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.
[Illustration: PLATE V.--Geographical distribution of the vanadium
deposits of the world.]
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.