Title of the invention: Hot-rolled steel sheet and its manufacturing method
Technical field
[0001]
　The present invention relates to a hot-rolled steel sheet and a method for producing the same.
　The present application claims priority based on Japanese Patent Application No. 2018-197935 filed in Japan on October 19, 2018, the contents of which are incorporated herein by reference.
Background technology
[0002]
　In recent years, in order to reduce the amount of carbon dioxide (CO 2 ) emitted from automobiles, the weight of automobile bodies has been reduced by using high-strength steel plates. Further, in order to ensure the safety of passengers, high-strength steel plates are often used in addition to mild steel plates for automobile bodies.
[0003]
　More recently, fuel efficiency regulations and NO X by further tightening of environmental regulations, such as the increase in plug-in hybrid and electric vehicles is expected. In these next-generation automobiles, it is necessary to install a large-capacity battery, and it is necessary to further reduce the weight of the vehicle body.
[0004]
　In order to further reduce the weight of the car body, it may be possible to replace the steel plate with a lightweight material such as aluminum alloy, resin, CFRP, or to further increase the strength of the steel plate, but from the viewpoint of material cost and processing cost, It is realistic to use ultra-high-strength steel sheets for mass-produced cars, excluding luxury cars.
[0005]
　Regarding weight reduction of automobile bodies, for example, 780 MPa class high-strength steel plates have been conventionally used for center pillars, which are skeleton parts, but in recent years, in order to further reduce the weight of car bodies, thin plates of 1180 MPa class have been used. Ultra-high-strength steel sheets are being adopted. Further, conventionally, a 590 MPa class high-strength hot-rolled steel sheet has been used for the lower arm, which is a suspension component, but for example, an ultra-high-strength hot-rolled steel sheet of 980 MPa class or higher as described in Patent Document 1 is used. It has been demanded.
[0006]
　On the other hand, recently, LCA (Life Cycle Assessment) has attracted attention, and attention has been paid not only to the environmental load during driving of automobiles but also during manufacturing.
[0007]
　For example, in the painting of automobile parts, zinc phosphate treatment, which is a kind of chemical conversion treatment, has been applied as a base treatment. The zinc phosphate treatment is low cost and has excellent coating film adhesion and corrosion resistance. However, the zinc phosphate treatment solution contains phosphoric acid as a main component and contains metal components such as zinc salt, nickel salt, and manganese salt. Therefore, there is concern about the environmental load caused by phosphorus and metals in the waste liquid that is discarded after use. In addition, a large amount of sludge containing iron phosphate as a main component that precipitates in the chemical conversion treatment tank has become a large environmental load as industrial waste.
[0008]
　Therefore, recently, a zirconium-based chemical conversion treatment liquid has been used as a chemical conversion treatment liquid that can reduce the environmental load. The zirconium-based chemical conversion treatment solution does not contain phosphate and does not require the addition of metal salts. Therefore, the amount of sludge generated is extremely small. For example, Patent Documents 2 and 3 describe techniques for forming a chemical conversion treatment film on a metal surface using a zirconium chemical conversion treatment liquid.
Prior art literature
Patent documents
[0009]
Patent Document 1: International Publication No. 2014/132868 Pamphlet
Patent Document 2: Japanese Patent Application Laid-Open No. 2004-218874
Patent Document 3: Japanese Patent Application Laid-Open No. 2008-202149
Outline of the invention
Problems to be solved by the invention
[0010]
　Even if a zirconium-based chemical conversion treatment solution is used, conventional high-strength steel sheets up to the strength class of 780 MPa can obtain corrosion resistance and coating film adhesion comparable to zinc phosphate chemical conversion treatment. However, in an ultra-high-strength steel sheet having a tensile strength of 980 MPa or more, the amount of alloying elements contained is large, so that zirconium-based chemical crystals are insufficiently adhered to the steel sheet surface, resulting in good corrosion resistance and coating film adhesion. I can't get it.
[0011]
　The present invention has been devised in view of the above-mentioned problems, and an object of the present invention is an ultra-high-strength steel sheet having a tensile strength of 980 MPa or more and sufficient low-temperature toughness, and a zirconium-based chemical conversion treatment. A hot-rolled steel sheet having chemical conversion treatment properties and coating adhesion that are equal to or better than those using a zinc phosphate chemical conversion treatment liquid even when a liquid is used, and a manufacturing method capable of stably producing the hot-rolled steel sheet. To provide.
Means to solve problems
[0012]
　The present inventors have conducted diligent studies in order to solve the above problems, and have found that the oxide on the surface layer of the steel sheet has a great influence on the chemical conversion treatment property and the coating film adhesion, as will be described later.
[0013]
[Correction based on Rule 91 24.04.2020] The
　present invention is based on　 these findings, and the gist thereof is as follows.
(1) The hot-rolled steel sheet according to one aspect of the present invention has a chemical composition represented by an average value in the entire plate thickness direction in mass%, C: 0.050% or more, 0.200% or less, Si: 0.05% or more, 3.00% or less, Mn: 1.00% or more and 4.00% or less, Al: 0.001% or more, 2.000% or less, N: 0.0005% or more, 0. 1000% or less, Ni: 0.02% or more, 2.00% or less, Nb: 0% or more, 0.300% or less, Ti: 0% or more, 0.300% or less, Cu: 0% or more, 2. 00% or less, Mo: 0% or more, 1.000% or less, V: 0% or more, 0.300% or less, Cr: 0% or more, 2.00% or less, Mg: 0% or more, 0.0100% Below, Ca: 0% or more, 0.0100% or less, REM: 0% or more, 0.1000% or less, B: 0% or more, 0.0100% or less, one of Zr, Co, Zn, and W. Or two or more types: 0 to 1.000% in total, Sn: 0 to 0.050%, P: 0.100% or less, S: 0.0300% or less, O: 0.0100% or less. The balance is composed of Fe and impurities, satisfies the following formula (i), the PCM represented by the following (ii) is 0.20 or more, and the Ms represented by the following (iii) is 400 ° C. or higher. When the thickness is t, the metallographic structure at the position t / 4 from the surface contains one or both of the tempered martensite and the lower baynite in a total volume ratio of 90% or more, and the tensile strength. Is 980 MPa or more, and the average Ni concentration on the surface is 7.0% or more.
　0.05% ≤ Si + Al ≤ 2.50% ... Equation (i)
　PCM = C + Si / 30 + Mn / 20 + Cu / 20 + Ni / 60 + Mo / 15 + Cr / 20 + V / 10 + 5 × B ・ ・ ・ Formula (ii)
Ms = 561-474 × C-33 × Mn-17 × Ni-17 × Cr-21 × Mo ・Formula (iii)
　The element shown in the above formula is the mass% of the element contained in the hot-rolled steel sheet.
(2) The hot-rolled steel sheet according to (1) above may contain Ni: 0.02% or more and 0.05% or less in mass% of the chemical composition.
(3) The hot-rolled steel sheet according to (1) or (2) has an average number density of iron-based carbides present in the tempered martensite and the lower bainite of 1.0 × 10 6 / mm 2. It may be the above.
(4) In the hot-rolled steel sheet according to any one of (1) to (3) above, the hot-rolled steel sheet has an internal oxide layer, and the average depth of the internal oxide layer is the surface of the hot-rolled steel sheet. May be 5.0 μm or more and 20.0 μm or less.
(5) In the hot-rolled steel sheet according to any one of (1) to (4) above, the standard deviation of the arithmetic mean roughness Ra of the surface of the hot-rolled steel sheet is 10.0 μm or more and 50.0 μm or less. You may.
(6) The hot-rolled steel sheet according to any one of (1) to (5) above has a chemical composition of B: 0.0001% or more and 0.0100% or less, Ti: 0.015% in mass%. One or two of the above 0.300% or less may be contained.
(7) The hot-rolled steel sheet according to any one of (1) to (6) above has a chemical composition of Nb: 0.005% or more, 0.300% or less, Cu: 0.01 in mass%. % Or more, 2.00% or less, Mo: 0.010% or more, 1.000% or less, V: 0.010% or more, 0.300% or less, Cr: 0.01% or more, 2.00% or less , One or more of the above may be contained.
(8) The hot-rolled steel sheet according to any one of (1) to (7) above has a chemical composition of Mg: 0.0005% or more, 0.0100% or less, Ca: 0.0005 in mass%. % Or more, 0.0100% or less, REM: 0.0005% or more, 0.1000% or less, and one or more of them may be contained.
(9) The method for producing a hot-rolled steel sheet according to another aspect of the present invention includes a casting step of casting molten steel having the chemical composition described in (1) above to obtain a steel piece, and at least preliminarily using the steel piece. A heating step of heating in a heating furnace equipped with a heat storage type burner having a heating zone, a heating zone and a soaking zone, and hot rolling of the heated steel pieces so that the finish rolling temperature becomes 850 ° C. or higher. The Ms point temperature or less so that the average cooling rate from the finish rolling temperature to the Ms point temperature calculated by the following formula (iv) is 50 ° C./sec or more. It has a primary cooling step of primary cooling the hot-rolled steel sheet to the temperature range of the above, and a winding step of winding the hot-rolled steel sheet at a temperature of less than 350 ° C., and in the heating step, in the preheating zone. The air ratio is 1.1 or more and 1.9 or less.
　Ms = 561-474 × C-33 × Mn-17 × Ni-17 × Cr-21 × Mo ・ ・ ・ Equation (iv)
(10) In the method for producing a hot-rolled steel sheet according to (9) above, the primary cooling is stopped at a temperature lower than the Ms point temperature and 350 ° C. or higher, and the hot-rolled steel sheet after the primary cooling is maximally cooled. It may be cooled to less than 350 ° C. so that the rate is less than 50 ° C./sec.
(11) In the method for producing a hot-rolled steel sheet according to (9) or (10) above, the air ratio in the heating zone is 0.9 or more and 1.3 or less in the heating step.
(12) The method for producing a hot-rolled steel sheet according to any one of (9) to (11) above has an air ratio of 0.9 or more and 1.9 or less in the heat equalizing zone in the heating step. May be.
(13) In the method for producing a hot-rolled steel sheet according to (11) or (12) above, the air ratio in the preheating zone may be larger than the air ratio in the heating zone.
(14) The method for producing a hot-rolled steel sheet according to any one of (9) to (13) above is that 1 to 10 wt% hydrochloric acid at a temperature of 20 to 95 ° C. is applied to the hot-rolled steel sheet after the winding step. A pickling step may be provided in which the solution is pickled under the condition of a pickling time of less than 30 to 60 seconds.
Effect of the invention
[0014]
　According to the above aspect of the present invention, an ultra-high strength steel sheet having a tensile strength of 980 MPa or more and good low temperature toughness, and a zinc phosphate chemical conversion treatment liquid was used even when a zirconium-based chemical conversion treatment liquid was used. It is possible to obtain a hot-rolled steel sheet having chemical conversion treatment property and coating adhesion which are equal to or higher than those in the case. Since the steel sheet according to the present invention is excellent in chemical conversion treatment property and coating film adhesion, it is excellent in corrosion resistance after coating. Therefore, the steel sheet according to the present invention is suitable for automobile parts that require high strength and corrosion resistance after painting.
A brief description of the drawing
[0015]
FIG. 1 is an example of surface EPMA measurement results of a hot-rolled steel sheet and a comparative hot-rolled steel sheet according to the present embodiment. (Measurement conditions: Acceleration voltage: 15 kV, Irradiation current: 6 × 10 -8 A, Irradiation time: 30 ms, Beam diameter: 1 μm)
[Fig. 2] Mechanism in which Ni concentrated on the surface becomes precipitated nuclei of zirconium-based chemical crystals. It is a figure which shows.
[Fig. 3] Fig. 3 is a diagram showing the mechanism by which the surface roughness of a hot-rolled steel sheet changes.
Mode for carrying out the invention
[0016]
　The present inventors have diligently studied the conditions under which good chemical conversion treatment and coating film adhesion can be stably obtained by chemical conversion treatment using a zirconium-based chemical conversion treatment liquid on an ultra-high-strength steel plate having a tensile strength of 980 MPa or more. Was piled up. As a result of the examination, it was found that the oxide on the surface layer of the steel sheet has a great influence on the chemical conversion treatment property and the coating film adhesion. Specifically, it is as follows.
　The steel sheet is usually pickled before the chemical conversion treatment. However, even after ordinary pickling, oxides such as Si and Al are formed on the surface of the ultra-high-strength steel plate, which deteriorates the chemical conversion treatment property and the coating film adhesion in the zirconium-based chemical conversion treatment. I found out. As a result of further studies by the present inventors, in order to improve the chemical conversion treatment property and the coating film adhesion, the formation of oxides such as Si and Al is suppressed, and the surface of the steel sheet is used as a precipitation core of zirconium-based chemical crystals. It has been found that it is effective to form a layer having a Ni-concentrated portion in the vicinity (sometimes referred to as a Ni-concentrated layer).
　Further, the present inventors limit the content of a small amount of Ni and the heating conditions in the heating step prior to hot rolling, assuming that the process for manufacturing a general hot-rolled steel sheet is inexpensive and mass-produced. By doing so, it was found that it is possible to form a Ni-concentrated layer near the surface of the steel sheet after pickling (before the chemical conversion treatment).
[0017]
　Hereinafter, the hot-rolled steel sheet according to the present embodiment will be described in detail.
[Components of Steel Sheet]
　First, the reason for limiting the chemical composition of the hot-rolled steel sheet according to the present embodiment will be described. Unless otherwise specified,% with respect to the content of the component indicates mass%.
　In addition, the display of the element name used in each formula in the present specification shall indicate the content (mass%) of the element in the steel sheet, and if it is not contained, 0 shall be substituted.
[0018]
C: 0.050% or more and 0.200% or less
　C is one of the important elements in the hot-rolled steel sheet according to the present embodiment. C is an element that contributes to increasing the strength and hardenability of the steel sheet. If the C content is less than 0.050%, the effect of improving the strength by strengthening the structure of the low temperature transformation generation phase cannot be obtained. Therefore, the C content is set to 0.050% or more. It is preferably 0.070% or more.
　On the other hand, C produces iron-based carbides such as cementite (Fe 3 C) that are precipitated when bainite and martensite are tempered . When the C content exceeds 0.200% , iron-based carbides such as cementite (Fe 3 C) , which is the starting point of cracking of the secondary sheared surface during punching , increases, and moldability such as hole expandability deteriorates. do. Therefore, the C content is set to 0.200% or less. Preferably, it is 0.180% or less.
[0019]
Si: 0.05% or more and 3.00% or less
　Si is one of the important elements in the hot-rolled steel sheet according to the present embodiment. Si is an element that contributes to increasing the strength of the base metal by improving the temper softening resistance, and is also an effective element as a deoxidizing material for molten steel. In addition, Si is an element that is also effective in suppressing the occurrence of scale-based defects such as scales and spindle scales. In order to obtain these effects, the Si content is set to 0.05% or more. Further, as the Si content increases, the precipitation of iron-based carbides such as cementite in the material structure is suppressed, and the strength and hole expandability are improved. Therefore, the Si content is preferably 0.10% or more.
　On the other hand, even if the Si content exceeds 3.00%, the effect of contributing to the increase in strength is saturated. Therefore, the Si content is set to 3.00% or less. It is preferably 2.50% or less.
[0020]
Mn: 1.00% or more and 4.00% or less
　Mn is an element that contributes to solid solution strengthening. Further, Mn is an element that enhances hardenability, and is contained in order to make the steel sheet structure tempered martensite or the main phase of lower bainite. If the Mn content is less than 1.00%, the effect of suppressing ferrite transformation and bainite transformation during cooling is not sufficiently exhibited, and the steel sheet structure cannot be the main phase of lower bainite and / or martensite. Therefore, the Mn content is set to 1.00% or more.
　On the other hand, even if the Mn content exceeds 4.00%, this effect is saturated. Therefore, the Mn content is set to 4.00% or less. Further, when the Mn content exceeds 3.00%, slab cracking is likely to occur during casting. Therefore, the Mn content is preferably 3.00% or less.
[0021]
Al: 0.001% or more and 2.000% or less
　Al is one of the important elements in the hot-rolled steel sheet according to the present embodiment. Al is an element that suppresses the formation of coarse cementite when bainite and martensite are tempered, and improves the hole-spreading property. It can also be used as a deoxidizing material. In order to obtain this effect, the Al content is set to 0.001% or more.
　On the other hand, the excessive content of Al increases the number of Al-based coarse inclusions, which causes deterioration of hole expandability and surface defects. From this, the Al content is set to 2.000% or less. Further, if the Al content is high, the tundish nozzle is likely to be blocked during casting, so the Al content is preferably 1.500% or less.
[0022]
N: If the
　N content is 0.0005% or more and 0.1000% or less , solid solution N remains in the steel and the ductility is lowered. Further, when Ti is contained, coarse TiN is precipitated and the hole expanding property is lowered. Therefore, the smaller the N content, the more preferable. If the N content exceeds 0.1000%, the ductility and hole-spreading property are particularly significantly reduced, so the N content is set to 0.1000% or less. Preferably, it is 0.0100% or less.
　On the other hand, it is economically undesirable to have an N content of less than 0.0005%. Therefore, the N content is set to 0.0005% or more.
[0023]
Ni: 0.02% or more and 2.00% or less
　Ni is one of the important elements in the hot-rolled steel sheet according to the present embodiment. Ni is concentrated in the vicinity of the steel sheet surface near the interface between the steel sheet surface and the scale under specific conditions, mainly in the heating process of the hot rolling process. When the zirconium-based chemical conversion treatment is performed on the surface of the steel sheet, this Ni becomes the precipitation nuclei of the zirconium-based chemical conversion treatment film, and promotes the formation of a film having no scale and good adhesion. If the Ni content is less than 0.02%, there is no effect, so the Ni content is set to 0.02% or more. The above-mentioned effect of improving adhesion can be obtained not only for a zirconium-based chemical conversion treatment film but also for a conventional zinc phosphate chemical conversion treatment film. In addition, the adhesion to the hot-dip galvanized layer by the hot-dip galvanized treatment and the base material of the alloyed zinc-plated layer that has been alloyed after plating is also improved.
　Further, Ni is an element effective for suppressing ferrite transformation during cooling as an element for enhancing hardenability and for tempering the steel plate structure into a tempered martensite or lower bainite structure.
　On the other hand, even if the Ni content exceeds 2.00%, not only the effect is saturated but also the alloy cost increases. Therefore, the Ni content is set to 2.00% or less. It is preferably 0.50% or less, more preferably 0.05% or less.
[0024]
　The above is the basic chemical composition of the hot-rolled steel sheet according to the present embodiment, and the hot-rolled steel sheet according to the present embodiment may contain the above elements and the balance may be Fe and impurities. However, for the purpose of improving various properties, the following components can be further contained. Since the following elements do not necessarily have to be contained, the lower limit of the content is 0%.
[0025]
Nb: 0% or more and 0.300% or less
　Nb forms a carbonitride, or the solid solution Nb delays the grain growth during hot rolling to reduce the particle size of the hot-rolled steel sheet. It is an element that contributes to the improvement of low temperature toughness through. When this effect is obtained, the Nb content is preferably 0.005% or more.
　On the other hand, even if the Nb content exceeds 0.300%, the above effect is saturated and the economic efficiency is lowered. Therefore, if necessary, the Nb content is set to 0.300% or less even when Nb is contained.
[0026]
Ti: 0% or more and 0.300% or less
　Ti forms a carbonitride, or the solid solution Ti delays the grain growth during hot rolling to reduce the particle size of the hot-rolled steel sheet. It is an element that contributes to the improvement of low temperature toughness through. When this effect is obtained, the Ti content is preferably 0.005% or more. Further, in order to contain B and exhibit the effect of improving the quenchability, it is necessary to minimize the amount of B precipitated as BN. When the Ti content is 0.015% or more, stable TiN is precipitated at a temperature higher than that of BN, and sufficient improvement in hardenability due to the solid solution B can be expected. Therefore, when B is contained at the same time, the Ti content is preferably 0.015% or more.
　On the other hand, even if the Ti content exceeds 0.300%, the above effect is saturated and the economic efficiency is lowered. Therefore, even when Ti is contained as needed, the Ti content is set to 0.300% or less.
[0027]
Cu: 0% or more, 2.00% or less
Mo: 0% or more, 1.000% or less
V: 0% or more, 0.300% or less
Cr: 0% or more, 2.00% or less
　Cu, Mo, V, Cr may contain any one or more as an element for enhancing hardenability in order to suppress ferrite transformation during cooling and to make the steel plate structure tempered martensite or lower bainite structure. Further, these elements are elements having an effect of improving the strength of the hot-rolled steel sheet by precipitation strengthening or solid solution strengthening, and one or more kinds may be contained in order to obtain this effect. In order to obtain the above effects, it is preferable that the respective contents of Mo and V are 0.010% or more, and the contents of Cu and Cr are 0.01% or more.
　On the other hand, even if the Cu content is more than 2.00%, the Mo content is more than 1.000%, the V content is more than 0.300%, and the Cr content is more than 2.00%, the above effect is saturated. Moreover, the economic efficiency is reduced. Therefore, even when Cu, Mo, V, and Cr are contained, if necessary, the Cu content is 2.00% or less, the Mo content is 1.000% or less, and the V content is 0.300% or less. The Cr content is 2.00% or less.
[0028]
Mg: 0% or more, 0.0100% or less
Ca: 0% or more, 0.0100% or less
REM: 0% or more, 0.1000% or less
　Mg, Ca and REM (rare earth elements) are the starting points of fracture of the steel plate. It is an element that controls the morphology of non-metal inclusions that cause deterioration of workability and improves the workability of steel sheets. Therefore, any one or more of these may be contained. When this effect is obtained, the contents of Ca, REM and Mg are preferably 0.0005% or more, respectively.
　On the other hand, even if the Mg content is more than 0.0100%, the Ca content is more than 0.0100%, and the REM content is more than 0.1000%, the above effects are saturated and the economic efficiency is lowered. Therefore, even when it is contained, it is desirable that the Mg content is 0.0100% or less, the Ca content is 0.0100% or less, and the REM content is 0.1000% or less.
　Here, REM refers to a total of 17 elements composed of Sc, Y and lanthanoid, and the content of REM refers to the total content of these elements. In the case of lanthanoids, they are industrially added in the form of misch metal.
[0029]
B: 0% or more and 0.0100% or less
　B is an element that enhances hardenability and is effective for delaying the ferrite transformation during cooling to make the steel sheet structure tempered martensite or lower bainite structure. It is an element and may be contained to obtain this effect. When this effect is obtained, the B content is preferably 0.0001% or more. It is more preferably 0.0005% or more, still more preferably 0.0007% or more.
　On the other hand, if the B content exceeds 0.0100%, not only the effect is saturated, but also the economic efficiency is lowered. Therefore, even when it is contained, the B content is set to 0.0100% or less. It is preferably 0.0050% or less, more preferably 0.0030% or less.
[0030]
Zr, Co, Zn, and W: 1 type or 2 or more types in total 0 to 1.000%
Sn: 0.050% or less For
　other elements, Zr, Co, Zn, W totals 1.000% Even if the following content is contained, the effect of the hot-rolled steel sheet according to the present embodiment is not impaired. Therefore, these elements may be contained in a total of 1.000% or less.
　Further, even if a small amount of Sn is contained, the effect of the hot-rolled steel sheet according to the present embodiment is not impaired. However, if the Sn content exceeds 0.050%, defects may occur during hot rolling, so it is desirable to set the Sn content to 0.050% or less.
[0031]
P: 0.100% or less
　P is an impurity contained in the hot metal, and is an element that segregates at the grain boundaries of the steel sheet and lowers the low temperature toughness as the content increases. Therefore, the lower the P content, the more desirable. If the P content is more than 0.100%, the workability and weldability are significantly adversely affected. Therefore, the P content is set to 0.100% or less. In particular, when considering weldability, the P content is preferably 0.030% or less.
　On the other hand, it is preferable that the amount of P is small, but reducing it more than necessary imposes a great load on the steelmaking process. Therefore, the P content may be 0.001% or more.
[0032]
S: 0.0300% or less
　S is an impurity contained in the hot metal, and if the content is too large, it is an element that causes cracking during hot rolling. Further, S is an element that produces inclusions such as MnS that deteriorates the hole expanding property. Therefore, the S content should be reduced as much as possible. However, if the S content is 0.0300% or less, it is within an acceptable range, so the S content is set to 0.0300% or less. However, from the viewpoint of hole expandability, the S content is preferably 0.0100% or less, and more preferably 0.0050% or less.
　On the other hand, it is preferable that the S content is small, but reducing it more than necessary imposes a great load on the steelmaking process. Therefore, the S content may be 0.0001% or more.
[0033]
O: 0.0100% or less
　O is an element that forms a coarse oxide that is the starting point of fracture in steel when the content is too large, and causes brittle fracture and hydrogen-induced fracture. Therefore, the O content is set to 0.0100% or less. From the viewpoint of on-site weldability, the O content is preferably 0.0030% or less.
　On the other hand, O is an element that disperses a large number of fine oxides when deoxidizing molten steel. Therefore, the O content may be 0.0005% or more.
[0034]
　As described above, the hot-rolled steel sheet according to the present embodiment contains basic elements, optionally contains arbitrary elements, and the balance is composed of Fe and impurities. Impurities refer to components that are unintentionally contained in the steel sheet manufacturing process from raw materials or other manufacturing processes.
[0035]
　0.05% ≤ Si + Al ≤ 2.50% In the
　hot-rolled steel sheet according to the present embodiment, the content of each element is controlled within the above range, and then Si + Al is controlled so as to satisfy the following formula (1). There is a need.
　0.05% ≤ Si + Al ≤ 2.50% ... Equation (1) If
　Si + Al is less than 0.05%, scale defects such as scales and spindle scales occur.
　On the other hand, when Si + Al is more than 2.50%, even if Ni is contained and the surface layer is sufficiently concentrated with Ni, the core effect of the chemical conversion-treated crystal cannot be obtained, and the chemical conversion treatment property and the coating film adhesion are obtained. The effect of improving sex cannot be obtained.
[0036]
　PCM ≧ 0.20
　Ms ≧ 400 (° C.) Further
　, in the hot-rolled steel sheet according to the present embodiment, after controlling the content of each element within the above range, the PCM obtained by the following formula (2) is 0. Must be 20 or more.
　PCM = C + Si / 30 + Mn / 20 + Cu / 20 + Ni / 60 + Mo / 15 + Cr / 20 + V / 10 + 5 × B
　... Equation (2) If the PCM is less than 0.20, the hardenability is insufficient and the main phase is tempered with martensite and / Or the microstructure as the lower bainite cannot be obtained.
　Further, in the hot-rolled steel sheet according to the present embodiment, it is necessary to set Ms represented by the following formula (3) to 400 (° C.) or more.
　If Ms is less than 400 (° C.), the auto temper (automatic tempering) during cooling becomes insufficient and the stretch flangeability deteriorates.
　Ms = 561-474 × C-33 × Mn-17 × Ni-17 × Cr-21 × Mo ・ ・ ・ Equation (3)
[0037]
　The content of each element in the hot-rolled steel sheet described above is the average content in the total plate thickness determined by ICP emission spectroscopic analysis using chips according to JISG1201: 2014.
[0038]
[Metal structure]
　The micro structure (metal structure) of the hot-rolled steel sheet according to the present embodiment will be described. Unless otherwise specified,% for microstructure indicates% by volume fraction.
[0039]
　The metal structure at the position of t / 4 (t: plate thickness) from the surface of the steel sheet is 90% or more in total of tempered martensite and / or both: volume ratio of the
　hot-rolled steel sheet according to the present embodiment. Then, the main phase is tempered martensite and / or lower bainite, and the total volume ratio is 90% or more.
[0040]
　If the total volume fraction of tempered martensite and lower bainite is less than 90%, a tensile strength of 980 MPa or more cannot be secured. Therefore, the lower limit of the total volume fraction of tempered martensite and lower bainite is 90%. Even if the volume fraction is 100%, high strength and excellent low temperature toughness can be obtained.
[0041]
　In the hot-rolled steel sheet according to the present embodiment, tempered martensite is the most important microstructure in order to have high strength and excellent low temperature toughness. Tempering martensite is a collection of lath-shaped crystal grains, and contains iron-based carbides with a major axis of 5 nm or more inside, and the carbides are in a plurality of variants, that is, a group of a plurality of iron-based carbides extending in different directions. It is an organization belonging to.
　The tempered martensite has a structure when the cooling rate at the time of cooling below the Ms point (martensite transformation start temperature) is lowered, or when the martensite structure is once formed and then tempered at 100 to 600 ° C. Can be obtained. In the hot-rolled steel sheet according to the present embodiment, precipitation is controlled by cooling control of less than 400 ° C.
[0042]
　The lower bainite is also an aggregate of lath-shaped crystal grains like tempered martensite, and contains iron-based carbides having a major axis of 5 nm or more inside. In lower bainite, the carbides belong to a single variant, i.e., a group of iron-based carbides extending in the same direction. By observing the elongation direction of the carbide, tempered martensite and lower bainite can be distinguished. Here, the iron-based carbide group extending in the same direction means that the difference in the extension direction of the iron-based carbide group is within 5 °. However, in the hot-rolled steel sheet according to the present embodiment, it is not necessary to clearly distinguish between tempered martensite and lower bainite from the viewpoint of material.
[0043]
　The microstructure may contain one or more of ferrite, fresh martensite, upper bainite, pearlite, and retained austenite as a structure other than tempered martensite and lower bainite in a total volume fraction of 10% or less. ..
[0044]
　In the present embodiment, the fresh martensite is martensite containing no carbide inside. Therefore, tempered martensite and fresh martensite can be easily distinguished from the viewpoint of carbides. That is, the inside of lath-shaped crystal grains can be observed using FE-SEM, and the presence or absence of iron-based carbides can be used for discrimination. Fresh martensite has high strength but is inferior in low temperature toughness. For this reason, the volume fraction needs to be limited to 10% or less.
　Residual austenite is a structure in which austenite generated during heating does not transform to room temperature and remains. do. Therefore, it has the same adverse effect as the fresh martensite mentioned above. Therefore, it is necessary to limit the volume fraction to 10% or less. Further, since the crystal structure of retained austenite is FCC and the other microstructures are BCC and they are different from each other, the volume fraction can be easily determined by the X-ray diffraction method.
[0045]
　Upper bainite is an aggregate of lath-shaped crystal grains containing carbides between laths. In the upper bainite, carbides are precipitated at the interface of the lath, which is clearly different from the case where the lower bainite precipitates carbides inside the lath. Therefore, it can be easily identified. That is, the interface of lath-shaped crystal grains can be observed using FE-SEM, and the presence or absence of iron-based carbides can be used for discrimination. Since the carbides contained between the laths serve as the starting point of fracture, if the volume fraction of the upper bainite is large, the low temperature toughness decreases. Further, since the upper bainite is formed at a higher temperature than the lower bainite, the strength is low, and excessive formation makes it difficult to secure a tensile strength of 980 MPa or more. Since this adverse effect becomes remarkable when the volume fraction of the upper bainite exceeds 10%, it is necessary to limit the volume fraction to 10% or less.
[0046]
　Ferrite is a lumpy crystal grain and has a structure that does not contain a substructure such as a lath inside. Ferrite is the softest structure, and it is necessary to limit it to 10% or less in order to secure a tensile strength of 980 MPa or more. Further, since it is extremely soft as compared with tempered martensite or lower bainite, which is the main phase, deformation is concentrated at the interface between ferrite and tempered martensite or lower bainite, and it is likely to be a starting point of fracture. Since this adverse effect becomes remarkable when the volume fraction exceeds 10%, it is necessary to limit the volume fraction to 10% or less.
　Pearlite is a lamellar metal structure in which cementite is deposited in layers between ferrites, and like ferrite, it causes a decrease in strength and deterioration of low temperature toughness. Therefore, it is necessary to limit the volume fraction to 10% or less. There is.
[0047]
　Identification of tempered martensite, fresh martensite, upper bainite, lower bainite, ferrite, pearlite, retained austenite and residual structure, confirmation of existence position, which constitute the microstructure of the hot-rolled steel sheet according to the present embodiment as described above. In addition, the volume ratio is measured by corroding the cross section in the rolling direction of the steel plate or the cross section in the direction perpendicular to the rolling direction using a bainite reagent and a reagent disclosed in JP-A-59-219473, and a scanning type of 1000 to 100,000 times. This is possible by observing with a transmissive electron microscope.
　Further, the structure can be discriminated from the crystal orientation analysis using the FESEM-EBSP method and the hardness measurement of a minute region such as the micro Vickers hardness measurement.
　For example, as described above, tempered martensite, upper bainite, and lower bainite have different carbide formation sites and crystal orientation relationships (elongation directions). By observing the carbides and examining their elongation direction, it is possible to easily distinguish between lower bainite and tempered martensite. However, in the hot-rolled steel sheet according to the present embodiment, it is not necessary to distinguish between these structures because the total volume fraction of the tempered martensite and the lower bainite may be controlled.
[0048]
　In the hot-rolled steel sheet according to the present embodiment, the volume ratios of ferrite, pearlite, upper bainite, lower bainite, and tempered martensite are t / from the surface of the steel sheet in the thickness direction of the steel sheet, where t is the thickness of the steel sheet. It is obtained by collecting a sample from a portion (generally t / 8 to 3 t / 8) including the position 4 and observing the rolling direction cross section (so-called L direction cross section) of the steel sheet.
[0049]
　Specifically, first, a sample is subjected to bainite etching, and after etching, an image analysis is performed on a microstructure photograph obtained in a field of view of 300 μm × 300 μm using an optical microscope to obtain the area ratios of ferrite and pearlite, respectively. And obtain the total area ratio of bainite, martensite, and retained austenite. Next, the nighttal-etched portion was subjected to repera-etching, and the microstructure photograph obtained in a field of view of 300 μm × 300 μm was subjected to image analysis using an optical microscope to determine the total area ratio of retained austenite and martensite. calculate. Further, using a sample surface-cut from the direction normal to the rolled surface to a depth of 1/4 of the plate thickness, the residual austenite area ratio is obtained by X-ray diffraction measurement described later. By this method, the area ratios of ferrite, bainite, martensite, retained austenite, and pearlite can be obtained.
　As described above, bainite is a collection of lath-shaped crystal grains. The bainite includes an upper bainite which is an aggregate of laths containing carbides between laths and a lower bainite containing iron-based carbides having a major axis of 5 nm or more inside. The iron-based carbides precipitated in the lower bainite belong to a single variant, i.e., a group of iron-based carbides extending in the same direction. Tempering martensite is a collection of lath-shaped crystal grains, and contains iron-based carbides having a major axis of 5 nm or more inside. The iron carbides in tempered martensite belong to a plurality of variants, i.e., a group of iron carbides extending in different directions. Further, in the present embodiment, martensite that is not tempered martensite is defined as a metallographic structure in which carbides having a diameter of 5 nm or more are not precipitated between laths and in laths. From this, at least three regions of 40 μm × 30 μm were observed at a depth of 1/4 of the plate thickness from the surface of the steel plate at a magnification of 1000 to 100,000 times using a scanning electron microscope, and whether the above-mentioned features were included. Based on somehow, the ratio of lower bainite and upper bainite in bainite and the ratio of tempered martensite and fresh martensite in martensite are obtained, and the area ratio of each phase is calculated. Assuming that the area fraction is equal to the volume fraction, this is taken as the volume fraction.
[0050]
　The volume fraction of retained austenite can be determined by X-ray diffraction. Since austenite has a different crystal structure from ferrite, it can be easily identified crystallographically. For example, it is a method of easily obtaining the volume fraction by using the following equation from the difference in the reflecting surface strength between austenite and ferrite using the Kα ray of Mo.
Vγ = (2/3) {100 / (0.7 × α (211) / γ (220) +1)} + (1/3) {100 / (0.78 × α (211) / γ (311)) +1)}
However, α (211), γ (220) and γ (311) are the X-ray reflecting surface intensities of ferrite (α) and austenite (γ), respectively.
[0051]
　The hot rolled steel sheet according to the present embodiment, in the tempered martensite and lower bainite is included in the microstructure, the iron-based carbides in average number density, 1.0 × 10 6 (pieces / mm 2 ) contain more than Is desirable.
　As-quenched martensite (fresh martensite) has excellent strength but poor toughness. On the other hand, in tempered martensite in which iron-based carbides such as cementite are precipitated, an excellent balance between strength and low temperature toughness can be obtained.
　The present inventors have, low-temperature toughness and was investigated the relationship between the number density of the iron-based carbide, 1.0 × 10 the number density of carbides martensite and in the lower bainite tempering 6 (pieces / mm 2 ) or more It was clarified that better low temperature toughness can be secured. Therefore, the average number density of iron-based carbide contained in martensite and lower bainite tempering, 1.0 × 10 6 (pieces / mm 2 is preferably a) More preferably, 5.0 × 10 6 (pieces / mm 2 and a) above, more preferably, 1.0 × 10 7 (pieces / mm 2 at) or more.
　The size of the carbides precipitated on the hot-rolled steel sheet according to the present embodiment obtained by the method described later is as small as 300 nm or less, and most of them are precipitated in the lath of martensite or bainite. Therefore, it is presumed that the low temperature toughness is not deteriorated.
[0052]
　In measuring the number density of carbides, a sample is taken with the plate thickness cross section parallel to the rolling direction of the steel plate as the observation surface, the observation surface is polished, and nightal etching is performed to 1/4 (t / 4) of the plate thickness. The range of 1/8 to 3/8 thickness centered on the position of is observed with a field emission scanning electron microscope (FE-SEM: Field Emission Scanning Electron Microscope). Observe 10 fields each at 200,000 times, measure the number density of iron-based carbides contained in tempered martensite and lower bainite in the observation field, and average the number density in each field to obtain the average number density. do.
[0053]
　In order to further improve the low temperature toughness, it is preferable that the main phase is tempered martensite or lower bainite and the average effective crystal grain size is 10 μm or less. More preferably, it is 8 μm or less. The effective crystal grain size described here means a region surrounded by grain boundaries having a crystal orientation difference of 15 ° or more described by the following method, and corresponds to a block grain size in martensite and bainite.
[0054]
　The effective crystal grain size is 15 °, which is the threshold value of the large-angle grain boundary, which is generally recognized as the crystal grain boundary, using EBSP-OIM TM (Electron Backscatter Diffraction Pattern Microscopy). The grain is visualized and obtained from the mapped image. In the EBSP-OIM TM method, a highly inclined sample is irradiated with an electron beam in a scanning electron microscope (SEM), and the Kikuchi pattern formed by backscattering is photographed with a high-sensitivity camera and irradiated by computer image processing. It consists of a device and software for measuring the crystal orientation of a point in a short waiting time. In the EBSP method, the microstructure and crystal orientation of the bulk sample surface can be quantitatively analyzed, and the analysis area is a region that can be observed by SEM, and analysis can be performed with a minimum resolution of 20 nm, depending on the resolution of SEM.
[0055]
　It is desirable that the aspect ratio of the effective crystal grains of tempered martensite and bainite (here, meaning a region surrounded by grain boundaries of 15 ° or more) is 2.0 or less. Grains flattened in a specific direction have a large anisotropy, and cracks propagate along the grain boundaries during the Charpy test, which often causes a decrease in toughness value. Therefore, it is preferable that the effective crystal grains are equiaxed as much as possible. In the hot-rolled steel sheet according to the present embodiment, the cross section of the hot-rolled steel sheet in the rolling direction is observed, and the ratio (= L /) of the length (L) of the effective crystal grains in the rolling direction and the length (T) in the plate thickness direction is observed. T) is defined as the aspect ratio.
[0056]
Average Ni concentration on the surface: 7.0% or more In
　order to obtain excellent chemical conversion treatment properties and coating adhesion of the zirconium-based chemical conversion treatment film even on the surface of ultra-high strength steel sheets after pickling (before chemical conversion treatment), It is preferable that oxides such as Si and Al on the surface of the pickling plate are reduced to a harmless level. In order to obtain the above effect only by controlling oxides such as Si and Al, Ar, He, N 2 in the preheating zone of the heating furnace in order to suppress the oxidation of the slab surface as much as possible in the heating process of hot rolling. It is necessary to create a substantially non-oxidizing atmosphere using an inert gas such as, or to set the air ratio to incomplete combustion of less than 0.9. However, when it is inexpensive and mass-produced in the process of manufacturing a general hot-rolled steel sheet, it is not possible to create a substantially non-oxidizing atmosphere using an inert gas in the heating process of hot rolling. It is possible. Further, even if the air ratio is set to less than 0.9 to control oxides such as Si and Al, the heat loss due to incomplete combustion increases remarkably, the thermal efficiency of the heating furnace itself decreases, and the production cost increases. Etc. occur.
　The present inventors have made zirconium-based chemical conversion in the above-mentioned chemical composition, structure, and ultra-high-strength steel plate having a tensile strength of 980 MPa or more and toughness on the premise of applying a manufacturing process capable of mass production at low cost. The adhesion of the coating film after the chemical conversion treatment using the treatment liquid was examined. Since the hot-rolled steel sheet is usually subjected to chemical conversion treatment after pickling, the steel sheet after pickling was evaluated in this embodiment as well. Pickling was carried out using a 1 to 10 wt% (% by weight) hydrochloric acid solution at a temperature of 20 to 95 ° C. and a pickling time of less than 30 to 60 seconds. If no scale is formed on the surface, evaluation may be performed without pickling.
　As a result of the examination, in the measurement using FE-EPMA, if the average Ni concentration on the surface is 7.0% or more in mass%, even if oxides such as Si and Al remain on the surface of the pickling plate, It was found that the coating peeling width evaluated by the method described later for all the samples was within 4.0 mm, which is the standard, and the coating film adhesion was excellent. Further, in such a case, no scale was observed in the chemical conversion-treated film. On the other hand, the coating peeling width was more than 4.0 mm in all the samples having an average Ni concentration of less than 7.0% on the surface.
　This is because, as shown in FIG. 2, the Ni-concentrated portion 3 is formed on the surface of the steel sheet, so that a potential difference is generated between the locally concentrated Ni on the surface and the base iron 1. It is considered that this is because Ni serves as a precipitation nucleus of the zirconium-based chemical crystal 4 and thus the formation of the zirconium-based chemical crystal 4 is promoted. The base iron 1 refers to the steel plate portion excluding the scale 2.
[0057]
　Therefore, in the hot-rolled steel sheet according to the present embodiment, the average Ni concentration on the surface (the surface after pickling and before the chemical conversion treatment) is 7.0% or more. When the average Ni concentration on the surface is 7.0% or more, even if oxides such as Si and Al remain on the surface, it is sufficient to form a precipitation nucleus of zirconium-based chemical crystals. In order to make the average Ni concentration on the surface 7.0% or more, in the heating process of hot rolling, Fe is selectively oxidized to some extent on the surface of the steel sheet, so that the iron side of the interface between the scale and the iron is used. In addition, it is necessary to concentrate Ni, which is less likely to be oxidized than Fe.
[0058]
　The average Ni concentration on the surface of the steel sheet is measured using a JXA-8530F field emission electron probe microanalyzer (FE-EPMA). The measurement conditions are acceleration voltage: 15 kV, irradiation current: 6 × 10-8 A, irradiation time: 30 ms, beam diameter: 1 μm. The measurement is performed on a measurement area of ​​900 μm 2 or more from a direction perpendicular to the surface of the steel sheet, and the Ni concentration in the measurement range is averaged (the Ni concentration at all measurement points is averaged).
　FIG. 1 shows an example of the surface EPMA measurement result.
　Ni is mainly concentrated on the ground iron side of the interface between the scale and the ground iron. In addition, pickling is usually performed before the chemical conversion treatment. Therefore, when scale is formed on the surface of the target steel sheet, the measurement is performed after pickling in the same manner as in the case of being subjected to chemical conversion treatment.
[0059]
　The coating film adhesion of the above-mentioned pickling plate is evaluated according to the following procedure. First, the produced steel sheet is pickled and then subjected to a chemical conversion treatment to attach a zirconium-based chemical conversion treatment film. Further, an electrodeposition coating having a thickness of 25 μm is applied to the upper surface thereof, and a coating baking process is performed at 170 ° C. for 20 minutes. Then, under the salt spray conditions shown in JIS Z 2371: 2015, 5% salt spray at a temperature of 35 ° C. was continuously performed for 700 hours, and then a tape having a width of 24 mm (Nichiban 405A-24 JIS Z 1522) was placed on the notch. : 2009) is pasted in parallel with the cut portion with a length of 130 mm, and the maximum peeling width of the coating film when this is peeled off is measured.
[0060]
Internal oxidation layer (region oxides generated inside base iron) is present in the hot-rolled steel sheet, the average depth from the surface of the hot-rolled steel sheet of the inner oxide layer is more than 5.0 .mu.m, less 20.0 .mu.m
　Ni on the surface Even if there is a thickened portion, if the coating ratio of oxides such as Si and Al is too large on the surface of the hot-rolled steel sheet, “scale” on which the zirconium-based chemical conversion treatment film does not adhere tends to occur. In order to suppress this, it is desirable that the oxidation of Si, Al, etc. is not an external oxidation that forms an oxide outside the ground iron, but an internal oxidation that forms an oxide inside.
　The present inventors observed the cross section of only a sample having an average Ni concentration of 7.0% or more on the surface with an optical microscope, and observed the coating peeling width and the average depth of the internal oxide layer from the steel sheet surface (internal oxide layer). The relationship between the positions of the lower ends of the above) was investigated. As a result, all the samples having an average depth of the internal oxide layer of 5.0 μm or more had a coating peeling width of 3.5 mm or less, whereas the average depth of the internal oxide layer was less than 5.0 μm. In all the samples, the paint peeling width was more than 3.5 mm and 4.0 mm or less.
　Therefore, in order to obtain better coating film adhesion, the average depth of the internal oxide layer from the surface of the hot-rolled steel sheet is preferably 5.0 μm or more and 20.0 μm or less.
　If the average depth of the internal oxide layers such as Si and Al is less than 5.0 μm, the internal oxidation is insufficient and the effect of suppressing “skeleton” to which the zirconium-based chemical conversion treatment film does not adhere is small. On the other hand, when the average depth exceeds 20.0 μm, not only the effect of suppressing “skeleton” on which the zirconium-based chemical conversion coating does not adhere is saturated, but also the hardness of the surface layer decreases due to the formation of a decarburized layer that occurs at the same time as internal oxidation. There is a concern that fatigue durability will deteriorate.
[0061]
　The average depth of the internal oxide layer is a mirror surface after embedding in a resin sample by cutting out a surface parallel to the rolling direction and the plate thickness direction as an embedding sample at the position of 1/4 or 3/4 in the plate width direction of the pickling plate. After polishing, 12 or more visual fields are observed with an optical microscope in a visual field of 195 μm × 240 μm (corresponding to a magnification of 400 times) without etching. When a straight line is drawn in the plate thickness direction, the position where it intersects the surface of the steel plate is taken as the surface, and the depth of the internal oxide layer (position of the lower end) of each field of view with respect to that surface is measured and averaged at 5 points per field of view. , The average value is calculated by excluding the maximum value and the minimum value from the average value of each visual field, and this is taken as the average depth of the internal oxide layer.
[0062]
　Standard deviation of arithmetic mean roughness Ra of the surface of hot-rolled steel sheet after pickling under predetermined conditions: 10.0 μm or more and 50.0 μm or less In the
　zirconium-based chemical conversion treatment film, the film thickness is several μm. The film thickness is very thin compared to the zinc acid acid film, and it is about several tens of nm. This difference in film thickness is due to the fact that the zirconium-based chemical conversion-treated crystals are extremely fine. When the chemical conversion-treated crystal is fine, the surface of the chemical conversion-treated crystal is very smooth, and it is difficult to obtain a strong adhesion to the coating film due to the anchor effect as seen in the zinc phosphate-treated film. ..
　However, as a result of the studies by the present inventors, it has been found that the adhesion between the chemical conversion coating film and the coating film can be improved by forming irregularities on the surface of the steel sheet.
　Based on these findings, the present inventors have applied a sample having an average Ni concentration of 7.0% or more and an average depth of the internal oxide layer of 5.0 μm or more to a pickling plate before the zirconium-based chemical conversion treatment. The relationship between the standard deviation of the arithmetic mean roughness Ra of the surface and the coating film adhesion was investigated. As a result, all the samples in which the standard deviation of the arithmetic mean roughness Ra of the surface of the pickling plate was 10.0 μm or more and 50.0 μm or less had a coating peeling width of 3.0 mm or less. The standard deviation of the arithmetic mean roughness Ra of the surface of the pickling plate was less than 10.0 μm or more than 50.0 μm, and the paint peeling width was more than 3.0 mm and less than 3.5 mm.
　Therefore, it is preferable that the standard deviation of the arithmetic mean roughness Ra of the surface of the steel sheet after pickling is 10.0 μm or more and 50.0 μm or less.
　If the standard deviation of the arithmetic mean roughness Ra of the steel sheet surface is less than 10.0 μm, a sufficient anchor effect cannot be obtained. On the other hand, if the standard deviation of the arithmetic mean roughness Ra of the steel sheet surface after pickling exceeds 50.0 μm, not only the anchor effect is saturated, but also zirconium on the uneven valleys and mountain sides of the steel sheet surface after pickling. System chemical conversion treatment Crystals are less likely to adhere and "scale" is more likely to occur.
　The surface roughness of the steel sheet varies greatly depending on the pickling conditions, but in the hot-rolled steel sheet according to the present embodiment, an acid of less than 30 to 60 seconds using a 1 to 10 wt% hydrochloric acid solution at a temperature of 20 to 95 ° C. It is preferable that the standard deviation of the arithmetic average roughness Ra of the surface of the hot-rolled steel sheet after pickling under the condition of the washing time is 10.0 μm or more and 50.0 μm or less.
[0063]
　For the standard deviation of the arithmetic mean roughness Ra, the value obtained by measuring the surface roughness of the pickling plate by the measuring method described in JIS B 0601: 2013 is adopted. After measuring the arithmetic mean roughness Ra on the front and back of 12 or more samples, the standard deviation of the arithmetic average roughness Ra of each sample is calculated, and the average is the standard deviation excluding the maximum and minimum values. Calculate the value.
[0064]
　The hot-rolled steel sheet according to the present embodiment having the above-mentioned chemical composition and metal structure may be a surface-treated steel sheet provided with a plating layer on the surface for the purpose of improving corrosion resistance and the like. The plating layer may be an electroplating layer or a hot-dip plating layer. Examples of the electroplating layer include electrogalvanization and electroZn—Ni alloy plating. Examples of the hot-dip plating layer include hot-dip zinc plating, alloyed hot-dip zinc plating, hot-dip aluminum plating, hot-dip Zn-Al alloy plating, hot-dip Zn-Al-Mg alloy plating, and hot-dip Zn-Al-Mg-Si alloy plating. NS. The amount of plating adhered is not particularly limited and may be the same as the conventional one. Further, it is also possible to further enhance the corrosion resistance by subjecting an appropriate chemical conversion treatment (for example, application and drying of a silicate-based chromium-free chemical conversion treatment liquid) after plating.
[0065]
[Method for manufacturing steel sheet]
　The hot-rolled steel sheet according to the present embodiment can be effective as long as it has the above-mentioned characteristics regardless of the manufacturing method. However, according to the production method shown below, stable production can be performed, which is preferable.
[0066]
[Slab manufacturing process (casting process)]
　The slab manufacturing process such as casting that precedes hot rolling is not particularly limited. That is, after melting in a blast furnace or an electric furnace, various secondary smelting is performed to adjust the components so as to have the above-mentioned components, and then a method such as ordinary continuous casting, casting by the ingot method, or thin slab casting is performed. You can cast it with.
　In the case of continuous casting, the ingot may be cooled to a low temperature and then heated again and then subjected to hot rolling, the ingot may be subjected to hot rolling without being cooled to room temperature, or the cast slab may be subjected to hot rolling. It may be continuously subjected to hot rolling. Scrap may be used as the raw material.
[0067]
[Heating step]
[Hot rolling step] In
　the production of the hot-rolled steel sheet according to the present embodiment, a cast slab (steel piece) having a predetermined chemical component is divided into three zones, a preheating zone, a heating zone, and a soaking zone. It is preferable that hot rolling is performed by heating to 1100 ° C. or higher using a heating furnace having a zone, and hot rolling is completed at 850 ° C. or higher.
　The slab heating temperature for hot rolling is 1100 ° C. or higher. If the slab heating temperature is less than 1100 ° C., the rolling reaction force increases in the subsequent hot rolling, and sufficient hot rolling cannot be performed, not only the desired product thickness cannot be obtained, but also the plate shape deteriorates. As a result, it may not be possible to wind it up. In addition, the austenite particle size may become smaller, and the hardenability may decrease, making it impossible to obtain the desired microstructure. When an element forming a carbonitride is contained in steel such as Ti, it is preferable to heat the steel to a temperature higher than the solution temperature of the austenite.
　On the other hand, although the upper limit of the slab heating temperature is not particularly set and the effect can be obtained, it is economically unfavorable to make the heating temperature excessively high. From this, it is desirable that the upper limit of the slab heating temperature is less than 1300 ° C.
　The finish rolling temperature is preferably 850 ° C. or higher. The hot-rolled steel sheet according to the present embodiment has a reduced hardenability in finish rolling in a temperature range of less than 850 ° C., and one or both of the target tempered martensite and lower bainite have a total volume fraction. It becomes impossible to obtain a microstructure containing 90% or more of bainite. Therefore, the finish rolling temperature is 850 ° C. or higher.
[0068]
　In order to obtain excellent coating film adhesion, it is important to control the air ratio of each zone of the heating furnace in slab heating. In order to control the air ratio in each zone, it is preferable that the burner equipment of the heating furnace is a heat storage type burner. This is because when "alternate combustion" is performed using a "regenerative burner" equipped with a burner with a built-in heat storage body, the heat storage type burner is in the furnace compared to the conventional burner that does not recover heat from the exhaust. This is because the heating furnace, which will be described later, can be controlled by having high temperature soaking property, high controllability of each zone, and strict control of the air ratio in each zone.
[0069]
　The preferred air ratio of each zone will be described.
By
　setting the air ratio in the preheating zone to 1.1 or more, Ni is concentrated on the surface of the hot-rolled steel sheet, and after pickling. The average Ni concentration on the surface of the hot-rolled steel sheet can be 7.0% or more.
　The scale growth behavior of the slab surface in the heating furnace is evaluated by the production scale thickness, and the linear law, which is the rate-determining rate of oxygen supply from the atmosphere on the slab surface, and the diffusion of iron ions in the scale are based on the air ratio (oxygen partial pressure). It is classified as a parabolic law that is rate-determining. In order to promote the growth of the scale of the slab to some extent and form a sufficient Ni-concentrated layer on the surface layer in the limited material furnace time in the heating furnace, the growth of the scale thickness needs to follow the parabolic law.
　If the air ratio in the preheating zone is less than 1.1, the scale growth does not become a parabolic rule, and a sufficient Ni-concentrated layer is formed on the surface layer of the slab in the limited material furnace time in the heating furnace. Can't. In this case, the average Ni concentration on the surface of the hot-rolled steel sheet after pickling does not exceed 7.0%, and as a result, good coating film adhesion cannot be obtained.
[0070]
　On the other hand, if the air ratio in the preheating zone exceeds 1.9, not only the scale-off amount increases and the yield deteriorates, but also the heat loss due to the increase in exhaust gas increases, the thermal efficiency deteriorates, and the production cost increases. ..
　The amount of scale produced in the heating furnace is dominated by the atmosphere of the preheating zone immediately after insertion of the heating furnace, and even if the atmosphere of the subsequent zone changes, the scale thickness is hardly affected. Therefore, it is very important to control the scale growth behavior in the preheating zone.
[0071]
In order
　to form the internal oxide layer, it is necessary to control the air ratio in the heating zone in the heating furnace process, and the air ratio in the heating zone is set to 0. By setting the value to 0.9 or more and 1.3 or less, the average depth of the internal oxide layer can be set to 5.0 to 20.0 μm.
　If the air ratio in the heating zone is less than 0.9, the average depth of the internal oxide layer will not be 5.0 μm or more. On the other hand, when the air ratio in the heating zone exceeds 1.3, not only the average depth of the internal oxide layer exceeds 20.0 μm, but also the hardness of the surface layer decreases due to the formation of the decarburized layer, resulting in fatigue durability. Is concerned about deterioration.
[0072]
In
　order to control the unevenness of the steel sheet surface after pickling , the air ratio in the heat equalizing zone, which is the zone immediately before extraction in the heating furnace process. It is effective to control. In the preheating zone, Ni, which is less likely to be oxidized than Fe, is concentrated on the ground iron side at the interface between the scale and the base iron. The Ni-concentrated layer having the Ni-concentrated portion suppresses oxidation in the surface layer, but suppresses external oxidation in the subsequent heating zone and promotes internal oxidation. After that, by controlling the air ratio in the soaking zone, for example, as shown in FIG. 3, the scale 2 erodes into the grain boundaries 5 and the like where diffusion is easy, and the ground caused by the difference in the concentration of Ni. Due to the difference in the Ni concentration on the surface of the iron 1, the way the interface between the scale 2 and the base iron 1 is oxidized becomes non-uniform, and the unevenness of the interface between the scale 2 and the base iron 1 becomes large. Further, although not shown in FIG. 3, unevenness is also generated by suppressing the erosion of the grain boundaries by the scale 2 by the Ni-concentrated portion 3 around the internal oxide 6. When this steel sheet is pickled, the scale 2 is removed, and the surface of the hot-rolled steel sheet has a predetermined roughness.
　By setting the air ratio in the soaking zone to 0.9 or more and 1.9 or less, after hot rolling, for example, using a 1 to 10 wt% hydrochloric acid solution at a temperature of 20 to 95 ° C. for less than 30 to 60 seconds. The standard deviation of the arithmetic mean roughness Ra of the surface of the hot-rolled steel sheet after pickling under the conditions of the pickling time can be 10.0 μm or more and 50.0 μm or less.
　If the air ratio in the soaking zone is less than 0.9, the oxygen potential is not reached to selectively generate oxide nuclei at the grain boundaries where diffusion is easy. Therefore, the standard deviation of the arithmetic mean roughness Ra of the surface of the steel sheet after pickling does not exceed 10.0 μm. On the other hand, when the air ratio in the soaking zone exceeds 1.9, the depth of the selectively oxidized grain boundaries in the plate thickness direction becomes too deep, which is the standard of the arithmetic mean roughness Ra of the steel sheet surface after pickling. The deviation exceeds 50.0 μm.
[0073]
Air ratio in
　preheating zone> Air ratio in heating zone Control of the air ratio in the preheating zone is important for controlling the Ni concentration on the surface of the hot-rolled steel sheet after pickling. On the other hand, control of the air ratio in the heating zone is important for controlling the degree of formation of the internal oxide layer. Therefore, it is necessary to promote the growth of the scale of the slab to some extent in the preheating zone in the limited furnace time to form a sufficient Ni-concentrated layer on the surface layer. For that purpose, a relatively high air ratio is required in which the growth of scale thickness follows a parabolic law. On the other hand, in order to control the average depth of the internal oxide layer within a preferable range, it is necessary to suppress the air ratio to be relatively low in the heating zone and suppress the rapid growth of the internal oxide layer. Further, if the air ratio is high in the heating zone, there is a concern that a decarburized layer is formed and grown, the hardness of the surface layer is lowered, and the fatigue durability is deteriorated. Therefore, it is preferable that the air ratio in the preheating zone is higher than the air ratio in the heating zone.
[0074]
[Cooling step]
　Average cooling rate from finish rolling temperature to Ms point temperature: 50 ° C / sec or more, maximum cooling rate below Ms point temperature: less than 50 ° C / sec In the
　cooling step, from finish rolling temperature to Ms point temperature Cool to a temperature range below the Ms point temperature so that the average cooling rate of the above is 50 ° C./sec or more (primary cooling). If the average cooling rate to the Ms point temperature is less than 50 ° C./sec, ferrite and upper bainite will be formed during cooling, and the volume fraction of tempered martensite and lower bainite, which are the main phases, will be 90% or more in total. Difficult to do. However, if ferrite is not formed during the cooling process, air cooling may be performed in the middle temperature range. When air cooling is performed in the cooling step, it is desirable that the temperature range is lower than the lower bainite formation temperature. If the temperature at which air cooling is performed is equal to or higher than the lower bainite formation temperature, upper bainite will be formed. Further, it is preferable that the cooling rate up to the air cooling temperature range is 50 ° C./sec or more. This is to avoid the formation of upper bainite. If the cooling rate between the Bs point temperature and the formation temperature of the lower bainite is less than 50 ° C./sec, the upper bainite is formed and fresh martensite is formed between the bainite laths, or the retained austenite is formed. (It becomes martensite with high dislocation density during processing), and low temperature toughness may decrease. The Bs point temperature is the formation start temperature of the upper bainite determined by the components, and is conveniently 550 ° C. The formation temperature of the lower bainite is also determined by the components, but is 400 ° C. for convenience. That is, between the finish rolling temperature and 400 ° C., it is preferable that the cooling rate between 550 and 400 ° C. is 50 ° C./sec or more, and the average cooling rate between the finish rolling temperature and 400 ° C. is 50 ° C./sec or more. ..
[0075]
　After stopping the above primary cooling in a temperature range of less than the Ms point temperature and 350 ° C. or higher, cooling (secondary cooling) is performed with the maximum cooling rate from the primary cooling stop temperature to the temperature range of less than 350 ° C. being less than 50 ° C./sec. Is preferable. This is to control the average number density of iron-based carbides in tempered martensite or lower bainite within a preferable range. When the maximum cooling rate in this temperature range is 50 ° C./sec or more, it is difficult to set the iron-based carbide in a preferable range. For this reason, it is preferable that the maximum cooling rate is less than 50 ° C./sec.
　Here, cooling at a maximum cooling rate of less than 50 ° C./sec in a temperature range of less than the Ms point temperature to less than 350 ° C. can be realized by, for example, air cooling. In addition, it does not mean only cooling, but also includes isothermal maintenance and the like. Furthermore, since the purpose of cooling rate control in this temperature range is to control the number density of iron-based carbides in the steel plate structure, the martensitic transformation end temperature (Mf point) once obtained by the following equation (5). ) After cooling to the following, the temperature may be raised and reheated.
Mf = 0.285 × Ms-460 × C + 232 ... (5)
[0076]
[Rewinding process]
Rewinding temperature: Less than 350 ° C.
　Generally, in order to obtain martensite, it is necessary to suppress ferrite transformation, and it is said that cooling at 50 ° C./sec or more is required. In addition, at low temperatures, there is a transition from a temperature range called the membrane boiling region, which has a relatively low heat transfer coefficient and is difficult to cool, to a temperature region, which has a large heat transfer coefficient called the nucleate boiling temperature region and is easy to cool. When the cooling stop temperature is set to a temperature range of less than 400 ° C., the winding temperature tends to fluctuate, and the material also fluctuates accordingly. For this reason, the normal winding temperature was often set to either more than 400 ° C. or room temperature winding.
　As a result, it is presumed that it has been difficult to find in the past that it is possible to simultaneously secure a tensile strength of 980 MPa or more and excellent low temperature toughness by winding at a temperature lower than 400 ° C. or lowering the cooling rate.
　By cooling the hot-rolled steel sheet according to the present embodiment as described above, it is possible to simultaneously secure a tensile strength of 980 MPa or more and excellent low-temperature toughness even when the hot-rolled steel sheet is wound at a temperature lower than 350 ° C.
　After winding, if necessary, shape correction by skin pass rolling or strain removal heat treatment at less than 400 ° C. may be performed.
[0077]
[Pickling step]
[Skin pass step] For the
　purpose of improving ductility by straightening the shape of the steel sheet and introducing movable dislocations, skin pass rolling with a reduction ratio of 0.1% or more and 2.0% or less may be performed. Further, the obtained hot-rolled steel sheet may be pickled, if necessary, for the purpose of removing scale adhering to the surface of the obtained hot-rolled steel sheet. In the case of pickling, it is preferable to pickle with a 1 to 10 wt% hydrochloric acid solution at a temperature of 20 to 95 ° C. under a pickling time of less than 30 to 60 seconds.
　Further, after pickling, the obtained hot-rolled steel sheet may be subjected to skin pass or cold rolling with a reduction ratio of 10% or less in-line or offline.
[0078]
　The hot-rolled steel sheet according to the present embodiment is manufactured through normal hot-rolling processes such as continuous casting, rough rolling, finish rolling, cooling, winding, pickling, etc., but a part of the hot-rolled steel sheet is removed. Even so, it is possible to secure a tensile strength of 980 MPa or more and excellent low temperature toughness. Further, even if the hot-rolled steel sheet is once manufactured and then heat-treated online or offline in the temperature range of 100 to 600 ° C. for the purpose of precipitating carbides, low-temperature toughness and tensile strength of 980 MPa or more are ensured. It is possible.
[0079]
　In the present embodiment, the steel sheet having a tensile strength of 980 MPa or more is a steel sheet cut out in a direction perpendicular to the rolling direction of hot rolling, and a tensile strength by a tensile test performed in accordance with JIS Z 2241: 2011. Means a steel sheet of 980 MPa or more.
　In the present embodiment, the steel sheet having excellent toughness at low temperature refers to a steel sheet having a fracture surface transition temperature (vTrs) of −40 ° C. or lower in a Charpy test conducted in accordance with JIS Z 2242: 2005. When the target steel sheet is mainly used for automobile applications, the plate thickness is about 0.8 to 8.0 mm, but in many cases, the plate thickness is about 3.0 mm. Therefore, in the present embodiment, the surface of the hot-rolled steel sheet is ground, and the steel sheet is processed into a 2.5 mm subsize test piece.
[0080]
　According to the above manufacturing method, a hot-rolled steel sheet according to the present embodiment can be obtained. According to the hot-rolled steel sheet according to the present embodiment, it is an ultra-high-strength steel sheet having a tensile strength of 980 MPa or more, and even when a zirconium-based chemical conversion treatment liquid is used, it is different from the case where a zinc phosphate chemical conversion treatment liquid is used. Equivalent or better chemical conversion treatment property and coating film adhesion can be obtained. Therefore, the hot-rolled steel sheet according to the present embodiment is suitable for automobile parts that require high strength and corrosion resistance after painting.
Example
[0081]
　Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[0082]
　Steel Nos. Of Table 1A and Table 1B (Table 1B is a continuation of Table 1A). Steels having the chemical compositions shown in A to V were melted and continuously cast to produce slabs having a thickness of 240 to 300 mm. The obtained slab was heated to the temperatures shown in Tables 2A and 2B using a heat storage type burner. At that time, the air ratios in the preheating zone (preheating zone), the heating zone (heating zone), and the soaking zone (equal tropical) were controlled as shown in Tables 2A and 2B.
[0083]
　The heated slab was hot-rolled at the finishing temperatures shown in Tables 2A and 2B. After hot rolling, cooling was performed under the cooling conditions shown in Tables 2A and 2B, and after cooling, winding was performed.
[0084]
　The obtained production No. The microstructure of the hot-rolled steel sheets of 1 to 35 was observed, and the volume fraction and average effective crystal grain size of each phase were determined.
[0085]
　The volume fraction of each phase was determined by the following method.
　First, the sample is nighttal-etched, and after etching, the microstructure photograph obtained in a field of view of 300 μm × 300 μm is subjected to image analysis to obtain the area ratios of ferrite and pearlite, and bainite and martensite. , The total area ratio of retained austenite was obtained. Next, the nighttal-etched portion was subjected to repera-etching, and the microstructure photograph obtained in a field of view of 300 μm × 300 μm was subjected to image analysis using an optical microscope to determine the total area ratio of retained austenite and martensite. Calculated. Furthermore, using a sample surface-cut from the direction normal to the rolled surface to a depth of 1/4 of the plate thickness, the residual austenite area ratio was obtained by X-ray diffraction measurement, and the area ratios of ferrite, bainite, martensite, retained austenite, and pearlite were calculated. Obtained. Then, at a depth of 1/4 of the plate thickness from the surface of the steel plate, at least 3 regions of 40 μm × 30 μm were observed at a magnification of 1000 to 100,000 times using a scanning electron microscope, and whether or not the above-mentioned features were included. Based on this, the proportions of lower bainite and upper bainite in bainite and the proportions of tempered martensite and fresh martensite in martensite were determined. From these, the area fraction of each phase was calculated and used as the volume fraction.
[0086]
　The average effective crystal grain size is determined by using EBSP-OIM TM (Electron Backscatter Diffraction Pattern Microscope) at a depth of 1/4 of the plate thickness from the surface of the steel plate, and the orientation difference of the crystal grains is generally set to the crystal grain. The grain was visualized and obtained from the mapped image defined as 15 °, which is the threshold value of the large-angle grain boundary recognized as the boundary. In addition, the aspect ratio was also measured.
[0087]
　The Ni concentration on the surface was determined by the following method.
　Using a JXA-8530F field emission electron probe microanalyzer (FE-EPMA), the target hot-rolled steel sheet was analyzed for Ni concentration over a measurement area of ​​900 μm 2 or more from the direction perpendicular to the surface of the steel sheet . The Ni concentration in the measurement range was averaged. At this time, the measurement conditions were an acceleration voltage: 15 kV, an irradiation current: 6 × 10-8 A, an irradiation time: 30 ms, and a beam diameter of 1 μm.
[0088]
　The number density of iron-based carbides was determined by the following method.
　A sample is taken with the cross section parallel to the rolling direction of the steel plate as the observation surface, the observation surface is polished, and night tar etching is performed. A field emission scanning electron microscope (FE-SEM: Field Emission Scanning Electron Microscope) was used to observe the range of 3/8 in 10 fields at a magnification of 200,000 times, and the number density of iron-based carbides was measured.
[0089]
　The average depth of the internal oxide layer was determined by the following method.
　A surface parallel to the rolling direction and the plate thickness direction is cut out as an embedding sample at a position 1/4 or 3/4 of the plate width direction of the pickling plate, and after embedding in the resin sample, mirror polishing is performed and the pickling plate is optical without etching. Twelve fields of view were observed with a microscope in a field of view of 195 μm × 240 μm (corresponding to a magnification of 400 times). When a straight line is drawn in the plate thickness direction, the position where it intersects the surface of the steel plate is taken as the surface, and the depth of the internal oxide layer (position of the lower end) of each field of view with respect to that surface is measured and averaged at 5 points per field of view. , The average value was calculated by excluding the maximum value and the minimum value from the average value of each visual field, and this was taken as the average depth of the internal oxide layer.
[0090]
　The standard deviation of the arithmetic mean roughness of the surface was calculated by the following method.
　After measuring the surface roughness of the pickling plate by the measurement method described in JIS B 0601: 2013, the arithmetic mean roughness Ra on the front and back sides of 12 samples was measured, and then the standard deviation of the arithmetic mean roughness Ra of each sample was calculated. Then, the average value was calculated from the standard deviation excluding the maximum value and the minimum value.
[0091]
　In addition, the obtained production No. Tensile strength and toughness (vTrs) were determined as mechanical properties of the steel sheets 1 to 35.
[0092]
　The tensile strength was determined by performing a tensile test in accordance with JIS Z 2241 using a JIS No. 5 test piece cut out in a direction perpendicular to the rolling direction of hot rolling.
　It was judged that preferable characteristics were obtained when the tensile strength was 980 MPa or more.
[0093]
　For toughness, the surface of the hot-rolled steel sheet was ground, the steel sheet was processed into a 2.5 mm subsize test piece, and a Charpy test conducted in accordance with JIS Z 2242 was performed to determine the fracture surface transition temperature (vTrs).
　When vTrs was −40 ° C. or lower, it was judged that preferable characteristics were obtained.
[0094]
　The chemical conversion processability was evaluated by the following method.
　The surface of the steel plate after the chemical conversion treatment was observed with a field emission scanning electron microscope (FE-SEM: Field Emission Scanning Electron Microscope). Specifically, 10 visual fields were observed at a magnification of 10000 times, and the presence or absence of "scale" to which the chemical conversion-treated crystals were not attached was observed. The observation was performed at an acceleration voltage of 5 kV, a probe diameter of 30 mm, and tilt angles of 45 ° and 60 °. Tungsten coating (ESC-101, Elionix) was applied for 150 seconds to impart conductivity to the sample.
　When no scale was observed in all the visual fields, it was judged that the chemical conversion processability was excellent (“OK” in the table).
[0095]
　The coating film adhesion was evaluated by the following method.
　25 μm thick electrodeposition coating is applied to the upper surface of the hot-rolled steel sheet after chemical conversion treatment, and after coating baking treatment at 170 ° C for 20 minutes, the electrodeposition coating film is long until it reaches the base metal with a knife with a sharp tip. A 130 mm cut was made. Then, under the salt spray conditions shown in JIS Z 2371, 5% salt spray at a temperature of 35 ° C. was continuously performed for 700 hours, and then a tape having a width of 24 mm (Nichiban 405A-24 JIS Z 1522) was placed on the notch. A length of 130 mm was pasted parallel to the cut portion, and the maximum peeling width of the coating film when this was peeled off was measured.
　When the maximum coating film peeling width was 4.0 mm or less, it was judged that the coating film adhesion was excellent.
[0096]
　The results are shown in Tables 3A and 3B.
　As can be seen from Tables 3A and 3B, Production No. which is an example of the present invention. 1 to 3, 7 to 10, 14, 17 to 28 have excellent toughness even when the tensile strength is 980 MPa, and even if chemical conversion treatment using a zirconium-based chemical conversion treatment liquid is performed, chemical conversion treatment is possible. Was good, and a chemical conversion treatment film having excellent coating film adhesion was obtained.
　On the other hand, the production No. in which the Ni concentration in the component, the metallographic structure, or the surface is not within the range of the present invention. In 4 to 6, 11 to 13, 15, 16, 29 to 35, the mechanical properties were not sufficient, or the chemical conversion processability and / or the coating film adhesion was inferior.
[0097]
[Table 1A]

[0098]
[Table 1B]

[0099]
[Table 2A]

[0100]
[Table 2B]

[0101]
[Table 3A]

[0102]
[Table 3B]

Industrial applicability
[0103]
　According to the present invention, it is an ultra-high-strength steel sheet having a tensile strength of 980 MPa or more, and even when a zirconium-based chemical conversion treatment liquid is used, the chemical conversion treatment property is equal to or higher than that when a zinc phosphate chemical conversion treatment liquid is used. It is possible to obtain a hot-rolled steel sheet having a coating film adhesion. Since the steel sheet according to the present invention is excellent in chemical conversion treatment property and coating film adhesion, it is excellent in corrosion resistance after coating. Therefore, the present invention is suitable for automobile parts that require high strength and corrosion resistance after painting.
Code description
[0104]
　1 Ground iron (steel plate)
　2 Scale
　3 Ni Concentrated part
　4 Zirconium-based chemical crystals
　5 Grain boundaries
　6 Internal oxides
The scope of the claims
[Claim 1]
　The chemical composition represented by the average value in the entire plate thickness direction is, in mass%,
　　C: 0.050% or more, 0.200% or less,
　　Si: 0.05% or more, 3.00% or less,
　　Mn: 1. .00% or more, 4.00% or less,
　　Al: 0.001% or more, 2.000% or less,
　　N: 0.0005% or more, 0.1000% or less,
　　Ni: 0.02% or more, 2.00 %
　　Or less, Nb: 0% or more, 0.300% or less,
　　Ti: 0% or more, 0.300% or less,
　　Cu: 0% or more, 2.00% or less,
　　Mo: 0% or more, 1.000% or less ,
　　V: 0% or more, 0.300% or less,
　　Cr: 0% or more, 2.00% or less,
　　Mg: 0% or more, 0.0100% or less,
　　Ca: 0% or more, 0.0100% or less,
　　REM : 0% or more, 0.1000% or less,
　　B: 0% or more, 0.0100% or less,
　　one or more of Zr, Co, Zn, and W: 0 to 1.000% in total,
　　Sn : 0 to 0.050%,
　　P: 0.100% or less,
　　S: 0.0300% or less,
　　O: 0.0100% or less, the
　　balance is composed of Fe and impurities, and the following formula (1) is satisfied, and the
　PCM represented by the following (2) is 0.20 or more. When the Ms shown in (3) below is 400 ° C. or higher and the
　thickness is t, the metallographic structure at the position t / 4 from the surface is either tempered martensite or lower bainite. A hot-rolled steel sheet containing one or both of 90% or more in total volume fraction, a
　tensile strength of 980 MPa or more, and an
　average Ni concentration of 7.0% or more on the surface
.
　0.05% ≤ Si + Al ≤ 2.50% ・ ・ ・ Equation (1)
　PCM = C + Si / 30 + Mn / 20 + Cu / 20 + Ni / 60 + Mo / 15 + Cr / 20 + V / 10 + 5 × B ・ ・ ・ Equation (2)
　Ms = 561-474 × C-33 × Mn-17 × Ni-17 × Cr-21 × Mo ・ ・ ・ Formula (3)
　The element shown in the above formula is the mass% of the element contained in the hot-rolled steel sheet.
[Claim 2]
　The hot-rolled steel sheet according to claim 1, 　wherein the chemical composition contains
　Ni: 0.02% or more and 0.05% or less
in mass% .
[Claim 3]
The hot-rolled steel sheet according to claim 1 or 2, 　wherein the average number density of iron-based carbides present in the tempered martensite and the lower bainite is 1.0 × 10 6 pieces / mm 2 or more.
..
[Claim 4]

Claims 1 to 3 　include an internal oxide layer present in the hot-rolled steel sheet, and the average depth of the internal oxide layer is 5.0 μm or more and 20.0 μm or less from the surface of the hot-rolled steel sheet. The hot-rolled steel sheet according to any one of the above items.
[Claim 5]
　The hot-rolled steel sheet according
to any one of claims 1 to 4 , wherein the standard deviation of the arithmetic mean roughness Ra of the surface of the hot-rolled steel sheet is 10.0 μm or more and 50.0 μm or less .
[Claim 6]
[Correction under Rule 91 24.04.2020]　
　The chemical composition, by
mass%, B: 0.0001% or more 0.0100% or
less, Ti: 0.015% or more 0.300% or less,
of one or of
The hot-rolled steel sheet according to any one of claims 1 to 5, which contains two types .
[Claim 7]
　The chemical composition is, in mass%,
Nb: 0.005% or more, 0.300% or less,
Cu: 0.010% or more, 2.00% or less,
Mo: 0.010% or more, 1.000% or less. ,
V: 0.010% or more, 0.300% or less,
Cr: 0.01% or more, 2.00% or less, wherein
one or two or more of them are contained. The hot-rolled steel sheet according to any one of the above items.
[Claim 8]
　The chemical composition is, in mass%,
Mg: 0.0005% or more, 0.0100% or less,
Ca: 0.0005% or more, 0.0100% or less,
REM: 0.0005% or more, 0.1000% or less. ,
containing one or two or more of the
hot-rolled steel sheet according to any one of claims 1 to 7, wherein the.
[Claim 9]

　A heating furnace provided with a 　casting step of casting a molten steel having the chemical composition according to claim 1 to obtain a steel piece, and a heat storage type burner having at least a preheating zone, a heating zone and a soaking zone for the steel piece. in a heating step of heating,
　the heated the steel strip, a hot rolling step of the finish rolling temperature to obtain a hot rolled steel sheet by performing a hot rolling so that the above 850 ° C.,
　the following formula from the finish rolling temperature ( as the average cooling rate to the Ms point temperature is calculated by 4) is 50 ° C. / sec or more, a primary cooling step of primary cooling said hot-rolled steel sheet to a temperature range below the Ms point temperature,
　the hot-rolled a winding step of winding the steel sheet at a temperature below 350 ° C.,
have,
　in the heating step, the air ratio in the pre-heating zone 1.1 or more and 1.9 or less
heat, characterized in that Manufacturing method of rolled steel plate.
　Ms = 561-474 × C-33 × Mn-17 × Ni-17 × Cr-21 × Mo ・ ・ ・ Equation (4)
[Claim 10]
　The primary cooling is stopped at a temperature lower than the Ms point temperature and 350 ° C. or higher, and the hot-rolled steel sheet after the primary cooling is cooled to less than 350 ° C. so that the maximum cooling rate is less than 50 ° C./sec.
The method for manufacturing a hot-rolled steel sheet according to claim 9, wherein the hot-rolled steel sheet is manufactured.
[Claim 11]
　The
method for producing a hot-rolled steel sheet according to claim 9 or 10, wherein in the heating step, the air ratio in the heating zone is 0.9 or more and 1.3 or less .
[Claim 12]
　The
method for producing a hot-rolled steel sheet according to any one of claims 9 to 11, wherein in the heating step, the air ratio in the heat equalizing zone is 0.9 or more and 1.9 or less .
[Claim 13]
　The
method for producing a hot-rolled steel sheet according to claim 11 or 12 , wherein the air ratio in the preheating zone is larger than the air ratio in the heating zone .
[Claim 14]
　The hot-rolled steel sheet after the winding step is provided with a pickling step of pickling with a 1 to 10 wt% hydrochloric acid solution at a temperature of 20 to 95 ° C. under a pickling time of less than 30 to 60 seconds.
The method for producing a hot-rolled steel sheet according to any one of claims 9 to 13, wherein the hot-rolled steel sheet is manufactured.