U.S. patent number 3,736,131 [Application Number 05/101,096] was granted by the patent office on 1973-05-29 for ferritic-austenitic stainless steel.
This patent grant is currently assigned to Armco Steel Corporation. Invention is credited to Ronald H. Espy.
United States Patent |
3,736,131 |
Espy |
May 29, 1973 |
FERRITIC-AUSTENITIC STAINLESS STEEL
Abstract
An austenitic-ferritic stainless steel consisting essentially of
up to about 0.06 percent carbon, about 4.0 to less than 11.0
percent manganese, about 19 to about 24 percent chromium, about
0.12 to about 0.26 percent nitrogen, nickel up to about 3.0
percent, and remainder substantially iron except for incidental
impurities. The austenite-ferrite balance, ranging between 10
percent and 50 percent austenite, is stable, and the steel exhibits
high toughness, corrosion resistance and excellent weldability.
Inventors: |
Espy; Ronald H. (Randallstown,
MD) |
Assignee: |
Armco Steel Corporation
(Middletown, OH)
|
Family
ID: |
22283022 |
Appl.
No.: |
05/101,096 |
Filed: |
December 23, 1970 |
Current U.S.
Class: |
420/34; 420/59;
420/56 |
Current CPC
Class: |
C22C
38/38 (20130101); C22C 38/001 (20130101) |
Current International
Class: |
C22C
38/00 (20060101); C22C 38/38 (20060101); C22c
039/14 () |
Field of
Search: |
;75/126J,126B,128N |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Bizot; Hyland
Claims
The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. A stainless steel having a two-phase structure comprising
between 10 percent and 50 percent austenite in a ferrite matrix,
consisting essentially of up to about 0.06 percent carbon, about
4.0 percent to less than 11.0 percent manganese, about 19 percent
to about 24 percent chromium, about 0.12 percent to about 0.26
percent nitrogen, nickel up to about 3.0 percent, phosphorus and
sulfur up to about 0.03 percent each, silicon up to about 1.0
percent, copper and cobalt up to about 0.5 percent each, and
remainder substantially iron.
2. The stainless steel of claim 1, containing about 0.02 percent
carbon, about 6.0 percent manganese, about 21.0 percent chromium,
about 0.20 percent nitrogen, about 0.20 percent nickel, and about
0.40 percent silicon.
3. The stainless steel of claim 1, wherein carbon is present in an
amount of about 0.02 percent.
4. The stainless steel of claim 1, wherein manganese is present in
the amount of about 6.0 percent.
5. The stainless steel of claim 1, wherein chromium is present in
the amount of about 21.0 percent.
6. The stainless steel of claim 1, wherein nitrogen is present in
the amount of about 0.20 percent.
7. The stainless steel of claim 1, wherein nickel is present in the
amount of about 0.20 percent.
8. The stainless steel of claim 1, wherein molybdenum is
substituted for chromium on a 1:1 basis in amounts up to about 5
percent.
9. The stainless steel of claim 1, including columbium in amounts
up to about 1 percent.
10. A stainless steel having a two-phase structure comprising
between 20 percent and 30 percent austenite in a ferrite matrix,
consisting essentially of about 0.02 percent carbon, about 6.0
percent manganese, about 21.0 percent chromium, about 0.20 percent
nitrogen, about 0.20 percent nickel, phosphorus and sulfur low,
about 0.40 percent silicon, copper and cobalt low, and balance
substantially iron.
11. Welded articles having a two-phase structure comprising between
10 percent and 50 percent austenite in a ferrite matrix, consisting
essentially of up to about 0.06 percent carbon, about 4.0 percent
to less than 11.0 percent manganese, about 19 percent to about 24
percent chromium, about 0.12 percent to about 0.26 percent
nitrogen, nickel up to about 3.0 percent, phosphorus and sulfur up
to about 0.03 percent each, silicon up to about 1.0 percent, copper
and cobalt up to about 0.5 percent each, and remainder
substantially iron.
12. Cold headed fasteners having a two-phase structure comprising
between 10 percent and 50 percent austenite in a ferrite matrix,
consisting essentially of up to about 0.06 percent carbon, about
4.0 percent to less than 11.0 percent manganese, about 19 percent
to about 24 percent chromium, about 0.12 percent to about 0.26
percent nitrogen, nickel up to about 3.0 percent, phosphorus and
sulfur up to about 0.03 percent each, silicon up to about 1.0
percent, copper and cobalt up to about 0.5 percent each, and
remainder substantially iron.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a modified chromium stainless steel (low
in nickel, copper and cobalt) of stable ferritic-austenitic
structure having excellent toughness, ductility, corrosion
resistance and welding characteristics. The alloy of the invention,
by reason of its compositional balance, achieves a structure of
from 10 percent to 50 percent austenite (preferably 20 percent to
30 percent) in a ferritic matrix which resists transformation into
martensite despite cold working, heat treatment, or welding.
The stainless steel of this invention has particular utility as
weldments in straight chromium steels, for fabrication into
fasteners which require cold heading, and a variety of other
applications requiring relatively high strength and ductility, good
weldability, and high resistance to intergranular corrosion in
strongly oxidizing media, as well as good resistance to stress
corrosion in chloride media.
2. Description of the Prior Art
Among the numerous alloys developed to offset the scarcity and high
cost of nickel are those disclosed in U.S. Pat. No. 2,778,731
issued Jan. 22, 1957, to D. Carney, consisting of 0.06 percent to
0.15 percent carbon, 14 percent to 20 percent manganese, 17 percent
to 18.5 percent chromium, 0.05 percent to 1.0 percent nickel, 0.25
percent to 1.0 percent silicon, 0.25 percent to 1.0 percent
nitrogen, and remainder iron; B & W CROLOY 299 consisting of
0.20 percent carbon, 15.0 percent manganese, 17.0 percent chromium,
1.5 percent nickel, 0.35 percent nitrogen, and remainder iron; and
other fully austenitic steels such as Armco 16-16-1 and Allegheny
Ludlum 205.
A fully austenitic stainless steel having excellent physical
properties and stress corrosion resistance at cryogenic
temperatures, coupled with great tensile strength when drastically
cold reduced, is described in copending application Ser. No.
868,893 filed Oct. 23, 1969, in the name of George N. Goller and
Ronald H. Espy. This steel is non-magnetic.
Straight chromium stainless steels such as A.I.S.I. Types 430, 442
and 446 have the serious disadvantages of being brittle and subject
to corrosion in the heat affected zone of the base metal of a
weldment. Further, the unaffected base metal may be low in impact
strength at room temperature.
Typical of austenitic stainless steels which transform with cold
working to less ductile martensite is A.I.S.I. Type 304, consisting
of 0.08 percent maximum carbon, 2.0 percent maximum manganese, 18
percent to 20 percent chromium, 8 percent to 10.50 percent nickel
and balance iron.
An alloy developed for cold heading applications which does not
transform to martensite is designated as IN 744X. This steel
contains about 26 percent chromium and is about half austenitic and
half ferritic. Due to the high alloy content the cost is
excessively high.
SUMMARY OF THE INVENTION
The principal object of this invention is to provide a magnetic
austenitic-ferritic stainless steel essentially consisting of
chromium, manganese, carbon and nitrogen which is stable against
transformation to martensite regardless of cold working, heat
treatment or welding, which has good ductility, toughness and
corrosion resistance in its as-welded condition, and high strength,
but which nevertheless is relatively low in cost because of lower
alloy content than prior art alloys offered for applications
requiring the above properties.
According to the invention a stainless steel having a two-phase
structure comprising between 10 percent and 50 percent austenite in
a ferrite matrix consists essentially of from about 4.0 percent to
less than 11.0 percent manganese, about 19 percent to about 24
percent chromium, and about 0.12 percent to about 0.26 percent
nitrogen. Carbon is of course present and is limited to a maximum
of about 0.06 percent. Phosphorus and sulfur, normally present as
impurities, are limited to a maximum of about 0.03 percent each.
Silicon is also normally present, in amounts up to 1.0 percent
maximum. Nickel may be present, ranging from trace amounts up to
about 3.0 percent. Copper and cobalt, if present as residual
elements, are limited to a maximum of about 0.5 percent each. The
balance is of course iron, together with incidental impurities.
Molybdenum may be substituted for chromium on a 1:1 basis in
amounts up to about 5 percent for improved resistance to corrosion
in pitting media.
Columbium may be added in amounts up to about 1 percent for
improved weld area corrosion resistance.
The austenite level, preferably 20 percent to 30 percent, is
achieved through addition of nitrogen (a strong austenite former)
within the range of 0.12 percent and 0.26 percent. Carbon, although
maintained at a low level, also contributes to some extent to
austenite formation. The austenite is maintained at a stable level
by reason of the chromium, manganese and nitrogen relationship. It
is thus apparent that the compositional balance among the essential
elements is in every sense critical. Unlike prior art
austeniticferritic alloys, the nickel, copper and cobalt contents
are maintained at low levels, and hence the steel of the invention
is not subject to stress corrosion failure when exposed to hot
chloride media. The use of manganese to stabilize the austenite
balance results in a ductile material which is also resistant to
stress cracking in hot chloride media. The low carbon content tends
to prevent intergranular corrosion when welded.
At least about 0.12 percent nitrogen is necessary in order to form
sufficient austenite. Nitrogen in excess of about 0.26 percent
would exceed the solubility limit of this element and hence would
result in porosity and unsoundness in the metal.
A minimum of about 4 percent manganese is required in order to
balance the chromium and thereby stabilize the austenite. Excessive
manganese adversely affects the balance with chromium, increasing
the austenite level above the desired range, and the maximum
manganese content is thus less than 11.0 percent.
Nickel, if present, is limited to a maximum of about 3.0 percent.
It has been found that the stress corrosion resistance of the metal
will be adversely affected if the nickel content exceeds 3.0
percent. Within the prescribed range, nickel will of course
increase the austenite level and thus cooperates with the nitrogen
in this function, without adversely affecting toughness.
PREFERRED EMBODIMENTS OF THE INVENTION
While, as indicated above, in its broad ranges the steel of the
invention consists essentially of carbon up to about 0.06 percent,
manganese about 4.0 percent to less than 11.0 percent, chromium
about 19 percent to about 24 percent, nitrogen about 0.12 percent
to about 0.26 percent, nickel up to about 3.0 percent, phosphorus
and sulfur up to about 0.03 percent each, silicon up to about 1.0
percent, copper and cobalt up to about 0.5 percent each, and
remainder substantially iron, a preferred composition comprises
about 0.02 percent carbon, about 6.0 percent manganese, phosphorus
and sulfur low, about 0.40 percent silicon, about 21.0 percent
chromium, about 0.20 percent nickel, about 0.20 percent nitrogen,
copper and cobalt low, and balance substantially iron.
A series of heats was prepared in order to establish parameters for
the composition which would achieve the novel combination of
properties. The compositions of these heats are set forth in Table
I below. Heats designated as B, E, H, I, J, K, L, P and Q are
steels of the invention. ##SPC1##
Table II below summarizes the effect of the austenite percentage
level on the hardness and toughness of the heats of Table I both in
the annealed and austenitized condition. In Table II the heats are
listed in the order of increasing austenite content. Heats L, I, B,
J and K fall within the preferred austenite levels of 20 percent to
30 percent, and heats I and B have optimum properties. ##SPC2##
A Charpy V notch impact strength of 2 kgm/cm.sup.2 in the annealed
condition is considered the minimum acceptable toughness.
The austenite percentage was measured on a calibrated permanent
magnet gauge known as a MAGNE-GAGE.
The data of Table II indicate that for nitrogen contents over about
0.20 percent, an average of at least 20 percent austenite is needed
to impart good toughness. With nitrogen contents less than about
0.20 percent, a minimum average austenite level of 10 percent is
sufficient to impart satisfactory toughness.
Tables III through VIII below list certain selected heats and
compare the effect on hardness and toughness of variation of
chromium, manganese, nitrogen, carbon, nickel, and chromium plus
nickel, respectively, all other elements in each Table being
substantially constant.
The data on hardness are included to show transformation to
martensite. High hardness indicates that transformation to
martensite has occurred. The magnetism values measure both ferrite
and martensite since both are magnetic, but if the hardness does
not increase after annealing or austenitizing, substantially all
the magnetic phase remains as ferrite. ##SPC3##
From Table III it will be noted that with all other elements
substantially constant, chromium contents of less than about 19
percent permit the austenite to transform to martensite, thereby
increasing the hardness and reducing the impact strength. Chromium
contents greater than about 24 percent decrease the quantity of
austenite and the impact toughness.
Table IV indicates that with all other elements substantially
constant manganese contents of less than about 4 percent result in
a transformation of austenite to ferrite.
Table V shows the effect of nitrogen in control of the
austenite-ferrite balance. Nitrogen contents of less than about
0.12 percent, with all other elements substantially constant,
result in too low an austenite content to provide good
toughness.
The effect of carbon in control of the austenite-ferrite balance is
shown in Table VI. With all other elements substantially constant,
carbon contents within the range of 0.013 percent to 0.055 percent
increase the austenite content but have little effect on
toughness.
Table VII shows the effect of nickel in control of the
austenite-ferrite balance. With all other elements substantially
constant, nickel contents in the range of 0.14 percent to 5.1
percent increase the austenite from about 20 percent to about 90
percent with good toughness over the entire range.
The effect on toughness of varying the chromium and nickel contents
while maintaining a constant austenite level is shown in Table
VIII. With all other elements substantially constant, a chromium
content of just over 24 percent with 1.2 percent nickel cause a
significant decrease in toughness.
Mechanical properties of the steels of the invention are set forth
in Table IX below. ##SPC4##
Weld area corrosion tests were conducted on samples of Heat B, a
preferred composition of the invention, with the following
results:
CuSo.sub.4 65% Boiling Boiling MgCl.sub.2 A 393 HNO.sub.3 240 Hours
Ann. Aus. Ann. Aus. Ann. Aus. No corro- No corro- .0020 IPM .0014
IPM No No sion sion No accel. No. accel. Cracks Cracks corr.
corr.
The boiling HNO.sub.3 tests comprised 3 48-hour periods.
From the above data it is apparent that there is provided a
stainless steel which, by reason of its composition and critical
balance of essential elements, achieves the objectives hereinbefore
stated.
* * * * *