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Опубликовано в библиотеке: 2021-11-12
Источник: Science in Russia, №6, 2013, C.59-65

by Academician Leopold LEONTYEV, Chairman of the RAS Scientific Council for Metallurgy and Metal Science; Ilya NEKRASOV, Cand. Sc. (Tech.), senior research assistant of the Institute of Metallurgy, RAS Ural Branch (Yekaterinburg)

 

The development of human civilization is indissolubly connected with metallurgy, which for many centuries passed a way from "alchemical magic" to an advanced branch of knowledge dealing with methods of the most called-for structural materials. However, achievements in this field would have been impossible without cooperation with chemistry. And today's metallurgy, when it is viewed not only in terms of economy, i.e. as one of the most important industry branches, but also in terms of science, is first of all high-temperature electrochemistry. So, how was this fruitful alliance forming?

 

Probably the first chemical technology in the history of mankind was represented by production of metals by ore reduction in primitive hearths. Therefore, the most ancient metallurgist was also a chemist. As fire was greatly value in the ancient world, it was not wasted. The bonfires were surrounded with stones which protected the flame from wind and rain. Combination of charcoal, several types of stones and, of course, high temperature produced occasionally an interesting effect: sometimes raking out ashes from the

 
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fire one could notice hardened drops of reduced metal. But a considerable amount of time elapsed before a fire designed for heating and cooking turned into a specialized chemical reactor--a Catalan furnace, ancient ancestor of a modern blast furnace.

 

Another proof of the "genetic" link between chemistry and metallurgy can be found in formulations of problems which were set by the first experimental chemists in ancient times and the Middle Ages. For example, there is the following definition of the 13th century British philosopher and natural scientist Roger Bacon: "Alchemistry is a science dealing with preparation of some compound or elixir, which when added to basic metals will turn them into perfect metals." It is evident that the definition includes absolutely practical targets related to production of metals through invention of "elixirstone". Without going into details of alchemistry we can note its contribution to science. First of all, it is conditioned by acquiring skills in experimental chemistry and widening of its technical possibilities, which prepared a further break between practice and magic.

 

It is alchemistry which at the final stage of its development gave birth to technical chemistry, which is closely related to metallurgy. This event was marked by publication of the following encyclopedic works, which summed up the experience of metallurgical and chemical technologies: De la Pirotechnia (10 volumes, in 1540) by the Italian alchemist and architect Vannoccio Biringuccio and De Re Metallica (12 volumes, in 1556) by the German scientist Georgius Agricola.

 

In the course of time technical chemistry turned into the exact science based not only on observations but also on measurements. Quantitative laws took the place of qualitative dependences, which testified to the fact that the concept of atoms set forth by the Ancient Greek philosopher Democritus (circa 460-circa 360 B.C.) replaced for good metaphysics of "elixir-stone" and started to yield practical results.

 

After the defeat of alchemistry, i.e. from the end of the 16th century, the fundamentals of chemistry as a science are formed. One of its main laws--the law of definite proportions--was discovered by the French chemist Joseph-Louis Proust early in the 19th century. The gist of it is that any definite chemically pure compound, irrespective of its method, consists of the same chemical elements, while their mass ratios are constant and relative numbers of their atoms are expressed by whole numbers. At the same time the British natural scientist John Dalton discovered the law of multiple proportions, introduced the concept of atomic weight, calculated it for a number of elements, made up the first table of atomic weights and thus laid the foundation of the theory of atomic structure of matter. A bit earlier the German chemist Ieremias Benjamin Richter (corresponding member of the Petersburg Academy of Sciences from 1800) in his works pioneered the application of quantitative equations of reactions and showed that in a chemical compound elements interact in a strictly determinate proportions named later equivalents. It should be noted that these discoveries are a basis for the

 
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theory of metallurgical processes and finally also for a practical aspect of metallurgy as a branch of modern industry.

 

It is believed that the foundations of physical chemistry were laid down by our great natural scientist Mikhail Lomonosov* in the 1740s, when he tried to explain chemical phenomena by laws of physics and the theory of structure of matter. According to his definition "physical chemistry is a science which explains through regulations and experiments of physics what takes place in mixed substances during chemical operations".

 

It is recognized that Lomonosov also concerned himself with metallurgy as an industry. In his works on metallurgy and mining First Foundations of Metallurgy or Ore Mining and On the Earth Strata he brought forward the idea of ore veins, their age and origin causes. He described the known methods of producing a number of metals and their properties. Besides, he made a series of original proposals, in particular, he was the first to express an idea of extraction of metals from ores by means of chemical reagent solutions, which is the basis for modern hydrometallurgy.

 

The Russian chemist Herman Hess (Academician of the Petersburg Academy of Sciences from 1830), author of the basic law of thermophysics--the law of constancy of heat--played a key role in creation of the theory of chemical reaction energetics. He lectured at the Peters-

 

See: E. Tropp, "Along the Way to Universal Knowledge", Science in Russia, No. 5, 2011.-Ed.

 

burg Mining Institute, the first higher technical college (today the National Mineral Resources University "Gorny") and is considered one of the founders of Russian chemical and metallurgical training and scientific schools.

 

The development of chemistry as a science and the theory of metallurgical processes was largely conditioned by formation of the concept on chemical equilibrium and also elaboration of estimation methods of rate and direction of reaction development. We shall mention here a number of scientists who made a considerable contribution to these branches of knowledge. The Norwegian physical chemist Cato Guldberg and his countryman chemist Peter Waage in 1864-1867 discovered the law of mass action, which underlies the chemical equilibrium theory. The theoretical physicist Josiah Willard Gibbs (USA), one of the founders of thermodynamics and statistical mechanics, won recognition for theoretical studies of chemical equilibrium. His works in equilibrium of heterogeneous systems are regarded as one of the greatest scientific achievements of the 19th century. The Swedish physical chemist Svante Arrhenius (Nobel Prize winner of 1903) made a substantial contribution to formal kinetics and the theory of solutions.

 

Among scientists of that time we must also single out those without whose pioneer works the emergence of electrometallurgy and electrolysis technologies would have been impossible. For example, the British experi-

 
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mental physicist and chemist Michael Faraday (foreign honorary member of the Petersburg Academy of Sciences from 1830) carried out basic research in electrolysis and induction. Besides, he ran experiments in smelting of steel with nickel and discovered stainless steel. The Italian physicist, chemist and physiologist Alessandro Volta in 1803 invented the first chemical source of electric energy, the so-called "voltaic pile". In the same year the Russian physicist Vasily Petrov, member of the Petersburg Academy of Sciences, invented the most powerful "voltaic pile". Besides, a year before he discovered electric arc and proved its application for melting, welding and reduction of metals from ores.

 

Noteworthy are also French chemists Claude Berthollet and Gaspard Monge, who already at the end of the 18th century in their works Different States of Iron and Steelmaking Directions made a conclusion that difference between iron, cast iron and steel was determined first of all by carbon content. Their ideas of the role of this element in iron alloys were elaborated later by other scientists and contributed to the development of metal science as an independent branch of knowledge.

 

The heritage of Russian scientist Dmitry Mendeleev* deserves special consideration. His Periodic Law discovered in 1869 is one of the most important events in the history of science. The key feature of the law is its "predictability". To put it otherwise, it provides description of properties of elements, which are not yet discovered. Modern science and technologies would not be possible without development of ideas of interrelation between atomic weights and physical and chemical characteristics. Mankind proved by this achievement

 

See: M. Savchenko, "Pride and Glorv of Russia", Science in Russia, No. 1, 2004.-Ed.

 
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that it becomes more and more familiar with the atomic world of Democritus.

 

The considerable part of Mendeleev's activity was devoted to feasibility studies of ore and coal deposits in Russia and organization, in modern phraseology, of "industrial clusters", first of all, in Siberia and Ural. Mendeleev also raised the fundamental problem of "direct extraction of iron and steel from ore leaving out cast iron", which is in the focus of attention even today.

 

The development of metallurgy as a science in the 19th century is associated with the names of a number of national scientists. For example, Pavel Anosov, a well-known organizer of mining and metallurgical industry, suggested a technology of production of damask steel. Dmitry Chernov in his works laid foundations for metal science and the theory of thermal processing of steel. Academician Mikhail Pavlov, who worked in late 19th-the first half of the 20th centuries, in 1894 published a theoretical research, the first in Russia, of blast-furnace thermal balance, working on a charcoal in a mining journal.

 

But how did specialists themselves appraise significance of chemistry in the formation of metallurgical science? Ivan Sokolov, considered by contemporaries father of the Russian and Soviet school of the theory of metallurgical processes, used extensively fundamental works of the French physicist and chemist Henri Le Chatelier, German chemist Walther Nernst (Nobel Prize winner of 1920) and Dutch chemist Jacobus van't Hoff (Nobel Prize of 1901) dealing with chemical equilibrium and thermodynamics. Another known metallurgist Vladimir Grum-Grzhimailo, corresponding member of the USSR Academy of Sciences from 1927, shared this opinion concerning the works of the above-mentioned scientists.

 

In this context, the fate of Ivan Sokolov himself arouses interest. In 1891, he graduated from the physico-mathematical department of the Petersburg University and for the next seven years taught mathematics

 
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in grammar schools of Vyborg and Arkhangelsk. As he wrote later, life in the northern regions excited his interest in geology, and he left his teaching activities and entered the Petersburg Mining Institute. There he became primarily a chemist, which is testified by his works On Reduction of Iron Ores (1909), Chemical Thermodynamics and the Theory of Metallurgical Processes (1933) and Thermodynamics of the Blast-Furnace Method (1933). According to Sokolov "metallurgy is high-temperature chemistry". After completing reconstruction of the Ural steel works, he turned to the problems of the blast-furnace production and preparation of raw materials. For many years the scientist lectured at higher education establishments in Yekaterinburg and Tomsk. Among his students were Oleg Yesin, Dr. Sc. (Tech.), later the founder of the Ural physico-chemical school of metallurgists and Grigory Chufarov, the author of works on physical chemistry of metallurgical processes, corresponding member of the USSR Academy of Sciences.

 

Apparently the next qualitative breakthrough in the development of metallurgy was realization by specialists of the fact that metallurgy was not simply high-temperature chemistry, it was high-temperature electrochemistry. In this respect, worthy of mention is the role of Academician Alexander Frumkin (1895-1976) in the formation of the theory of this new research trend. His works were mainly associated with electrochemistry of aqueous media but they also dealt with fundamental problems of surface phenomena and interactions on interphase boundaries and therefore were fundamental for the whole electrochemical science (including melt electrochemistry or ion liquids).

 

Frumkin's ideas had substantial influence on the development of the Ural electrochemical schools dealing with problems of metallurgy since the 1920s, includ-

 
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ing the corresponding member of the USSR Academy of Sciences Sergei Karpachev, Armin Stromberg, Dr. Sc. (Chem.) and the abovementioned Oleg Yesin and Grigory Chufarov.

 

Sergei Karpachev carried out pioneer studies of electrochemical properties of ion melts. His works devoted to studies of technological processes of producing magnesium and aluminum, promoted solution of a number of theoretical and practical problems. He worked out a measurement procedure for oxide melt viscosity and achieved important results in studies of viscosity of many oxide systems, including blast-furnace slags.

 

Sergei Karpachev is considered the founder of the Ural school of electrochemistry, which greatly contributed to the development and perfection of technologies of getting refractory and rare, primarily strategic, metals. He was twice granted the State Award for great achievements in the development of science and defense technology, handling the problems related to the creation of the USSR nuclear shield.

 

Armin Stromberg was a staff member of the electrochemistry laboratory of melted salts, established by Karpachev in 1932. In their joint research they managed to determine values of zero-charge potentials of ten liquid metals and experimentally prove some theoretical conclusions of Academician Frumkin. Later on Stromberg became known as one of the creators of a new highly sensitive electrochemical analysis method, i.e. inversion voltammetry, which is successfully developing nowadays by his students and followers.

 

Oleg Yesin was the first to apply the laws of electrochemistry to analyze interaction processes of main metallurgical phases, i.e. metal and slag. Thus, he created a new scientific trend, namely, the electrochemical theory of metal-slag (molten electrolyte) interaction. He won world recognition due to his studies of the combined ion discharge in electrolytic process and the work in the theory of double electrical layer at the metal-slag interface. He was the first to advance an idea that molten slags (silicates) corresponded to polyanionic liquids and were microheterogeneous systems. It is just these ideas that are the basis of the theories of melted slag structure, which are developing today in Russia and abroad. Yesin also made invaluable contribution to the development of the school of scientists-metallurgists at the Ural Polytechnical Institute.

 

Pavel Geld, Corresponding Member of the USSR Academy of Sciences from 1970 together with Yesin authored the two-volume work Physical Chemistry of Pyrometallurgical Processes. His main research is devoted to problems of pyrometallurgy. Geld promoted development of the high-temperature reduction theory and revealed a stepped character of silica reduction. He studied a link between physical properties of solid and liquid alloys and compounds of variable composition, thermophysical characteristics of transient metals and alloys on their basis and also parameters which characterize hydrogen behavior in them. He also studied and generalized data on the atomic and electronic structure of borides, carbides, nitrides, silicides and hydrides of transient metals.

 

Grigory Chufarov made a considerable contribution to studies of thermodynamics, kinetics and mechanism of the heterogeneous oxidation-reduction processes in systems containing metal oxides. His scientific ideas are used in industrial processing of iron, cobalt and niobium ores, decarbonizing and etching of magnetic sheets, in creation of grease for metal rolling, etc.

 

Thus, the decades of development of chemistry and metallurgy not only as sciences but also as industries brought scientists and production engineers to the atomic level of the structure of matter (the term "nano" was not yet used at that time) already in the mid-20th century. Without such research and studies it would be hardly possible to produce alloys with phenomenal properties for the needs of defense, aviation and shipbuilding. The medieval alchemists would see a magic in it. But we know that these successes are a result of collective efforts of several generations of scientists who were always conscious of their responsibility towards the future.

 

Illustrations supplied by the authors


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© Leopold LEONTYEV, Ilya NEKRASOV () Источник: Science in Russia, №6, 2013, C.59-65

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