U.S. patent number 3,798,075 [Application Number 05/018,045] was granted by the patent office on 1974-03-19 for method of making stainless steel containing borides.
This patent grant is currently assigned to Carpenter Technology Corporation. Invention is credited to Lee P. Bendel.
United States Patent |
3,798,075 |
Bendel |
March 19, 1974 |
METHOD OF MAKING STAINLESS STEEL CONTAINING BORIDES
Abstract
A method for making stainless steel containing small, uniformly
distributed boride particles and the product of such process having
an improved absorption cross-section for thermal neutrons, in which
a stainless steel containing about 0.1 to 4 percent by weight boron
after being prepared in a convenient intermediate form is heated at
or just above a critical temperature of from 2,275.degree. to
2,325.degree. F. at least long enough for it to be heated
throughout to temperature and then it is rapidly cooled. The
intermediate form is then worked to effect substantially uniform
distribution of the boride particles. When necessary to prevent
sagging and tearing of the intermediate form while it is being heat
treated, it is supported while at heat. After cooling the support
is removed before working.
Inventors: |
Bendel; Lee P. (Lebanon,
NJ) |
Assignee: |
Carpenter Technology
Corporation (Reading, PA)
|
Family
ID: |
21785962 |
Appl.
No.: |
05/018,045 |
Filed: |
March 10, 1970 |
Current U.S.
Class: |
148/608;
148/326 |
Current CPC
Class: |
C21D
8/005 (20130101); C22C 38/54 (20130101) |
Current International
Class: |
C22C
38/54 (20060101); C21D 8/00 (20060101); C21d
007/00 (); C21d 007/14 () |
Field of
Search: |
;148/12,12.3,12.4,135,136 ;75/128F |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Stallard; W. W.
Attorney, Agent or Firm: Jay; Edgar N.
Claims
I claim:
1. In the method for making stainless steel articles containing
substantially uniformly distributed fine boride particles, the
steps of making an intermediate form comprising in weight percent
about
2. The method set forth in claim 1 in which the longest dimension
of said boride particles as calculated by intercept counting is
less than about 5 microns.
3. The method set forth in claim 1 in which the intermediate form
is supported while being heated to prevent sagging and tearing.
4. The method set forth in claim 1 in which said intermediate form
prior to heating is enclosed in a canister formed of a material
which can support said intermediate form therein during said
heating.
5. The method set forth in claim 4 in which said intermediate form
is removed from said canister after cooling and before said
working.
6. The method set forth in claim 5 in which the stainless steel
article has an essentially austenitic microstructure and comprises
in weight percent about
and the balance substantially iron.
7. The method set forth in claim 6 in which the longest dimension
of said boride particles as calculated by intercept counting is
less than about 5 microns.
8. The method set forth in claim 6 which comprises at least about
12 percent nickel and no more than about 2 percent boron.
9. The method set forth in claim 8 in which said assembly is heated
to a temperature no higher than about 2,340.degree. F. to
2,365.degree. F.
Description
BACKGROUND OF THE INVENTION
This invention relates to a method of making a stainless steel
alloy, and, more particularly, to a method for making a stainless
steel alloy containing substantial amounts of boron having an
improved absorption cross-section for thermal neutrons, and the
product of such process. It is to be understood that here and
throughout this specification and claims, the term "boron" when it
appears alone is used in its generic sense to include naturally
occurring boron (which usually contains about 18 percent boron-10),
natural boron enriched with boron-10, or boron-10. The present
invention is applicable to stainless steels containing any one or
more of those forms of boron.
It has hitherto been known that naturally occurring boron is a
desirable addition to stainless steel for use in the fabrication of
nuclear reactor control rods because it has a favorable absorption
cross-section for thermal neutrons. Its isotopic form boron-10 has
a substantially higher absorption cross-section. Control rods have
been made of austenitic stainless steel containing about 0.1 to 2.0
percent boron, but they left much to be desired whatever the form
of the boron because of the difficulty hitherto experienced in
ensuring the formation of small enough boride particles.
In practice, when control rods containing boron are in use in a
nuclear reactor, thermal neutrons effect a transmutation of
boron-10 to helium. To the extent that the boron-10 present in the
alloy is converted to helium, the control rod is weakened, and the
useful life of such control rods depends upon the distribution of
boron-10 in the alloy. The more uniform the distribution of a given
amount of boron-10, the less adverse is the effect of such helium
formation.
Usually, boron, when present in stainless steel, is in the form of
borides having a more-or-less complex structure, depending upon the
composition of the steel. In the case of a chromium-nickel
stainless steel, particles comprising M.sub.2 B are formed in the
steel matrix with M equal to varying amounts of the elements Fe, Ni
and Cr. While the size of such particles alone does not determine
the degree to which the distribution of the boron departs from the
desired uniformity, it is evident that the larger the size of such
particles, the more boron each contains, and the less uniform is
the distribution of the boron in the steel alloy. That is to say,
when the borides are large, the boron is segregated even though the
particles themselves may be uniformly distributed in the steel
alloy. And, as a result of such segregation, the formation of
helium during exposure of the steel to thermal neutrons has a
greater weakening effect because the voids formed by the
transformation are larger than those formed from the smaller
particles.
In recognition of the desirability of more uniform boron
distribution in such materials, the users thereof have required
that the boron-containing particles be small, less than a
calculated length of about 5 microns as determined by the intercept
method of counting borides in stainless steel. However, in
practice, I have found that the size of the boride particles could
not be controlled by means of conventional manufacturing practices
to provide the desired small boron-containing particle size.
SUMMARY OF THE INVENTION
It is therefore a principal object of my invention to provide a
method for making stainless steel containing boron in which the
boron is more uniformly distributed than hitherto.
Another object is to provide a process which ensures the attainment
of boride particle sizes consistently less than about 5 microns
long or even less than about 2 microns long as calculated from
intercept counting of borides in stainless steel, with the
particles substantially uniformly distributed throughout the matrix
of the steel.
I have discovered that when the stainless steel containing
relatively large boride particles is heated to a critical
temperature, the borides undergo a high temperature reaction such
that when the steel is rapidly cooled from that temperature, very
fine boride particles are produced. Then the steel is hot and/or
cold worked to the size required for fabrication into the
desired-end products, and the working serves uniformly to
distribute the fine boride particles.
The process of the present invention is preferably carried out by
starting with the stainless steel alloy in an intermediate form
such as a billet of convenient size. The temperature to which the
intermediate form must be heated throughout for the required
reaction to take place is sharply critical. The minimum temperature
required can vary in practice from about 2,275.degree. F. to
2,325.degree. F. depending upon such variables as the composition
of the steel and the accuracy of the temperature measuring
equipment used. But in practice, the required temperature is
readily determined as will be more fully pointed out
hereinbelow.
Care must be exercised when the steel is subjected to the high
temperature treatment that the intermediate form does not sag or
tear to such an extent as to be unsuitable for hot or cold working
to a finished shape. When necessary to prevent such damage, the
form can be supported in a suitable tray or by means of a canister
which is removed before the intermediate form is worked.
BRIEF DESCRIPTION OF THE DRAWING
Further objects and advantages of the present invention will be
apparent from the following detailed description thereof and the
accompanying drawing in which
FIG. 1 is a view of a photomicrograph showing the microstructure of
a stainless steel alloy containing 1 percent boron under a
magnification of 500 times treated in accordance with the present
invention;
FIG. 2 is a similar view at the same magnification of the same type
of alloy but with 0.37 percent boron at an intermediate stage of
the method of the present invention;
FIG. 3 is a similar view at the same magnification showing the
microstructure of the alloy shown in FIG. 2 after completion of the
method of the present invention; and
FIG. 4 is a similar view at the same magnification showing the
microstructure of the alloy having the analysis shown in FIG. 2 but
without the benefit of the treatment in accordance with the method
of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In carrying out the present invention, a stainless steel alloy is
prepared comprising in weight percent within the tolerances of good
commercial melting practices:
Percent Carbon up to 0.25 Manganese up to 10 Silicon up to 2
Chromium 12-26 Nickel up to 22 Molybdenum up to 4 Copper up to 4
Aluminum up to 4 Titanium up to 1.25 Columbium up to 1.25 Nitrogen
up to 0.7 Boron 0.1-4
the balance iron except for incidental impurities and such other
elements as may be desired which do not detract from desired
properties or objectionably interefere with the formation and
substantially uniform distribution of fine borides. For example, if
better free-machining properties are desired up to about 1 percent
of the customarily used free-machining additives can be included.
In this category, I include up to about 1 percent of one or more of
the elements phosphorus, sulfur, selenium and tellurium.
In carrying out the present invention, a steel of the desired
composition within the foregoing broad range is prepared utilizing
conventional melting and casting techniques. In general, the
composition of the steel and the shape and properties required in
the products to be formed therefrom will dictate whether the alloy
should be prepared using air melting techniques or whether a
controlled atmosphere should be used. It can also be readily
determined by those skilled in the art whether the alloy is to be
melted and cast as ingots which are then worked into intermediate
forms or whether such intermediate forms are to be directly cast
from the melt. For the production of control rods containing boron
for use in nuclear reactors, I prefer to melt the steel in a
vacuum-induction furnace and then cast the melt into ingots which
are in turn hot worked to a suitably sized billet as the
intermediate form. Up to this point my process does not differ in
any way from conventional practices.
Then, in accordance with my invention the intermediate form of the
steel, which can be a billet as was seen, is heated to
2,275.degree. F. to 2,325.degree. F. or just above long enough for
the billet or other intermediate form to be heated throughout. Then
the billet is rapidly cooled.
This results in the formation of extremely small boride particles,
calculated as being less than 5 microns long. In practice, particle
sizes calculated to be about 2 microns or less can be consistently
provided. Now the thus treated intermediate form is processed by
hot and/or cold working to the finished form using conventional
working practices. The boride particles retain the small size, but
may become spheroidized and are uniformly distributed.
The mechanism by which such small boride particles characteristic
of the present invention are formed is not fully understood.
However, though I do not wish to be bound thereby, I believe at
this time that a eutectic reaction takes place and thereafter when
the steel is rapidly cooled the extremely small boride particles
are formed.
It is to be noted that unless the temperature is carefully
controlled and/or, depending upon the size and shape of the
intermediate form, the form may not be fully self-supporting at the
treating temperature. In that event, the intermediate form is
supported mechanically while it is at the treating temperature. For
this purpose, a tray or other suitable support means can be used. A
preferred form of support is provided when the intermediate form is
enclosed in a canister formed of a material such as iron or another
steel which remains solid and self-supporting at temperatures
somewhat above the treating temperature. The shape of the canister
should conform closely enough to that of the intermediate form so
as to be able to support the latter at the elevated temperature
used. The canister and the form within it are then heated to at
least about 2,275.degree. F. to 2,325.degree. F., and the whole is
maintained at that temperature until the intermediate form is
heated throughout to that temperature. Then the assembly is rapidly
cooled, and the canister is removed by chemical or mechanical
means. As before, the intermediate form is then hot and/or cold
worked to the desired finished form.
EXAMPLE NO. 1
As an example of my invention, a billet was prepared by hot working
from an ingot, formed in an air induction furnace, containing 0.039
percent carbon, 1.69 percent manganese, 0.83 percent silicon, 0.016
percent phosphorus, 0.006 percent sulfur, 18.77 percent chromium,
15.11 percent nickel, 0.20 percent molybdenum, 0.17 percent copper,
1.00 percent boron, and the balance iron except for incidental
impurities.
The thus formed billet after surface preparation, e.g. machining,
was entirely enclosed in a canister formed of A.I.S.I. Type 304
stainless steel, and the assembly was heated at a temperature of
about 2,310.degree. F. for 1 hour which was long enough for all the
billet, about a 1.7 inch round in transverse cross-section, to be
brought to that temperature throughout. Whereupon the assembly was
rapidly cooled by quenching in water, and then the canister was
removed from the billet by machining. In this condition, the boride
particles have the desired small calculated size of less than 5
microns but are not usually uniformly distributed as is also
required.
The billet was then forged to 11/8 inch square from a furnace
temperature of 2,100.degree. F. followed by hot rolling to a 7/16
inch round cornered square rod, also from a starting temperature of
2,100.degree. F. Then, by cold rolling, the 7/16 inch round
cornered square rod was then reduced to 3/16 inch strip. In FIG. 1
there is shown a photomicrograph of the structure of a portion of
the resulting strip at a magnification of 500 times which can be
compared to the structure of similar material treated in the
conventional way and illustrated in FIG. 4 yet to be described in
detail hereinbelow. Using a standard metallographic inspection
procedure for intercept counting of borides, the boride size of
Example 1 as shown in FIG. 1 was calculated to be less than 1.79
microns in radius.
EXAMPLE NO. 2
As a further example of my invention, a billet was prepared and
treated as was described in connection with Example 1 except as
follows. The billet had an analysis containing 0.035 percent
carbon, 1.73 percent manganese, 0.53 percent silicon, 0.013 percent
phosphorus, 0.008 percent sulfur, 18.57 percent chromium, 14.11
percent nickel, 0.11 percent molybdenum, 0.05 percent copper, 0.37
percent boron, and the balance iron except for incidental
impurities. The microstructure of the billet at this stage showing
the undesirably larger borides is shown in FIG. 4 at a
magnification of 500 times. The billet was 1 in. .times. 2 in.
.times. 6 in., was not enclosed in a canister and no special
support was provided, and was heat treated at about 2,300.degree.
F. for 1 hour followed by cooling rapidly by quenching in water.
The resulting microstructure as shown in FIG. 2 at a magnification
of 500 times is seen to contain the desirably small boride
particles, but without the effects of working which bring about the
desired more uniform distribution and also tend to spheroidize the
particles.
Following the step of quenching in water, the billet was hot worked
to one-fourth inch thick from a furnace temperature of
2,100.degree. F. and then cold rolled to 0.038 inch thick strip. A
photomicrograph was prepared showing the resulting structure, also
at a magnification of 500 times, and is shown in FIG. 3.
A comparision of FIGS. 2, 3 and 4 clearly shows the significant
reduction in the size and improved distribution of the boride
particles provided by the present invention. Though no special
precautions need to be taken in carrying out my process, it is to
be noted that the temperature at which the heat treatment is
carried out is critical and relatively narrow. For any given
composition the optimum temperature is readily determined. Test
specimens of the desired composition are heated long enough for the
high temperature reaction to take place at selected temperatures
until substantially the minimum temperature for the reaction is
found. Then an upper limit is determined by examining the effects
of high temperatures on different specimens. For example, in the
case of the composition of Examples 1 and 2, it was found that the
heat treatment had to be carried out between about 2,300.degree. F.
and about 2,340.degree. F. because at lower temperatures below
about 2,275.degree.-2,300.degree. F. the desired reaction did not
occur and above about 2,340.degree.-2,365.degree. F. the formation
of shrinkage voids became objectionable and resulted in unsound
material. When 1-inch cube specimens having the same composition as
the billet of Example 2 were heat treated at about 2,200.degree. F.
for 1, 4 and 8 hours, there was no apparent effect upon the size of
the boride particles.
While a wide variety of compositions falling within the broad range
hereinabove stated can be used in carrying out the process of my
invention, the compositions of Example 1 and 2 are illustrative of
my preferred range which consists essentially of, in weight
percent, up to about 0.03 to 0.08 percent carbon, up to about 2
percent manganese, up to 0.045 percent phosphorus, up to 0.03
percent sulfur, up to about 1 percent silicon, 17 to 20 percent
chromium, 7 to 15 percent nickel, 0.1 to 2 percent boron and the
remainder iron except for incidental impurities. Within that range,
nickel is included in an amount of at least about 12 percent when
its effect on corrosion resistance and other properties is
desired.
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.
* * * * *