U.S. patent number 3,917,492 [Application Number 05/477,469] was granted by the patent office on 1975-11-04 for method of making stainless steel.
This patent grant is currently assigned to Sandvik Aktiebolag. Invention is credited to Anders Lars Erik Backman, Stig Gunnar Forsberg.
United States Patent |
3,917,492 |
Backman , et al. |
November 4, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Method of making stainless steel
Abstract
Spring steel (in wire or strip form) is produced from an
austenitic stainless steel, the chromium content of which is
sufficient to give the steel a metastable austenitic
microstructure, by (1) annealing and (2) quenching under conditions
to give it a wholly austenitic condition, followed by (3) a very
substantial cold reduction which transforms its structure to an at
least partially martensitic structure and produces increased
hardness.
Inventors: |
Backman; Anders Lars Erik
(Sandviken, SW), Forsberg; Stig Gunnar (Sandviken,
SW) |
Assignee: |
Sandvik Aktiebolag (Sandviken,
SW)
|
Family
ID: |
20317718 |
Appl.
No.: |
05/477,469 |
Filed: |
June 7, 1974 |
Foreign Application Priority Data
Current U.S.
Class: |
148/610;
148/580 |
Current CPC
Class: |
C21D
8/005 (20130101); C22C 38/44 (20130101) |
Current International
Class: |
C21D
8/00 (20060101); C22C 38/44 (20060101); C21D
007/02 () |
Field of
Search: |
;148/12E,12.4
;75/128C,128W,128A |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rutledge; L. Dewayne
Assistant Examiner: Steiner; Arthur J.
Attorney, Agent or Firm: Pierce, Scheffler & Parker
Claims
We claim:
1. A method of making austenitic stainless steels having high
tensile strength in excess of 250,000 p.s.i. but not in excess of
400,000 p.s.i. and preferably not in excess of 390,000 p.s.i., with
high ductility in excess of 45% in terms of contraction of area
before rupture and good properties under elevated temperature
conditions in terms of relaxation permanence, the steps of said
method comprising, selecting an austenitic stainless steel of the
transformation hardening type and containing from 0.01 to 0,20%
carbon, up to about 5% silicon, up to about 10% manganese, from 13
to 20% chromium, from 3 to 10% nickel, up to about 25% molybdenum,
up to about 25% aluminum and the balance essentially iron;
annealing the steel at a temperature of 950.degree.-1100.degree. C.
thereby stabilizing the austenite; rapidly quenching the steel from
said annealing temperature; cold-working said steel to reduce its
cross-sectional area between 40 and 90%, preferably between 60 and
85%; then tempering the steel at a temperature in the range between
200.degree. and 550.degree. C., preferably 250.degree.-450.degree.
C. and thereafter cold-working said steel to reduce its
cross-sectional area between 5 and 40%.
2. A method according to claim 1, including the step of finally
cold-working the steel to reduce its cross-sectional area between
10 and 30%.
3. A method according to claim 1, including the step of tempering
the steel at a temperature in the range between 300.degree. and
550.degree. C., preferably between 350.degree. and 500.degree. C.,
after the final cold working for a period of 2-5 hours.
Description
The present invention relates to a stainless chromium-nickel steel
with high strength, and which at the same time has good ductility.
This invention also relates to a new method of treating such
stainless steel in the form of band or wire to achieve these new
characteristics of stainless steel, said steel then being adaptable
for use as a spring material in the form of wire or strip.
High strength material which at the same time has a good ductility
is increasingly called for. One method of strengthening steel
consists in subjecting the steel to an appreciable cold reduction.
This method is especially adaptable for certain types of austenitic
stainless steel in which an austenitic structure is partially
transformed by cold deformation into a hard martensitic structure.
The mechanism of this structural transformation is well known and
is disclosed in, for instance, British Pat. Nos. 722,427 and
766,971. These unstable austenitic steels have been in wide use
especially as spring materials, and are available in the form of
round wire or bands.
The requirement for good ductility often implies that it must be
possible to carry out a succession of deformations of such material
without any ensuing fractural formations. If the material is in the
form of wire there is a requirement that it must be possible to
have such wire wound around a bar the diameter of which is
approximately the same as that of the wire itself. The normal
procedure of processing such steel is to carry out a cold reduction
to a level of strength and ductility such that the material then is
able to be subjected to a shaping procedure into a final product.
Such a product is often also subjected to a final heat treatment at
a temperature of 200.degree.-550.degree.C. during a few hours for
strengthening purposes.
In order to achieve a sufficiently high ductility with these high
strength steels, however, it has been necessary to accept a lower
non-optimal strength level. This has been so because the
achievement of an increased strength is -- in principle --
accompanied by a decrease in ductility. In extreme cases a high
strength might be attainable but then the material also exhibited
such an embrittlement that fracture occurred at minor deformations
thereof. This is an effect that closely related with a blocking of
dislocations that occurs in martensite as well as in austenite
phases in deformation hardening. If the reduction is too high
further dislocation movements are impossible due to the mutual
blocking thereof. This implies that an additional reduction of said
material would result in micro-cracking, which results in an
appreciable decrease in ductility.
According to the present invention it surprisingly has now been
found that it is possible to avoid the above related lessening of
ductility. The invention thus resides in a new stainless steel
which exhibits the unique combination of high strength and
ductility and which also exhibits good properties under elevated
temperature conditions. The articles of the invention also have
good resistance to corrosion and to oxidation at the working
temperatures.
It is an object of the invention to provide a stainless
chromium-nickel steel that is hardenable by cold-work into an
austenitic-martensitic microstructure, said steel in the
cold-worked condition having a tensile strength in excess of
250,000 p.s.i., but not in excess of 400,000 p.s.i. and preferably
not in excess of 390,000 p.s.i., and a high ductility which,
measured as contraction of area immediately before rupture, is in
excess of 45% and which in addition also exhibits good properties
under elevated temperature conditions in terms of relaxation
permanence. In its broader aspects, the invention provides such an
alloy having a composition consisting essentially of, by weight,
about 0.01 to 0.20% carbon, up to about 5% silicon, up to about 10%
manganese, from about 13 to about 20% chromium, about 3 to 10%
nickel, up to about 2.5% molybdenum, up to about 2.5% aluminum, and
the balance being essentially iron except for small amounts of
other elements which do not adversely affect the desired properties
of the alloy.
It is another inventive object to provide a method for processing
an austenitic stainless chromium-nickel steel to high strength and
ductility levels. Briefly, such steel is subjected to deformation
hardening as a result of cold-deformation through cold-working at
large reduction of area after which it is annealed at a temperature
between 200.degree. and 550.degree.C. Subsequently, this steel is
subjected to a moderate cold-working in which the cross-sectional
area is reduced by between 5 and 40%, preferably between 10 and
30%. Due to this method of processing, a deformation hardening
occurs such that a considerable gain in ductility is achieved
whilst retaining a high tensile strength.
According to the invention, I start with an austenitic stainless
steel in the form of wire or strip, this steel having been hot
rolled in the usuall manner and which has a composition comprising
chromium in amounts sufficient to give the steel a metastable
austenitic microstructure. After said hot rolling the steel is (or,
may be) subjected to a conventional surface treatment such as
pickling, grinding, sandblasting or similar treatment. Such a
material is then transformed into a wholly austenitic condition by
annealing at a temperature of 950.degree.-1100.degree.C. and then
quenching in water. Subsequently the steel is subjected to a cold
reduction in one or several steps without intermediate annealings
at a very large reduction of area, thus partially transforming the
austenitic structure into a martensitic structure, an increased
hardness simultaneously being obtained.
It heretofore had been known to cold-reduce an austenitic steel in
a series of cold deformations with high reductions upon quenching
same, thus effecting a so-called deformation hardening of the
material. However, it was not derivable from prior knowledge that
such a material subjected to a cold deformation next to entering
the brittle state if subjected to a subsequent tempering should
have a considerable margin of ductility such that even an increase
thereof could be gained when carrying out further deformation. By
choosing an optimum of reductions and tempering time-temperature
relations in such method of processing unexpected combinations of
steel characteristics have been found to be achievable. It has thus
been possible to achieve a considerable gain in ductility yet
retaining or even also increasing the tensile strength level.
FIG. 1 is a diagramatic showing of the effect of total reduction on
the ratio between yield point and ultimate tensile strength;
FIG. 2 shows the effect of total reduction on the contraction of
area immediately before rupture;
FIG. 3 diagramatically represents the improvement in properties
under elevated temperature conditions in the case of a steel of the
18-8 type; and
FIG. 4 is a modified Schaeffler diagram showing microstructures,
attainable through practice of the present invention, in the cases
of selected chromiumnickel steels.
The starting material, treated as related hereinbefore, is upon
quenching subjected to cold deformation with high reduction of area
next to entering the brittle state, said area reduction amounting
to 40-90%, preferably 60-85% thus partially transforming the
austenitic structure into martensite -- the amount of which being
30-90%, usually 45-85% -- while the remainder is austenite with
small amounts of ferrite. Subsequently, the material is subjected
to tempering at a temperature of 200.degree.-550.degree.C.,
preferably 250.degree.-450.degree.C., for a suitable time which,
according to several factors such as the tempering temperature and
the dimensions of the objects may be from some minutes up to 10-12
hours or even longer. The tempering time usually is between 15
minutes and 10 hours, and preferably between 2 and 5 hours. This
tempering is necessary so as to relieve those stresses which appear
to a locally high degree in the microstructure as a result of the
cold working. After said treatment the material is further cold
reduced to a moderate reduction of area amounting to 5-40%,
preferably 10-30%. The last reduction of area must amount to at
least some 5-10% so as to achieve any increased ductility whereas a
reduction of area in excess of about 40% will cause a decrease in
ductility. This circumstance will be apparent from the diagrams
illustrated in the appended drawings. The steel material may be
subjected to another tempering after said last moderate cold
reduction, the temperature of which final step then being
300.degree.-550.degree. C., preferably 300.degree.-500.degree. C.
for a time of 2-5 hours, an increased tensile strength being
obtained as a result thereof.
Various measures are used so as to indicate the ductility of a
material, such as: ultimate elongation, contraction of area before
rupture, i.e. the percentual decrease of area at the place of
rupture; and the ratio between yield point and ultimate tensile
strength, ##EQU1## 0.2 indicating stress applied to effect a
plastic deformation of 0.2%. FIG. 1 illustrates the effect of total
reduction on the ratio ##EQU2## and in FIG. 2 there is illustrated
the effect of total reduction on the contraction of area
immediately before rupture. In both figures there are also curves
illustrating the common method of processing not within the scope
of the invention in comparison with those illustrating the method
of the invention. For purposes of comparison, steel alloys were
prepared and test specimens were made therefrom for carrying out
tests the results of which are set forth in the Table following
hereinafter. The material made subject of these tests was stainless
steel wire subjected to cold drawing upon quench-annealing from
1050.degree. C., the analysis of which was as follows:
C Si Mn Cr Ni Mo Fe ______________________________________ 0.09
1.15 1.25 17 8 0.7 bal. ______________________________________
TABLE
__________________________________________________________________________
Yield Ultimate Ultimate Contraction of Dimension point strength
elongation area before Treatment mm .differential..sub.0.2
kp/mm.sup.2 .differential..sub.B kp/mm.sup.2 .DELTA..sub.50 %
rupture %
__________________________________________________________________________
Reduction .phi.1.0 220 230 1.8 40 83% Reduction 80% + tem- pering
425.degree.C 4 h .phi.1.0 230 235 1.4 30 Reduction 80% + tem-
pering 425.degree.C 4 h + reduc- tion 20% .phi.1.0 220 240 3.5 50
Reduction 80%+tempe- ring 425.degree.C, 4 h + reduc- tion 20% +
tempering 425.degree.C, 4 h .phi.1.0 230 255 2.5 40
__________________________________________________________________________
It is apparent from the data in this Table that all three measures
of ductility have been improved by practicing the treatment of the
invention, i.e. contraction of area before rupture, ultimate
elongation and the ratio ##EQU3## the last moderate cold reduction
having been effected upon tempering at about 425.degree. C. The
ultimate elongation is measured as .delta..sub.50, i.e. percentual
elongation of a wire of 50 mm length as indicated between two
points thereon, said last measure being 3.5% after tempering at
425.degree. C. for a period of 4 hours and subsequent cold
reduction at 20% reduction of area. It is also apparent from the
Table that the common method of processing resulted in a
considerably lower ultimate elongation, i.e., a lower
ductility.
The Table is also illustrative of the improved ultimate strength
reached with the alloy of the invention, which amounts to 240
kp/mm.sup.2 (343,000 p.s.i.) upon tempering at 425.degree. C. for a
time of 4 hours plus 20% reduction of area. After another tempering
at 425.degree. C. for a period of 4 hours the strength reached a
level of 255 kp/mm.sup.2 (364,000 p.s.i.) whilst the material
retained a high ductility, 2.5% in terms of ultimate elongation.
The results of these tests thus established that it is possible to
achieve a considerable increase of ductility yet retaining a high
strength level by carrying out a method of processing according to
the invention.
In addition, a considerable gain in the properties under elevated
temperature conditions appeared as a result of the cold-work
processing related above. This improvement of steel characteristics
is illustrated in FIG. 3 and refers to the relaxation permanence,
which expression means the percentual loss of applied load at a
certain temperature and for a length of time. The diagram of FIG. 3
shows such a curve of steel "1" of 18-8 type not cold-worked
according to the invention in comparison with steel "2" which is
within the scope of the invention. The curves refer to the
percentual loss of an applied load of 60 kp/mm.sup.2 for a period
of 24 hours at differing temperatures. The diagram clearly shows
the very good relaxation permanence of steel 2, this being a very
important property of steels adapted for use as spring
material.
Thorough studies of microstructure and steel characteristics have
shown that the improvement of ductility thus reached is closely
related with changes that occur in dislocation structure by reason
of the tempering within the range earlier set forth. Measurements
of micro-stresses of cold-reduced and tempered wire of the steel
analysis earlier referred to have indicated a drastic decrease of
said micro-stresses -- primarily in martensite -- after said
tempering. This implies that stress-relieving occurs along with a
lessened risk of fracture during a subsequent deformation. By
avoiding occurrence of interior fracture formations in cold
reduction, a further increase of dislocation denseness is possible,
thus enabling an increased ductility to be obtained.
The effect thus achievable by the method of the invention applies
to all those austenitic, or essentially austenitic, steels wherein
austenite is partially transformed into martensite as a result of
deformation and where a heat treatment gives rise to precipitations
which give rise to an increased strength level. The chemical
analysis thus must comprise an amount of chromium, usually in
excess of 13%, that is sufficient to provide a metastable
austenitic microstructure under the conditions that apply while
deforming the steel. The method of the invention is applicable to
steel alloys having a composition in weight percentages, consisting
essentially of about 0.01 to 0.20% carbon, up to about 5% silicon,
up to about 10% manganese, about 13 to 20% chromium, about 3 to 10%
nickel, up to about 2.5% molybdenum, up to about 2.5% aluminum, and
the balance being essentially iron except for small amounts of
other elements which do not adversely affect the desired properties
of the alloy.
In FIG. 4 there is shown a modified Schaeffler diagram from which
is derivable the microstructure that will be the result of a
certain steel analysis. The dotted rectangle indicates the area
within which the alloys appear in the broader aspects of the
invention, whereas the smaller square therein corresponds to the
more narrow and preferred ranges of analysis according to the
practices of my invention, this last squared area being limited by
the lines set by chromium equivalents in amounts of 15-25% and
nickel equivalents in amounts of 5-15%, said chromium equivalent
being given by the relation (%Cr + %Mo + 1.5 .times. % Si + 2
.times. % Nb + 3 .times. % Ti) and said nickel equivalent being
given by the relation (%Ni + 0.5 .times. %Mn + 30 .times. %C + 11.5
.times. %N).
* * * * *