Chapter VIII: Vanadium

BY R. B. MOORE

USES OF VANADIUM

The main use of vanadium is in steel. It is used where great toughness and torsional strength are required, as in automobile parts, gears, piston rods, tubes, boiler plates, transmission shafts, bolts, gun barrels, gun shields and forgings of any kind which have to withstand heavy wear and tear. The vanadium content of such steels varies from 0.1 to 0.4 per cent. Vanadium is occasionally used in certain tungsten alloys for making high-speed tool steel, the introduction of a small proportion of vanadium decidedly reducing the proportion of tungsten required to give such alloys the desired hardness and toughness.

Arnold has given some illustrations of the effect of vanadium on steels of different types:

One plain carbon steel containing about 1 per cent. of carbon had a
yield point of 35 tons per square inch, a maximum stress of 60 tons
per square inch, an elongation of 10 per cent. on 2 inches, and a
reduction of area of 10 per cent. The addition to this steel of about
0.6 per cent. of vanadium raised the yield point from 35 to 65 tons,
the maximum stress from 60 to 86 tons per square inch, still leaving
an elongation of 7 per cent. and a reduction of area of 8 per cent.

A steel containing 0.25 per cent. of carbon and 3.3 per cent. of
nickel gave a yield point of 33 tons, a maximum stress of 42 tons
per square inch, an elongation of 26 per cent. on 2 inches, and a
reduction of area of 53 per cent. A practically identical steel,
containing in addition about 0.25 per cent. of vanadium, gave a yield
point of 50 tons instead of 33, and a maximum stress of 68 instead of
42 tons per square inch. The elongation was 17 per cent. on 2 inches
and the reduction of area 36 per cent.

A steel containing 0.25 per cent. of carbon and about 1 per cent. of
chromium registered a yield point of 27 tons and a maximum stress
of 41 tons per square inch, with an elongation of 36 per cent. on 2
inches and a reduction of area of 55 per cent. The addition of 0.25
per cent. of vanadium raised the yield point from 27 to 40 and the
maximum stress from 41 to 55 tons per square inch. The elongation was
lowered from 36 to 26 per cent., and the reduction of area from 55 to
53 per cent.

Vanadium, therefore, differs from tungsten in having an extremely beneficial effect, not only on tool but also on structural steel. Arnold has shown that vanadium seemingly does not form a double carbide with iron, but gradually takes the carbon from the carbide of iron until, if about 5 per cent. of vanadium is present, Fe₃C can not exist, and only a vanadium carbide, V₄C₃, containing 15 per cent. of carbon, is present; and this constituent is constant, at least in tool steels containing 5 to 14 per cent. of vanadium. The micrographic analysis of such alloys has resulted in the discovery of three new constituents, namely, vanadium pearlite, vanadium hardenite, and vanadium cementite.

Chromium-vanadium steels are the latest development in structural alloy steels that have gained an extensive market. Almost all these steels are made in the open-hearth furnace; the chromium and vanadium alloys being added shortly before casting. In their physical properties these steels are much like chrome-nickel steels, but they have a greater contraction of area for a given elastic limit than the latter. The greater part of the chrome-vanadium steels made goes into automobiles. Some manufacturers prefer such steels because of their greater freedom from surface imperfections, notably seams, which steels containing nickel are prone to have if the ingots are at all unsound. These steels are almost always used in the heat-treated condition, but even in automobiles some frames, forgings and shafts are made of the steel in its natural state.

Some chrome-vanadium steel is said to be used in armor plate of medium thickness, which is not face-hardened but has high resistance imparted by heat treatment.

Vanadium is also used to some extent in making bronzes, in medicine and in dyeing.

=Substitutes.=--Several substitutes, chiefly titanium and molybdenum, have been claimed to give the properties of vanadium in steel. Both of those metals give to steel some of the properties that are usually associated with vanadium, but neither one takes the place of vanadium entirely.

CHANGES IN PRACTICE

The Primos Chemical Co. (see later) has its own patented method for treating roscoelite, the ore found at Newmire, Colorado. This method consists in roasting the ore with salt containing a little pyrite, and is a method that is applicable to some extent to most vanadium ores that do not carry lead. The American Vanadium Co. has a secret process for the treatment of its Peruvian ores. This method has not been published. The treatment of vanadinite, cuprodescloizite and carnotite ores has been studied by the U. S. Bureau of Mines, at Golden, Colorado. Whatever change in practice takes place is likely to be mainly in the concentration of vanadinite and in the treatment of this mineral and cuprodescloizite.

GEOLOGICAL AND GEOGRAPHICAL DISTRIBUTION

=Peruvian Deposits.=--The largest deposits of vanadium in the world, and the most important, were until recently controlled by the American Vanadium Co. of Pittsburgh, Pennsylvania, which in 1919 was absorbed by the Vanadium Products Corporation, allied to the Bethlehem Steel Corporation. These deposits are at Minasragra, Peru, 20 miles from Cerro de Pasco. The area lies along the western limit of a broad anticline in Juratrias and Cretaceous rocks. A section shows the series in this locality to be composed of green shales, thin beds of limestone, and red shales. Vanadium is found only in the red shales. The deposit proper appears to be a lens-shaped mass, 28 feet wide and 350 feet long. The ore contains several minerals. The mineral that constitutes the large portion of the deposit is called “quisqueite”; it is a black carbonaceous substance containing sulphur. There is also a lesser quantity of a coke-like material. Neither of these contains vanadium. The vanadium is mostly at the southern end of the ore body, and to a depth of 20 feet is largely in the form of red calcium vanadate, which is brighter colored then the calcium vanadate in Colorado and Utah, and carries as much as 50 per cent. vanadium oxide. It occurs in small pockets and fills the cracks and fissures in a fine shale. Below this shale is the “mother lode,” which is 9 to 30 feet thick, extends along the greater length of the deposit, and carries as high as 10 per cent. vanadium oxide and nearly as much sulphur. On the east and south sides, below the “mother lode,” is a hard blue-black vanadium shale, carrying as much as 13 per cent. vanadium oxide and 4 to 5 per cent. sulphur. Patronite, the main vanadium mineral, is greenish black and contains 19 to 24.8 per cent. vanadium oxide and in places 50 to 55 per cent. of combined sulphur. The patronite originally almost reached the surface and is most abundant in the north half of the lens. The whole ore body is almost completely inclosed by porphyry dikes and contains two or three intrusions. These deposits are controlled by the American Vanadium Co., and its successor, the Vanadium Products Corporation, through a concession from the Peruvian government. They are large, but are by no means inexhaustible, and as they are entirely local they are not likely to be duplicated. No similar deposits are known, either in Peru or in any other part of the world.

In 1917 the American Vanadium Co. treated 5,236 gross tons of ore, from which it extracted 2,122,005 pounds of vanadic acid. From this vanadic acid the company manufactured 4,925,014 pounds of ferrovanadium. The company did not buy any ore in this country, but relied entirely upon its Peruvian production.

=Other Foreign Deposits.=--The deposits in Peru are the only deposits of any commercial importance outside of the United States. Vanadium is found in South Australia, associated with carnotite and other uranium minerals. Small quantities of vanadic oxide are obtained as a by-product in the treatment of these ores.

Vanadium is also associated with uranium minerals in the Andijan district, Central Asiatic Russia. The vanadium is usually found as turanite, or copper vanadate; ferganite, an ortho-vanadate of uranium; and as several other new minerals. The amount of ore seems to be reasonably large, and this district may ultimately become a source of both uranium and vanadium.

The lead ores of Mexico contain some vanadium, the best known deposits being in the northeastern part of the State of Chihuahua. Other deposits are reported in Zacatecas, Guanajuato, San Luis Potosi, and Hidalgo.

=Deposits in the United States.=--The principal vanadium deposits of the United States occur in a metallographic province covering southern and southwestern Colorado, southeastern Utah, and parts of Arizona and New Mexico. Uranium and radium characterize the same province.

Probably the largest deposits of vanadium yet discovered in the United States are in southwestern _Colorado_ in San Miguel County. These deposits were visited by Ransome and Spencer in 1899 and their description, together with notes on the chemical analyses and composition of roscoelite by Hillebrand, was published in 1900. Fleck and French have also described the deposits. Fleck and Haldane later published additional descriptions, with notes on mining operations. Hess, in 1912, published an excellent description of these deposits with notes on the possible origin, etc.

According to Cross and Purington, the country rock is composed of Jurassic and Triassic sediments, divisible into three formations, the Dolores below, La Plata above and McElmo above La Plata. The latter is composed of two heavy beds of light-colored sandstone, separated by a thin bed of limestone. The vanadium-bearing rock is the lower sandstone. It is a light to dull green, and fine-grained. Occasionally splotches of carnotite are found in the cracks and fissures, but the uranium content is too small to be worth saving.

According to Hillebrand, the green vanadium mineral to which the sandstone owes its color is not a chlorite, but is closely related to the mica, roscoelite. The ore mined has an average content of 1¹⁄₂ per cent. V₂O₅. These low-grade roscoelite deposits can be mined at a profit, because they are large and easily worked.

Undoubtedly these deposits have been feeling the effects of the rather large production of the last few years, and the average grade of the ore is now probably at least half of a per cent. lower in V₂O₅ than it was a few years ago. There is still considerable ore untouched that will average 1 per cent., or a little less. The British government for several years, according to reports, has been interested in obtaining control of vanadium deposits.

The Primos Chemical Co., with works at Newmire, Colorado, and Primos, Pennsylvania, is mining these deposits, and in 1917 made this production:

Treated 60,907,000 pounds of ore; from this was produced 496,731 pounds of vanadium in the form of iron vanadate running about 34 per cent. metallic vanadium. From this was produced 417,770 pounds of contained vanadium in the form of regular 40 per cent. ferrovanadium. In 1918, up to and including July, this company mined 17,449,000 pounds of ore, from which was produced 149,343 pounds of contained vanadium in the form of vanadate of iron and 133,666 pounds of contained vanadium made in the form of 40 per cent. ferrovanadium.

In 1919 the Primos Chemical Co., was absorbed by the newly organized Vanadium Products Corporation.

Vanadium ore has been discovered in Huerfano County, Colorado, near the Sangre de Cristo Range. The vein is said to be well defined and 1 to 4 feet in width. A number of assays show 2 to 7 per cent. V₂O₅ content, and others 2 to 4 per cent. copper. The ore is heavy, black and banded; it contains small quantities of uranium oxide, but should be classed as a vanadium, rather than a uranium mineral. There has been no commercial production up to date.

In Eagle County, 7 miles southeast of the town of Eagle, a silver ore has been found that carries vanadium. This was located mostly in the Lady Bell mine. The ore, a dark-greenish sandstone similar in appearance to the darker types of roscoelite ore found in San Miguel County, assayed from 25 to 1,000 ounces of silver to the ton. The mine has been largely worked out for silver, the vanadium being lost during the smelting process. There is still, however, an appreciable amount of vanadium ore left, as the low-grade silver ore was not mined or treated.

A considerable amount of vanadium is obtained as a by-product from the treatment of carnotite (uranium and radium) ore. It is difficult to say just what the yield from this ore is, but it is probable that it averages about 200,000 pounds of vanadic oxide per annum. This is produced by five or six operating radium companies. These deposits are found in southwestern Colorado, around the Paradox Valley, and in southeastern Utah, extending as far as the San Rafael Swell, southwest of Green River, Utah.

There is considerable ore running one-half to 1 per cent. uranium oxide which carries from 4 to 10 per cent. vanadic oxide. In the past this ore has not been mined, because the extraction of radium from it would not pay. With a strong demand and a high price for vanadium, at least the higher grades of this ore could be mined at a profit. There is considerable of such ore at certain localities north of the Paradox Valley; unfortunately, these deposits are somewhat scattered and some would involve not only long wagon hauls, but also transportation by burro to wagon roads. Only the higher-grade ore could be handled in this way at a profit, and the difficulty is to get enough to justify building a treatment plant.

The writer has been told that there are deposits of this same type of ore at Temple Mountain, 40 miles south of Green River, Utah.

A small vanadinite deposit, containing traces of wulfenite, has been found near Klinefelter Station, on the main line of the Santa Fe Railroad, near the eastern border of San Bernardino County, _California_. The ore is largely calcite and is low grade, averaging probably from 1 to 2 per cent. vanadic oxide.

A deposit of vanadinite in Sierra County, _New Mexico_, on the Atchison, Topeka & Santa Fe Railroad, was mined for a short period in 1912 and 1913. Besides vanadium, the veins contain galenite, copper carbonates, barite, fluorite and other minerals. The ore was treated at a mill close to the mine, but the whole undertaking was unsuccessful, probably because the ore was so low grade, and because of metallurgical difficulties. There are a number of other deposits of vanadinite in New Mexico, but none of them have been commercially developed in any way.

Vanadinite is found in a considerable number of places in _Arizona_, frequently associated with wulfenite, or lead molybdate. Indeed, one of the difficulties of producing both vanadium and molybdenum from vanadinite and wulfenite is the fact that the two minerals are frequently so closely associated that, because of the slight difference in specific gravity, it is not easy to separate them by mechanical methods. At the Mammoth mine, in Arizona, the upper levels are richer in vanadinite than in wulfenite, but at the lower levels, the reverse is true. Undoubtedly a considerable amount of vanadinite could be produced from this mine and others in the vicinity, but it is doubtful whether it could be done at a profit, even at a high price for vanadium.

The United States Vanadium Co. has a mine 4 miles from Ray Junction, Arizona, and at the mine a small mill to concentrate the ore, which is low grade, and produces vanadium from the concentrates. The amount of ore that can be obtained from this mine is somewhat doubtful. This is the trouble with vanadinite as a whole; it exists over a wide territory, but the deposits are all low grade and apparently are not extensive in any one locality.

One of the most promising deposits, as regards increased production of vanadium, is at the Shattuck mine, Bisbee, Arizona, where a large vug, or cavity, is lined with a vanadium mineral, probably cuprodescloizite. The ore carries about 8 to 10 per cent. vanadic oxide, in addition to copper and lead. This seems to be one of the best opportunities for an increased production of vanadium in this country. The Golden, Colo., station of the United States Bureau of Mines made a metallurgical study of the treatment of this ore.

The distribution of the vanadium deposits of the world is shown in Plate V.

POSITION OF LEADING COMMERCIAL NATIONS

The United States is peculiarly fortunate as regards vanadium products, for it is practically the only producer of vanadium in the world, the Peruvian deposits being under the control of an American company. Therefore, England, France, Germany, Japan and other nations are forced to buy of American companies.

DEVELOPMENTS AND CHANGES IN KNOWN GEOGRAPHICAL DISTRIBUTION IN THE NEAR FUTURE

The larger part of the vanadium that has been used in this country has come from the mines of the American Vanadium Co. in Peru, but the Primos Chemical Co. produced an amount of vanadium from its claims at Newmire, San Miguel County, Colorado, that at least tended to give some real competition to the American Vanadium Co. As already stated, these claims are not nearly as rich or productive as they were, but they are probably good for several years more. The ore from Peru can be counted on probably for several years at something like the present output. The same statement applies to carnotite ore, and it is likely that the production of vanadium from carnotite may increase to some extent, as the demand for radium is strong, and there may be a consequent increase in the treatment of lower-grade carnotite. As this low-grade material usually carries more vanadium, the production of vanadium from this source may increase.

Vanadinite may prove to be a source of vanadium, although it is doubtful whether any large quantity can be produced from this mineral. As already stated, cuprodescloizite is probably the best source for an immediate increase in production.

As regards foreign countries other than Peru, Russia is the only one likely to produce any appreciable amount of vanadium ores, and undoubtedly no such production will be obtained until industrial conditions are more settled.

POLITICAL AND COMMERCIAL CONTROL

The American Vanadium Co. holds its mines in Peru through a concession from the Peruvian government. Thus at least two-thirds of the vanadium production of the world is practically in the hands of the Peruvian government, although the company operating is American.

Formerly the American Vanadium Co. was the only producer of vanadium products and ferrovanadium in the world. The price of vanadium was then somewhere around $5.00 per pound for the metallic vanadium content of the ferrovanadium. Later the Primos Chemical Co. came into the field, and the American Vanadium Co. cut the price. On account of the large deposits of ore that the Primos Chemical Co. had in Colorado, the result was simply a lowering of the price of ferrovanadium. Undoubtedly, if it were not for this competition the price of vanadium during that period would have been higher than it was, and if it were not for the Primos Chemical Co., the American Vanadium Co. would have had practically a monopoly of the whole vanadium production, as the output from carnotite was not large enough to affect the market seriously. As it was, these two companies controlled more than 90 per cent. of the ore supply, and thus the recent change of ownership to the Vanadium Products Corporation will enable the latter to fix the price, as well as to regulate the consumption and thus prolong the availability of a useful metal which otherwise would be likely to soon become exhausted. The principal vanadium deposits of Chihuahua, Mexico, are controlled by the Madero estate (Mexican).

This dominance of control of sources of supply has made control through ownership of reduction plants, patents and secret processes of less importance.