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Sergey Venezky
STORIES ON METALS

MANGANESE

ETERNAL COMPANION OF IRON

The columns of the underground Palace. - Wonderful black powder. - "Glass soap". - Gan or Rims? - Takes the baton Scheele. - "Hell fire" is doing its job. - Deficit heavenly phone - Try to crack the safe. - Will it be possible to collect Veche? - Two-faced alloy. - "Simple" name. - Replace platinum and palladium. - Familiar from childhood. - Why red ants red? - Pink pearls. - In the teeth of a shark. _- By conservative estimates. - No bacteria no cost. - Garlands on the reefs. - In the loops of the underwater cable. - Misunderstanding overboard. - Unusual medal. - To work in the depths. - "Make" from space. - Needed it for Russia? - The path lies in Martin.

If you've been in the Moscow metro, you must have noticed one of his most beautiful stations "Mayakovskaya". Columns of the underground Palace is decorated with a thin rim of pink stone. This rhodonite mineral containing manganese. Delicate pink color ("Rodon" in Greek - rose) and good machinability make beautiful stone cladding and ornamental material. Products from rhodonite is stored in the Hermitage, the Peter and Paul Cathedral and many other museums of our country. Large deposits of it are found in the Urals, where he found a lump weighing 47 tons. Nowhere else on our planet there is no such significant accumulation of this mineral, as it is here. Yes and beauty of the Ural rhodonite has no equal.

But the main industrial mineral manganese is not rhodonite, and pyrolusite, which represents an oxide of manganese. This black mineral known to man since ancient times.

Even in the first century Pliny the Elder, historian and naturalist of Ancient Rome, who died during the eruption of Vesuvius, pointed to the miraculous ability of black powder (ground pyrolusite) to lighten the glass. Later, in the middle ages, the Italian scientist and engineer, Vannoccio Biringuccio wrote in his encyclopedic work on mining and metallurgy "Pirotechnia", published in 1540: "...pyrolusite is dark brown; ...if we add to it the vitreous substances, it paints them in a beautiful purple color. Master steklobutylki paint them with glass in a stunning purple color; master potters also use it for education purple patterns on the dishes. In addition, pyrolusite has a special property - by alloying with molten glass to clean it and make white instead of green or yellow.

The name "pyrolusite" came to the mineral later, and in those days because of the ability to decolorize glass it was called "glass soap", or "manganese" (from the Greek "manganese" - clear). It was known by another name mineral - black magnesia: pyrolusite from ancient times was mined in Asia Minor near the city of magnesia, by the way, there were extracted and "white magnesia or magnesia Alba", - magnesium oxide.

History of chemistry attributes the discovery of manganese as metal Swedish chemist Johan Gottlieb Ghana (1774). However, there is reason to believe that the first person who got the grains of manganese metal, was Ignatius Gottfried Kyme, who described it in his thesis, published in 1770 in Vienna. Kyme brought this research to the end, and so they remained unknown to most chemists of the time. However, in one of the chemical dictionaries is mentioned about the opening of the Border: "Heating a mixture of one part powdered pyrolusite with two parts of black flux, Kyme received bluish-white brittle metal in the form of a crystal with countless brilliant faces of different shapes, the fracture of which in all colors from blue to yellow.

The next attempt to get acquainted with manganese did the Swedish scientist Torbern Bergman. "Mineral, which is called black chalk, he wrote, " is a new earth, which should not be confused neither with burnt lime or magnesia Alba". But none of manganese from pyrolusite him and failed.

The study of this mineral has continued each Bergman famous chemist Carl Wilhelm Scheele. In early 1774 he presented to the Swedish Academy of Sciences report on the pyrolusite and its properties, which reported about the opening of chlorine. Scheele argued that the composition of pyrolusite is another element that is different from all known at that time. But to get this item, it failed.

What had not been done Bergman and Scheele, managed to make Ghana. In may 1774 Scheele sent him cleaned pyrolusite, along with the following note: "I look forward messages about what the results of this pure pyrolusite, when You apply Your "hell fire", and I hope You will send me a small bead of metal as soon as possible".

Gan had a reputation among chemists skilled experimenter, especially when it came to metallurgical experiments. In the crucible, the inner wall of which was covered with wet dust, he put the milled mixture of pyrolusite and oil, and on top poured the powder of charcoal. Now it is the turn of "Hellfire". After strong heating of the mixture for one hour in the crucible was discovered Wren. This speck brought Ghana to international fame, and the family of metals has been enriched by a new member of manganese.

However, the grade of the metal element is not found immediately. The fact that at the end of the eighteenth century were still heard the echo of ancient ideas of the alchemists, which essentially boils down to a short and clear statement: "Seven metals created light on the seven planets." Once the number of known metals and really matched the number of "active" heavenly bodies (Sun, Pune and five planets, not counting the Ground). It would be good if the shelf metals did not come; with the advent of new planets, the situation was much worse (another planet in the Solar system was discovered only in 1781). Due to the shortage of the heavenly bodies do not suffer slim theory, the number of new chemical elements, claiming the role of metals, had to include in the category of semimetals.

This term was preserved in science and later, when it became clear that astronomy and chemistry are not as strong ties, as I thought the alchemists. Many scientists for a long time called semimetals the body, which in density, color, shape seemed metals, but did not possess high ductility inherent in gold, silver, copper, iron, lead and tin - elements, whose metallic reputation was never in doubt. The semimetals attributed, for example, mercury, antimony, bismuth, zinc, cobalt. One of the last elements that are not immediately admitted into the circle of metals, was manganese. So, at the end of June 1774, i.e. soon after the discovery of this element; Scheele sent Ghana letter thanking him for sending a grain of manganese and shared their thoughts: "...I believe that Wren obtained from pyrolusite, is a semimetal that is different from all other semimetals and having a close bond with the metal. But chemists eventually abandoned rather dubious term, and manganese on the right took place in a number of metals.

In Russia manganese began to receive in the first quarter of the XIX century in the form of an alloy with iron - ferromanganese. "Mining magazine" in 1825 mentioned steelmaking using manganese. Since that time, the fate of the item is inseparably connected with metallurgy, which is now the main consumer of manganese ore.

Wonderful Russian Metallurgist P.P. Anosov in his famous work About damask steel", published in 1841, described research steels with different manganese content. To introduce into the steel Anosov used ferromanganese obtained in the crucibles. Since 1876 begins industrial ferromanganese smelting in blast furnaces Nizhny Tagil plant.

A milestone in the history of manganese 1882 was when English Metallurgist Robert Hadfield melted steel with a high content of this element (about 13%). In 1878 Hadfield began the study of alloys of iron with other elements, in particular with manganese. Four years later, a young Sheffield Metallurgist made the following entry in my research journal: "I started these experiments, referring to the steel, which would be solid and at the same time viscous. The experiments led to some interesting results, is very important and can change the existing views of metallurgists on alloys of iron".

In 1883 Hadfield was issued the first British patent for manganese steel, manufactured by additive to iron-rich ferromanganese. In subsequent years, Hadfield continued to study the problems associated with manganese steel. In 1883 appeared his work On manganese and its application in metallurgy", "About some newly discovered properties of iron and manganese", "manganese steel". Studies have shown that quenching in water gives this new useful properties. Hadfield received a number of patents relating to heat treatment of manganese steel, and in 1901 they were patented design of the furnace designed to heat the steel before quenching.

Steel, Hadfield steel has quickly gained recognition metallurgists and mechanical engineers. Due to their high durability it has been used for the manufacture of those parts, which during operation caused when high specific pressure - rail crossings, cheeks crushers, balls, ball mills, crawler tracks, etc. the most surprising Thing was that, under the action of loads this steel was becoming harder and harder. The reason for this strange phenomenon is the following. After casting manganese steel at the grain boundaries, which causes excess carbides, reducing its strength. Therefore, the steel must be quenched, resulting in the boundary carbides are dissolved in the metal. During the service details due to work hardening (strain) in the surface layer is allocated carbon - this explains the hardening of steel. No wonder that steel, Hadfield steel is very interested in firms producing safes and locks.

Try to crack the safe!

Property samorodnitsky has iron and manganese. So, excavators, which were installed into the bearings of this iron was in use without repair twice longer than the same machine with bronze bearings.

Manganese and iron eternal companionsIn metallurgy manganese is widely used for deoxidation and desulfurization of steel. As alloying element it is part of the spring steels, steels for oil and gas pipes, steel with non-magnetic properties. However, it is hardly necessary to enumerate steel containing manganese: in particular the number of the item, outdoor gang, is present in almost all steels and cast iron. It is no coincidence that it is called the eternal companion of iron. Yes and in the Periodic system of the elements they occupy adjacent squares No. 25 and 26. (Along with iron, manganese gets... even in the teeth of a shark, but this will be discussed below).

After the 1917 Russian scientists SF Pearl and V.K. Petrushevich found that even slight additive copper (about 3.5%) give the manganese plasticity, metallurgists began to show interest in manganese alloys.

Modern techniques use a large number manganin alloys of manganese, copper and Nickel having a high electric resistance, which is practically independent of temperature. The ability of manganin to change resistance depending on the pressure, which is an alloy based principle of electric gauges. In those cases when it is necessary to measure pressure, for example, several tens of thousands of atmospheres, use the standard gauge does not work: liquid or gas under such pressure escape through the walls gauge tube, as would strong it was. The electric gauge copes with this task: measuring the resistivity of manganin under defined pressure can be known to calculate the pressure with any degree of accuracy.

Manganini have another valuable property - damping, i.e. the ability to absorb vibrational energy. If some clever person came up with the idea to cast from manganin bell, it hardly would have been able to collect Veche: instead nabatnaya ringing manganin bell ring would be only a short voiceless sounds.

But if bell silence is an obvious drawback, for railway or tramway wheels, rail joints and many other sounding detail ability to "keep his mouth shut", without creating unnecessary noise, is an obvious advantage. In forging, stamping Metalworking shops with "dumb" alloys can significantly reduce harmful industrial noise. The greatest ability not to fuss different alloys containing 70% manganese and 30% copper. Some of them strength not inferior to steel.

Interestingly, manganese bronze is an alloy of manganese with copper - can be magnetized, although neither component alone does not exhibit magnetic properties.

In recent years gained wide popularity alloys with "memory" (about the most famous of them - the nitinol is told in the essay "the bronze devil"). The number of such alloys is growing every year. Scientists have developed, for example, based alloy of manganese (with the addition of copper), which is the ability to remember their original shape is not inferior to the famous nitinol. The alloy is easy to manufacture, easily processed and will surely find many interesting applications.

Manganese is part of developed by Polish scientists another curious alloy: depending on the voltage it can be either magnetic or semiconducting properties. For such a "two-faced" alloy there is a variety of work in many electronic devices and appliances.

Manganese alloys had already visited in space: in the course of a technological experiment "Reaction"made in 1976 on Board the orbital station "Salyut-5", the manganese-Nickel solder was molten and with it, the cosmonauts Boris Volynov and Vitaly Zholobov connected by soldering tubular samples of stainless steel. Held then on the Ground tests showed that the soldering quality excellent: interface successfully withstood a pressure of about 500 atmospheres. The experiment is of practical importance, since the soldering of the tubular parts is considered to be one of the promising methods for fabrication of work which will need to perform in outer space in the near future.

The car has always sought to make the engine powerful, and fuel consumption is minimal. To solve these two tasks, you need to raise the compression ratio in the cylinders, but often there was a detonation and engine quickly went out of order. Help had to call antiknock additives - additives to fuel, with the role which successfully lead compounds. But their toxicity has become a byword. Like it or not, I had to find a replacement. The perennial search for new anti-knock led scientists to Organoelement compounds of manganese. It turned out that these harmless substances with simple names (e.g., tributylamine-cyclopentadienyl-griersonian) antidetonation properties as those of its lead predecessors.

When ultrapure nitrogen has long had as a catalyst to use such expensive metals like platinum and palladium. In the Institute of inorganic chemistry and electrochemistry of the Georgian Academy of Sciences developed a technique in which the catalyst is successfully performs manganese. On Rustavi synthetic fiber factory already established industrial unit for obtaining from the air completely sterile nitrogen, which is required for the production of nylon.

With one of the compounds manganese - potassium permanganate, or, simply, "manganese", " we met in childhood: as a disinfectant it is used for washing wounds, rinsing, lubricating burns. In chemical laboratories this compound is widely used in quantitative analysis - permanantely.

Like many elements, manganese is essential for the normal development of animals and plants. Typically, the content of manganese does not exceed a few thousandths of a percent, but some species of flora and fauna exhibit to this item increased interest. In the body, red ants, for example, contains up to 0.05% manganese. Richer they rust fungi, sea grass, water chestnuts. In some species of bacteria, the manganese content up to several percent. In human blood is present 0,002-0,003% manganese. The daily demand for it in our body is 3-8 milligrams. When the diet of experimental mice to practically exclude manganese, the poor have lost the ability to reproduce, but the stall to add food chloride of this element, as mice regained the ability to get offspring.

On the coast of the Japanese Islands, there are many plantations, where it is grown artificial pearls. As the scientists, its color depends on the chemical composition of water in which live shell. Especially highly prized pearls with a pinkish tinge. To products, "produced by mollusks, had exactly this color, it is only necessary to increase the content of manganese in water. Adding other elements to grow a pearl for every taste: blue, green, orange, purple.

Since we are talking about plants and animals, it's time to think about the fish or the shark, which was mentioned above. Scientists analyzed the tooth of this marine predator that had lain on the bottom of the ocean thousands of years. And it turned out the tooth well preserved, but all covered with iron and manganese compounds. Where do they come from?

Where manganese on the shark teeth?

In the last century, and more precisely in 1876, the British three-masted sailing ship "Challenger"during the three years plied with the scientific objectives of the seas and oceans, among other production brought to England mysterious pineal education dark colored, raised from various areas of the seabed. Since the main part of the cones was manganese, they came to be called manganese kidneys, or, to put it scientifically, iron-manganese nodules. Subsequent expeditions have shown that the vast accumulations of manganese kidneys lie in many areas of the ocean floor. However, until the mid-XX century, no one showed limited interest. And only in recent years due to a relative deficiency of manganese ore underwater wealth attracted the attention of scientists. The nodule were carefully studied and the results were stunning. According to the preliminary (and you can easily add, modest) estimates, only in the Pacific ocean has accumulated hundreds of billions (!) tons of fine iron-manganese ore. It is ore: the content of manganese in it reaches 50%, iron up to 27%. (Concentrates some nodules contain 98% of manganese dioxide and can be used without further processing, for example, in the production of electric batteries).

Not less wealth has the Atlantic ocean. Not so long ago by the Soviet expedition of scientists on the "Vityaz" iron-manganese nodules found on the bottom of the Indian ocean. Calculations show that this ocean is not poorer than their "colleagues".

Believed to oceanographers, nodules occurred in the concentration of mineral substances from aqueous solutions around any body. Some scientists believe that here it was not without the participation of marine bacteria, "microbacteria". Leningrad biologists have discovered a previously unknown species of so-called metallogenic bacteria capable of removing from the water and concentrate manganese. In laboratory conditions "underwater metal" has shown a good performance: for two or three weeks they created manganese nodules the size of a match head. Given that these workers are barely distinguishable under the microscope, such performance cannot be considered high.

Unexpected results were obtained by staff of the University of Hawaii who breed the fry in coastal waters. To ensure that their wards housing, they created artificial reefs, flooding near the coast a few hundred old cars. What surprise ichthyologists, when six months later, they explored their fish camp: it turned out that all the cars were literally covered with garlands of lumps of selected manganese ore. I do not do scientific cultivation of manganese from sea water?

But let us return to our nodules. Its shape they resemble nodules potatoes. Their color from brown to black, depends on what they are dominated by iron or manganese. With high content of manganese their color becomes completely black.

Usually the sizes of the nodules range from fractions of a millimeter up to 10-15 cm. However, sometimes education is much larger. In the Museum Skipcaptcha Oceanographic Institute (USA) is the concretion weight 57 kg, found in and around the Hawaiian Islands. Even bigger was the concretion accidentally entangled loops underwater Telegraph cable when lifting it in for repair - it weighed 136 pounds. Unfortunately, this unique pattern was not destined to become a Museum piece: after studying and sketches he was mistakenly thrown overboard. However, all records were broken by five-foot iron-manganese the concretion raised on Board of the "Vityaz" in the Pacific ocean: block weighed nearly a ton.

Experiments on the development of extraction technology of iron and of manganese nodules already brought the first results. The number of scientists who have made a significant contribution to the development of the oceans, given the unusual commemorative medal: material for it was the metal produced from the nodules, which were raised from the ocean floor at a depth of about five kilometers.

The problem of development of ocean warehouses seriously interested in many countries. Already created a special submarines, tractors amphibious excavators on floats and other equipment for mining treasures from the ocean floor. Oceanography ore industry will have a distinct advantage over mining: no need to pave roads and communications, as on land. The court will deliver men and equipment anywhere in the ocean and will be able to transport the extracted minerals by any desired route. Dutch designers, for example, has developed a design for an underwater crawler excavator is a machine designed for seafloor mining of manganese and other ores, and this auto miner capable of working at depths of up to 5 kilometers. All of its mechanisms will operate by electricity. In the role of the engineer is expected to use a television camera, which will allow the operator aboard the ocean rugulosa, extracted from the depths minerals. Helical rotor excavator will capture a portion of the ore and send it in the body of the machine.

Robots get manganese from the ocean depths

Complex scientific-research and design works aimed at the development of underwater resources, held in our country. In 1983, the stocks in the black sea shipyard in the city of Nikolaev came down the ship of a new type, called "Marine geologist". The vessel, which is a big floating laboratory, will search for iron-manganese nodules. "Marine geologist will be able to take samples of the underwater ground at almost any depth.

Hundreds of expeditions annually in the oceans and seas, covering over 70% of the Earth's surface. Not far off is the time when you begin industrial development of the resources of the World ocean, while geologists and miners are developing the earth's interior.

The content in the earth's crust manganese yields few chemical elements. Geologists have determined that almost all of its fields are about the same age. According to a number scientists, this indicates the cosmic origin of manganese accumulations. The hypothesis that about two billion years ago on the surface of the Earth was rich in manganese meteoritic dust that formed the deposits of this element on the land and on the bottom of seas and oceans.

Manganese ores are found in many countries, but none of them can compete reserves of manganese with the Soviet Union. Our country has one of the largest fields - of Chiatura. Simple fact: water flowing in these parts of the small river Kvirila a tributary of the Rioni - annually carried to the Black sea over a hundred thousand tons of manganese.

Industrial production Chiatura ores began in the late 70-ies of the last century. Later in Russia began to give manganese another major field in the area of Nikopol. Oddly enough, but tsarist Russia "is not needed in this metal: so, almost all produced in 1913 manganese ore was abroad. During the great Patriotic war were involved in the exploitation of deposits of manganese in the Urals, Kazakhstan, Siberia. In these days of the Soviet Union for the production of this valuable ore firmly holds the leading position in the world.

The main consumer of manganese ore, Ferroalloy plants. Here as a result of various technological processes receive manganese alloys (iron, silicon or metal in its purest form. On the path of manganese lies in the steel shop.

 

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