WO2021206047A1 - スラブおよびその連続鋳造方法 - Google Patents

スラブおよびその連続鋳造方法 Download PDF

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Publication number
WO2021206047A1
WO2021206047A1 PCT/JP2021/014477 JP2021014477W WO2021206047A1 WO 2021206047 A1 WO2021206047 A1 WO 2021206047A1 JP 2021014477 W JP2021014477 W JP 2021014477W WO 2021206047 A1 WO2021206047 A1 WO 2021206047A1
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Prior art keywords
mass
slab
content
temperature
steel
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Ceased
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PCT/JP2021/014477
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English (en)
French (fr)
Japanese (ja)
Inventor
慎 高屋
謙治 田口
加藤　雄一郎
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Nippon Steel Corp
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Nippon Steel Corp
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Application filed by Nippon Steel Corp filed Critical Nippon Steel Corp
Priority to US17/913,367 priority Critical patent/US12599957B2/en
Priority to JP2022514060A priority patent/JP7222443B2/ja
Priority to BR112022018829A priority patent/BR112022018829A2/pt
Priority to CN202180025228.4A priority patent/CN115380129B/zh
Priority to KR1020227035031A priority patent/KR102792419B1/ko
Publication of WO2021206047A1 publication Critical patent/WO2021206047A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • B22D11/1226—Accessories for subsequent treating or working cast stock in situ for straightening strands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • B22D11/124—Accessories for subsequent treating or working cast stock in situ for cooling
    • 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
    • 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
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium

Definitions

  • the present invention particularly relates to a steel slab containing a large amount of Al and a method for continuously casting the slab.
  • the present application claims priority based on Japanese Patent Application No. 2020-069313 filed in Japan on April 7, 2020, the contents of which are incorporated herein by reference.
  • Straightening stress is applied to the slab at the straightening point in the curved or vertical bending type continuous casting machine.
  • Lateral cracks are known to occur along the old austenite grain boundaries on the surface layer of slabs, and are in the form of austenite grains embrittled by precipitation of AlN, NbC, etc., or film forms formed along the old austenite grain boundaries. Lateral cracks occur due to the concentration of straightening stress on the ferrite. Further, this lateral crack is likely to occur particularly in a temperature range slightly higher than the phase transformation region from austenite to ferrite, but lateral crack also occurs even in a non-transformation composition.
  • a method is adopted in which the surface temperature of the slab is controlled so as to avoid a temperature range (embrittlement temperature range) in which ductility decreases at the straightening point, and the occurrence of lateral cracks is suppressed.
  • Patent Document 1 Ti is added in an amount of more than 0.010% by mass and 0.025% by mass or less, and the surface temperature of the slab in the upper part of the secondary cooling zone having a solidification shell thickness of the slab of 10 mm to 30 mm is AlN.
  • a technique for setting the temperature above the precipitation start temperature of the above is disclosed.
  • An object of the present application is to provide a slab having excellent manufacturability that does not require lateral crack maintenance for a slab obtained by continuous casting.
  • Patent Document 1 targets low-carbon aluminum killed steel having an Al concentration of 0.063% by mass to 0.093% by mass, and a high-Al steel containing 0.20% by mass or more of Al. The effect is unknown.
  • the present invention provides a slab of high Al steel containing 0.20% by mass or more of Al, which has excellent surface crack resistance, and a method for continuously casting the slab. The purpose.
  • the present inventors focused on the fact that high-temperature embrittlement in slabs of high-Al steel was caused by a large amount of AlN precipitation, and investigated the precipitation control of nitrides. Specifically, the high-temperature ductility of steel added with Zr, which has a higher N-fixing ability than Al, was investigated. As a result, it was found that the high temperature ductility was greatly improved by adding a small amount of Zr. It was found that Zr produces ZrN immediately after solidification and immobilizes N, so that a large amount of AlN precipitation at the grain boundaries can be suppressed and high-temperature embrittlement of high-Al steel can be drastically improved.
  • (1) C A slab of high Al steel containing 0.02% by mass to 0.50% by mass and 0.20% by mass to 2.00% by mass of Al.
  • [Zr], [Ti], [Al], and [N] each represent the content (mass%) in the slab.
  • the slab is further The item according to any one of (1) to (3) above, which contains Si: 0.20% by mass to 3.00% by mass, and Mn: 0.50% by mass to 4.00% by mass. Described slab.
  • a method for continuously casting a slab which comprises bending and straightening the slab in a surface temperature range of 800 ° C. to 1000 ° C. when bending and straightening the slab.
  • the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value. Numerical values indicated by “greater than” or “less than” do not include that value as the lower or upper limit.
  • the present inventors considered adding Zr in order to straighten the slab at the straightening point in a general temperature range. ..
  • steel type D is an example in which both Zr and Ti are contained in a relatively large amount.
  • the balance of each is composed of Fe and impurities.
  • impurity refers to an ore, scrap, or a substance mixed from the manufacturing environment when the slab is industrially manufactured.
  • the tensile temperature was changed in the range of 700 ° C. to 1100 ° C., and the cross-sectional shrinkage rate (RA: Reduction Area) (%) was determined for these four types of steel. Specifically, based on JIS G0567: 2020, each steel grade produced by 25 kg of vacuum melting was forged to ⁇ 15 and then made into a ⁇ 10 tensile test piece (parallel portion 90 mm).
  • a high-frequency induction heating type high-temperature tensile test device having a cold crucible is used, and the tensile test piece is cooled to a predetermined tensile temperature at a cooling rate of 1.0 ° C./s after melting, and then brought to a predetermined tensile temperature. While holding, tension was applied until fracture at a strain rate of 3.3 ⁇ 10 -4 (1 / s).
  • the difference between the fractured surface area of the tensile test piece after the test and the cross-sectional area of the test piece before the test was calculated by dividing the cross-sectional area of the test piece before the test by the percentage (%) as the cross-sectional shrinkage rate (throttle).
  • the tensile test results are shown in Fig. 1.
  • the circles in FIG. 1 represent the cross-sectional shrinkage rate of the steel type D, and the triangular marks represent the cross-sectional shrinkage rate of the steel type C.
  • the diamond-shaped mark represents the cross-sectional shrinkage rate of the steel type B, and the square mark represents the cross-sectional shrinkage rate of the steel type A.
  • R. A If is 50% or more, it can be considered that lateral cracks do not occur due to the straightening stress. Since it is easy to operate the straightening point in the range of 800 to 1000 ° C., lateral cracking is prevented by adding Zr and Ti without performing temperature control to avoid the embrittlement temperature range. I found that I could do it.
  • the slab according to the present embodiment is a high Al steel containing 0.20% by mass to 2.00% by mass of Al, and is mainly intended for thin plates.
  • the preferable lower limit value of Al is 0.50% by mass.
  • the Al content is 0.50% by mass or more, lateral cracks are likely to occur as described above, so that the effect of the present embodiment can be obtained more remarkably.
  • the slab according to the present embodiment contains an amount of Zr and Ti that satisfies the following equation (1).
  • [Zr], [Ti], [Al], and [N] each represent the content in the slab (mass% with respect to the total mass of the slab).
  • the steel type C having a small amount of Zr satisfied the condition of the formula (1), but the cross-sectional shrinkage rate was low.
  • Ti is an element that fixes N like Zr and Al, and the affinity with N is in the order of Zr> Ti> Al.
  • TiN cannot be precipitated from a high temperature, and a large amount of AlN is precipitated, so that the improvement in high temperature ductility is small and no effect can be obtained.
  • N is fixed as (Zr, Ti) N which is thermally stable at high temperature, and high temperature ductility is greatly improved.
  • N is fixed from a higher temperature than the addition of Ti alone. High temperature ductility is improved.
  • Zr and Ti as described above, N is fixed in the composition of (Zr, Ti) N.
  • the slab according to the present embodiment has a Zr content that satisfies the following equation (2). 0.0010% by mass ⁇ [Zr] ... (2)
  • the upper limit of the Zr content is not particularly limited, but since Zr is an expensive metal, the Zr content is preferably 0.0050% by mass or less from the viewpoint of suppressing the amount of Zr added as much as possible. Further, the upper limit and the lower limit of the N content are not particularly limited, but the N content is 0.0080 mass as a range included through a normal refining step and a continuous casting step without intentionally increasing the N content. % Or less is preferable. Further, considering the cost in the refining step, the N content is preferably 0.0010% by mass or more. Further, although high Al steel is targeted, if the Al content exceeds 2.0% by mass, the Zr content and the Ti content also increase from the equation (1), which causes a wasteful cost increase. Therefore, the Al content is 0.20 to 2.00% by mass, preferably 0.50 to 2.00% by mass, more preferably 0.55 to 2.00% by mass, and further preferably 0.60 to 0.60 to 2.00% by mass. It is 2.00% by mass.
  • the following equation (3) is used in the ratio of [Ti] to [Zr] ([Ti] / [Zr]). It is preferable to satisfy. More preferably, the above ratio is 3 or more.
  • the upper limit is not particularly limited, but is preferably 10 or less. If [Ti] / [Zr] exceeds 10, the content of Zr decreases, so that N-fixing (Zr, Ti) N may not be sufficiently generated. [Ti] / [Zr] ⁇ 1 ⁇ ⁇ ⁇ (3)
  • the relationship between the contents of Zr, Ti, Al and N satisfies the above-mentioned equations (1) and (2).
  • the upper limit of the Ti content is not particularly limited, but the Ti content is preferably 0.5% by mass or less because the effect is saturated even if the Ti content is excessively contained, which causes a wasteful cost increase.
  • the lower limit of the Ti content is not particularly limited, but it is preferable that the Ti content is 0.0020% by mass or more as determined by the formulas (1) and (2).
  • the content of other elements is not particularly limited, but C, Si, and Mn are preferably contained in the following ranges, as long as they are in the range of C, Si, Mn, etc. shown in the present application. It was confirmed that the problem of the invention could be solved.
  • C 0.02% by mass to 0.50% by mass>
  • C is an element for improving the strength of steel, and if the C content is less than 0.02% by mass, it does not satisfy the use as a high-strength steel plate. Further, if the C content exceeds 0.50% by mass, the hardness becomes too high and the required bendability cannot be guaranteed. Therefore, the C content is set to 0.02% by mass to 0.50% by mass.
  • Si 0.20% by mass to 3.00% by mass>
  • Si is an element for improving the strength of steel, and if the Si content is less than 0.20% by mass, it does not satisfy the use as a high-strength steel plate. Further, if the Si content exceeds 3.00% by mass, the weldability is adversely affected. Therefore, the Si content is preferably 0.20% by mass to 3.00% by mass.
  • Mn 0.50% by mass to 4.00% by mass>
  • Mn is an element for improving the strength of steel, and if the Mn content is less than 0.50% by mass, it does not satisfy the use as a high-strength steel plate. Further, when the Mn content exceeds 4.00% by mass, since Mn is a segregating element, it may cause uneven strength in slabs and steel sheets. Therefore, the Mn content is preferably 0.50% by mass to 4.00% by mass.
  • the rest other than the above is iron and impurities, but some components may be contained instead of a part of iron.
  • the “impurity” refers to an ore as a raw material, scrap, or a substance mixed from a manufacturing environment or the like when the slab is industrially manufactured. Therefore, the slab according to the present embodiment has, for example, Al: 0.20 to 2.00%, Zr: 0.0050% or less, N: 0.0010 to 0.0080%, C: 0.02 in mass%.
  • N is fixed from a high temperature as compared with the addition of Ti alone, and the high temperature ductility is improved.
  • N is fixed with the composition of (Zr, Ti) N.
  • the mass ratio of (Zr, Ti) N in the total nitride in the surface layer portion of 5 mm in which the slab surface structure is uniformly present is preferably 50.0 mass% or more, preferably 60.0. It is more preferably 75.0% by mass or more, and further preferably 75.0% by mass or more. As a result, lateral cracks in the slab can be suppressed more reliably.
  • the mass ratio of (Zr, Ti) N in the surface layer portion of the slab is measured by the following method.
  • a sample for observing the surface layer of the slab (for example, 25 mm wide, 25 mm long and 25 mm thick from the center of the slab width) is cut out from the manufactured slab, and the surface at a depth of 5 mm from the surface of the slab is mirror-polished to prepare an observation surface.
  • the exposed surface is observed with SEM / EDS (scanning electron microscope equipped with an energy dispersive X-ray analyzer).
  • SEM / EDS scanning electron microscope equipped with an energy dispersive X-ray analyzer
  • examples of the nitrides that can be observed include (Zr, Ti) N, AlN, NbN, BN, VN and the like. Then, from the area ratio of (Zr, Ti) N in the total nitride obtained based on the specific result, it is assumed that the total nitride in the surface layer of the slab is uniformly distributed, and the area ratio is set to the volume. It can be regarded as a ratio, and the mass ratio of (Zr, Ti) N in the total nitride is obtained from the volume ratio.
  • the total mass of Zr and Ti in the nitride particles is 50% by mass or more with respect to the total mass of the nitride particles, and the mass% of Zr is 10% by mass or more. Defined as a nitride.
  • the average cooling rate in the surface layer portion of the slab is preferably 120 ° C./min or less, and more preferably 60 ° C./min or less.
  • the mass ratio of ZrN in the surface layer portion can be 50.0 mass% or more.
  • the mass ratio of ZrN in the surface layer portion can be 60.0 mass% or more.
  • the average cooling rate on the surface of the slab is measured by the following method. That is, the temperature of the surface of the central part in the width direction of the slab is measured by thermoelectric pair, etc., and the average cooling rate from that position to a depth of 5 mm (measurement position) from 1450 to 1000 ° C.
  • the average cooling rate in the surface layer portion of the slab is measured.
  • the average cooling rate at the surface layer of the slab can be adjusted by the amount of secondary cooling water.
  • the lower limit of the average cooling rate may be, for example, 20 ° C./min.
  • This condition is an example of a condition for confirming the feasibility and effect of the present invention, and the present invention is limited to the description of this example. is not it.
  • the present invention can be carried out by various means for achieving the object of the present invention without departing from the gist of the present invention.
  • the mass ratio of (Zr, Ti) N in the surface layer portion of the slab was measured by the method described above. Furthermore, in some slabs, the cross-sectional shrinkage rate (RA) (%) at 900 ° C. was determined as in the first experiment. Furthermore, the lateral cracks in the slab were evaluated according to the following evaluation criteria. That is, after grinding the front and back surfaces of the slab by 0.7 mm, the presence or absence of lateral cracks was visually confirmed. If no lateral cracks were present, it was evaluated as "0", and if one or more lateral cracks were present but could be removed by light care (additional grinding of 0.7 mm), it was evaluated as "1".
  • the underline in Tables 3A and 3B is an example in which the conditions of the present invention are not satisfied.
  • Tables 3A and 3B when the conditions of the equations (1) and (2) were satisfied, no lateral cracks were present regardless of the contents of Al and N.
  • the Zr content was insufficient, it was considered that a large amount of AlN remained, and lateral cracks were generated.
  • No. 7 it was considered that a large amount of AlN remained, and lateral cracks were generated.
  • the formula (1) or the formula (2) was not satisfied, the mass ratio of (Zr, Ti) N in the surface layer portion of the slab was also less than 50.0 mass%.
  • the mass ratio of (Zr, Ti) N in the surface layer portion of the slab is set to 60.0 mass by setting the average cooling rate in the surface layer portion of the slab to 60 ° C./min or less. It was possible to make it more than%. In this case, no defects due to lateral cracks were confirmed even after hot rolling.
  • the average cooling rate on the surface layer of the slab is 120 ° C./min, or when [Ti] / [Zr] is 10 or more even if the average cooling rate is 60 ° C./min or less
  • the slab The mass ratio of ZrN in the surface layer portion was 50.0 mass% or more and less than 60.0 mass%. In this case, no lateral cracks were confirmed before hot rolling, but defects due to lateral cracks were confirmed after hot rolling.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Continuous Casting (AREA)
PCT/JP2021/014477 2020-04-07 2021-04-05 スラブおよびその連続鋳造方法 Ceased WO2021206047A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US17/913,367 US12599957B2 (en) 2020-04-07 2021-04-05 Slab and continuous casting method thereof
JP2022514060A JP7222443B2 (ja) 2020-04-07 2021-04-05 スラブおよびその連続鋳造方法
BR112022018829A BR112022018829A2 (pt) 2020-04-07 2021-04-05 Placa de aço alto al, e, método de lingotamento contínuo da placa
CN202180025228.4A CN115380129B (zh) 2020-04-07 2021-04-05 板坯及其连续铸造方法
KR1020227035031A KR102792419B1 (ko) 2020-04-07 2021-04-05 슬래브 및 그 연속 주조 방법

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Application Number Priority Date Filing Date Title
JP2020069313 2020-04-07
JP2020-069313 2020-04-07

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US (1) US12599957B2 (https=)
JP (1) JP7222443B2 (https=)
KR (1) KR102792419B1 (https=)
CN (1) CN115380129B (https=)
BR (1) BR112022018829A2 (https=)
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