WO2009099010A1 - 耐リジング性と加工性に優れたフェライト・オーステナイト系ステンレス鋼板およびその製造方法 - Google Patents
耐リジング性と加工性に優れたフェライト・オーステナイト系ステンレス鋼板およびその製造方法 Download PDFInfo
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- WO2009099010A1 WO2009099010A1 PCT/JP2009/051611 JP2009051611W WO2009099010A1 WO 2009099010 A1 WO2009099010 A1 WO 2009099010A1 JP 2009051611 W JP2009051611 W JP 2009051611W WO 2009099010 A1 WO2009099010 A1 WO 2009099010A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
Definitions
- the present invention relates to a ferritic / austenitic stainless steel sheet excellent in ridging resistance and workability and a method for producing the same.
- Austenitic stainless steel represented by SUS304 is a stainless steel excellent in corrosion resistance and workability, and is most commonly used in a wide range of fields such as kitchen equipment, home appliances, and electronic equipment. However, since austenitic stainless steel contains a large amount of rare and expensive Ni, there is a problem in the spread and economy in the future.
- ferritic stainless steels with improved corrosion resistance and workability by adding stabilizing elements such as Ti and Nb have become applicable to a wide range of fields due to improvements in refining technology that have enabled extremely low carbon and nitrogenization. is there.
- the major factor is that ferritic stainless steel is more economical than austenitic stainless steel containing a large amount of Ni.
- ferritic stainless steel is greatly inferior in terms of workability, particularly material elongation and uniform elongation, as compared to austenitic stainless steel.
- austenitic ferritic stainless steel located between the austenitic and ferritic types has attracted attention.
- austenitic ferritic stainless steel represented by SUS329J4L contains more than 5% Ni and further contains a few percent of Mo which is rarer and more expensive than Ni. is there.
- Patent Document 1 Mo is a selective additive element, and the amount of Ni is limited to more than 0.1% and less than 1% (Patent Document 1) or 0.5% to 1.7% (Patent Document 2).
- An austenitic ferritic stainless steel is disclosed.
- the steels shown in the examples of Patent Documents 1 and 2 contain more than 0.1% N and have an Mn content of more than 3.7% in order to reduce Ni.
- Patent Document 3 and Patent Document 4 with the intention of improving total elongation and deep drawability, the amount of Ni is substantially restricted to 3% or less, and the (C + N) amount and component balance in the austenite phase are adjusted.
- Austenitic ferritic stainless steel is disclosed.
- a ferritic stainless steel having excellent ductility is disclosed in the example of Patent Document 5 in which the N amount is less than 0.06%, the ferrite phase is a parent phase, and the retained austenite phase is less than 20%. Has been.
- Patent Document 6 and Patent Document 7 disclose improvements in resistance to crevice corrosion and intergranular corrosion in an austenitic ferritic stainless steel similar to Patent Document 3 and Patent Document 4.
- the steel shown in the example of Patent Document 6 includes an N content exceeding 0.3% when the Mn content is limited to less than 2% and a Ni content exceeding 0.5% is added.
- the steel shown in the example of Patent Document 7 is a steel in which the M content is more than 2% and less than 4% and the N content is less than 0.15% when the Ni content is less than 0.6%.
- the ferrite phase inherits the rolling texture even if hot-rolled sheet annealing or cold rolling and annealing are repeated, and it is difficult to obtain a recrystallized texture.
- the rolling texture means that accumulation in ⁇ 001 ⁇ orientation and ⁇ 112 ⁇ orientation is strong, and in ferritic stainless steel, ridging is likely to occur when accumulation in such orientation is strong. Therefore, it is considered that the ridging generated in the duplex stainless steel is also due to the strong accumulation in the rolling texture as in the case of the ferritic stainless steel and the lack of recrystallization of the ferrite phase.
- Patent Documents 1 to 7 mentioned above do not have any suggestion about the occurrence of ridging and the texture mentioned above. Specifically, although the austenitic ferritic stainless steels disclosed in Patent Documents 3 to 7 have good formability, the generation of ridging due to processing and the countermeasures have not been clarified.
- the present invention regulates the texture of the ferrite phase of the steel sheet and the phase balance between the ferrite phase and the austenite phase, and controls the steel components and hot rolling conditions, thereby providing a ferrite with excellent ridging resistance and workability.
- -It aims at providing an austenitic stainless steel plate and its manufacturing method.
- the present inventors have a relationship between a texture and a phase balance that satisfy both ridging resistance and workability of ferrite-austenitic stainless steel oriented to a low Ni, low-Mo alloy.
- the ridging height is reduced by reducing the ferrite phase ⁇ 111 ⁇ + ⁇ 101 ⁇ area ratio (ND // ⁇ 111 ⁇ ⁇ 10 °) with crystal grains having crystal orientation (crystal orientation grains) and ND //
- ND // ⁇ 111 ⁇ + ⁇ 101 ⁇ area ratio of the ferrite phase it is effective to increase the total area ratio of crystal grains having a crystal orientation satisfying ⁇ 101 ⁇ ⁇ 10 ° (crystal orientation grains). It was found that the low alloy type duplex stainless steel is superior to the high alloy type duplex stainless steel.
- the volume fraction of the austenite phase ( ⁇ phase ratio%) is in the range of 15 to 70%, the uniform elongation becomes the target of 30% or more, and the uniform elongation increases due to the work-induced martensitic transformation of the ⁇ phase. I found out.
- the controlling factors of ridging resistance and workability are the crystal orientation ( ⁇ 111 ⁇ + ⁇ 101 ⁇ area ratio) and the ⁇ phase ratio of the ferrite phase.
- the crystal orientation of the ferrite phase is affected by the hot rolling conditions in addition to the influence of the components.
- the austenite phase It has been found that it is preferable to perform rough rolling in a high temperature range where the amount of ferrite phase produced is large.
- the ⁇ phase ratio is affected by the finish annealing temperature after cold rolling, and the finish annealing temperature is preferably in the range of 900 to 1200 ° C. in order to control the ⁇ phase ratio to maximize the uniform elongation. I found out.
- the present invention has been completed based on these findings, and the gist of the invention is as follows.
- the steel is further mass%, Al: 0.2% or less, Mo: 1% or less, Ti: 0.5% or less, Nb: 0.5% or less, B: 0.01% or less And (2) characterized by containing one or more selected from Ca: 0.01% or less, Mg: 0.01% or less, and rare earth elements: 0.5% or less Ferritic / austenitic stainless steel sheet with excellent ridging resistance and workability as described in 1.
- a step of heating the stainless steel slab having the steel component according to any one of (1) to (3) at 1150 to 1300 ° C., hot rough rolling, and hot finishing after the hot rough rolling A hot-rolled sheet by subjecting the heated stainless steel slab to hot rolling, and annealing the hot-rolled sheet.
- a rolling start temperature is set.
- the austenite has a two-phase structure composed of a ferrite phase and an austenite phase by performing multi-pass rolling with 1150 ° C. or more, rolling end temperature of 1050 ° C.
- the volume fraction of the phase is 15 to 70%, and the ferrite phase grains and ND // ⁇ 101 have a crystal orientation satisfying ND / ⁇ 111 ⁇ ⁇ 10 ° on the plate surface (ND) at the plate thickness center.
- ⁇ Results satisfying ⁇ 10 ° Method for producing a ridging resistance and excellent formability ferritic-austenitic stainless steel sheet, wherein the crystal grains of the ferrite phase having an orientation to produce a steel sheet that exist 10 or more area% in total.
- the pass with a reduction rate of 20% or more occupies 1/2 or more of the total pass, and the reduction rate of one pass with the largest reduction rate is 50% or more, or the reduction rate
- the inventions related to the steels (1) to (4) and the inventions related to the manufacturing methods (5) to (8) are referred to as the present invention.
- the inventions (1) to (8) may be collectively referred to as the present invention.
- a ferritic / austenitic stainless steel sheet that is excellent, and particularly has a uniform elongation of 30% or more in a tensile test, which is an index of workability, can be obtained.
- FIG. 1 is a diagram showing the relationship between ridging and texture.
- FIG. 2 is a graph showing the relationship between uniform elongation and volume fraction of austenite phase ( ⁇ phase ratio%).
- Hot-rolled sheet annealing was performed at 1000 ° C., pickled and cold-rolled to produce a 1 mm-thick cold-rolled sheet.
- Cold-rolled sheet annealing was performed at 900 to 1200 ° C., and then cooled by forced air cooling to an average cooling rate up to 200 ° C. in the range of 35 to 40 ° C./second.
- the texture at the plate thickness center, the volume fraction of austenite phase (hereinafter referred to as ⁇ phase rate), ridging height, and uniform elongation were measured.
- ⁇ phase rate volume fraction of austenite phase
- ridging height As a comparative material, Steel No.
- the relationship between texture and ridging height was examined using the normal SUS329J4L product shown in FIG.
- the texture of the steel and the volume fraction of the ⁇ phase were changed depending on the hot rolling conditions and the cold-rolled sheet annealing temperature performed in the range of 900 to 1200 ° C.
- the texture of the plate surface at the center of the plate thickness was determined by identifying the crystal structure of fcc ( ⁇ phase) and bcc (ferrite phase) by the EBSP method and measuring the crystal orientation of the ferrite phase. .
- the measurement magnification was x100. From the measurement results of the crystal orientation, the ferrite phase crystal grains (crystal orientation grains) having a crystal orientation oriented at ND // ⁇ 111 ⁇ ⁇ 10 ° and the crystal orientations oriented at ND // ⁇ 101 ⁇ ⁇ 10 ° are obtained.
- the total area ratio of the crystal grains (crystal orientation grains) of the ferrite phase was determined.
- ND // ⁇ 111 ⁇ ⁇ 10 ° means that ⁇ 111 ⁇ is oriented in a range of ⁇ 10 ° to + 10 ° with respect to the plate surface (ND)
- ND // ⁇ 101 ⁇ ⁇ 10 ° means that ⁇ 101 ⁇ is oriented in the range of ⁇ 10 ° to + 10 ° with respect to the plate surface (ND).
- the area ratio of the crystal grain of the ferrite phase which has the said crystal orientation is an area ratio with respect to the whole plate surface.
- the volume fraction of the ⁇ phase ( ⁇ phase ratio) was determined by observing with an optical microscope after etching the plate section with resin and polishing it with a red blood salt solution (trade name: Murakami Reagent).
- the ferrite phase When etched with an erythrocyte salt solution, the ferrite phase can be identified as gray and the austenite phase as white.
- the ridging height was obtained by collecting a JIS No. 5 tensile test piece parallel to the rolling direction and measuring the surface undulation after 16% tension with a roughness meter. For uniform elongation, a JIS 13B tensile test piece was taken in parallel with the rolling direction, and the elongation until constriction occurred at a tensile speed of 10 mm / min (range of tensile speed defined by JIS Z 2241) was determined.
- FIG. 1 shows the total area ratio of the ferrite phase crystal grains having the crystal orientations of ND // ⁇ 111 ⁇ ⁇ 10 ° and ND // ⁇ 101 ⁇ ⁇ 10 ° described above (hereinafter, ⁇ 111 ⁇ + ⁇ 101 ⁇ area ratio) and the ridging height. From FIG. 1, when the ⁇ 111 ⁇ + ⁇ 101 ⁇ area ratio is 10% or more, the ridging height becomes 5 ⁇ m or less as a target, and surface undulations are visually observed as in the austenitic stainless steel represented by SUS304. It becomes impossible. In order to reduce the ridging height, it is effective to increase the ⁇ 111 ⁇ + ⁇ 101 ⁇ area ratio of the ferrite phase.
- the low alloy type dual phase with low Ni and reduced Mo Steel (steel Nos. 1 and 2) is superior.
- the Ni content and the N content are lower (steel No. 1 is more preferable). This reason is considered to be related to the recrystallization state of the ferrite phase during hot rolling and subsequent annealing. That is, by aiming at low alloying, recrystallization of the ferrite phase is promoted, and ⁇ 111 ⁇ , which is the recrystallization orientation of the ferrite phase, develops in the cold rolled material after hot-rolled sheet annealing.
- FIG. 2 shows the relationship between the above-described ⁇ phase ratio and uniform elongation. From FIG. 2, in the range of ⁇ phase ratio of 15 to 70%, the uniform elongation is 30% or more, which is the target, and the ferrite system with improved corrosion resistance and workability by adding known stabilizing elements such as Ti and Nb. It reaches to the extent that it is inferior to austenitic stainless steel, far exceeding stainless steel.
- the crystal orientation of the ferrite phase is affected by hot rolling conditions in addition to the influence of the components described in (b) above.
- rough rolling is performed in a relatively low temperature range where the amount of austenite phase is large, cracks may be induced due to extreme strain concentration in the soft ferrite phase.
- the ⁇ phase ratio is affected by the finish annealing temperature after cold rolling.
- the finish annealing temperature is preferably in the range of 900 to 1200 ° C. in order to control the ⁇ phase ratio that maximizes the uniform elongation.
- the present inventions (1) to (8) have been completed based on the findings (a) to (g).
- the ferrite-austenitic stainless steel of the present invention has the ferrite orientation crystal orientation ( ⁇ 111 ⁇ + ⁇ 101 ⁇ area ratio) which is the governing factor in order to combine the ridging resistance and workability targeted by the present invention. And ⁇ phase ratio.
- the crystal orientation of the ferrite phase can be determined by the EBSP method.
- the EBSP method is described in, for example, a microscope; Seiichi Suzuki, Vol. 39, no. 2, 121-124, the crystal structure of the austenite phase (fcc) and the ferrite phase (bcc) can be identified, and the crystal orientation of the ferrite phase can be visualized.
- the crystal orientation of the ferrite phase which is the governing factor of ridging resistance, that is, crystals oriented at ND // ⁇ 111 ⁇ ⁇ 10 ° and ND // ⁇ 101 ⁇ ⁇ 10 °.
- the total area ratio ( ⁇ 111 ⁇ + ⁇ 101 ⁇ area ratio) of the ferrite phase crystal grains having an orientation can be obtained.
- the numerical notation of ⁇ 111 ⁇ or ⁇ 101 ⁇ follows the notation of the inverse pole figure shown by the above-described analysis system of the EBSP method.
- the sample was a plate surface (ND) near the plate thickness center of the steel plate, and the measurement magnification was 100.
- ⁇ Means a notation of a Miller index indicating a crystal plane. That is,-is a negative sign, (-1-1-1), (-111), (1-11), (11-1), (-1-11), (1-1-1), etc.
- the equivalent crystal plane is represented by ⁇ 111 ⁇ using ⁇ .
- the area ratio is 10% or more in order to obtain the target ridging resistance of the present invention. As is apparent from the experimental results of FIG. 1, it is preferably 12% or more, more preferably 20% or more.
- the upper limit is not particularly specified, but it is difficult to obtain a ⁇ 111 ⁇ + ⁇ 101 ⁇ area ratio exceeding 50% from the viewpoint of workability ( ⁇ phase ratio) and manufacturability described later. Therefore, the upper limit is preferably 50% or less.
- the ⁇ phase ratio can be determined based on observation with an optical microscope. After embedding and polishing the cross section of the steel sheet in a resin, an etching process is performed so that the ferrite phase and the austenite phase can be distinguished. That is, when etched with a red blood salt solution (trade name: Murakami Reagent), the ferrite phase can be identified as gray and the austenite phase as white.
- the ⁇ phase ratio can be measured by taking a visual field observed with an optical microscope into an image analysis apparatus and performing a binarization process.
- Optical microscope observation is a magnification that can binarize the ferrite phase and austenite phase (for example, 400 times, if the magnification is low, the phase boundary may be unclear and binarization may not be possible) to eliminate bias toward a specific field of view. Therefore, the observation area used for image processing was set to 1 mm 2 or more.
- ⁇ phase ratio is in the range of 15 to 70% in order to ensure the target processability of the present invention.
- ⁇ phase ratio is less than 15% or more than 70%, it is difficult to obtain a target uniform elongation of 30% or more in the low alloy type duplex steel targeted by the present invention.
- the preferable range of the ⁇ phase ratio is 30 to 60%, as is apparent from the experimental results of FIG. A more preferred range is 40 to 60%.
- the ferrite-austenitic stainless steel having a metal structure of the present invention has a ridging height of 5 ⁇ m or less, a uniform elongation that is an index of workability is 30% or more, ridging resistance comparable to SUS304, and ferritic stainless steel. Processability close to or equivalent to SUS304, which is significantly higher, can be obtained.
- the ridging height is a value obtained by taking a JIS No. 5 tensile test piece in parallel with the rolling direction and measuring the surface undulation after 16% tension with a roughness meter. The reason for limitation regarding the component (B) will be described below.
- the metal structure described in (A) is affected by the components.
- the components are preferably in the following ranges.
- ⁇ phase ratio volume fraction of the austenite phase
- ⁇ phase ratio volume fraction of the austenite phase
- ⁇ phase ratio volume fraction of the austenite phase
- containing 0.001% or more is preferable.
- it is made 0.1% or less. More preferably, it is 0.05% or less.
- Cr is an essential element that ensures corrosion resistance, and in order to ensure corrosion resistance, the lower limit must be 17%. However, if it exceeds 25%, toughness and elongation are reduced, and it is difficult to produce an austenite phase in the steel. Therefore, it is made 25% or less. From the viewpoint of corrosion resistance, workability and manufacturability, the preferred range is 19 to 23%. A more preferred range is 20 to 22%.
- Si may be added as a deoxidizing element. In order to acquire the said effect, it is preferable to contain 0.01% or more. On the other hand, when Si exceeds 1%, the solid solubility of N, which is an essential element of the present invention, is lowered, and sensitization due to nitride precipitation may be induced to significantly reduce the corrosion resistance. Furthermore, it becomes difficult to ensure the workability that is the object of the present invention. Therefore, it is 1% or less. Excessive addition leads to an increase in refining costs. From the viewpoint of processability and manufacturability, the preferred range is 0.02 to 0.6%. A more preferable range is 0.05 to 0.2%.
- Mn is an element that increases the volume fraction of the austenite phase, concentrates in the austenite phase, adjusts the components of the austenite phase itself, and is effective in developing workability. Furthermore, it is also an effective element from the viewpoint of increasing the solid solubility of N in the austenite phase. It is also an effective element as a deoxidizer. In order to acquire the said effect, it is preferable to contain 0.5% or more. However, if it exceeds 3.7%, it leads to a decrease in corrosion resistance. Therefore, it is 3.7% or less. From the viewpoint of workability, corrosion resistance and manufacturability, the preferred range is 2 to 3.5%. A more preferred range is 2.5 to 3.3%.
- Ni like Mn, increases the volume fraction of the austenite phase and concentrates in the austenite phase to adjust the components of the austenite phase itself and is an effective element for expressing workability. In order to acquire the said effect, it is necessary to contain 0.6% or more. However, if it exceeds 3%, the raw material cost is increased, and recrystallization of the ferrite phase in rough rolling becomes insufficient, which may lead to a decrease in ridging resistance as an object of the present invention. Therefore, it is 3% or less. From the viewpoint of ridging resistance, processability, and economical efficiency which are the objects of the present invention, a preferred range is 0.7 to 2%. A more preferable range is 0.9 to 1.7%.
- Cu is an austenite-forming element like Mn and Ni, and has the same effect on the expression of workability. Furthermore, it is an element effective for improving the corrosion resistance. In order to acquire the said effect, it is necessary to contain 0.1% or more. However, if it exceeds 3%, the cost of raw materials is increased, and similarly to Ni, the ridging resistance as the object of the present invention may be lowered. Therefore, it is 3% or less. From the viewpoint of ridging resistance, processability, and economy, which are the object of the present invention, the preferred range is 0.3 to 1%. A more preferable range is 0.4 to 0.6%.
- N is a strong austenite generating element and is an effective element for the expression of workability. Moreover, it is an element which improves the corrosion resistance by dissolving in the austenite phase. In order to acquire the said effect, it is necessary to contain 0.06% or more. However, when it is 0.15% or more, there is a possibility that the ridging resistance aimed at by the present invention may be lowered. Therefore, the content is less than 0.15%. Further, the addition of N reduces blow-fall generation and hot workability during melting.
- the preferred range is 0.07 to 0.14% from the viewpoint of ridging resistance, processability and manufacturability which are the objects of the present invention. A more preferable range is 0.08 to 0.12%.
- Al is a strong deoxidizer and can be added as appropriate. In order to acquire the said effect, adding 0.001% or more is preferable. However, if it exceeds 0.2%, nitrides are formed, which may lead to generation of surface flaws and deterioration of ridging resistance and workability, which are the object of the present invention. Therefore, the upper limit in the case of adding is made 0.2% or less. The preferred range when added is 0.005 to 0.1%.
- Mo may be added to improve the corrosion resistance.
- the content is preferably 0.2% or more. However, if it exceeds 1%, the ridging resistance intended by the present invention may be lowered. Therefore, the upper limit when added is 1% or less. A preferable range in the case of adding is 0.2 to 0.8%.
- Ti and Nb may be added to suppress sensitization caused by C or N and improve corrosion resistance.
- adding it is preferable to set it as 0.01% or more, respectively. However, if it exceeds 0.5%, the economic efficiency is impaired, and the ridging resistance and processability of the present invention may be impaired. Therefore, it is preferable that the upper limit in the case of adding is 0.5% or less.
- a preferable range in the case of addition is 0.03 to 0.3%, respectively.
- B, Ca, Mg may be added in a timely manner in order to improve hot workability.
- adding it is preferable to make it 0.0002% or more, respectively. However, if it exceeds 0.01%, the manufacturability may be significantly impaired. Therefore, the upper limit when added is 0.01% or less.
- the preferable range in the case of adding is 0.0005 to 0.005%, respectively.
- Rare earth elements one or more selected from Sc, Y, and lanthanoids La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu
- B, Ca, and Mg Rare earth elements
- it may be added in a timely manner in order to improve hot workability.
- it is preferable to make it 0.005% or more, respectively.
- the productivity and economy may be impaired. Therefore, the upper limit in the case of adding is 0.5% or less.
- a preferable range in the case of addition is 0.02 to 0.2%.
- the stainless steel of this invention contains iron and an unavoidable impurity as a remainder other than said component.
- P and S are elements harmful to hot workability and corrosion resistance.
- P is preferably 0.1% or less. More preferably, it is 0.05% or less.
- S is preferably 0.01% or less. More preferably, it is 0.005% or less.
- the crystal orientation of the ferrite phase may be influenced by conditions of hot rolling (hot rough rolling and hot finish rolling) in addition to the influence of components.
- hot rolling hot rough rolling and hot finish rolling
- the slab heating performed prior to hot rolling is preferably 1150 to 1300 ° C.
- the temperature is lower than 1150 ° C., the amount of austenite phase generated is increased, and when it exceeds 1300 ° C., the crystal grain size of the ferrite phase becomes coarse, which may impair manufacturability.
- the temperature is in the range of 1180 to 1270 ° C., more preferably 1200 to 1250 ° C.
- Rough rolling preferably has a start temperature of 1150 ° C. or higher and an end temperature of 1050 ° C. or higher. More preferably, in rough rolling, the start temperature is set to 1200 ° C. or higher and the end temperature is set to 1100 ° C. or higher.
- onset temperature of 1150 ° C. or higher deformation concentrates on the soft ferrite phase and promotes recrystallization of the ferrite phase.
- cracking may be induced by extreme strain concentration on the soft ferrite phase.
- the upper limit value of the starting temperature is preferably 1250 ° C., whereby the texture can be controlled to the target state of the present invention.
- the upper limit of the end temperature is preferably 1100 ° C., whereby the texture can be controlled to the state intended by the present invention.
- the pass with a reduction rate of 20% or more should be 1 ⁇ 2 or more of the total pass, the reduction rate of 1 pass with the highest reduction rate should be 50% or more, or the total of the reduction rates of 2 passes with a high reduction rate Is more preferably 50% or more.
- the end temperature of the hot finish rolling after the hot rough rolling is 900 ° C. or more from the viewpoint of avoiding cracks during rolling. More preferably, it is 950 degreeC or more, More preferably, it is 1000 degreeC or more.
- the annealing temperature is preferably in the range of 950 to 1150 ° C.
- the temperature is lower than 950 ° C., recrystallization of the ferrite phase may be insufficient.
- the temperature exceeds 1150 ° C. the crystal grain size of the ferrite phase becomes coarse, and cracks may occur at the phase boundary of the ferrite phase / austenite phase during cold rolling. More preferably, the temperature is in the range of 1000 to 1100 ° C.
- Cold rolling may be performed once by hot-rolled sheet annealing or twice or more with intermediate annealing.
- the intermediate annealing temperature may be the same as the above-described hot rolled sheet annealing temperature.
- the total rolling reduction of cold rolling is set to 50% or more in order to ensure ridging resistance by promoting recrystallization in cold rolled sheet annealing. If it is less than 50%, the target ridging resistance may not be achieved.
- the upper limit of the total rolling reduction is not particularly specified, but is preferably 90% or less. If it exceeds 90%, there is a risk of inducing ear cracks during cold rolling.
- ⁇ phase ratio is affected by the finish annealing temperature after cold rolling.
- the ⁇ phase ratio needs to be in the range of 15 to 70%, preferably 30 to 60%, in order to ensure the target processability of the present invention.
- the finish annealing temperature should be in the range of 900 to 1200 ° C. If it is less than 900 ° C., the cold rolled sheet itself may be insufficiently annealed. When the temperature exceeds 1200 ° C., it becomes difficult to obtain a target uniform elongation due to the coarsening of crystal grains and a decrease in the ⁇ phase ratio. More preferably, it is in the range of 950 to 1150 ° C., and more preferably 950 to 1050 ° C.
- Hot rolling was performed under other conditions in addition to the preferable conditions specified in the present invention. These hot-rolled steel sheets were annealed and pickled at 1000 ° C., and then the thickness was set to 1 mm by one cold rolling, and the manufacturing method in which finish annealing was performed as a basis was also performed under other conditions.
- the other conditions are those in which the annealing and pickling of the hot-rolled steel sheet have been completed (hot-rolled annealed sheet) and the finish annealing is performed with a thickness of 3 mm by one cold rolling.
- Various test pieces were collected from the obtained hot-rolled annealed plate and cold-rolled annealed plate, and the crystal orientation, ⁇ phase ratio, ridging height and uniform elongation of the ferrite phase were evaluated.
- the crystal orientation of the ferrite phase the ⁇ 111 ⁇ + ⁇ 101 ⁇ area ratio was determined by the EBSP method.
- the ⁇ phase ratio was obtained by observing an optical microscope after embedding and polishing a cross section of a steel sheet in a resin, performing an etching treatment that can distinguish between a ferrite phase and an austenite phase.
- the ridging height was obtained by collecting a JIS No. 5 tensile test piece parallel to the rolling direction and measuring the surface undulation after 16% tension with a roughness meter.
- the uniform elongation was also measured by a method in which a JIS 13B tensile test piece was taken in parallel with the rolling direction and the elongation until constriction occurred at a tensile speed of 10 mm / min (the range of the tensile speed specified by JIS Z 2241) was measured.
- Tables 3 and 4 The production conditions are shown in Tables 3 and 4, and the structure and characteristics of the finish annealed plate are shown in Tables 5 and 6.
- Tables 5 and 6 As a comparative example, the ridging height and uniform elongation of an actual SUS304 product having a thickness of 1 mm are also shown.
- T 1 indicates the rough rolling start temperature.
- T 2 represents the rough rolling end temperature.
- T 3 indicates the finish rolling end temperature.
- “Two-pass rolling reduction” indicates the total rolling reduction of two consecutive passes in which the rolling reduction is set high during rough rolling.
- “*” Indicates that cold rolling was performed twice including intermediate annealing.
- “M” indicates that a martensite phase was observed.
- the underline means that the manufacturing method defined in the present invention and the target organization / characteristic requirements are not satisfied.
- Sample No. Nos. 6, 7, 9 to 25, 27, and 29 satisfy both the preferable components and the production method defined in the present invention. These examples of the present invention satisfy the structure defined by the present invention, that is, the ⁇ 111 ⁇ + ⁇ 101 ⁇ area ratio of 10% or more and the ⁇ phase ratio of 15 to 70%, and the uniform ridging height of 5 ⁇ m or less targeted by the present invention. The elongation reached 30% or more.
- the ferritic / austenitic stainless steel obtained by carrying out both the preferred components and the production method specified in the present invention has ridging resistance comparable to SUS304 and workability close to or equivalent to SUS304. Yes.
- Sample No. 8 26, and 28 have the preferable component prescribed
- Sample No. 1 and 4 have the components specified by the present invention, and are carrying out the preferred production method specified by the present invention. These satisfy the structural requirements defined in the present invention, and the ridging height and uniform elongation targeted by the present invention are obtained. Thus, in order to obtain the target characteristics of the present invention, if the preferred production method defined in the present invention is carried out, it may not be necessary to limit the components to the preferred ranges defined in the present invention.
- Sample No. Nos. 37 to 42 have preferable components specified by the present invention, and a preferred hot rolling manufacturing method specified by the present invention is carried out. These satisfy the requirements of the structure defined in the present invention, and the ridging height and uniform elongation which are the targets of the present invention are obtained. From this, in order to obtain the target characteristics of the present invention, the preferred components specified in the present invention and the conditions for hot rolling are implemented, and the manufacturing method related to cold rolling after hot rolling is specified in the present invention. In some cases, it is not necessary to limit to the preferable range.
- a ferritic / austenitic stainless steel sheet having ridging resistance comparable to that of SUS304, excellent workability close to or equivalent to SUS304, and particularly having a uniform elongation of 30% or more.
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Abstract
Description
本願は、2008年2月5日に出願された日本国特許出願第2008-25112号及び2008年12月25日に出願された日本国特許出願第2008-330428号に対し優先権を主張し、その内容をここに援用する。
また、関係するものとして、特許文献5の実施例には、N量を0.06%未満とし、フェライト相を母相として残留オーステナイト相を20%未満含む延性に優れたフェライト系ステンレス鋼が開示されている。
これら文献において、フェライト相は、熱延板焼鈍や冷間圧延と焼鈍を繰り返しても圧延集合組織を継承し、再結晶集合組織を得るのが困難であると報告されている。ここで、圧延集合組織とは、{001}方位ならびに{112}方位への集積が強いことを意味し、フェライト系ステンレス鋼ではこのような方位への集積が強いとリジングが発生しやすい。従って、二相鋼で発生するリジングも、フェライト系ステンレス鋼と同様に圧延集合組織への集積が強くフェライト相の再結晶が不足していることによると考えられる。
その結果、リジング高さの低減には、フェライト相の{111}+{101}面積率(ND//{111}±10°を満たす結晶方位を有する結晶粒(結晶方位粒)とND//{101}±10°を満たす結晶方位を有する結晶粒(結晶方位粒)の合計の面積率)を増やすことが有効であり、フェライト相の{111}+{101}面積率を増やすには、高合金型の二相鋼と比較し、低合金型の二相鋼の方が優位であることを知見した。また、オーステナイト相の体積分率(γ相率%)が15~70%の範囲において、均一伸びは目標とする30%以上となり、均一伸びは、γ相の加工誘起マルテンサイト変態により上昇することを知見した。
まず、本発明を完成させるに至った代表的な実験結果について説明する。
ここで、ND//{111}±10°とは、板面(ND)に対して、{111}が-10°~+10°の範囲に配向していることを意味し、ND//{101}±10°とは、板面(ND)に対して、{101}が-10°~+10°の範囲に配向していることを意味する。また、上記結晶方位を有するフェライト相の結晶粒の面積率は、板面全体に対する面積率である。
γ相の体積分率(γ相率)は、板断面を樹脂に埋め込み研磨した後、赤血塩溶液(商標名:村上試薬)でエッチングして光学顕微鏡観察により求めた。赤血塩溶液にてエッチングすると、フェライト相は灰色、オーステナイト相は白色で判別することができる。
リジング高さは、圧延方向と平行にJIS5号引張試験片を採取し、16%引張り後の表面起伏を粗さ計で測定して求めた。
均一伸びは、圧延方向と平行にJIS13B引張試験片を採取し、引張速度10mm/分(JIS Z 2241で規定する引張速度の範囲)でくびれが生じるまでの伸びを求めた。
図1から、{111}+{101}面積率が10%以上の場合、リジング高さは目標とする5μm以下となり、SUS304に代表されるオーステナイト系ステンレス鋼と同様に目視にて表面起伏は見られなくなる。リジング高さの低減には、フェライト相の{111}+{101}面積率を増やすことが有効である。
この理由は、熱間圧延時やその後の焼鈍によるフェライト相の再結晶状態に関係していると考えられる。すなわち、低合金化を指向することにより、フェライト相の再結晶が促進し、熱延板焼鈍後の冷間圧延素材においてフェライト相の再結晶方位である{111}が発達する。
図2から、γ相率が15~70%の範囲において、均一伸びは目標とする30%以上となり、公知のTiやNbなどの安定化元素の添加により、耐食性と加工性を高めたフェライト系ステンレス鋼を遥かに超える、オーステナイト系ステンレスと遜色ない程度まで到達する。
この理由は、同一成分の鋼においても、γ相率によってγ相自体の成分が異なり、それにともない加工誘起マルテンサイト変態の生成量が変化するためと考えられる。そのため、加工性の指標とする均一伸び30%以上を得るという視点から、γ相率の上下限を考慮する必要がある。
この理由は、粗圧延において軟質なフェライト相へ変形が集中して、フェライト相の再結晶が促進するためである。一方、オーステナイト相の生成量が多い比較的低温域で粗圧延すると、軟質なフェライト相への極度の歪集中により割れを誘発する恐れがある。さらに、粗圧延では、フェライト相の再結晶を促進させるために、圧延時のパス間時間を取る、圧下率を大きくして歪を蓄積することが好ましい。粗圧延に続く仕上げ圧延において、圧延時の割れを回避する視点から、圧延終了温度を低くするのは好ましくない。
(A)金属組織に関する限定理由を以下に説明する。
{111}や{101}の数値表記は、上述したEBSP法の解析システムで示される逆極点図の表記に従う。試料は、鋼板の板厚中心付近の板面(ND)、測定倍率は100とした。{}は、結晶面を示すミラ-指数の表記を意味する。すなわち、-を負の符号とし、(-1-1-1)、(-111)、(1-11)、(11-1)、(-1-11)、(1-1-1)などの等価な結晶面は{}を使用して{111}で代表する。
光学顕微鏡観察は、フェライト相とオーステナイト相の2値化処理ができる倍率(例えば400倍、倍率が低いと相境界が不明瞭で2値化できない場合がある)とし、特定視野への偏りをなくすために画像処理に供する観察面積を1mm2以上とした。
(B)成分に関する限定理由を以下に説明する。
不可避的不純物の一部としてP、Sを下記の範囲で含有してもよい。P、Sは、熱間加工性や耐食性に有害な元素である。Pは、0.1%以下とするのが好ましい。より好ましくは0.05%以下である。Sは、0.01%以下とするのが好ましい。より好ましくは0.005%以下である。
フェライト・オーステナイト系ステンレス鋼において、(A)項に述べた金属組織を得るには、前記(B)項の成分を有していれば、特に限定しなくても良い場合がある。より好ましくは、前記(B)項の成分を有し、加えて以下の製造条件とすることが好ましい。
そのために熱間圧延に先立って実施するスラブ加熱は1150~1300℃とすることが好ましい。1150℃未満の場合、オーステナイト相の生成量が多くなり、1300℃超の場合、フェライト相の結晶粒径が粗大化して製造性を阻害する場合もある。より好ましくは1180~1270℃、さらに好ましくは1200~1250℃の範囲とする。
粗圧延は開始温度を1150℃以上、終了温度を1050℃以上とすることが好ましい。より好ましくは、粗圧延は開始温度を1200℃以上、終了温度を1100℃以上の範囲とする。
1150℃以上の開始温度では、軟質なフェライト相へ変形が集中して、フェライト相の再結晶が促進する。1150℃未満の開始温度では、軟質なフェライト相への極度の歪集中により割れを誘発する恐れがある。開始温度の上限値は、好ましくは1250℃であり、これにより集合組織を本発明の目的とする状態にコントロールすることができる。
1050℃以上の終了温度では、続く仕上げ圧延でのフェライト相の割れを回避することができる。終了温度の上限値は、好ましくは1100℃であり、これにより集合組織を本発明の目的とする状態にコントロールすることができる。
さらに、フェライト相の再結晶を促進させる手段として、各パスの間隔が2秒以上、60秒以下、好ましくは30秒以下である多パス圧延を繰り返すことが好ましい。その際、圧下率20%以上のパスを総パスの1/2以上とし、圧下率の最も大きい1パスの圧下率を50%以上とするか、あるいは圧下率の大きい2パスの圧下率の合計を50%以上とすることがより好ましい。
表2に成分を示すフェライト・オーステナイト系ステンレス鋳片を溶製した後、鋼塊とし、熱間圧延を行い板厚5.0mmの熱延鋼板とした。鋼No.1、2は、本発明で規定する成分を示すものである。鋼No.3~16は、本発明で規定する好ましい成分に該当するものである。鋼No.17~22は、本発明で規定する好ましい成分に該当し、微量元素を含有するものである。鋼No.23~29は、本発明で規定する成分に該当しないものである。なお、いずれの鋼も残部として、鉄と不可避的不純物を含む。
表2中、REMは希土類元素を示し、『-』は添加なしを意味し、下線は、請求項に規定する成分から外れるものを意味する。また、備考欄のAは、請求項1に該当する成分を示し、Bは、請求項2に該当する成分を示し、Cは、請求項3に該当する成分を示し、Dは、請求項1~3に該当しない成分を示す。
表3,4中、『T1』は、粗圧延開始温度を示す。『T2』は、粗圧延終了温度を示す。『T3』は、仕上げ圧延終了温度を示す。『2パス圧下率』は、粗圧延中で圧下率を高く設定した連続する2パスの圧下率の合計を示す。『*』は、中間焼鈍を含む2回の冷間圧延を行ったことを示す。『M』は、マルテンサイト相が観察されたことを示す。下線は、本発明で規定する製造方法や目標とする組織・特性要件から外れることを意味する。
Claims (8)
- 質量%にて、C:0.1%以下、Cr:17~25%、Si:1%以下、Mn:3.7%以下、N:0.06%以上、0.15%未満を含有し、
フェライト相とオーステナイト相からなる二相組織を有し、前記オーステナイト相の体積分率が15~70%であり、
板厚中心の板面(ND)において、ND//{111}±10°を満たす結晶方位を有するフェライト相の結晶粒とND//{101}±10°を満たす結晶方位を有するフェライト相の結晶粒が合計で10面積%以上存在することを特徴とする耐リジング性と加工性に優れたフェライト・オーステナイト系ステンレス鋼板。 - 質量%にて、C:0.1%以下、Cr:17~25%、Si:1%以下、Mn:3.7%以下、Ni:0.6~3%、Cu:0.1~3%、及びN:0.06%以上、0.15%未満を含有し、残部としてFeおよび不可避的不純物を含み、
フェライト相とオーステナイト相からなる二相組織を有し、前記オーステナイト相の体積分率が15~70%であり、
板厚中心の板面(ND)において、ND//{111}±10°を満たす結晶方位を有するフェライト相の結晶粒とND//{101}±10°を満たす結晶方位を有するフェライト相の結晶粒が合計で10面積%以上存在することを特徴とする耐リジング性と加工性に優れたフェライト・オーステナイト系ステンレス鋼板。 - 前記鋼が、さらに質量%にて、Al:0.2%以下、Mo:1%以下、Ti:0.5%以下、Nb:0.5%以下、B:0.01%以下、Ca:0.01%以下、Mg:0.01%以下、及び希土類元素:0.5%以下から選択される1種または2種以上を含有していることを特徴とする請求項2に記載の耐リジング性と加工性に優れたフェライト・オーステナイト系ステンレス鋼板。
- 引張試験における均一伸びが30%以上であることを特徴とする請求項1~3のいずれかに記載の耐リジング性と加工性に優れたフェライト・オーステナイト系ステンレス鋼板。
- 請求項1~3のいずれかに記載の鋼成分を有するステンレス鋼スラブを1150~1300℃で加熱する工程と、熱間粗圧延と前記熱間粗圧延後の熱間仕上げ圧延とを有する熱間圧延を前記加熱されたステンレス鋼スラブに施して熱延板とする工程と、前記熱延板を焼鈍する工程とを有し、
前記熱間粗圧延では、圧延開始温度を1150℃以上、圧延終了温度を1050℃以上とし、かつ各パスの間隔が2秒以上、60秒以下である多パス圧延を行い、
フェライト相とオーステナイト相からなる二相組織を有し、前記オーステナイト相の体積分率が15~70%であり、板厚中心の板面(ND)において、ND//{111}±10°を満たす結晶方位を有するフェライト相の結晶粒とND//{101}±10°を満たす結晶方位を有するフェライト相の結晶粒が合計で10面積%以上存在する鋼板を製造することを特徴とする耐リジング性と加工性に優れたフェライト・オーステナイト系ステンレス鋼板の製造方法。 - 前記熱間粗圧延において、圧下率20%以上のパスが総パスの1/2以上を占め、圧下率の最も大きい1パスの圧下率が50%以上となるか、あるいは圧下率の大きい2パスの圧下率の合計が50%以上となることを特徴とする請求項5に記載の耐リジング性と加工性に優れたフェライト・オーステナイト系ステンレス鋼板の製造方法。
- 前記熱間仕上げ圧延の終了温度を900℃以上とすることを特徴とする請求項5又は6に記載の耐リジング性と加工性に優れたフェライト・オーステナイト系ステンレス鋼板の製造方法。
- 前記焼鈍した熱延板に、1回の冷間圧延を50%以上の圧下率で行うか、または中間焼鈍を挟む2回以上の冷間圧延を、合計圧下率が50%以上の条件で行い、冷延板とする工程と、前記冷延板に900~1200℃で仕上げ焼鈍を行う工程とを更に有することを特徴とする請求項5~7のいずれかに記載の耐リジング性と加工性に優れたフェライト・オーステナイト系ステンレス鋼板の製造方法。
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KR101227274B1 (ko) | 2013-01-28 |
JP5337473B2 (ja) | 2013-11-06 |
EP2251449B1 (en) | 2017-12-13 |
JP2009209448A (ja) | 2009-09-17 |
EP2251449A1 (en) | 2010-11-17 |
CN101903554A (zh) | 2010-12-01 |
ES2655362T3 (es) | 2018-02-19 |
CN101903554B (zh) | 2012-06-27 |
KR20100097699A (ko) | 2010-09-03 |
US8226780B2 (en) | 2012-07-24 |
US20110000589A1 (en) | 2011-01-06 |
EP2251449A4 (en) | 2016-07-13 |
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