Patent Application
20230279531
The present disclosure relates to an austenitic stainless steel which may be utilized as various materials for an outer panel of a vehicle, a component for construction, and the like and a manufacturing method thereof.
Austenitic stainless steels have been applied for various uses to manufacture components for transportation and construction due to excellent formability, work hardenability, and weldability. However, 304 series stainless steels or 301 series stainless steels, which are representative general-use austenitic stainless steels, have low yield strengths of 200 to 350 MPa, and thus there are limits to apply these stainless steels to structural materials due to low strength.
Although a skin pass rolling process may additionally be performed as a method for increasing yield strength of austenitic stainless steels, this method causes problems in increasing manufacturing costs due to the additional process and significantly deteriorating elongation of materials.
Patent Document 1 discloses a method for manufacturing a 300 series stainless steel having a small curvature even after half etching by performing stress relief (SR) heat treatment twice after skin pass rolling a cold-rolled, annealed material for a laser metal mask for photoetching. However, Patent Document 1 relates to a manufacturing method to control etchability and curvature after etching. Because an austenitic stability parameter (ASP) value is from 30 to 50, strain-induced martensite transformation rapidly occurs during formation, resulting in deterioration of elongation.
Patent Document 2 relates a nuclear power component. In order to manufacture an austenitic stainless steel having an average grain size of 10 μm or less, heat treatment was performed for a long time over 48 hours at a temperature of 600 to 700° C. According to Patent Document 2, heat treatment is required for a long time, productivity decreases in the case of being implemented in a real production line, and manufacturing costs increase.
To solve the foregoing problems, provided is an ultrafine-grained 300 series stainless steel having simultaneously satisfying high yield strength and excellent elongation.
In accordance with an aspect of the present disclosure, an austenitic stainless steel includes, in percent by weight (wt %), 0.005 to 0.03% of C, 0.1 to 1% of Si, 0.1 to 2% of Mn, 6 to 9% of Ni, 16 to 19% of Cr, 0.2% or less of N, and the remainder being Fe and unavoidable impurities, wherein assuming that a total thickness of the steel material is t, a value of an average grain size d in a thickness range of ¼t to ¾t is 5 μm or less, an ASP value represented by Formula (1) below is from 10 to 25, a value represented by Formula (2) below is 435 or more, and a value represented by Formula (3) below is 6000 or more.
551−462*([C]+[N])−9.2*[Si]−8.1*[Mn]−13.7*[Cr]−29*([Ni]+[Cu])−18.5*[Mo]−68*([Nb]+[V]) (1)
(1600*[N])+(700/)+(4*ASP)−(20*[Ni])+100 (2)
YS*EL−500*([Ni]+[Cr]) (3)
In Formulae (1), (2), and (3), [C], [N], [Si], [Mn], [Cr], [Ni], [Cu], [Mo], [Nb], and [V] represent weight percentages (wt %) of respective elements, YS represents a yield strength (MPa), and EL represents an elongation (%).
In addition, in the austenitic stainless steel according to the present disclosure, a value of Formula (4) below may be 200 or more.
Hv−([Ni]+[Cr]) (4)
In Formula (4), Hv represents a Vickers hardness (Hv) and [Ni] and [Cr] represent weight percentages (wt %) of respective elements.
In addition, the austenitic stainless steel according to the present disclosure may further include, in percent by weight (wt %), at least one of 0.4% or less of Cu, 0.2% or less of Mo, 0.25% or less of Nb, and 0.25% or less of V.
In addition, in the austenitic stainless steel according to the present disclosure, the t may be from 0.4 to 2.0 mm.
In addition, in the austenitic stainless steel according to the present disclosure, a pitting potential, measured by dipping in a 3.5% NaCl solution at 30° C., may be 250 mV or more.
In accordance with another aspect of the present disclosure, a method of manufacturing the austenitic stainless steel includes: hot rolling a slab comprising, in percent by weight (wt %), 0.005 to 0.03% of C, 0.1 to 1% of Si, 0.1 to 2% of Mn, 6 to 9% of Ni, 16 to 19% of Cr, 0.2% or less of N, and the remainder being Fe and unavoidable impurities, and cold rolling the hot-rolled steel material at room temperature with a reduction ratio of 40% or more; and annealing the cold-rolled steel material at a temperature of 700 to 850° C.
In addition, in the method of manufacturing the austenitic stainless steel according to the present disclosure, the slab may be hot-rolled and then cold-rolled without being annealed.
In addition, the method of manufacturing the austenitic stainless steel according to the present disclosure may further include skin pass rolling with a reduction ratio of 60% or more.
The present disclosure may provide an ultrafine-grained 300 series stainless steel simultaneously satisfying high strength and high ductility.
The present disclosure provides an austenitic stainless steel simultaneously satisfying high strength and high ductility with high economic feasibility by reducing the contents of Ni and Cr which are high-priced alloying elements.
The present disclosure provides an austenitic stainless steel simultaneously satisfying high strength and high ductility with excellent corrosion resistance.
An austenitic stainless steel according to an embodiment of the present disclosure includes, in percent by weight (wt %), 0.005 to 0.03% of C, 0.1 to 1% of Si, 0.1 to 2% of Mn, 6 to 9% of Ni, 16 to 19% of Cr, 0.2% or less of N, and the remainder being Fe and unavoidable impurities, wherein assuming that a total thickness of the steel material is t, a value of an average grain size d in a thickness range of ¼t to ¾t is 5 μm or less, an ASP value represented by Formula (1) below is from 10 to 25, a value represented by Formula (2) below is 435 or more, and a value represented by Formula (3) below is 6000 or more.
551−462*([C]+[N])−9.2*[Si]−8.1*[Mn]−13.7*[Cr]−29*([Ni]+[Cu])−18.5*[Mo]−68*([Nb]+[V]) (1)
(1600*[N])+(700/)+(4*ASP)−(20*[Ni])+100 (2)
YS*EL−500*([Ni]+[Cr]) (3)
wherein in Formulae (1), (2), and (3), [C], [N], [Si], [Mn], [Cr], [Ni], [Cu], [Mo], [Nb], and [V] represent weight percentages (wt %) of respective elements, YS represents yield strength (MPa), and EL represents elongation (%).
Hereinafter, preferred embodiments of the present disclosure will now be described. However, the present disclosure may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The terms used herein are merely used to describe embodiments. Thus, an expression used in the singular encompasses the expression of the plural, unless it has a clearly different meaning in the context. In addition, it is to be understood that the terms such as “including” or “having” are intended to indicate the existence of features, steps, functions, components, or combinations thereof disclosed in the specification, and are not intended to preclude the possibility that one or more other features, steps, functions, components, or combinations thereof may exist or may be added.
Meanwhile, unless otherwise defined, all terms used herein have the same meaning as those commonly understood by one of ordinary skill in the art to which this disclosure belongs. Thus, these terms should not be interpreted in an idealized or overly formal sense unless expressly so defined herein. As used herein, the singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise.
In addition, the terms “about”, “substantially”, etc. used throughout the specification mean that when a natural manufacturing and substance allowable error are suggested, such an allowable error corresponds a value or is similar to the value, and such values are intended for the sake of clear understanding of the present disclosure or to prevent an unconscious infringer from illegally using the disclosure of the present disclosure.
Although austenitic stainless steels have been used for various uses due to excellent formability, work hardenability, and weldability, yield strength thereof is low. In the case of performing skin pass rolling to increase yield strength, a problem of deteriorating elongation may occur. The present inventors have focused on an ultrafine austenitic stainless steel as a steel material simultaneously satisfying high yield strength and excellent elongation. However, not all of ultrafine stainless steels satisfy both high yield strength and excellent elongation. Ultrafine grained austenitic stainless steels may have considerably different yield strength and elongation, because the Ni content and the Cr content vary according to steel types, the amount of martensite transformation during cold working may vary according to the stability of the austenite phase, and tensile curve characteristics may vary according to the transformation induced plasticity (TRIP) transformation behavior. The present inventors have found an ultrafine grained austenitic stainless steel capable of simultaneously satisfying high strength and high ductility in consideration the above-described effects.
An austenitic stainless steel according to an embodiment of the present disclosure includes, in percent by weight (wt %), 0.005 to 0.03% of C, 0.1 to 1% of Si, 0.1 to 2% of Mn, 6 to 9% of Ni, 16 to 19% of Cr, 0.2% or less of N, and the remainder being Fe and unavoidable impurities. In addition, the austenitic stainless steel may further include at least one of 0.4% or less of Cu, 0.2% or less of Mo, 0.25% or less of Nb, and 0.25% or less of V.
Hereinafter, reasons for numerical limitations on the contents of alloying elements in the embodiment of the present disclosure will be described.
The content of carbon (C) is from 0.005 to 0.03 wt %.
C is an austenite phase-stabilizing element. In consideration thereof, C is added in an amount of 0.005 wt % or more. However, since an excess of C causes a problem of forming a chromium carbide during low-temperature annealing to deteriorate grain boundary corrosion resistance, the C content is controlled to 0.03 wt % or less in the present disclosure.
The content of silicon (Si) is from 0.1 to 1 wt %.
Si is an element added as a deoxidizer during a steel-making process and has an effect on improving corrosion resistance of a steel by forming an Si oxide in a passivated layer in the case of performing a bright annealing process. In consideration thereof, Si is added in an amount of 0.1 wt % or more in the present disclosure. However, since an excess of Si causes a problem of deteriorating ductility, the Si content is controlled to 1.0 wt % or less in the present disclosure.
The content of manganese (Mn) is from 0.1 to 1.0 wt %.
Mn is an austenite phase-stabilizing element. In consideration thereof, Mn is added in an amount of 0.1 wt % or more in the present disclosure. However, since an excess of Mn causes a problem of deteriorating corrosion resistance, the Mn content is controlled to 1.0 wt % or less in the present disclosure.
The content of nickel (Ni) is from 6.0 to 9.0 wt %.
Ni, as an austenite phase-stabilizing element, has an effect on softening a steel material. In consideration thereof, Ni is added in an amount of 6.0 wt % or more in the present disclosure. However, since an excess of Ni causes a problem of increasing costs, the Ni content is controlled to 9.0 wt % or less in the present disclosure.
The content of chromium (Cr) is from 16.0 to 19.0 wt %.
Cr is a major element for improving corrosion resistance of a stainless steel. In consideration thereof, Cr is added in an amount of 16.0 wt % or more in the present disclosure. However, since an excess of Cr causes problems of hardening of a steel material and inhibiting strain-induced martensite transformation during cold rolling, the Cr content is controlled to 19.0 wt % or less in the present disclosure.
The content of nitrogen (N) is 0.2 wt % or less.
N is an austenite phase-stabilizing element and improves strength of a steel material. However, since an excess of N causes problems of hardening a steel material and deteriorating hot workability, the N content is controlled to 0.2 wt % or less in the present disclosure.
Hereinafter, reasons for numerical limitations on the contents of optional alloying elements Cu, Mo, Nb, and V will be described in detail.
The content of copper (Cu) may be from 0.4 wt % or less.
Cu is an austenite phase-stabilizing element. However, since an excess of Cu causes problems of deteriorating corrosion resistance of a steel material and increasing costs, the Cu content is controlled to 0.4 wt % or less in the present disclosure.
The content of molybdenum (Mo) may be 0.2 wt % or less.
Mo has an effect on improving corrosion resistance and workability. However, since an excess of Mo causes a problem of increasing costs, the Mo content is controlled to 0.2 wt % or less in the present disclosure.
The contents of niobium (Nb) or vanadium (V) may be 0.25 wt % or less.
Nb and V have an effect on suppressing the growth of grains by forming (Nb,V)(C,N) precipitates. However, when the contents of Nb and V are excessive, a problem of increasing manufacturing coast may occur, and thus the contents of Nb and V are controlled to 0.25 wt % or less, respectively, in the present disclosure.
The remaining component of the composition of the present disclosure is iron (Fe). However, the composition may include unintended impurities inevitably incorporated from raw materials or surrounding environments, and thus addition of other alloying elements is not excluded. These impurities are known to any person skilled in the art of manufacturing and details thereof are not specifically mentioned in the present disclosure.
As well as limiting the contents of the alloying elements of the stainless steel according to the present disclosure as described above, the relationships therebetween may further be limited as follows.
An Austenitic Stability Parameter (ASP) value represented by Formula (1) below may be from 10 to 25.
551−462*([C]+[N])−9.2*[Si]−8.1*[Mn]−13.7*[Cr]−29*([Ni]+[Cu])−18.5*[Mo]−68*([Nb]+[V]) (1)
In Formula (1) above, [C], [N], [Si], [Mn], [Cr], [Ni], [Cu], [Mo], [Nb], and [V] represent weight percentages (wt %) of respective elements. For an element not added, 0 wt % is substituted into Formula (1).
Formula (1) indicates a temperature at which 50% of austenite is transformed into martensite when a stainless steel is deformed with a true strain of 0.3 and is used as an index of stability of the austenite phase. A lower value of Formula (1) means higher stability of the austenite phase indicating a smaller amount of strain-induced martensite during transformation.
When the value of Formula (1) is less than 10, a fraction of martensite in a cold-rolled steel material decreases and a fraction of the retained austenite increases due to a low amount of TRIP transformation, which is transformation from an austenite phase into a martensite phase by cold rolling. As the amount of strain-induced martensite decreases, a ratio of reverted austenite by low-temperature annealing decreases, and the fraction of the retained austenite phase without being transformed into martensite increases, making it difficult to obtain ultrafine grains. When the value of Formula (1) exceeds 25, TRIP transformation by cold rolling is activated, but a problem of decreasing elongation occurs due to a too high TRIP transformation rate.
A value of Formula (2) below may be 435 or more.
(1600*[N])+(700/)+(4*ASP)−(20*[Ni])+100 (2)
In Formula (2), [N] and [Ni] represent weight percentages (wt %) of respective elements. ASP means the ASP value of Formula (1). Assuming that a total thickness of the steel material is t, d indicates an average grain size in a thickness range of ¼t to ¾t.
According to an embodiment of the present disclosure, t may be from 0.4 to 2.0 mm. A material having a thickness of 0.4 to 2.0 mm has been widely applied to structural components. According to the present disclosure, an austenitic stainless steel having high strength and high ductility may be provided within the above-described thickness range.
According to an embodiment of the present disclosure, d may be 5 μn or less.
When d exceeds 5 μm, a yield strength decreases by Hall-Petch equation, resulting in a decrease in a YS*El value.
Formula (2) is a parameter to obtain high strength, derived in consideration of factors affecting strength, such as the N content, the Ni content, grain size, and austenitic stability parameter. When the value of Formula (2) is less than 435, sufficient strength cannot be obtained.
A value of Formula (3) below may be 6000 or more.
YS*EL−500*([Ni]+[Cr]) (3)
In Formula (3), YS represents yield strength (MPa), EL represents elongation (%), and [Ni] and [Cr] represent weight percentages (wt %) of respective elements.
In Formula (3), the YS*EL value is considerably affected by the contents of Cr and Ni. For example, in the case where the contents of Cr and Ni are small, TRIP transformation easily occurs and the YS*EL value tends to increase. When the value of Formula (3) is less than 6000, high strength and high ductility cannot be satisfied simultaneously.
A value of Formula (4) below may be 200 or more.
Hv−([Ni]+[Cr]) (4)
In Formula (4), Hv represents Vickers hardness (Hv) and [Ni] and [Cr] represent weight percentages (wt %) of respective elements.
In Formula (4), the Hv value is considerably affected by the contents of Cr and Ni. For example, in the case where the contents of Cr and Ni are small, TRIP transformation easily occurs, and thus an amount of strain-induced martensite transformation increases during cold deformation. As a result, hardness of a steel material increases. When the value of Formula (4) is less than 200, sufficient hardness cannot be obtained.
The austenitic stainless steel according to the present disclosure has not only high strength and high ductility but also excellent corrosion resistance.
The austenitic stainless steel according to an embodiment may have a pitting potential of 250 mV or more when measured by dipping in an 3.5% NaCl solution at 30° C.
The austenitic stainless steel according to an embodiment of the present disclosure may have a tensile strength of 1750 MPa or more after skin pass rolling.
A method of manufacturing an austenitic stainless steel according to an embodiment of the present disclosure includes: hot rolling a slab including, in percent by weight (wt %), 0.005 to 0.03% of C, 0.1 to 1% of Si, 0.1 to 2% of Mn, 6 to 9% of Ni, 16 to 19% of Cr, 0.2% or less of N, and the remainder being Fe and unavoidable impurities, and cold rolling the hot-rolled steel material at room temperature with a reduction ratio of 40% or more; and annealing the cold-rolled steel material at a temperature of 700 to 850° C.
When the reduction ratio is less than 40% during cold rolling, the austenitic stainless steel of the present disclosure having an ASP value of 10 to 25 has a too low amount of TRIP transformation, resulting in a decrease in the fraction of martensite in the cold-rolled steel material and an increase in the fraction of the retained austenite phase. As the amount of the strain-induced martensite decreases, the ratio of the reverted austenite phase during the subsequent low-temperature annealing decreases, and the fraction of the retained austenite phase without being transformed into martensite increases, making it difficult to obtain ultrafine grains.
According to the present disclosure, the hot-rolled material is cold-rolled and annealed at a low temperature of 700 to 850° C. When the temperature of the low-temperature annealing is below 700° C., recrystallization from the strain-induced martensite phase into the reverted austenite phase does not occur. On the contrary, when the temperature of the low-temperature annealing is higher than 850° C., the grain size of the reverted austenite may increase, thereby decreasing the yield strength.
According to an embodiment of the present disclosure, the slab may be hot-rolled and then cold-rolled without conducting annealing.
In addition, the method may further include skin pass rolling with a reduction ratio of 60% or more to further increase strength.
Hereinafter, the present disclosure will be described in more detail through examples. However, it is necessary to note that the following examples are only intended to illustrate the present disclosure in more detail and are not intended to limit the scope of the present disclosure. This is because the scope of the present disclosure is determined by matters described in the claims and able to be reasonably inferred therefrom.
Slabs having the compositions of alloying elements shown in Table 1 below were hot-rolled and cold-rolled with a total reduction ratio of 40% or more at room temperature without conducting annealing. Subsequently, the resultant was annealed at a temperature of 700 to 850° C. to prepare a cold-rolled, annealed material with a thickness of 0.4 to 2.0 mm.
In Table 1 below, ASP refers to a value obtained by substituting the contents of alloying elements of Table 1 into Formula (1) below indicating stability of an austenite phase.
551−462*([C]+[N])−9.2*[Si]−8.1*[Mn]−13.7*[Cr]−29*([Ni]+[Cu])−18.5*[Mo]−68*([Nb]+[V]) (1)
In Formula (1), [C], [N], [Si], [Mn], [Cr], [Ni], [Cu], [Mo], [Nb], and [V] represent weight percentages (wt %) of respective elements.
In Table 2, assuming that a total thickness of the cold-rolled, annealed material of Table 1 is t, d indicates an average grain size (μm) in a thickness range of ¼t to ¾t. Formula (2) of Table 2 means a value obtained by Formula (2) below.
(1600*[N])+(700/)+(4*ASP)−(20*[Ni])+100 (2)
The value of Formula (2) was obtained by substituting the contents (wt %) of [N] and [Ni] and the ASP value of Table 1 and substituting the d value of Table 2 thereinto.
Formula (3) of Table 2 means a value obtained by Formula (3) below.
YS*EL−500*([Ni]+[Cr]) (3)
The value of Formula (3) was obtained by substituting a yield strength (YS, MPa) and an elongation (EL, %) measured under the conditions described below and the contents (wt %) of [Ni] and [Cr] of Table 1 thereinto.
The yield strength (YS, MPa) and the elongation (EL, %) were measured after preparing a sample of the cold-rolled, annealed material according to the JIS13B standards and conducting a tensile test at room temperature in a crosshead range of 10 mm/min to 20 mm/min.
Formula (4) of Table 2 represents a value obtained by Formula (4) below.
Hv−([Ni]+[Cr]) (4)
The value of Formula (4) was derived by substituting a Vickers hardness (Hv) measured under the conditions described below and the contents (wt %) of [Ni] and [Cr] of Table 1 thereinto.
The Vickers hardness (Hv) is a value measured using a Vickers hardness tester with a load of 2 kgf.
Pitting potential (mV) of Table 2 is a value measured after dipping a cold-rolled, annealed material in a 3.5% NaCl solution at 30° C.
Referring to Tables 1 and 2, Inventive Examples 1 to 8 satisfied the ASP values of 10 to 25, the d value of 5 μm or less, the value of Formula (2) of 435 or more, and the value of Formula (3) of 6000 or more, and thus high strength, high ductility, and excellent corrosion resistance were obtained. Also, referring to Table 2, in Inventive Examples 1 to 8, the values of Formula (4) were at least 200 and pitting potentials were at least 250 mV. In Comparative Examples 6 to 18, the ASP values were out of the range defined in the present disclosure. In Comparative Examples 6 to 13 and 18 in which the ASP values exceeded 25, low elongation was observed due to too high TRIP transformation rates during formation. In Comparative Examples 14 to 17 in which the ASP values were less than 10, ultrafine grains could not be obtained due to high fractions of the retained austenite phase.
In Comparative Examples 1 to 5, 7, 10, and 13 to 17, coarse grains were formed because the d values were out of the range suggested by the present disclosure. As a result, high strength and high ductility could not be satisfied simultaneously.
The range of Formula (2) suggested by the present disclosure was not satisfied in Comparative Examples 3 to 5 and 13 to 17. As a result, high strength and high ductility could not be satisfied simultaneously.
The range of Formula (3) suggested by the present disclosure was not satisfied in Comparative Examples 2 and 5 to 17. As a result, high strength and high ductility could not be satisfied simultaneously.
The range of Formula (4) suggested by the present disclosure was not satisfied in Comparative Examples 1, 3 to 5, 7, 10, 12, and 14 to 17. As a result, sufficient hardness could not be obtained.
Corrosion resistance deteriorated in Comparative Example 18 due to a large amount of Mn contained therein, and a pitting potential of 30 mV was obtained.
While the present disclosure has been particularly described with reference to exemplary embodiments, it should be understood by those of skilled in the art that the scope of the present disclosure is not limited thereby and various changes in form and details may be made without departing from the spirit and scope of the present disclosure.
The austenitic stainless steel according to an embodiment of the present disclosure may have both high strength and high ductility, be economically feasible by reducing the contents of Ni and Cr which are high-priced alloying elements, have excellent corrosion resistance. Therefore, the austenitic stainless steel may be applied to outer panels of vehicles, components for construction, and the like, as various materials.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0112382 | Sep 2020 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2021/011462 | 8/26/2021 | WO |
