U.S. patent number 3,645,727 [Application Number 04/871,968] was granted by the patent office on 1972-02-29 for method for melting titanium alloys.
This patent grant is currently assigned to Crucible Inc.. Invention is credited to Howard B. Bomberger, Jr., Walter L. Finlay.
United States Patent |
3,645,727 |
Finlay , et al. |
February 29, 1972 |
METHOD FOR MELTING TITANIUM ALLOYS
Abstract
This invention relates to a method of making a homogeneous ingot
of a titanium base alloy by mixing particles of titanium with a
master alloy in the form of fine granules, said master alloy
containing 30 to 75 percent by weight of molybdenum, 25 to 70
percent by weight of at least one of the elements selected from the
group consisting of chromium, titanium, zirconium, nickel and
copper, but not over 30 percent chromium, not over 25 percent
titanium, not over 40 percent zirconium, not over 10 percent nickel
and not over 10 percent copper, compacting the mixture into the
form of a compacted article and then melting said compacted article
in a vacuum.
Inventors: |
Finlay; Walter L. (New York,
NY), Bomberger, Jr.; Howard B. (Canfield, OH) |
Assignee: |
Crucible Inc. (Pittsburgh,
PA)
|
Family
ID: |
25358566 |
Appl.
No.: |
04/871,968 |
Filed: |
October 28, 1969 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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523866 |
Feb 1, 1966 |
3508910 |
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Current U.S.
Class: |
420/429; 420/580;
420/588 |
Current CPC
Class: |
C22C
1/02 (20130101); C22C 1/03 (20130101) |
Current International
Class: |
C22C
1/03 (20060101); C22C 1/02 (20060101); C22c
001/02 () |
Field of
Search: |
;75/135,175.5,65,84,.5,176,10,134 |
References Cited
[Referenced By]
U.S. Patent Documents
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3004848 |
October 1961 |
Hansley et al. |
|
Primary Examiner: Dean; Richard O.
Parent Case Text
This application is a continuation-in-part of copending application
Ser. No. 523,866, filed Feb. 1, 1966, now U.S. Pat. No. 3,508,910.
Claims
We claim:
1. A method of making a homogeneous ingot of a
molybdenum-containing titanium base alloy, said method comprising
the steps of mixing particles of titanium with a master alloy in
the form of fine granules, said master alloy consisting essentially
of 30 to 75 percent by weight of molybdenum, 25 to 70 percent by
weight of at least one of the elements selected from the group
consisting of chromium, titanium, zirconium, nickel and copper, but
not over 30 percent chromium, not over 25 percent titanium, not
over 40 percent zirconium, not over 10 percent nickel and not over
10 percent copper, compacting the mixture into the form of a
compacted article and then melting said compacted article in a
vacuum.
2. The method of claim 1 wherein said master alloy contains 20 to
40 percent zirconium, 30 to 75 percent molybdenum and 25 percent
max. titanium.
Description
It has long been known and appreciated that it is exceedingly
difficult to produce molybdenum-containing beta-type titanium-base
alloys on a commercial scale. Titanium-base alloys of the
alpha-beta type, such as the alloy comprising 7 percent aluminum, 4
percent molybdenum, balance titanium, are known, and these alloys
can be melted as a homogeneous composition rather readily by using
a master alloy consisting of aluminum and molybdenum. In making
beta-type titanium-base alloys, this approach is not available
because aluminum in the preparation required to form suitable
master alloys with molybdenum is harmful to the properties of such
titanium-base alloys.
Various alternative procedures have been considered for effecting
the inclusion of molybdenum in alloys of this type and obtaining a
homogeneous composition, but all of these are considerably more
tedious and complex in commercial use than the practice which is
made possible by the use of master alloys in accordance with the
instant invention.
The earliest known procedure for the production of relatively
high-molybdenum titanium-base alloys involved the repeated
vacuum-induction melting of small quantites, for example, about 50
grams, of the alloy, starting with titanium sponge or powder and
powders of molybdenum and the other alloy constituents. Although a
homogeneous alloy can be obtained in this manner, this method is
entirely too time-consuming and costly to be useful in the
production of molybdenum-containing beta-type titanium-base alloys
on a commercial scale.
Another method which has been considered for use in producing such
alloys involves the mixing of titanium powder with molybdenum
powder and other alloy constituents to form a homogeneous powder
mixture, compacting the powder mixture into a briquette, and then
vacuum consumable-electrode melting such a briquette. Powdered
molybdenum is required as a starting material, and the mixing step
is exceedingly difficult to perform adequately on anything but a
very small scale, because the molybdenum powder is more dense than
the other involved powders. The finest-particle-size molybdenum
powder commercially available is nevertheless sufficiently large,
and the rate of diffusion of molybdenum in solid titanium is
sufficiently low, that it takes an impractically long time to
achieve homogeneity in even a perfectly blended powder-metallurgy
compact. The long diffusion time is aggravated by the necessity to
use relatively coarse titanium granules to avoid excessive oxygen
pickup. Moreover, if one melts even a perfectly blended electrode,
the titanium melts and the solid molybdenum particles drop from the
melting electrode into the molten titanium pool. The latter is very
reducing, i.e., nonoxidizing, and the molybdenum particles
doubtless have chemically clean surfaces wetted by titanium. They
are also high melting, and so do not immediately dissolve in the
titanium; they are denser, and so drop rapidly to the bottom of the
molten titanium bath--here, it is believed, there is a liquid-solid
slush, and also there is often some swirl and the interface between
solid and liquid is usually concave upwards, with the result that
some of the chemically clean-surfaced molybdenum particles become
jostled together and thus become sintered into agglomerates to form
the large dense inclusions subsequently found in the ingot. A
master alloy of zirconium-molybdenum, on the other hand, is lower
melting and less dense than molybdenum, and so melts quickly into
liquid solution into the molten titanium, and in the instant
invention advantage is taken of this fact.
Yet another possibility is the mixing of titanium powder with
molybdenum powder and other alloy constituent powders in the manner
described above, followed by compaction to a high theoretical
density (somewhat in excess of 90 percent), for example, in an
argon-filled or evacuated enclosure or under other suitable
protective conditions. Although such a method avoids the expense of
the final melting step, the expense of the initial powder-mixing
step and the use of molybdenum powder militate strongly against the
commercial usefulness of such approach. The tendency of titanium
powder to become contaminated with oxygen, as noted above, is a
further drawback. Similarly, dense metallic compacts produced in
this manner have been found too brittle to be useful and/or too
inclined, when welded, to cause weld porosity to be os use in any
applications involving welding.
Yet another method for producing molybdenum-containing beta-type
titanium-base alloys is that disclosed in U.S. Pat. No. 3,269,825,
issued Aug. 30, 1966. This involves mixing powders of molybdenum
and tin, rolling the molybdenum-tin mixture to extreme thinness so
that it forms flakes, placing the flakes uniformly over the surface
of a bed of titanium powder, building up the bed by adding
additional layers of titanium powder and flakes, and then
briquetting and double vacuum-consumable-electrode melting as
indicated above. This procedure is very time consuming and
expensive and requires considerable care and skill on the part of
the persons practicing it.
Thus, it will be seen that the art of titanium metallurgy has been
faced for a period of at least 10 years with a problem, the
production of alloys of this type on a large scale, for which no
satisfactory solution has yet been proposed.
In accordance with the instant invention, it has been discovered
that by making first a master alloy of molybdenum with zirconium,
alone or with one or more other elements, and comminuting that
master alloy into fine granular form, and then mixing the fine
granular master alloy with granular powder or sponge titanium, it
becomes possible to produce, far more readily than in any manner
hitherto known, beta-type titanium-base alloys containing
substantial quantities of molybdenum. It has further been
discovered that by replacing part, or possibly all, of the
zirconium with iron, the melting point of the master alloy can be
lowered still further, and the ease with which such
molybdenum-containing beta-type titanium-base alloys can be
produced is yet further enchanced. The introduction of iron into
the master alloy has the further advantage that it makes possible
the use as a starting material of a relatively inexpensive
material, ferromolybdenum, in place of the relatively expensive
material, powdered molybdenum, hitherto considered necessary as a
source of the molybdenum in the alloys. This latter aspect is based
upon work that has revealed, rather surprisingly, that although
silicon, even in amounts as small as 0.1 percent by weight, tends
to affect detrimentally the cold workability of the desired
titanium-base alloys, nevertheless the amounts of silicon that are
present as an impurity in ferromolybdenum are sufficiently small
that when ferromolybdenum is used in the formation of the master
alloy which is ultimately incorporated in a molybdenum-containing
beta-type titanium-base alloy, the silicon present does not worsen
the properties of the product titanium-base alloy substantially, at
least if the silicon content of the ferromolybdenum is less than
about 1 percent.
It has also been discovered that the melting point of the master
alloy can be further lowered, and the properties of the alloy thus
produced can be further enhanced, by the inclusion in the master
alloy of a substantial proportion of chromium, up to about 30
percent. If desired, up to about 10 percent in total amount of one
or more elements selected from the group consisting of manganese,
hafnium, columbium, tantalum, vanadium, nickel, copper, and cobalt
may be incorporated in the master alloy with a view to further
lowering its melting point and/or enhancing the properties of the
titanium-base alloy to be produced by its use.
In brief summary, the instant invention comprises the concept of
providing, in fine granular form, a molybdenum-containing master
alloy containing 20 to 40 percent zirconium, and at least about 30
percent molybdenum. In the broadest aspect of the invention, the
zirconium may be replaced with iron in whole or in part on the
basis of about one part for one by weight, and preferably this is
done, as aforesaid, by using the commercial ferromolybdenum as a
source of at least part of the molybdenum in the master alloy.
Commercial ferromolybdenum contains about 55 to 75 percent of
molybdenum by weight, the balance being substantially iron, so that
in most circumstances only a relatively small part of the
molybdenum contained in the master alloy would need to be supplied
in the form of pure molybdenum. It is considered essential that
zirconium be included in a master alloy intended for use in the
production of titanium-base alloys, because otherwise the final
titanium-base alloy has a relatively high content of iron, and its
ductility suffers.
In its broadest aspects, the instant invention comprises master
alloys that contain 30 to 75 percent molybdenum, 0 to 40 percent
zirconium, 0 to 20 percent iron, 0 to 30 percent chromium, and 0 to
25 percent titanium, but 25 to 70 percent in total amount of one or
more of the elements zirconium, iron, chromium, and titanium.
Preferably, such alloys contain 20 to 40 percent of zirconium, and
desirably, also at least 3 percent in total amount of an element
selected from the group consisting of iron and chromium. It is
understood that other alloying elements desired in the final
titanium-base alloy may in many cases be included in the master
alloy without detriments. For example, tin, vanadium and aluminum
could be so added singly or in combination in amounts up to 25, 35
and 10 percent respectively. More specifically, one desirable range
of molybdenum-zirconium-iron master alloys consists of 40 to 75
percent molybdenum, 25 to 35 percent zirconium, and 5 to 20 percent
iron. Another example of a master alloy within the scope of the
present invention is one consisting essentially of 45 to 70 percent
molybdenum, 25 to 35 percent zirconium, 5 to 20 percent iron, 3 to
10 percent chromium, and 15 to 25 percent titanium.
Another feature of the instant invention is that the master alloys
are provided in the form of fine granules. By this, it is meant
that the particles of master alloy are substantially all of such
size as will pass through a No. 3 U.S. Standard sieve and be
retained upon a sieve such as a No. 80 U.S. Standard sieve, or
perhaps slightly finer. The considerations in choosing a suitable
size range for a given master alloy include the readiness with
which the particular alloy melts and the size and chemical
composition of the material with which it is to be mixed to form
the desired final alloy. Master alloys that are quite readily
meltable, having a low melting point in comparison with that of the
material with which the master alloy is to be mixed, can often be
used in the form of fairly coarse particles, e.g., with a maximum
dimension of about one inch. It is generally desirable, however, to
adhere to a somewhat smaller top size, such as a No. 8 U.S.
Standard sieve or finer. On the other hand, it is essential, in the
interest of obtaining a relatively uniform mixture of the master
alloy with the other materials contained in the composition of the
desired final alloy, to avoid the use of any substantial amount of
particles that are so fine as to separate out or be carried away as
dust. The sizes of the particles of the titanium sponge, titanium
fines, or other similar material should be considered. Finer
material in the master alloy can be tolerated if there is a
suitable portion of the material with which it is to be mixed which
is also comparatively fine. For admixture with common sponge
titanium, the use of a master alloy not containing particles which
will pass through a No. 80 U.S. Standard sieve is preferred.
The invention also comprises the method of using certain of the
master alloys of the invention to produce homogeneous ingots of
molybdenum-rich titanium-base alloys which consists in mixing said
alloys in the form of fine granules with particles of titanium,
preferably titanium sponge, compacting the mixture thus obtained
into an object to be melted, preferably a consumable electrode, and
then melting said object in the substantial absence of oxygen,
nitrogen, and carbon preferably in a vacuum.
A complete understanding of the invention may be obtained from a
consideration of the following specific examples, illustrating how
master alloys in accordance with the present invention are made and
used.
EXAMPLE I
Ten parts by weight of molybdenum chips or molybdenum rondelles are
blended with 5 parts by weight of zirconium sponge, then melted in
a carbon arc furnace to produce an ingot. The ingot is dumped,
crushed, and screened to obtain a sized fraction which will pass
through a No. 8 U.S. Standard sieve but will be retained upon a No.
30 U.S. Standard sieve. If desired, the sized material is again
carbon-arc-melted to form a second ingot which is subsequently
crushed and screened to obtain a material of the same consistency.
Thus, it is found that the master alloy is in fine, granular form
and contains about 67 percent molybdenum, about 33 percent
zirconium, and only about 0.01 percent of carbon. That is how a
fine, granular master alloy in accordance with the present
invention is made.
Such a master alloy is used in the following manner. Fifteen parts
by weight of the master alloy, prepared as mentioned above, are
mixed with 4 parts by weight of tin and 81 parts by weight of
sponge titanium. The mixture is blended and is then compacted into
the form of briquettes, for example, about 8 inches in diameter and
10 inches high. The briquettes are then assembled to form a
consumable electrode, in any desired fashion, for example, by
forming a cluster composed of three strands, each strand containing
8 or more of said briquettes, a titanium rod 1 inch in diameter
being used, together with a welding torch, to weld the cluster
together. An adapter piece, preferably of titanium metal, is welded
to the upper end of the electrode, which is then placed in a vacuum
consumable-electrode melting furnace and then melted in accordance
with known practices. As is known, the ingot thus produced is
upended, an adapter is welded to its upper end, and the ingot is
remelted, to yield an ingot of titanium-base alloy consisting
essentially of 10 percent molybdenum, 5 percent zirconium, 4
percent tin, balance titanium. In this manner, a titanium-base
alloy is produced which is considerably freer from dense-metal
inclusions than any other titanium-base alloy of like molybdenum
content produced without the use of special and costly melting
practices.
EXAMPLE II
Example I was repeated, except that after the first carbon-arc melt
was conducted and a sized fraction of molybdenum-zirconium alloy
was obtained, there were added to 15 parts by weight of said
molybdenum-zirconium alloy 5 parts by weight of titanium sponge.
This mixture was thoroughly blended and carbon-arc melted a second
time as in Example I, and the resulting ingot was crushed and
screened. Twenty parts by weight of such master alloy were mixed
with 4 parts by weight of tin and 76 parts by weight of sponge
titanium, and then further treated as in Example I to yield a
titanium-base alloy containing 10 weight percent molybdenum, 5
percent zirconium, 4 percent tin, balance titanium.
EXAMPLE III
A mixture was formed consisting of 59 parts by weight of molybdenum
rondelles, 29 parts by weight of zirconium sponge and 12 parts by
weight of iron pellets. The mixture was thoroughly blended, then
carbon-arc-melted, screened, remelted, and again screened, as
indicated in Example I. This yields a master alloy in fine,
granular form, consisting essentially, by weight, of 59 percent
molybdenum, 29 percent zirconium, and 12 percent iron. One hundred
parts by weight of such mixture were then thoroughly blended with
24 parts by weight of tin and 466 parts by weight of titanium
sponge, and then further processed as indicated in Example I, to
yield a final titanium-base alloy consisting essentially of 10
percent molybdenum, 5 percent zirconium, 4 percent tin, 2 percent
iron, balance titanium. The addition of iron further lowers the
melting point of the master alloy and yields a final doubly
consumable-electrode-melted product of improved homogeneity.
EXAMPLE IV
Example III was repeated except that ferromolybdenum was used as a
source of iron, in place of iron pellets. That is, a mixture was
formed consisting of 36 parts by weight of ferromolybdenum
(containing 67 percent molybdenum and the balance essentially
iron), 35 parts by weight of molybdenum rondelles, and 29 parts by
weight of zirconium sponge. The mixture was thoroughly blended and
carbon-arc-melted, screened, remelted, and again screened as
indicated in Example I. One hundred parts by weight of such mixture
were then thoroughly blended with 24 parts by weight of tin and 466
parts by weight of titanium sponge, and then further processed as
indicated in Example I, to yield a titanium-base alloy consisting
essentially of 10 percent molybdenum, 5 percent zirconium, 4
percent tin, 2 percent iron, balance titanium.
EXAMPLE V
Example IV was repeated, except that some titanium was added to the
master-alloy composition immediately before the second
carbon-arc-melting. That is, a mixture was formed consisting of 36
parts by weight of ferromolybdenum (containing 67 percent
molybdenum and the balance essentially iron), 35 parts by weight of
molybdenum rondelles, and 29 parts by weight of zirconium sponge.
The mixture was thoroughly blended, then carbon-arc-melted, and
screened. To this screened product there was added sufficient
titanium sponge to yield a titanium content of 20 percent in the
master alloy after the second carbon-arc melt. That is, 100 parts
by weight of the screened product of the first carbon-arc melt were
mixed with 25 parts by weight of titanium sponge, and then further
processed as indicated in Example I. This yielded a screened master
alloy in fine, granular form, consisting essentially, by weight of
47 percent molybdenum, 23 percent zirconium, 10 percent iron, 20
percent titanium. One hundred parts by weight of such mixture were
then thoroughly blended with 19 parts by weight of tin and 351
parts by weight of titanium sponge, and then further processed as
indicated in Example I, to yield a final titanium-base alloy
consisting essentially of 10 percent molybdenum, 5 percent
zirconium, 4 percent tin, 2 percent iron, balance titanium.
EXAMPLE VI
A mixture was formed consisting of 53 parts by weight of molybdenum
rondelles, 30 parts by weight of zirconium sponge, 12 parts by
weight of iron pellets, and 6 parts by weight of chromium chips.
The mixture was thoroughly blended then carbon-arc-melted,
screened, remelted, and again screened as indicated in Example I.
One hundred and one parts by weight of such mixture were then
thoroughly blended with 24 parts by weight of tin and 464 parts by
weight of titanium sponge, and then further processed as indicated
in Example I to yield a titanium-base alloy consisting essentially
of 9 percent molybdenum, 5 percent zirconium, 4 percent tin, 2
percent iron, 1 percent chromium, balance titanium.
EXAMPLE VII
Example VI was repeated, except that ferromolybdenum was used as a
source of iron in place of iron pellets. That is, a mixture was
formed consisting of 36 parts by weight of ferromolybdenum
(containing 67 percent molybdenum and the balance essentially
iron), 29 parts by weight of molybdenum rondelles, 30 parts by
weight of zirconium sponge, and 6 parts by weight of chromium
chips. The mixture was thoroughly blended, then carbon-arc-melted,
screened, remelted, and again screened as indicated in Example I.
One hundred and one parts by weight of such mixture were then
thoroughly blended with 24 parts by weight of tin and 464 parts by
weight of titanium sponge, and then further processed as indicated
in Example I, to yield a final titanium-base alloy consisting
essentially of 9 percent molybdenum, 5 percent zirconium, 4 percent
tin, 2 percent iron, 1 percent chromium, balance titanium.
EXAMPLE VIII
Example VII was repeated, except that titanium was introduced to
the master alloy immediately before the second carbon-arc melt.
That is, a mixture was formed consisting of 36 parts by weight of
ferromolybdenum (containing 67 percent molybdenum and the balance
essentially iron), 29 parts by weight of molybdenum rondelles, 30
parts by weight of zirconium sponge, and 6 parts by weight of
chromium chips. The mixture was thoroughly blended then
carbon-arc-melted and screened. To this screened product there was
added sufficient titanium sponge to yield a titanium content of 20
percent in the master alloy after the second carbon-arc-melt. That
is, 101 parts by weight of the screened product of the first
carbon-arc-melt were mixed with 25 parts by weight of titanium
sponge, and then further processed as indicate in Example I. This
yielded a screened master alloy in fine, granular form having
substantially the following composition: 42 percent molybdenum, 24
percent zirconium, 9 percent iron, 5 percent chromium, 20 percent
titanium. One hundred twenty-six parts by weight of such mixture
were then thoroughly blended with 24 parts by weight of tin and 439
parts by weight of titanium sponge, and then further processed as
indicated in Example I, to yield a final titanium-base alloy
consisting essentially of 9 percent molybdenum, 5 percent
zirconium, 4 percent tin, 2 percent iron, 1 percent chromium,
balance titanium.
EXAMPLE IX.
Example VIII was repeated, except that ferrochromium (consisting of
70 percent chromium, balance essentially iron) was used as a source
of chromium in place of chromium chips, and molybdenum rondelles
were used as a source of part of the molybdenum. That is, a mixture
was formed consisting of 41 parts by weight of molybdenum
rondelles, 33 parts by weight of ferromolybdenum, 35 parts by
weight of zirconium sponge, and 10 parts by weight of
ferrochromium. The mixture was thoroughly blended and then
carbon-arc-melted, screened, and remelted, and again screened as
indicated in Example I. One hundred nineteen parts by weight of
such mixture were then thoroughly blended with 28 parts by weight
of tin and 553 parts by weight of titanium sponge and further
processed as indicated in Example I, to yield a final titanium-base
alloy consisting essentially of 9 percent molybdenum, 5 percent
zirconium, 4 percent tin, 2 percent iron, 1 percent chromium,
balance titanium.
EXAMPLE X
Example IX was repeated, except that titanium was introduced to the
master alloy immediately before the second carbon-arc-melt. That
is, a mixture was formed consisting of 41 parts by weight of
molybdenum rondelles, 33 parts by weight of ferromolybdenum, 35
parts by weight of zirconium sponge, and 10 parts by weight of
Ferrochromium. The mixture was thoroughly blended then
carbon-arc-melted and screened. To this screened product there was
added sufficient titanium sponge to yield a titanium content of 20
percent in the master alloy after the second carbon-arc-melt. That
is, 119 parts by weight of the screened product of the first
carbon-arc-melt were mixed with 30 parts by weight of titanium
sponge, and then further processed as indicated in Example I. This
yielded a screened master alloy in fine, granular form having
substantially the following composition: 42 percent molybdenum, 35
percent zirconium, 9 percent iron, 5 percent chromium, and 20
percent titanium. One hundred forty-nine parts by weight of such
mixture were then thoroughly blended with 28 parts by weight of tin
and 523 parts by weight of titanium sponge, and then further
processed as indicated in Example I, to yield a final titanium-base
alloy consisting essentially of 9 percent molybdenum, 5 percent
zirconium, 4 percent tin, 2 percent iron, 1 percent chromium,
balance titanium.
EXAMPLE XI
A mixture was formed consisting of 60 parts by weight of molybdenum
chips, 30 parts by weight of zirconium sponge and 10 parts by
weight of tin cuttings. The mixture was thoroughly blended, then
tungsten-arc-melted, crushed, screened, remelted and again crushed
and screened as in Example I. One hundred parts by weight of such
mixture were then thoroughly blended with 400 parts by weight of
titanium sponge and then further processed as in Example I, to
yield a final titanium-base alloy consisting essentially of 12
percent molybdenum, 6 percent zirconium, 2 percent tin, balance
titanium.
Another way in which the master alloy according to the invention
may be used is to place together in a furnace in a vacuum or a
protective (oxygen- and nitrogen-free) atmosphere particles of
master alloy and particles of titanium, and then arc-melt, using a
nonconsumable electrode, for example, of carbon or tungsten.
While we have shown and described certain embodiments of our
invention, we intend to cover as well any change or modification
therein which may be made without departing from the spirit and
scope of the invention.
* * * * *