U.S. patent number 3,615,920 [Application Number 05/029,261] was granted by the patent office on 1971-10-26 for high temperature braze heat treatment for precipitation hardening martensitic stainless steels.
Invention is credited to John A. Talento.
United States Patent |
3,615,920 |
Talento |
October 26, 1971 |
HIGH TEMPERATURE BRAZE HEAT TREATMENT FOR PRECIPITATION HARDENING
MARTENSITIC STAINLESS STEELS
Abstract
A brazing and heat treating cycle is described as applied to
semiaustenitic stainless steel sheet material. The steps include a
brazing operation, solution annealing, trigger annealing, subzero
cooling and tempering. The brazed assembly exhibits good mechanical
properties and good corrosion resistance.
Inventors: |
Talento; John A. (Pittsburgh,
PA) |
Assignee: |
|
Family
ID: |
21848102 |
Appl.
No.: |
05/029,261 |
Filed: |
April 16, 1970 |
Current U.S.
Class: |
148/517; 148/528;
428/679; 228/231; 428/685 |
Current CPC
Class: |
B23K
35/304 (20130101); Y10T 428/12979 (20150115); Y10T
428/12937 (20150115) |
Current International
Class: |
B23K
35/30 (20060101); C21d 001/00 (); C22c
039/20 () |
Field of
Search: |
;148/34,37,38,125,127,135,136 ;29/497,498,504 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lovell; Charles N.
Claims
I claim as my invention:
1. In the method of improving the mechanical and corrosion
properties of a semiaustenitic stainless steel assembly in which
the members are fabricated employing a high-temperature brazing
cycle, the steps comprising:
a. rapidly heating the stainless steel braze assembly to a
temperature within the range between about 2,045.degree. and about
2,150.degree. F. for a time period of up to about 5 minutes to
effect a joining of the members,
b. cooling the braze assembly to a temperature within the range
between about 1,900.degree. and about 1,925.degree. F. in a time
period of less than about 30 minutes and holding said assembly at
said temperature range for a time period of between about 50
minutes and about 70 minutes,
c. cooling the braze assembly to a temperature within the range
between about 1,700.degree. and about 1,725.degree. F. in a time
period of less than about 30 minutes and holding said assembly at
said temperature range for a time period of between about 50 and
about 70 minutes,
d. quenching the braze assembly to a temperature below about
1,100.degree. F. in a time period not exceeding about 20 minutes
and to room temperature within a time period not exceeding about 1
hour,
e. subzero cooling the braze assembly within 48 hours of the
completion of step (d) to a temperature within the range between
about -100.degree. and -125.degree. F. for a time period of between
about 170 and about 190 minutes and thereafter warming to room
temperature, and,
f. tempering the braze assembly at a temperature within the range
between about 985.degree. and about 1,015.degree. F. for a time
period of between about 170 minutes and about 190 minutes and
thereafter cooling to room temperature.
2. The method of claim 1 in which each heat treatment step prior to
the subzero cooling step (e) is performed in hydrogen having a dew
point of not greater than -90.degree. F.
3. The method of claim 1 in which the tempering treatment is
performed in a vacuum of less than 1.times.10.sup.-.sup.4 mm. of
Hg.
4. The method of claim 3 in which the cooling from the tempering
temperature in step (f) to a temperature of 600.degree. F. is
accomplished in less than 1 hour.
5. In the method of improving the mechanical and corrosion
properties of a semiaustenitic stainless steel braze assembly in
which the members are fabricated employing a high-temperature
brazing cycle, the steps comprising,
a. rapidly heating the stainless steel braze assembly to a
temperature within the range between about 2,100.degree. and about
2,150.degree. F. and holding for a time period of up to about 5
minutes,
b. cooling the braze assembly to a temperature within the range
between about 1,900.degree. and abut 1,925.degree. F. in a time
period of less than about 30 minutes and holding said assembly at
said temperature range for a time period of between about 50
minutes and about 70 minutes,
c. quenching the braze assembly to room temperature through the
temperature range between 1,710.degree. F. and 1,100.degree. F. in
a time period not exceeding about 20 minutes and to room
temperature within a time period not exceeding about 1 hour,
d. subzero cooling the braze assembly to a temperature within the
range between about -100.degree. and -125.degree. F. for a time
period of between about 170 and about 190 minutes and thereafter
warming to room temperature, and,
e. tempering the braze assembly at a temperature within the range
between about 985.degree. and about 1,015.degree. F. for a time
period of between about 170 minutes and about 190 minutes and
thereafter cooling to room temperature.
6. The method of claim 5 in which each heat treatment step prior to
the subzero cooling step (e) is performed in hydrogen having a dew
point of not greater than -90.degree. F.
7. In the method of improving the mechanical and corrosion
properties of a semiaustenitic stainless steel braze assembly in
which the members are fabricated employing a high-temperature
brazing cycle, the steps comprising,
a. rapidly heating the stainless steel braze assembly to a
temperature within the range between about 2,100.degree. and about
2,150.degree. F. for a time period of up to about 5 minutes,
b. cooling the braze assembly to a temperature within the range
between about 1,900.degree. and about 1,925.degree. F. in a time
period of less than about 30 minutes and holding said assembly at
said temperature range for a time period of between about 50
minutes and about 70 minutes,
c. cooling the braze assembly to a temperature of about
1,750.degree. F. in a time period of less than about 30 minutes and
holding said assembly at said temperature for a time period of
between about 50 minutes and about 70 minutes,
d. quenching the braze assembly to a temperature below about
1,100.degree. F. in a time period not exceeding about 20 minutes
and to room temperature within a time period not exceeding about 1
hour,
e. subzero cooling the braze assembly within 24 hours of the
completion of step (d) to a temperature within the range between
about -100.degree. and -1,250.degree. F. for a time period of
between about 170 and about 190 minutes and thereafter warmed to
room temperature, and,
f. tempering the braze assembly at a temperature within the range
between about 985.degree. and about 1,015.degree. F. for a time
period of between about 170 minutes and about 190minutes and
thereafter cooling to room temperature.
Description
The present invention was conceived during the performance of work
in or under a U.S. Government contract with the Atomic Energy
Commission identified as AT-11-1-GEN-14.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a heat treatment and braze cycle
which is useful for producing good mechanical properties and good
corrosion resistance in semiaustenitic stainless steels.
2. Description of The Prior Art
Semiaustenitic stainless steels have an attractive combination of
mechanical and corrosion resistance characteristics which have been
developed through control of the chemical composition of the steel,
together with a specific processing related to such control of the
chemical composition. Thus it is possible to develop a
predetermined set of mechanical and corrosion resistance properties
in a product of finished form by means of a given heat
treatment.
Semiaustenitic stainless steel has found use in corrosive
environments and one of the methods of fabricating said steel for
use in such corrosive environment includes the step of brazing the
material either to itself or to some other structural component.
The temperature to which the semiaustenitic stainless steel is
heated during such high-temperature brazing heat treatment of
necessity alters the corrosion resistance and mechanical properties
exhibited by such semiaustenitic stainless steel. Typically, these
steels, as supplied, have a composition as set forth in U.S. Pat.
No. 2,799,602 and contain up to about 0.15 percent carbon from
about 12 to about 18 percent chromium from about 3.5 to about 7
percent nickel from about 2 to about 3 percent molybdenum up to
about 0.5 percent silicon from about 0.25 to about 20 percent
manganese and from about 0.5 to 0.15 percent nitrogen with the
balance essentially all iron and incidental impurities.
Depending upon the heat treatment and chemistry, these steels may
be characterized as being substantially completely austenitic in
the annealed condition or their microstructure may contain up to
about 30 percent delta ferrite with the balance being substantially
all austenite when the material is cooled to room temperature from
the prescribed annealing heat treatment. It has been found however
that such annealing heat treatment must be limited to a temperature
of about 2,000.degree. F. because heating above such temperature
may cause excessive grain growth regardless of the inclusion
content. Moreover, excessive temperatures causes large amounts of
delta ferrite to be formed and this material will not transform
upon subsequent cooling regardless of the temperature to which the
steel is cooled; consequently, the steel will exhibit poor
mechanical properties which may be difficult to adjust in order to
provide the proper balance of mechanical properties commensurate
with the desired degree of corrosion resistance.
The brazing treatment to which the steel is usually subjected
during fabrication includes a brazing at a temperature within the
range between about 2,045.degree. and about 2,150.degree. F.
depending upon the brazing alloy employed. While a short
temperature excursion not exceeding about 5 minutes in duration to
this temperature range will not produce significantly large amounts
of delta ferrite in excess of that already present, nonetheless the
mechanical properties exhibited by this steel will be far from
optimum and as a result thereof it becomes necessary to re-heat
treat this steel in order to reestablish the desired level of
mechanical properties commensurate with the required degree of
corrosion resistance and combine the same in the brazing cycle to
which the steel undergoes.
SUMMARY OF THE INVENTION
The method of the present invention provides for the combination of
a brazing and heat treatment cycle which is designed for improving
the mechanical and corrosion resistance properties of the
semiaustenitic stainless steels containing up to about 30 percent
delta ferrite in their annealed condition at room temperature.
During the brazing cycle the brazing assembly is rapidly heated to
a temperature within the range between about 2,045.degree. and
about 2,150.degree. F. for a time period of up to about 5 minutes.
Following the high-temperature braze cycle the assembly is cooled
to a temperature within the range between about 1,900.degree. and
about 1,925.degree. F. in a time period of less than about 30
minutes. The assembly is held at the temperature range for a time
period between about 50 minutes and about 70 minutes. The assembly
in next step is cooled to a temperature within the range between
about 1,700.degree. and about 1,725.degree. F. in a time period of
less than about 30 minutes. The assembly is held within such
trigger annealing temperature range for a time period between about
50 minutes and about 70 minutes. Thereafter the assembly is
quenched to a temperature below about 1,100.degree. F. in a time
period not exceeding about 20 minutes and to room temperature
within the time period not exceeding about 1 hour. Thereafter the
assembly is subzero cooled, preferably within a 48-hour period of
the completion of the quenching operation, to a temperature within
the range between about -100.degree. and about -125.degree. F. for
a time period between about 170 and 190 minutes. Thereafter the
assembly is warmed to room temperature following which the assembly
is tempered at a temperature within a range between about
985.degree. and about 1,015.degree. F. for a time period of between
about 170 and about 190 minutes and thereafter cooled to room
temperature. The foregoing treatment has been found to be effective
for not only brazing material into its fabricated form but also for
developing within the brazed structure an optimum combination
between mechanical properties and corrosion resistance properties
making the brazed structure suitable for use in a corrosive
environment where the material is subject to cyclical stressing
both at room temperature and at elevated temperatures.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The parts to be brazed are assembled in the desired manner with the
interposition of a suitable brazing alloy between the surfaces to
be joined. In this respect it has been noted that a composition
which is sold under the trade name of AMDRY 100 and which contains
between about 18.5 and about 19.5 percent chromium, about 9.8 to
about 10.3 percent silicon, up to about 1 percent iron, up to about
1 percent manganese and the balance essentially nickel has proved
to be quite useful in joining the semiaustenitic stainless steel
surfaces into a joined structure. Such a brazing composition has a
melting temperature of nominally 2,050.degree. F. However, other
brazing alloys can be used, such as those manufactured and sold
under the trade name J-8100 and which are also a
nickel-chromium-silicon-type brazing compositions with slightly
higher melting points. In this respect it is preferred to maintain
the brazing temperature as low as possible in order to minimize any
grain growth as well as prevent the formation of excessive amounts
of delta ferrite when the brazing assembly is heated to the
required temperature. It has been found however that so long as a
temperature of about 2,150.degree. F. is not exceeded for a time
period of up to about 5 minutes no significant grain growth occurs
and the delta ferrite component of the microstructure is normally
within acceptable limits to provide a required degree of mechanical
properties commensurate with the required degree of corrosion
resistance.
The assembly is then subjected to heat, that is, to a temperature
within the range between about 2,045.degree. and about
2,150.degree. F. for a time period of up to about 5 minutes in
order to join the surfaces in assembled relationship. Preferably,
such brazing is performed in a regular brazing furnace which is
provided with a controlled atmosphere to protect the surface of the
semiaustenitic stainless steel. Any protective atmosphere can be
employed and particular success has been had employing a hydrogen
atmosphere having a dew point of not greater than about -90.degree.
F.
Following heating to a temperature within the range between
2,045.degree. and 2,150.degree. F., the assembly is cooled to a
temperature within the range between about 1,900.degree. and
1,925.degree. F. in a time period of less than about 30 minutes.
The brazed assembly is held at this temperature range between about
50 minutes and about 70 minutes. Once again it is preferred to
employ a protective atmosphere while holding the brazed assembly at
this temperature range for the time period indicated, such
protective atmosphere preferably being hydrogen having a dew point
of about less than -90.degree. F. By holding the brazed assembly at
this particular temperature range any thermal distortion or
stresses induced resulting from a rapid heating to the brazing
temperature as well as the rapid cooling therefrom are minimized
and the same is accomplished without unduly altering the
microstructure through inordinate grain growth or the production of
untoward amounts of delta ferrite.
After holding at a nominal temperature of about 1,900.degree. F.,
the brazed assembly is cooled to a temperature within the range
between about 1,700.degree. and about 1,725.degree. F. and held at
this so-called "trigger annealing" temperature range for a time
period within the range between about 50 minutes and about 70
minutes. Once again the brazed assembly is subjected to a
protective atmosphere and good success has been obtained with the
utilization of dry hydrogen having a dew point of about -90.degree.
F. It is believed that by holding at the temperature range, that is
between 1,700.degree. and 1,725.degree. F., an equilibrium amount
of carbides will precipitate from the microstructure.
Characteristically, these carbides form at the austenite-delta
ferrite interface as well as within the austenite grain and as a
result thereof, since the delta ferrite is discontinuous, such
grain boundary carbides are also discontinuous thereby not
adversely affecting the corrosion resistance of the steel. At the
same time however the austenite becomes unbalanced to such a degree
that M.sub.s temperature is raised to approximately room
temperature so that with subsequent treatment, as will be set forth
hereinafter, the austenite can be transformed to martensite with
its enhanced mechanical properties being developed thereby. It has
been found that about 1 hour at the trigger annealing temperature
range is usually sufficient time to approach the equilibrium amount
of carbides being precipitated.
Following the holding period at the trigger annealing temperature
range the brazed assembly is thereafter quenched to a temperature
below about 1,100.degree. F. in a time period not exceeding about
20 minutes and to room temperature within a time period not
exceeding about 1 hour. It has been found that the quenching rate
between about 1,700.degree. and about 1,100.degree. F. is very
highly critical in that if the material, that is, the brazed
assembly, is not cooled to a temperature below about 1,100.degree.
F. within a 20 -minute time period, sufficient carbides and/or
nitrides will precipitate which will adversely affect the corrosion
resistance. In addition, the M.sub.s temperature will be raised to
a sufficiently high degree that with most of carbon and nitrogen
being out of solution any transformation which does take place will
not significantly improve the mechanical properties of the material
from that exhibited by the material in the annealed condition. That
is, the material will be in what may be referred to as an overaged
condition having poor mechanical properties and poor corrosion
resistance properties. It has been found that so long as the brazed
assembly is quenched to a temperature below about 1,100.degree. F.
in a time period not exceeding that 20 minutes sufficient carbon
and nitrogen will be retained within the austenitic component so
that the proper mechanical properties can be developed together
with enhanced corrosion resistance. It is highly desirable, in fact
necessary, that the quenching be continued to room temperature and
room temperature be achieved within the brazed assembly within the
period not exceeding about 1 hour. While such quenching will be
effective for preventing further carbide precipitation nonetheless
the austenitic phase which is retained at room temperature is quite
metastable.
After quenching and preferably within a period of 48 hours, the
brazed assembly is subjected to a subzero cooling treatment.
Subzero cooling treatment includes the treatment at a temperature
within the range between about -100.degree. and about -125.degree.
F. for a time period ranging between about 170 and about 190
minutes. Thereafter the brazed assembly is warmed to room
temperature.
The attainment of a temperature range between about -100.degree.
about -125.degree. F. can be accomplished in any number of ways
including the immersion of the brazed assembly within a
refrigerated chest or where desired a mixture of dry ice and
acetone will usually produce a temperature within the desired
range. During the subzero cooling treatment the metastable
austenitic component of the microstructure is transformed to
martensite, such martensitic transformation being accompanied by an
increase in the strength characteristics exhibited by the
alloy.
Following warming to the room temperature the brazed assembly is
thereafter tempered at a temperature within the range between about
985.degree. and about 1,015.degree. F. for a time period of between
about 170 and 190 minutes and thereafter the brazed assembly is
cooled to room temperature. Such tempering treatment is preferably
carried out in a vacuum, said vacuum being less than about
1.times.10.sup.-.sup.4 millimeters of mercury. Once again it has
been found desirable to cool the tempered assembly to a temperature
of less than about 600.degree. F. in a time period not exceeding
about 1 hour. The tempering treatment is effective for optimizing
the mechanical properties by decreasing the strength and increasing
the ductility. Since the carbides have not been precipitated at the
grain bounding the optimum combination of strength, ductility and
corrosion resistance is achieved.
It has been found that due to furnace size limitations, the brazed
assembly may be sufficiently large or the bulk of the material is
of such size that the assembly cannot be cooled from a temperature
of about 1,700.degree. to a temperature of about 1,100.degree. F.
in less than 20 minutes. In such circumstance the 1 -hour holding
period at a temperature within the range between about
1,700.degree. and about 1,725.degree. is omitted and the alloy is
allowed to cool directly from 1,900.degree. F. to room temperature
at a rate such that the cooling time through the temperature range
between about 1,700.degree. and about 1,100.degree. does not
appreciably exceed 20 minutes. When such cooling directly from
1,900.degree. F. to room temperature is employed it is usually
preferred to decrease the temperature of the subzero cooling
treatment and a temperature as low as -320.degree. F. can be
employed to accomplish the transformation of the metastable
austenite to martensite.
The process of the foregoing braze-heat treatment cycle is
effective for producing sound brazed assemblies employing
semiaustenitic stainless steel, such brazed assembly exhibiting the
optimum mechanical properties developable within the semiaustenitic
stainless steel commensurate with outstanding corrosion resistance.
As an example of the effectiveness of the braze-heat treatment of
the present invention, material given the designated heat treatment
with the brazing done in hydrogen exhibited a room temperature
tensile strength of about 185,000 p.s.i. and a yield strength of
about 150,000 p.s.i. with an elongation of about 13 percent.
This material was heated in a brazing operation to 2,125.degree. F.
and held at said temperature for a period of 5 minutes. Thereafter
the brazed assembly was furnace cooled to 1,900.degree. F. and held
for 60 minutes at 1,900.degree. following which the assembly was
furnace cooled to 1,710.degree. F. and held at that temperature for
60 additional minutes. Thereafter the assembly was cooled to room
temperature following which the assembly was subzero cooled to
-100.degree. F. and held at said temperature for 3 hours following
which the brazed assembly was heated to room temperature and
thereafter tempered at 1,000.degree. F. for 3 hours and cooled to
room temperature. Room temperature tensile testing revealed the
following listed properties.
Tensile Strength Yield Strength Elongation
__________________________________________________________________________
180 kpsi 150 kpsi 8 %
Extensive in-pile and out-of-pile corrosion testing of material
subjected to the braze-heat treatment disclosed herein has shown
adequate corrosion resistance under various reactor environments
from a standpoint of galvanic, stress and general corrosion.
* * * * *