the human body, causes disorder nervous system. With its excess, metabolism is disturbed. And protective agents are vitamin C, calcium, zinc compounds.
When aluminum burns in oxygen and fluorine, a lot of heat is released. Therefore, it is used as an additive to rocket fuel. The Saturn rocket burns 36 tons of aluminum powder during its flight. The idea of using metals as a component of rocket fuel was first proposed by F.A. Zander.

3. Consolidation of the studied material

No. 1. To obtain aluminum from aluminum chloride, calcium metal can be used as a reducing agent. Write an equation for this chemical reaction, characterize this process using the electronic balance.
Think! Why can't this reaction be carried out in an aqueous solution?

No. 2. Complete the equations of chemical reactions:
Al+H 2 SO 4 (solution) ->
Al + CuCl 2 ->
Al + HNO 3 (conc) - t ->
Al + NaOH + H 2 O ->

Number 3. Solve the problem:
An aluminum-copper alloy was exposed to an excess of concentrated sodium hydroxide solution while being heated. 2.24 liters of gas (n.o.s.) were released. Calculate the percentage composition of the alloy if its total mass was 10 g?

4. Homework slide 2

AL Element III (A) of the table group D.I. Mendeleev Element with serial number 13, its Element of the 3rd period The third most common in the earth's crust, the name is derived from lat. "Aluminis" - alum

Danish physicist Hans Oersted (1777-1851) For the first time, aluminum was obtained by him in 1825 by the action of potassium amalgam on aluminum chloride, followed by distillation of mercury.

Modern production of aluminum The modern production method was developed independently by the American Charles Hall and the Frenchman Paul Héroux in 1886. It consists in dissolving alumina in a cryolite melt followed by electrolysis using consumable coke or graphite electrodes.

As a student at Oberlin College, he learned that you can get rich and get the gratitude of mankind if you invent a way to produce aluminum on an industrial scale. Like a man possessed, Charles conducted experiments on the production of aluminum by electrolysis of a cryolite-alumina melt. On February 23, 1886, a year after graduating from college, Charles produced the first aluminum by electrolysis. Hall Charles (1863 - 1914) American chemical engineer

Paul Héroux (1863-1914) - French chemical engineer In 1889 he opened an aluminum plant in Fron (France), becoming its director, he designed an electric arc furnace for steel smelting, named after him; he also developed an electrolytic method for producing aluminum alloys

8 Aluminum 1. From the history of the discovery Main Next During the discovery of aluminum, the metal was more expensive than gold. The British wanted to honor the great Russian chemist D.I. Mendeleev with a rich gift, they gave him a chemical balance, in which one cup was made of gold, the other - of aluminum. A cup made of aluminum has become more expensive than gold. The resulting "silver from clay" interested not only scientists, but also industrialists and even the emperor of France. Further

9 Aluminum 7. Content in the earth's crust main Next

Finding in nature The most important aluminum mineral today is bauxite. The main chemical component of bauxite is alumina (Al 2 O 3) (28 - 80%).

11 Aluminum 4. Physical properties Color - silver-white t pl. = 660 °C. t b.p. ≈ 2450 °C. Electrically conductive, thermally conductive Lightweight, density ρ = 2.6989 g/cm 3 Soft, ductile. home Next

12 Aluminum 7. Found in nature Bauxite – Al 2 O 3 Alumina – Al 2 O 3 main Next

13 Aluminum main Insert the missing words Aluminum is an element of group III, the main subgroup. The charge of the nucleus of an aluminum atom is +13. There are 13 protons in the nucleus of an aluminum atom. There are 14 neutrons in the nucleus of an aluminum atom. There are 13 electrons in an aluminum atom. The aluminum atom has 3 energy levels. The electron shell has a structure of 2e, 8e, 3e. At the outer level, there are 3 electrons in an atom. The oxidation state of an atom in compounds is +3. The simple substance aluminum is a metal. Aluminum oxide and hydroxide are amphoteric in nature. Further

14 Aluminum 3 . Structure a simple substance Metal Bond - metallic Crystal lattice - metallic, cubic face-centered main More

15 Aluminum 2. Electronic structure 27 A l +13 0 2e 8e 3e P + = 13 n 0 = 14 e - = 13 1 s 2 2 s 2 2p 6 3s 2 3p 1 Short electronic record 1 s 2 2 s 2 2p 6 3s 2 3p 1 Filling order main Next

Aluminum \u003d 2AlCl 3 4Al + 3C \u003d Al 4 C 3 C non-metals (with halogens, with carbon) (Remove the oxide film) 2 Al + 6 H 2 O \u003d 2Al (OH) 2 + H 2 C with water 2 Al + 6 HCl \u003d 2AlCl 3 + H 2 2Al + 3H 2 SO 4 \u003d Al 2 (SO 4) 3 + H 2 C acids and 2 Al + 6NaOH + 6H 2 O \u003d 2Na 3 [Al (OH ) 6] + 3H 2 2Al + 2NaOH + 2H 2 O \u003d 2NaAlO 2 + 3H 2 C with alkalis and 8Al + 3Fe 3 O 4 \u003d 4Al 2 O 3 + 9Fe 2Al + WO 3 \u003d Al 2 O 3 + W C oxi d a m e t a l l

17 Aluminum 8. Obtaining 1825 H. Oersted: AlCl 3 + 3K = 3KCl + Al: Electrolysis (t pl. = 2050 ° C): 2Al 2 O 3 = 4 Al + 3O 2 Electrolysis (in melting cryolite Na 3 AlF 6, t pl ≈ 1000 ° С): 2Al 2 O 3 \u003d 4 Al + 3O 2 main Next

As a manuscript

PHASE EQUILIBRIUM IN SYSTEMS NITROGEN - ALUMINUM - TRANSITION METAL IV - V GROUP.

04/01/07 - Condensed Matter Physics

Moscow 2004

The work was performed at the Department of General Chemistry, Faculty of Chemistry, Lomonosov Moscow State University. M.V. Lomonosov and at the Institute of Metal Science and Physics of Metals. G.V. Kurdyumov TsNIIchermet them. I.P. Bardin.

scientific adviser

Doctor of Physical and Mathematical Sciences, Professor Zaitsev A.I. Scientific consultant

Candidate of Chemical Sciences, Leading Researcher Kalmykov K.B. Official opponents:

doctor of technical sciences, professor Kraposhin B.C.

Doctor of Physical and Mathematical Sciences, Professor Kaloshkin S. D.

Lead organization:

Institute of Metallurgy and Materials Science. A.A. Baikova

The defense of the dissertation will take place on November 12, 2004 at D hours at a meeting of the dissertation council D 141.04.02 FSUE TsNIIchermet im. I.P. Bardin at the address: 105005, Moscow, st. 2nd Baumanskaya; 9/23.

The dissertation can be found in the technical library of the TsNIIchermet named after V.I. I.P. Bardin.

Phone for inquiries: 777-93-50

Scientific Secretary

dissertation council D 141.04.02, candidate of technical sciences,

older Researcher¿^G^sä^A-^ Aleksandrova N. M.

GENERAL DESCRIPTION OF WORK.

RELEVANCE OF THE THEME: Compositions based on complex nitrides of aluminum and transition metals IV - V groups are increasingly used in various industries and technology. They are the basis for creating wear-resistant and protective coatings, diffusion barriers in microelectronics, high-temperature ceramic-metal, composite materials, ceramics, etc. An equally important role is played by the compounds of A1 and elements of groups IV - V with nitrogen in the design and production of a wide range of steel grades and alloys, especially with a high nitrogen content. Naturally, the physical, physicochemical, and mechanical properties of these materials are directly related to the type and amount of nitrogen-containing phases formed. Accurate data on the composition and conditions for the existence of complex compounds are also of fundamental theoretical importance for understanding the nature chemical bond and other key characteristics that determine the degree of their sustainability. To predict the conditions of synthesis and the stability of nitrides, reliable data on phase equilibria are required. The construction of multicomponent state diagrams with the participation of nitrogen is a very difficult task due to low thermodynamic incentives for the formation of mixed compounds from binary phases adjacent in the state diagram, 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 in terms of the composition of the triple nitrides and in terms of the position of the phase equilibrium lines. It is mainly obtained by annealing powder compacts, in which it is difficult to achieve an equilibrium state of the alloy.

PURPOSE OF THE WORK: Development of a new approach to the study of state diagrams of multicomponent nitride systems, based on the use of a complex of modern experimental methods of physicochemical analysis, methods of thermodynamic analysis and calculation, which allows one to determine the conditions for the coexistence of phases with high accuracy and obtain exhaustive evidence of their compliance with equilibrium. Study of phase equilibria in the solid phase region of ternary systems aluminum - nitrogen - metal 1U-U groups at a temperature of 1273 K. SCIENTIFIC NOVELTY:

The methods of thermodynamic analysis and calculation show the inconsistency of the available experimental data on the conditions of phase equilibrium in the T1-A1-N and r-A1-M systems;

Thermodynamic modeling, analysis and calculation of phase equilibria in the &-A1-H and Sh-A1-K systems were carried out. For the first time found

thermodynamic functions of ternary compounds formed in these systems;

The solid phase regions of the state diagrams of the systems Ti-Al-N, Zr-Al-N and Hf-Al-N at 1273 K were constructed;

The nature of phase equilibria in the Nb-Al-N system at a temperature of 1273 K has been established. SCIENTIFIC AND PRACTICAL SIGNIFICANCE OF THE WORK:

The obtained information about the equilibrium conditions and thermodynamic functions of the phases in the M-A1-N systems (hereinafter, M = Ti, Zr, Hf, Nb) is a fundamental scientific basis for the development of coatings, ceramic and cermet, composite materials important for microelectronics , energy, 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 different methods of physicochemical analysis on alloy samples 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.

Fig. 2. The structure of the solid-phase region of the isothermal section of the Ti-Al-N phase diagram at a temperature of 1273 K.

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

4. The structure of the solid-phase regions of the phase diagrams of the systems Zr-Al-N, Hf-Al-N, Nb-Al-N at 1273 K.

APPROBATION OF THE WORK AND PUBLICATIONS. The main results of the work were reported at: International conference "VIII International conference of crystal chemistry of intermetallic compounds" (Lviv, Ukraine, 2002); International Conference of Students and Postgraduates in Fundamental Sciences "Lomonosov-2003", (Moscow, 2003); International conference "Theory and practice of technologies for the production of products from composite materials and new metal alloys (T11KMM)", (Moscow, Moscow State University, 2001, 2003). Based on the materials of the dissertation, 4 articles were published. VOLUME AND STRUCTURE OF THE THESIS. The dissertation consists of an introduction, a literature review, an experimental part, a discussion of the results,

conclusions and a list of references in the amount of 204 titles. The work is presented on 138 typewritten pages, including 70 figures and 26 tables.

In the second part, the regularities of the interaction of nitrogen with elements of groups IV-V are considered, information is presented on the physicochemical properties and methods for the synthesis of nitrides. It is shown that double diagrams M-N states not fully studied. Only the existence of MN and M2N nitrides has been reliably established, while the formation of other nitride phases is doubtful due to possible stabilization by oxygen.

The main part of the literature review is devoted to the analysis of information about the structure of M-A1-N state diagrams. State diagrams M-A1-N have been studied to a much lesser extent than binary alloys. Data on the conditions of phase equilibrium in the systems Zr-Al-N, Hf-Al-N and Nb-Al-N are currently practically absent. Information about the state diagram of the Ti-Al-N system contains a number of fundamental contradictions. EXPERIMENTAL PART. §one. Sample Preparation Method.

Ti, Zr, Hf-iodide and in the form of powders with a purity of 99.5%, Nb - sheet vacuum melting with a purity of 99.99% and powder with a purity of 99.5%, nitrogen GOST 9293-74 OSCH (99.996 vol. % N2) 02< 0,001 об.%, массовая доля паров воды < 0,005 %). Порошки HfN, ZrN и AIN - марки «Ч», пластины AIN, полученные методом спекания с добавками У2О3.

Binary alloys M-A1 were obtained by alloying weighed portions of components in an arc furnace "LAYBOLD HERAUES" with a non-consumable tungsten electrode in a purified argon atmosphere. To improve the homogeneity of the ingots, they were remelted five times. The synthesized samples were wrapped in niobium foil and subjected to homogenizing annealing at 1273 K (100 hours) in evacuated quartz ampoules in electrical resistance furnaces, followed by quenching in water. The alloy compositions, their phase composition, and homogeneity were controlled by electron probe microanalysis on a CAMEBAX-microbeam device (Table 1). §2. Methodology for the study of samples.

The following research methods were used in the work:

Electron probe microanalysis on the device "CAMEBAX-microbeam" at accelerating voltages of 15 and 30 kV; preliminary analysis for impurities was carried out on a KEVEX energy-dispersive analyzer.

Scanning electron microscopy on JEOL and CAMEBAX-microbeam devices; the image was obtained in secondary electrons at accelerating voltages of 15 and 20 kV. The obtained images were processed and the phase ratio in the studied samples was determined.

Optical microscopy", dark field, bright field methods, polarized light, differential interference contrast according to Nomarski. The studies were carried out on a VEYA8AMET-2 device using a magnification ><300 и х400.

X-ray phase analysis by the powder method was carried out on DRON-4 and 8TAB1-R diffractometers manufactured by Yashe (CuKb CoKn radiation).

Table 1.

Chemical and phase composition of binary alloys of M-A1 systems.

No. Composition (EZMA), at.% Phase composition No. Composition (EZMA), at.% Phase composition

System I - A1

1 25.6 74.4 t13, T1A12 4 69.6 30.1 T13A1

2 38.3 61.7 T1A12, T1A1 5 77.1 22.9 Ti, A1

s 54.9 45.1 T1A1, T13A1 6 89.1 10.9 “SP)

System Hg - A1

1 28.5 71.5 rA13, bgMg 5 60.1 39.9 XmPAb Tr2M

2 33.3 66.7 bxc/g 6 65.8 34.2

3 47.5 52.5 2r2A13, 2GA1 7 76.7 23.3 7X2A\,

4 58.3 41.7 Xm4A1b bcrA\r

Sh - A1 system

1 31.7 68.3 H£A13, SHA12 4 53.8 46.2 NSh, H£(A1z

2 36.8 63.2 НШ2, ША13 5 62.4 [37.6 Ш3А12, Zh5А13

3 43.2 56.8 NG2A13, NSh 6 77.8 | 22.2 102A1, a(H0

System No. - A1

1 37.8 62.2 HbAb, Nb2A1 4 71.3 28.7 Mb2A1, N>3A1

2 51.2 48.8 1MbA13, Mb2A1 5 82.8 17.2 N>3A1, a(N>)

3 63.5 36.5 Nb2A1

§ 3. Development of a method for studying phase diagrams with the participation of nitrogen.

The complex modern methods physical and chemical analysis, which included: nitriding powders of M-A1 binary alloys in a nitrogen atmosphere, diffusion vapors and long-term homogenizing annealing of alloys.

For nitriding, M-A1 binary alloy powders were placed in A1203 crucibles and subjected to isothermal holding in a thermocompression annealing unit of an original design in a nitrogen atmosphere at a pressure of 5 MPa and a temperature of 1273 K for 1, 4, 9, and 16 hours. The phase composition of the samples was studied by X-ray phase analysis after each annealing.

To determine the effect of nitriding duration on the change in the composition of binary nitride phases within the homogeneity region, we studied the dependence of the lattice parameter of zirconium and hafnium nitrides on

annealing time in a nitrogen atmosphere at a temperature of 1273 K and a pressure of 5 MPa. The lattice parameters of ZrN and HfN did not change during annealing for 4 and 13 hours, which indicates that in the systems under study, the duration of high-temperature nitriding has practically no effect on the composition of the resulting nitride.

Diffusion pairs were prepared according to the M/A1N/M "sandwich" type in two ways: diffusion welding and surfacing. Diffusion welding was carried out in a vacuum on a DSVU installation at temperatures: 1273 K for titanium, 1373 K for zirconium and niobium, and 1433 K for hafnium. The welding pressure was 17-20 MPa. Surfacing of Ti, Zr, Hf, or Nb onto a 2x4x4 mm AIN plate was carried out in an electric arc furnace in a purified argon atmosphere. The resulting vapors were annealed in evacuated quartz ampoules for 100 and 670 hours and the structure of the resulting transition zones was studied by electron probe microanalysis, optical and scanning electron microscopy. The use of two methods for obtaining diffusion pairs excluded the possibility of the influence of physicochemical processes occurring on the interfaces when dissimilar materials are combined into a single composition, on the structure of diffusion zones and the nature of the results obtained.

To carry out studies of the third type, samples of two types were synthesized:

1) Mixtures of a certain composition were prepared from Zr, Hf, Nb, and AIN powders. The mixtures were pressed at room temperature and a pressure of 10 MPa. The pellets were remelted in an electric arc furnace in an argon atmosphere and subjected to long-term homogenizing annealing at 1273 K in evacuated quartz ampoules for 200 and 670 hours to achieve an equilibrium phase configuration.

2) A1N plates were wrapped in titanium or niobium foil and then remelted in an electric arc furnace. Then the samples were subjected to long-term annealing according to the described procedure. The criterion for achieving an equilibrium state was the invariance of the type and number of phases with an increase in the duration of annealing.

The calculation and analysis of phase equilibria in the systems under study was carried out in accordance with the fundamental laws of thermodynamics. When analyzing each specific composition, all possible combinations of phases were considered, the combination of which it can be represented. The combination of phases corresponding to the minimum Gibbs energy of the system was considered to correspond to stable equilibrium, and its characteristics (the nature and number of coexisting phases) were used in constructing the state diagram. All other phase combinations were considered metastable and their characteristics were not taken into account. To reduce the thermodynamic functions to the same standard states of the components, the available information about their stability parameters or the Gibbs energy of phase transitions was used. The calculation algorithm was implemented in the form of a special computer program, which involves the repeated procedure for determining the phase composition of the system for the set

points covering the entire range of compositions in the space of component concentrations at a given temperature.

Preliminary experiments and calculations made it possible to formulate the principles for choosing the compositions of the studied samples, the modes of their nitriding and heat treatment, which allow one and the same state of the alloy to be reached in different ways and to obtain exhaustive evidence of its compliance with equilibrium. RESULTS AND DISCUSSION. § 1. Phase equilibria in the T1-A1-1Ch system.

The results of preliminary experiments have shown that the most effective method for studying phase equilibria in the Ti-A1-N system is the nitriding of powder samples from the gas phase. Table 2 presents the results of X-ray phase analysis of samples after annealing in a nitrogen atmosphere at 1273 K for 1 hour. In the first five alloys, the ternary compound T12AM is formed. The results obtained testify to the existence of the following phase fields in the Tb-A1-M system: T1A1s-ThA1K-ASh, TSrAM-AM-Sh, TS3-T^A^-UrASh, and ^-Tm-OOP).

Table 2.

Phase composition of powder samples of the T1-A1-N system before and after annealing in a nitrogen atmosphere at T = 1273 K, p(N2) = 5 MPa.

Alloy No. Phase composition

before nitriding after nitriding

1 TiAl3, TiAl2 Ti2AlN, TiAl3, A1N

2 TiAl2, TiAl Ti2AlN, TiAl3, TiAl2

3 TiAl, T13AI Ti2AlN, TiNi.x, A1N

4 Ti3Al Ti2AlN, TiN,.x

5 Т1зА1 TijAIN, TiNi.x

6 a(Ti) TiNi.jb Ti2N, a(Ti)

To study the region of the phase diagram rich in titanium, the methods of diffusion pairs and long-term homogenizing annealing were used. In the diffusion zone of the A1N/Ti sample, after 200 hours of isothermal exposure T=1273 K, the formation of two intermediate layers was recorded: a titanium nitride layer containing inclusions of the Ti3AlN ternary phase, and a solid solution layer based on a(Ti) with an aluminum concentration of up to 19 at.% . Figure 1(a) shows the structure of an AlN sample/titanium interlayer with a thickness of 150 µm/AIN. After 200 hours of annealing, a titanium nitride layer with a thickness of about 30 μm is formed on the surface of aluminum nitride, the middle of the interlayer is a Ti3AlN phase with inclusions of titanium nitride TiN].x. The results obtained indicate the existence of conodes AlN-TiNi.„ TiN!.x-Ti3AlN, Ti3AlN-a(Ti).

To accurately determine the position of the equilibrium lines in titanium-rich alloys with the participation of the slowly formed Ti3AlN complex nitride, two samples were synthesized by fusing weighed portions of titanium and aluminum nitride powder in a mole ratio of 3/1 and 2/1. The first alloy after 200 hours of annealing acquired a constant phase composition

TP^-x+"PsAP^+aSP). According to the data of scanning electron microscopy and X-ray phase analysis (Fig. 1b), 4 phases were present in the second sample after 200 hours of annealing: TO^." "PzAGY, a(Tl) and "PzA1.

Moreover, T13AM inclusions were found around titanium nitride particles, which indicates insufficient homogenization time. After 670 hours of annealing, the phase composition of the sample acquired a stable configuration: TOL-PzASh+a(T0 (Fig. 2).

THASH THA1 -

Rice. 1. Microstructure of samples of the "L - A1 - >1" system:

a - AMHP/AM after annealing for 200 h, 1273 K, secondary e, x1000; b - A1K + 2GP after annealing for 200 h, 1273 K, secondary e, x1000.

n -^zash A -0(14)

20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 20 Fig. 2. X-ray diffraction pattern of the A1N+2T1 sample after annealing for 670 h, 1273 K.

Thermodynamic calculations were used to determine the position of phase equilibrium lines at low nitrogen concentrations. The existence of a liquid solution based on aluminum and α- and 3-solid solutions based on titanium was not taken into account, since the melt lies outside the region of interest for solid-phase equilibria, and equilibria with solid solutions have been experimentally studied in detail. Currently, experimental data on the Gibbs energy of formation ( A / 7) phases "PsAPCH, T12A1H, T1A12 are absent. There are only estimates. Therefore, at the first stage, these unknown characteristics were found by indirect optimization. The essence of the method was to select the A /? values of these compounds so that they satisfy the experimentally established conditions phase equilibrium As a result, the following values were found: A/7(T13A1K) = -360.0 kJ/mol; D/7SP2A1M) = -323.3 kJ/mol; A/7 (T1A12) = -80.8 kJ /mol Later they were used to calculate phase equilibria in alloys, pilot study which is difficult or impossible. The constructed isothermal (T=1273 K) section of the state diagram of the P-ANCh system is shown in fig. 3.

I - compositions of the initial binary alloys "P-A1. X - compositions of nitrided alloys, ♦ - compositions of ternary alloys T1 + A1KG, - - - ■ diffusion path. The background highlights the results of thermodynamic calculations.

The results obtained are in some contradiction with the existing data, shown schematically in Fig. 4. As can be seen, the authors found that AM is in equilibrium with "PAb, T1A12> T1A1, T12A1Y and TO^.* (Fig. 4 a). Figure 4 (b) shows the results of thermodynamic analysis and calculation of phase equilibria performed in work. Aluminum nitride is in equilibrium only with "NAL, T ^ AM and TN ^. This agrees well with the present results.

Rice. 4. Isothermal section of the system at 1273 K:

a - according to the data; b - according to the data, trIsASh, r-T^AM, 1-T1A1s, 2-T\cA\u, 3-T1A1, 6-T1A1).

The thermodynamic analysis of phase equilibria in the P-A!-^ system performed in this work made it possible to reveal the reasons for the noted contradictions. It turned out that the formation of ternary nitrides from the initial binary alloys in many cases is accompanied by an insignificant change in the Gibbs energy, amounting to only a few hundred J/mol. Therefore, The authors who used the method of annealing powder mixtures of binary compositions needed very long annealing time intervals to achieve an equilibrium state.This, apparently, was not always successful.On the contrary, the interaction of powders of titanium-aluminum alloys with nitrogen used in the proposed work is accompanied by a significant (hundreds of kJ/mol) gain in the Gibbs energy, which makes it possible to quickly reach an equilibrium state.§ 2. Conditions for equilibrium phases in the system r-A1-P*.

The study of phase equilibria in the r-AMH system was carried out according to a similar scheme. Preliminarily, thermodynamic modeling and calculation of phase equilibria in the system were carried out using the available information on the thermodynamic properties of binary phases (Table 3) and data on the state diagram at 1273 and 1573 K (Fig. 5). The calculation makes it possible to completely reproduce the experimental data on phase equilibria at 1573 K. On the other hand, information on the conditions of phase equilibrium at 1273 K cannot be reproduced by thermodynamic calculations.

In particular, the equilibrium A1N-2r3AM is realized only for the values (1/5)A/7(7r3A1M)< -92,0 кДж/моль. Однако, при этом устойчивой оказывается комбинация фаз АМ~гг3А1^-7гА12. Увеличение энергии Гиббса образования 7г3АГМ приводит к появлению трехфазного равновесия г^-АМ-ггА12.

Table 3

Gibbs energy of formation of binary compounds of the bx - A1 - N system from hcp-g, fcc-A1 and N2(gas).

Phase D /J=a+bT, J/mol. Phase AfG=a+bT+cTlnT, J/mol.

(l/4)Zr3Al 36163 4.421 (l/2)ZrAl 64950 11.014 0

(l/3)Zr2Al 48358 6.492 (l/5)Zr2Al3 55323 27.830 4.329

(l/8)Zr5Al3 51484 5.749 (l/3)ZrAl2 51266 29.726 4.417

(l/5)Zr3Al2 55180 6.734 (l/4)ZrAl3 47381 24.373 3.854

(l/7)Zr4Al3 58480 8.236 (l/2)ZrN 181795 46.024 0

(l/9)Zr5Al4 55424 5.320 (1/2) AIN 163532 57.760 0

The ArN-Zr3AlN-Zr2Al3 phases established in the coexistence are not reproduced at any values of A//(Zr3AlN). In addition, to ensure the equilibrium of AlN-Zr3AlN, it is necessary to reduce (l/5)A/?(Zr3AIN) from -73.0 kJ/mol at 1573 K to -92.0 kJ/mol at 1273 K. The latter is unlikely, since can take place only at unrealistically low values of the entropy of formation of the analyzed compound A£(Zr3AlN) = -380.0 J/mol-K.

Thus, the data on the conditions of phase equilibrium in the Zr-Al-N system found in the work for different temperatures of 1573 and 1273 K are internally contradictory and require detailed experimental verification.

Annealing of alloys of the Zr-Al system in a nitrogen atmosphere at a pressure of 5 MPa for 1 hour led to the formation of zirconium nitride ZrN and zirconium aluminide ZrAl3, regardless of the composition of the original sample. An exception was observed only for alloys nos. 5–7 (Table 4), whose diffraction patterns contained peaks corresponding to the ZrÀl2 compound. The presented results indicate the possibility of the existence of a heterogeneous field AlN-ZrAl3-ZrN, which contradicts the results of thermodynamic calculation. According to thermodynamic analysis, the equilibrium of ZrAl3 and ZrN phases in Zr-Al-N alloys should not take place, both in the presence and in the absence of complex nitrides. Indeed, an additional isothermal holding of the samples in a nitrogen atmosphere for 4 hours led to a decrease in the intensity of the peaks corresponding to the ZrAl3 compound and the appearance of lines of the ZrAl2 phase in the diffraction patterns; longer annealing caused the lines of the ZrAl3 compound to disappear in the diffraction patterns.

The described phenomenon has a kinetic nature. Zirconium reacts with nitrogen much more intensively than aluminum; therefore, zirconium nitride and the ZrAl3 phase, which is maximally depleted in zirconium, are first formed in the samples. With an increase in the isothermal holding time, aluminum interacts with nitrogen to form aluminum nitride A1N. As a result, the phase

XmA\3 transforms into XmA\2, forming the equilibrium composition rA12-Am-7rN. Thus, the study of the interaction of powdered Zr-A1 alloys with nitrogen confirmed the adequacy of the thermodynamic calculation and indicates the existence of two key phase fields in the 2x-A1-Ni A1N-2rA1r-7rA12 and AlN-2rAl-2rA12 system.

Rice. 5. Diagram of the state of the system 2g-A1-1M:

a - according to , 1273 K; b - according to , 1573 K; c - real calculation, 1273 K; d - real calculation, 1573 K.

X-ray phase and electron probe analysis of a sample obtained by fusing powders of zirconium and aluminum nitride at a mole ratio of Xr/Ash=3/1 after homogenization for 670 hours at 1273 K showed the presence of phases: 7rM, 7.r5A13M1_x and 2r3A1>1, which stable configuration. The study of the structure of the transition zones of the diffusion pairs AGY/r/Ash and AlM/7,r made it possible to reveal the existence of two more phase fields 2rH-2r3A1K-a(2r) and 2rK-r2A13-r5A13N1.x (Fig. 6).

Table 4

Phase composition of powdered Zr-Al alloys before and after annealing in a nitrogen atmosphere at T = 1273 K, p0(2) = 5 MPa.

Alloy No. Phase composition

Before nitriding After nitriding

1 ZrAl3, ZrAl2 1h. ZrN, AIN, ZrAl3

4 hours ZrN, AIN, ZrAl3, ZrAl2

2 ZrAl2 1 h. ZrN, ZrAlj

4 hours ZrN, ZrAl3, ZrAb

3 Zr2Al3, ZrAl ZrN, AIN, ZrAl3

4 Z14AI3, Zr3Al2 ZrN, AIN, ZrAl3

5 ZrjAlz, ZrzAl ZrN, ZrAI2, ZrAI3

6 ZrsAlî, Zr2Al ZrN, ZrAl2, ZrAl3

7 ZTОAI, 3(Zr)ZrN, ZtA12, ZrAl3

Rice. Fig. 6. The structure of the transition zones of diffusion containers AIN with Zr: a - AIN/Zr/A1N 200 hours, x 1500; b - A1N/Zr, 200 hours, x 2000.

Due to the high rates of interaction between zirconium and nitrogen, the equilibrium with the participation of the ZrAl, Zt4A13, ZrAl2, and Zr2Al phases could not be determined experimentally. To establish them, a thermodynamic calculation was used. At the first stage, the method of indirect optimization was used to find the Gibbs energy of formation of ternary nitrides: (l/5)A/?(Zr3AlN) = -76.0 kJ/mol; (1 / (9-x)) D / Z ^ ^ AU ^. *) \u003d -63.0 kJ / mol. The obtained values are used to find unknown conditions for phase equilibrium. The results obtained are shown in fig. 7.

The constructed phase diagram of the Zr-Al-N system at 1273 K is in conflict with the data for this temperature, however, it practically coincides with the results obtained for 1573 K. Apparently, the duration of the annealing used in the annealing was not enough to achieve the equilibrium state of the alloy at a lower temperature 1273 K.

aA1z 2xAI ¿GdA^

gA1 4 bA\

Rice. Fig. 7. Phase diagram of the 2r-A1-N system, 1273 K. ■ - compositions of the initial binary alloys of the 2r-A1 system, o - compositions of nitrided alloys, □ - composition of the ternary alloy 2r + AM.

Diffusion paths in the bx - A1 - N system at 1273K. ааааа - sample (¿ly+ТхгАЦуТт 670 hours.

Sample AMa/ASh 200 hours

Sample A1Y/yy 200 hours.

§ 3. The structure of the state diagram of the Hf-Al-N system.

A similar situation takes place for the Hf-AI-N system. On fig. Figure 8 shows the structure of the state diagram at 1273 K, obtained in this work together with the data.

Almost all phases of the Hf-Al binary system are in equilibrium with hafnium nitride HfN. This is due to the low value of the Gibbs energy of HfN formation. The ternary compound Hf3AlN forms regions of three-phase equilibria only with the Hf5Al3, HfN, and a(Hf) phases. Binary compounds Hf2Al and Hf3N2 occur only in very limited ranges of compositions of the ternary system. Aluminum nitride is in equilibrium with HfAl3 and HfN. § 4. Phase equilibria in the Nb-Al-N system.

On fig. Figure 9 shows the state diagram of the Nb-Al-N (T=1273 K) system constructed in this work. The results obtained practically coincide with the data of the work for a temperature of 1773 K, shown below. The only difference is that at 1273 K, niobium nitride NbN is stable in the Nb-N system, which is in equilibrium with aluminum nitride and the Nb2N-based phase. The Na > 4N3 compound is present only in a limited range of ternary alloy compositions. The ternary compound Nb3Al2N is in equilibrium with the AIN, NbAl3, NbAl2, and Nt^N phases. The Nb3Al-based phase and the niobium-based solid solution form a three-phase region with niobium nitride Nb2N. CONCLUSION.

In conclusion, the main results of the work are summarized. It is shown that, at high nitrogen contents, the most promising method for studying phase diagrams of three- and more-component nitride systems is the nitriding of powdered binary alloys. At low nitrogen concentrations, the methods of diffusion pairs and prolonged homogenizing annealing give the most adequate results. The commonly used technique for annealing powdered compacts requires a long isothermal exposure and, at temperatures below 1473–1573 K, in many cases does not allow reaching the equilibrium state of the alloy.

State diagrams of the Ti-Al-N, Zr-Al-N, Hf-Al-N and Nb-Al-N systems at 1273 K were constructed using a complex of modern methods of physicochemical analysis. An approach based on the implementation of different ways to achieve the same final state of the alloy. The data found using different methods are in good agreement both with each other and with the results of thermodynamic calculations; therefore, they can be recommended for predicting phase equilibria in these systems and compositions based on them.

A general regularity in the structure of state 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 MN and A1N binary phases increases. Thus, the prediction of 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.

Rice. 8 Status diagram Sh-A1-M:

a - according to the data of 1273 K; b - according to 1673 K data; c - according to the data of this work ■ - compositions of the initial binary alloys of the system Hg-Al. - compositions of nitrided alloys (1 hour). A - compositions of nitrided alloys (4 hours), o - composition of the ternary alloy HX + AM. -*- - diffusion paths in the W "-A1-K system at 1273 K.

Rice. 9. Status diagram >1b-A1-K:

a - according to the present work, 1273 K:

■ - compositions of the initial binary alloys of the Mb-A! system. - compositions of nitrided alloys □ - composition of the ternary alloy ZKL+ASh.

Diffusion paths in the ML-A1-N system at 1273K.

b - according to 1773 K.

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

3. Using a complex of modern methods of physical and chemical analysis, the regularities of the interaction of elements in 85 samples of binary and ternary alloys of the M-A1-1Ch systems were studied.

4. A solid phase diagram of the state of the Ti-ANH system at 1273 K was constructed. It was found that aluminum nitride is in equilibrium with the phases T1A13, Tl2ASh and "PM,.,. The ternary compound T13A1Y forms three-phase regions with the phases T12AGM, T1A1, T13A1, a T1) and Tm1^.*.The parameters are determined

crystal lattices of the ternary phases Ti2AlN (a=2.986(9)Â, c=13.622(5)Á), Ti3AIN (a=4.1127(17)Â), 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 Zr-A!--N crystalline alloys at 1273 K have been studied. The positions of all regions of three-phase equilibria have been reliably established. Aluminum nitride is in equilibrium with the ZrAl3, ZrAl2, and ZrN phases. The ternary Zr3AlN phase forms fields of three-phase equilibria with the ZrN, Zr5Al3Ni.x phases and the a(Zr-based) solid solution. The lattice parameters of the complex nitride Zr3AlN are a=3.366(6)Â, è=l 1.472(10)Â, c=8.966(9)Â, the Gibbs energy of formation Ap = -460.0 kJ/mol.

6. It has been established that in solid compositions of the Hf-Al-N system at 1273K, almost all binary phases of the Hf-Al system are in equilibrium with hafnium nitride HfN. The ternary Hf3AlN compound forms regions of three-phase equilibria with the Hf5Al3, HfN phases and a(Hf-based) solid solution. Binary phases Hf2Al, Hf3N2 occur only in limited ranges of compositions of the ternary system. Aluminum nitride is in equilibrium with HfAI3 and HfN.

7. For the first time, an isothermal T=1273 K section of the solid-phase part of the state diagram of the Nb-AI-N system was constructed. The ternary compound Nb3Al2N is in equilibrium with the AIN, NbAI3, NbAl2, and Nb2N phases. 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 NbzN.

LIST OF CITED LITERATURE:

Schuster J.C., Bauer J. The Ternary System Titanium-Aluminum-Nitrogen. //J.

Solid State Chem. 1984. V.53. p 260-265.

Chen G., Sundman B. Thermodynamic Assessment of the Ti-Al-N System. //J.

Phase Equilibria. 1998.V.19. No. 2, p. 146-160.

Schuster J.C., Bauer J., Debuigne J. Investigation of Phase Equilibria

Fusion Reactor Materials: l.The Ternary System Zr-Al-N. //J. Nucl. mater. 1983.

V.116, p.131-135.

Schuster J.C., Bauer J. Investigation of Phase Equilibria Related to Fusion Reactor

Materials: P. The Ternary System Hf-Al-N. //J. Nucl. mater. 1984. V.120, p. 133-136.

Determination of the phase composition of such materials showed the presence of only double nitride phases. Nevertheless, recent, thorough studies of M - Al - N alloys (hereinafter M = Ti, Zr, Hf, Nb) made it possible to reveal the existence of complex nitrides: Ti3AlN, TÎ2A1N, Ti3Al2N2; Zr3AlN, ZrsAbNj.x; Hf3AlN, Hf5Al3N; Nb3Al2N . Their properties are practically not studied, although there are good reasons to believe that they may be unique. This is evidenced by the fact that composite materials based on a combination of A1 and M double nitrides have the maximum level of physical characteristics precisely in the regions of triple phase compositions. For example, the abrasive properties of ternary compounds Ti - Al - N are twice as high as those of corundum and even than those of tungsten carbide.

An equally important role is played by the compounds of A1 and elements of groups IV - V with nitrogen in the design and production of a wide range of steel grades and alloys, especially with a high nitrogen content. Naturally, the physical, physicochemical, and mechanical properties of these materials are directly related to the type and amount of nitrogen-containing phases formed. Accurate data on the composition and conditions for the 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 conditions of synthesis and the stability of nitrides, reliable data on phase equilibria are required. The construction of multicomponent state diagrams with the participation of nitrogen is a very difficult task due to low thermodynamic incentives for the formation of mixed compounds from binary phases adjacent in the state diagram, 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 in terms of the composition of ternary nitrides and the position of phase equilibrium lines. It was mainly obtained by one group of researchers by the method of annealing powder compacts, in which it is difficult to achieve an equilibrium state of the alloy.

PURPOSE OF THE WORK:

Development of a new approach to the study of state diagrams of multicomponent nitride systems, based on the use of a complex of modern experimental methods of physical and chemical analysis, methods of thermodynamic analysis and calculation, which allows one to determine the conditions for the coexistence of phases with high accuracy and obtain exhaustive evidence of their compliance with equilibrium. Investigation of phase equilibria in the solid-phase region of ternary systems aluminum - nitrogen - group IV - V metal at a temperature of 1273 K.

SCIENTIFIC NOVELTY:

The methods of thermodynamic analysis and calculation show the inconsistency of the available experimental data on the conditions of phase equilibrium in the systems Ti-A1-Nurr-A1-K;

A technique has been developed for studying the phase diagrams of nitride systems, which is based on a complex of modern methods of physicochemical analysis and the implementation of different ways to achieve the same final state of the alloy, which makes it possible to obtain exhaustive evidence of its compliance with equilibrium;

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

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

A1-Y and NG-A1-Y at 1273 K; The nature of phase equilibria in the Nb - Al - N system at a temperature of 1273 K was established.

SCIENTIFIC AND PRACTICAL SIGNIFICANCE OF THE WORK:

The obtained information about the equilibrium conditions and thermodynamic functions of the phases in the systems M - A1 - N (M = T1, bx, H £ Nb), are the fundamental scientific basis for the development of coatings, ceramic and metal-ceramic, composite materials important for microelectronics, energy, 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 alloy samples 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 FOR DEFENSE:

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

Fig. 2. The structure of the solid-phase region of the isothermal section of the state diagram "L - A1 - N at a temperature of 1273 K.

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

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

II. LITERATURE REVIEW

Dissertation conclusion on the topic "Physics of Condensed Matter"

VI. conclusions.

1. A technique has been developed for studying phase diagrams of multicomponent nitride systems based on a combination of methods for nitriding binary alloys, long-term homogenizing annealing of ternary compositions, diffusion pairs, thermodynamic calculation, and modeling of phase equilibria. It makes it possible to realize different ways of achieving the same final state of the alloy and to obtain exhaustive evidence of its compliance with equilibrium. It has been established that the most reliable and informative method of nitriding binary alloys when studying the regions of state diagrams with high nitrogen concentrations. At low nitrogen concentrations, the diffusion pair method gives the best results.

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

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

4. A solid-state diagram of the state of the T1-A1-K system at 1273 K was constructed. It was found that aluminum nitride is in equilibrium with the phases IA13, NgAsh, and T13A1.*. a(II) and The crystal lattice parameters of the ternary phases T12ASh (a=2.986(9)A, c=13.622(5)A), T13Ash (a=4.1127(17)A), and the Gibbs energies 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 have been studied. The position of all regions of three-phase equilibria has been reliably established. Aluminum nitride is in equilibrium with the ZrA13, ZmA\2, and ZrN phases. The triple phase r3ANH 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 q=3.366(6)A, ¿"=11.472(10)Â, c=8.966(9)Â, the Gibbs energy of formation is A/3 = -380.0 kJ/mol.

6. It has been established that in solid compositions of the Hf-Al-N system at 1273K, almost all binary phases of the Hf-Al system are in equilibrium with hafnium nitride HfN. The ternary compound Hf^AlN forms regions of three-phase equilibria with the HfsAh and HfN phases and the a(Hf-based) solid solution. Binary phases Hf2Al, ^N2 are realized only in limited ranges of compositions of the ternary system. Aluminum nitride is in equilibrium with Hg Al3 and HfN.

7. For the first time, an isothermal T=1273 K 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 AIN, NbAb, NbAb, and Nb2N phases. 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

A general regularity in the structure of state 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 MN and A1N binary phases 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) \u003d -110.7 kJ / mol. So 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, when 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 to the ZrsAb intermetallic compound. On the state 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 a maximum aluminum concentration. 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, the prediction of 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 studies carried out made it possible to develop a method for adequately constructing phase diagrams for multicomponent nitrogen-containing systems and to establish the following regularities. 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 a low nitrogen content, the best results are obtained by methods of long homogenizing annealing and diffusion pairs. Distinctive feature The latter is the possibility of obtaining a large array of data on the conditions of phase equilibrium in the study of one sample. The commonly used technique for annealing powdered compacts requires a long isothermal exposure and, at temperatures below 1473–1573 K, in many cases does not allow reaching the equilibrium state of the alloy.

An experimental study of phase equilibria in alloys with a 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 state diagrams, it is effective to use the methods of thermodynamic modeling and calculation of phase equilibria. They, based on data on the conditions of phase equilibrium, found for more experimentally accessible parts of the state diagram and the available information on thermodynamic functions, make it possible to unambiguously establish the missing information. When solving the problem posed, the corresponding system of equations, as a rule, turns out to be overdetermined, so the calculation not only allows one to establish the position of the equilibrium lines, but also to obtain exhaustive evidence of the adequacy of the solution. So, when carrying out thermodynamic calculations for all the studied systems, the result did not depend on which experimentally found phase fields were used as initial data.

Another important direction in the use of thermodynamic modeling and calculation is the prediction of the conditions of the experiment and the choice of the initial compositions of the 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 the present work, using a set of modern methods of physicochemical analysis, four isothermal sections of the phase diagrams of the ternary systems T1 - A1 - N. bm - A1 - N. W - A1 - N and N> - A1 - N at 1273 K are constructed. consistently applied approach based on the implementation of different ways to achieve the same final state of the alloy. The data found using various methods are in good agreement both with each other and with the results of thermodynamic analysis, therefore, they can be recommended for predicting phase equilibria in these systems and compositions based on them.

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