U.S. patent number 3,634,072 [Application Number 05/039,545] was granted by the patent office on 1972-01-11 for magnetic alloy.
This patent grant is currently assigned to Carpenter Technology Corporation. Invention is credited to Friedrich W. Ackermann, Ronald T. Casani, Gerald B. Heydt, William A. Klawitter.
United States Patent |
3,634,072 |
Ackermann , et al. |
January 11, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
MAGNETIC ALLOY
Abstract
A magnetic alloy that is ductile and can be cold rolled
containing by weight about 0.5-2.5 percent vanadium, 45-52 percent
cobalt, at least one element selected from the group consisting of
about 0.02-0.5 percent niobium and about 0.07-0.3 percent
zirconium, and the balance iron except for incidental
impurities.
Inventors: |
Ackermann; Friedrich W.
(Wyomissing, PA), Casani; Ronald T. (Holbrook, NY),
Klawitter; William A. (Reading, PA), Heydt; Gerald B.
(Glen Oley Farms, PA) |
Assignee: |
Carpenter Technology
Corporation (Reading, PA)
|
Family
ID: |
21906048 |
Appl.
No.: |
05/039,545 |
Filed: |
May 21, 1970 |
Current U.S.
Class: |
420/581; 148/313;
420/435; 148/311; 148/315 |
Current CPC
Class: |
C22C
38/10 (20130101); C22C 19/07 (20130101); H01F
1/147 (20130101) |
Current International
Class: |
C22C
38/10 (20060101); H01F 1/147 (20060101); C22C
19/07 (20060101); H01F 1/12 (20060101); C22c
019/00 () |
Field of
Search: |
;75/122,123H,123J,123K,170 ;148/31.55,31.57 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
404,011 |
|
Jan 1934 |
|
GB |
|
496,774 |
|
Dec 1938 |
|
GB |
|
367,134 |
|
Jan 1939 |
|
IT |
|
Other References
Bozorth, Richard M. Ferromagnetism, Nostrand Co., Inc., New York
1951, pp. 405-410..
|
Primary Examiner: Rutledge; L. Dewayne
Assistant Examiner: Legru; J. E.
Claims
What is claimed is:
1. A magnetic alloy that is ductile and can be cold rolled when
quenched after being for up to about 3 hours at a temperature above
its order-disorder transformation temperature and as high as just
above its ferrite-austenite transformation temperature, which
consists by weight essentially of about 0.5-2.5 percent vanadium,
about 45-52 percent cobalt, at least one element selected from the
group consisting of 0.02-0.5 percent niobium and 0.07-0.3 percent
zirconium, and the balance essentially iron except for incidental
impurities.
2. The alloy of claim 1 which contains about 1.5-2.5 percent
vanadium.
3. The alloy of claim 2 which contains about 48.5- 49.5 percent
cobalt.
4. The alloy of claim 3 which contains about 48.5-49.5 percent
iron.
5. The alloy of claim 1 which contains about 0.05-0.3 percent
niobium.
6. The alloy of claim 1 which contains about 0.1-0.3 percent
zirconium.
7. The alloy of claim 5 which contains about 1.8-2.2 percent
vanadium, about 48.5-49.5 percent cobalt, and about 48.5-49.5
percent iron.
8. The alloy of claim 6 which contains about 1.8-2.2 percent
vanadium, about 48.5-49.5 percent cobalt, and about 48.5-49.5
percent iron.
Description
This invention relates to a magnetic alloy and, more particularly,
to a vanadium-iron-cobalt alloy having improved ductility.
As pointed out in U.S. Pat. No. 3,024,141 granted to R. E. Burket
et al. on Mar. 6, 1962, a well-known soft magnetic alloy contains
about 45 to 52 percent cobalt, about 45 to 52 percent iron, and
about 0.5 to 2.5 percent vanadium except for incidental impurities.
The alloy has highly desirable magnetic properties particularly
when prepared so as to contain about 2 percent vanadium, 49 percent
cobalt, and 49 percent iron. Unfortunately, it has proven to be
extremely difficult on a commercial scale to reproduce consistently
the desired combination of magnetic properties and ductility. In
the case of small experimental test specimens, there is no
difficulty in heating them to about 1,650.degree. F. to transform a
small proportion of the ferrite to austenite which on reversion to
secondary ferrite along the grain boundaries of the much coarser
primary ferrite ensures the fine-grain size necessary for
ductility. However, in the case of the coils usually provided for
cold rolling which may weigh from about 500 to 1,000 pounds or
more, heating of the entire mass through the subtransformation
range extending from about 1,400.degree. to 1,600.degree. F. cannot
be carried out fast enough in conventional batch heating equipment
so as to avoid grain growth and consequent embrittlement of the
alloy.
Said U.S. Pat. No. 3,024,141, in order to overcome the loss of
ductility when such alloys were heat treated in the usual way,
describes a two-stage heat treatment to replace the annealing
treatment theretofore used of heating at about 1,650.degree. F.,
which consists of preheating the alloy to about 1,020.degree. to
1,120.degree. F. for about 3-10 hours followed, without
intermediate cooling, by heating between
1,425.degree.-1,475.degree. F. between 1.5-3 hours, then quenching
to 30.degree.-50.degree. F. and after which the temperature is
permitted to rise to room temperature. However, that process leaves
much to be desired in that it does not provide the optimum or best
possible ductility that can be had in such alloys.
Having in mind that vanadium is a well-known grain-refining agent
and is often included in alloys to provide that effect, and having
in mind also that the addition of a fourth alloying element to the
V-Co-Fe alloy would be expected to adversely affect the alloy's
desired magnetic properties, it was therefore very much unexpected
to discover that small but controlled additions of the elements
niobium and zirconium made possible the attainment of the desired
degree of ductility without resort to special heat treatments or
equipment and without adversely affecting the magnetic properties.
Titanium and aluminum, well known for use as grain refiners, were
also found to be ineffective in the V-Co-Fe alloy.
The objects and advantages of the present invention are attained by
providing an alloy which by weight consists essentially of 0.5-2.5
percent vanadium, 45-52 percent cobalt, 45-52 percent iron, one or
both of 0.02-0.5 percent niobium and 0.07-0.3 percent zirconium,
plus incidental impurities. By incidental impurities it is intended
no more than about 2 percent and preferably less than about 1
percent of other elements that may be present for one reason or
another including those elements which may be present in amounts
ranging up to a few hundredths of a percent and those which may be
present in amounts ranging up to a few tenths of a percent. For
example, carbon should not exceed about 0.03 percent and preferably
no more than about 0.015 percent, manganese should not exceed about
0.8 percent and preferably no more than about 0.3 percent, silicon
should not exceed about 0.4 percent and preferably no more than
about 0.2 percent, phosphorus and sulfur should each not exceed
about 0.02 percent and preferably no more than about 0.01 percent,
chromium should not exceed about 0.1 percent, nickel should not
exceed about 0.8 percent and preferably no more than about 0.3
percent and molybdenum should not exceed about 0.2 percent and
preferably no more than about 0.1 percent.
For best magnetic properties, cobalt and iron are each included in
an amount of about 48.5-49.5 percent and preferably in equal
amounts. The larger amounts of vanadium, that is above about 1.5
percent, give the better mechanical properties, and about 1.8-2.2
percent vanadium is preferred.
Niobium in an amount ranging from about 0.02 percent has a
significant effect upon the ductility of the alloy, but when
present in amounts above about 0.5 percent, niobium adversely
affects the magnetic properties of the alloy so that a minimum
induction of 18,500 gauss with a magnetizing force of 3 oersteds
after a 4-hour anneal at about 1,500.degree.-1,550.degree. F.
cannot be attained. Preferably from about 0.05- 0.3 percent niobium
is included. When zirconium instead of niobium is used for its
effect on controlling the ductility of the alloy, at least about
0.07 percent zirconium is required and preferably at least about
0.1 percent is used. Above about 0.3 percent zirconium adversely
affects the magnetic properties of the alloy so that the desired
minimum induction of 18,500 gauss under the conditions just stated
cannot be attained. Niobium is considered a more desirable additive
than zirconium for this purpose of ensuring the required ductility;
but, if desired, zirconium can be used alone, or both elements can
be used so long as their combined content is not so large as to
adversely affect the magnetic properties of the alloy.
The alloy is prepared, worked and formed into products using
conventional techniques. It can be melted in air as by means of an
electric arc furnace or it can be melted under a controlled
atmosphere using well-known vacuum techniques. After being melted
and cast as an ingot, it is forged into billets or slabs from a
furnace temperature of about 1,950.degree.-2,250.degree. F. After
the usual surface preparation, it is then hot rolled to strip, also
from a furnace temperature of about 1,950.degree.-2,250.degree. F.
and formed into a coil while still hot. The thus-formed strip is an
intermediate product substantially thicker than the finished size
which is then formed by cold working to the final thickness or
gauge. It is to be noted that a somewhat higher forging and rolling
temperature than 2,250.degree. F. can be used if desired.
In its hot rolled condition, the strip is too brittle to be cold
worked, and, as in the case of the prior alloy described in said
U.S. Pat. No. 3,024,141, it is necessary to heat treat the present
alloy in order to condition the coiled strip by increasing its
ductility so that it can be cold worked successfully. Such heat
treatment hitherto has had two objectives. One objective was to
heat the entire mass of the material being treated to or just above
the ferrite-to-austenite transformation temperature so as to
inhibit grain growth and then quench. For the alloy of the present
invention and the prior art V-Co-Fe alloy, the ferrite-austenite
transformation temperature is substantially the same and is about
1,650.degree. F. Variations in composition will, as is known, shift
the transformation point, but it can be readily determined. The
other objective is to ensure the disordered condition of the alloy
by rapidly quenching through the order-disorder temperature range
which for the type of alloys under discussion occurs at about
1,350.degree. F.
The presence of both phenomena provides a greater assurance of the
required degree of ductility because when both are substantially
uniformly present throughout the microstructure of the material,
the possibility of localized areas of brittleness is precluded.
To this end, the hot rolled material of the present invention,
prior to cold rolling, is annealed preferably at or just above the
ferrite-to-austenite transformation temperature which occurs at
about 1,650.degree. F. The duration of the heat treatment is
preferably just long enough to bring the entire mass to the desired
temperature. Because the material is most conveniently heated while
coiled, some portions require longer heating than others, and,
therefore, some parts of the mass may be in the grain-growth
temperature range, which extends from just above the order-disorder
temperature to the neighborhood of or just above the
ferrite-austenite transformation temperature, for as long as 2 to 3
hours. It is an important advantage of the alloy of the present
invention that it can withstand such long periods in the
grain-growth temperature range without the grain-growth
characteristic of the prior alloy and the consequent loss in
ductility. After being brought to heat, the alloy is then quenched
rapidly in water and cold rolled to final size. Prior to cold
rolling, the material may be pickled or otherwise prepared as
desired.
The finished material is given a final annealing treatment in dry
hydrogen, which, as desired, may or may not be in the presence of a
magnetizing force. The final anneal can be carried out at a
temperature ranging from about 1,400.degree. to 1,550.degree. F.
and preferably is carried out at about 1,500.degree. to
1,550.degree. F. for 4 hours.
As was pointed out hereinabove, it was very much unexpected to
discover that niobium and zirconium could be successfully used to
improve the ductility of the V-Co-Fe alloy while such well-known
grain refiners as vanadium, aluminum and titanium failed to work.
The best explanation now available, based on X-ray diffraction and
electron microscopic studies, appears to be that niobium and
zirconium are unique in that when either is present in the alloy
within the ranges stated herein, it forms a very fine intermetallic
compound along the grain boundaries known as Laves phase which is
very small compared to the grain structure of the alloy matrix. The
intermetallic compound known as Laves phase is usually in the form
AB.sub.2 where A and B are metallic elements. Corresponding
examinations of specimens of the V-Co-Fe alloy with and without the
other grain-refining elements aluminum and titanium failed to
disclose any Laves phase, and did not have the desired
ductility.
EXAMPLE NO. 1
As an example of this invention, a 13-inch wide ingot was cast
containing by weight about 1.95 percent vanadium, 48.93 percent
cobalt, 0.14 percent niobium and the balance iron except for
incidental impurities, which amounted to no more than about 0.4
percent. The ingots were forged to 9-inch by 3-inch slabs, cogged
to 7.5 -inch by 3-inch, cut in half and then hot rolled to 7.5-inch
by 0.1-inch thick strip forming coils weighing about 500 pounds
each. Hot working was carried out from a furnace temperature of
about 2,150.degree. F. The coils were then heated for 2 hours at
about 1,650.degree. F. followed by quenching in water. The
as-quenched hardness was found to be Rockwell B 96 with a grain
size of ASTM 7-8. The 0.2 percent yield strength was measured at
66,000 and 68,300 p.s.i. Ultimate tensile strength was found to be
108,500 and 108,900 p.s.i. Elongation was measured as 19.3 and 17.6
percent in 2 inches, values which are considered excellent for
V-Co-Fe alloys. Cold rolling to thicknesses of from 0.01 to 0.016
inch were carried out without difficulty. Strip, 0.016-inch thick,
was annealed for 4 hours at about 1,530.degree. F. in dry hydrogen
and then, when subjected to a magnetizing force of 10 oersteds, had
an induction of 22,100 gauss, when subjected to a magnetizing force
of 50 oersteds had an induction of 23,450 gauss, and when subjected
to a magnetizing force of 100 oersteds had an induction of 23,900
gauss.
It may also be noted that as a test of ductility, material of this
composition was hot rolled into 2-inch wide by 0.1-inch thick strip
and quenched in water. Test specimens were then cut from the strip
and were heat treated for 2 hours at temperatures ranging from
1,400.degree. to 1,650.degree. F. and water quenched. Each specimen
was then subjected to 120.degree. bends until at least surface
cracks appeared. The material was found to be ductile following
each heat treatment.
As further illustrations of the present invention, examples 2-5
were prepared as experimental 17-pound vacuum induction heats
having analyses in weight percent as indicated in Table I.
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TABLE I
Ex. No. V Co Nb Zr
__________________________________________________________________________
2 2.04 49.07 0.05 -- 3 2.00 48.89 0.31 -- 4 1.99 49.10 -- 0.12 5
1.97 48.83 -- 0.27
__________________________________________________________________________
In Examples 2-5 the balance was iron except for incidental
impurities which amounted to about 0.28 percent for example 2,
about 0.25 percent for example 3, about 0.28 percent for example 4,
and about 0.28 percent for example 5. The heats were cast into
ingots and then forged from a furnace temperature of about
2,150.degree. F. to 2-inch by 1-inch bars. Following surface
preparation, the bars were hot rolled from the same furnace
temperature of 2,150.degree. F. to 0.1-inch thick strip from which
3/4-inch test specimens were cut for further testing. Test
specimens of each of the examples 2-5 were heat treated for 2 hours
at temperatures extending from 1,400.degree. to 1,650.degree. F. in
50.degree. intervals. Each specimen following its particular heat
treatment was quenched in water. The ductility of the heat-treated
test specimens was then evaluated by bending each through
120.degree. and noting the number of 120.degree. bends that could
be made before each failed. The results are set out in table II
opposite each example and under the temperature at which the
particular specimens were heat treated.
The grain size of each specimen was measured and found to be ASTM 6
or smaller.
Material from each of the examples 2-5, that had been hot rolled
and quenched as was described, was then heated at 1,650.degree. F.
for one hour, quenched in water, and then cold rolled to strip
0.014-inch thick. Each specimen was then heated in dry hydrogen at
1,430.degree. F. for 2.5 hours. Specimens of each example which had
been thus treated were then subjected to three different
magnetizing fields of 3, 6 and 12 oersteds; the induction in gauss
was measured and is set out in table III.
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TABLE III
Ex. No. 3 Oe. 6 Oe. 12 Oe.
__________________________________________________________________________
2 20.3000 21,400 22,200 3 20,300 21,100 22,200 4 18,800 20,300
21,300 5 18,600 20,200 21,300
__________________________________________________________________________
Because of its ductility and magnetic properties, this alloy is
well suited for use in making cold rolled magnetic laminations.
Depending upon the use intended, such laminations may range in
thickness from about 0.004 to 0.016 inch or larger. The alloy can
also be readily formed into cold rolled strip for use as tape cores
which typically range in thickness from about 0.001 to 0.006
inch.
The terms and expressions which have been employed are used as
terms of description and not of limitation, and there is no
intention in the use of such terms and expressions of excluding any
equivalents of the features shown and described or portions
thereof, but it is recognized that various modifications are
possible within the scope of the invention claimed.
* * * * *