JP2008024980A - High-strength galvannealed steel sheet and producing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-strength galvannealed steel sheet capable of stably obtaining higher fatigue durability than heretofore. <P>SOLUTION: In the high-strength galvannealed steel sheet having galvannealed layer on the high-strength steel sheet, the high-strength steel sheet has ≥5% the volume ratio of the retained austenite and ≥10% the total of volume ratios of bainite and martensite, and in the interface between the galvannealed layer and the high-strength steel sheet, the thickness of a range, in which Fe concentration with GDS (glow discharge spectrometry) becomes 20-90%, is ≥1.2μm. Thereby, the high strength, high workability and high fatigue-durability can simultaneously be obtained. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a high-strength galvannealed steel sheet and a method for producing the same. In particular, the present invention relates to a high-strength alloyed hot-dip galvanized steel sheet capable of stably obtaining high fatigue durability as compared with the prior art and a method for producing the same.

  An alloyed hot-dip galvanized steel sheet is available as a plated steel sheet having good corrosion resistance. This alloyed hot-dip galvanized steel sheet is usually degreased and then preheated in a non-oxidizing furnace or straightening furnace, and subjected to reduction annealing in a reducing furnace to clean the surface and secure the material, It is manufactured by alloying after being immersed in and controlling the adhesion amount of molten zinc. Since this steel plate is excellent in corrosion resistance, plating adhesion, and the like, it is widely used mainly for automobiles, building materials and the like.

  Particularly in recent years, in the automobile field, it has been necessary to increase the strength of plated steel sheets in order to achieve both a function for protecting passengers in the event of a collision and weight reduction for the purpose of improving fuel consumption. However, since increasing strength generally causes deterioration of workability, establishment of a method for increasing strength while maintaining workability has been desired.

  As methods for increasing the strength while maintaining the workability, there are methods described in Patent Documents 1 and 2, for example. In this method, residual austenite is dispersed in steel, and the use of the fact that residual austenite induces stress and processing induction during processing provides high strength and high workability at the same time. The steel sheets described in Patent Documents 1 and 2 use C, Si, and Mn as basic alloy elements, and after annealing in a two-phase region, heat treatment is performed in a temperature range of about 300 to 450 ° C., thereby performing bainite transformation. Utilized and obtained retained austenite even at room temperature. However, carbide such as cementite is likely to be produced during heat treatment at 300 to 450 ° C., and austenite is decomposed. Therefore, Si or Al needs to be added.

  However, since Si and Al are easier to oxidize than Fe, the above steel sheet tends to form an oxide containing Si or Al on the surface. These oxides have poor wettability with molten Zn. For this reason, in the steel plate which added Si or Al, there exists a problem that a non-plating part is easy to be formed. Further, the above oxides delay the alloying reaction between Zn and Fe. For this reason, steel sheets to which Si or Al is added require an alloying treatment at a high temperature and a long time as compared with a mild steel plate, which not only leads to a decrease in productivity, but austenite is converted to pearlite or carbide by the high temperature and long time treatment. It decomposes into a bainite structure containing, and excellent workability cannot be obtained.

  As a method for solving these problems, there is a method described in Patent Document 3. This method is intended to improve the wettability between the steel sheet and the molten Zn and to promote the alloying reaction by adding an appropriate concentration of Al to the molten Zn.

However, none of the techniques described above considers improving fatigue durability. Fatigue durability is a deformation characteristic when a sufficiently low stress is repeatedly applied to the maximum tensile strength, and is an indispensable characteristic for structural members such as automobiles, construction machines, and building materials that receive repeated stress. When subjected to repeated stress, even if the magnitude of the stress is less than the yield stress, fine deformation occurs inside the steel sheet, and the steel sheet will break due to the accumulation of this. This rupture is caused by a crack formed on the surface and propagating inside.
Therefore, in order to improve the fatigue durability, it is important to suppress the formation of fatigue cracks or to suppress the propagation of cracks.

Strengthening the structure of soft ferrite with a hard structure such as hard martensite and retained austenite, which suppresses the propagation of fatigue cracks propagating in soft ferrite with a hard structure. The phase fraction contributes to the improvement of fatigue durability. However, since fatigue cracks propagate through soft tissue, there is a problem that the fatigue limit is difficult to increase only by increasing the hard tissue fraction. As a result, when the hard structure fraction exceeds a certain level, the strength of the steel sheet increases, but the fatigue limit does not increase. Therefore, it is difficult to achieve both high strength and fatigue durability. (For example, refer nonpatent literature 1).
On the other hand, thin steel plates used in automobiles and construction machinery have a thin plate thickness, and therefore, when a fatigue crack is formed, the plate thickness may be penetrated immediately, leading to breakage. For this reason, suppression of fatigue crack formation is particularly important.
In addition, when considering application to automobile parts, there is a concern that even if it is a minute crack, it may become a starting point of destruction at the time of vehicle collision, and there is a concern that the predetermined collision safety cannot be obtained. It is considered important for improving the characteristics.
For this reason, suppressing the formation of cracks on the surface is particularly important in improving fatigue durability.

  As a general technique for improving fatigue durability, there is a method using precipitation hardening (see, for example, Patent Document 4). However, in order to use precipitation hardening, it is necessary to cool the steel sheet after it has been heated to such a high temperature that precipitates (for example, Nb and Ti carbonitrides) melt. It is difficult to apply to rolled steel sheets.

  In Patent Document 5, fatigue characteristics are improved by isolating and dispersing the soft phase (ferrite) in the hard second phase and making the thickness of the hard phase larger than the value determined by the particle size of the soft phase. The technology to be described is described. However, this technique suppresses the propagation of cracks formed on the surface, and does not suppress the formation of cracks on the surface. For this reason, it is difficult to sufficiently improve the fatigue durability of the steel sheet with this technology.

Patent Document 6 describes a technique for improving fatigue durability by setting the grain boundary oxide depth at the plating layer / steel plate interface to 0.5 μm or less. The fatigue durability is improved because the stress concentration at the plating layer / steel plate interface is suppressed by reducing the grain boundary oxide depth.
However, even with this technique, it has been difficult to sufficiently suppress the formation of cracks on the surface.

Yokomaku Toshinori, 3 others, The 40th Annual Conference of the Japan Institute of Metals, 1991, p16 Japanese Patent Laid-Open No. 05-70886 JP 05-195143 A JP 2003-105516 A JP 2006-57120 A JP 2005-194586 A JP 2003-171752 A

  As described above, in order to improve the fatigue endurance characteristics of the steel sheet, it is necessary to suppress the formation of cracks on the surface. However, it has been difficult to stably suppress the formation of cracks on the surface with conventional techniques. The present invention has been made in consideration of such circumstances, and its purpose is to make a high-strength alloy that can stably obtain high fatigue durability by stably suppressing the formation of cracks on the surface. An object of the present invention is to provide a hot-dip galvanized steel sheet and a method for producing the same.

The gist of the present invention aimed at solving the above problems is as follows.
(1) In mass%,
C: 0.07 to 0.25%,
Si: 0.8-2.0%,
Mn: 1.1 to 2.5%
Al: 0.001 to 2.0%,
N: 0.01% or less,
S: 0.01% or less,
O: A high-strength galvanized steel sheet having an alloyed hot-dip galvanized layer containing Fe on a high-strength steel sheet containing 0.01% or less and the balance being Fe and unavoidable impurities. ,
The high-strength steel sheet has a volume ratio of retained austenite of 5% or more, and a total volume ratio of bainite and martensite of 10% or more,
A high-strength galvannealed steel sheet having a thickness of 1.2 μm or more in a region where the Fe concentration by GDS is 20 to 90% at the interface between the galvannealed layer and the high-strength steel sheet .

(2) One or more Si oxides selected from FeSiO ₃ , Fe ₂ SiO ₄ , MnSiO ₃ , and Mn ₂ SiO ₄ are present in one or both of the galvannealed layer and the steel sheet. And either one or both of the plated layer and the steel plate, SiO ₂ is present, and the peak of the concentration distribution of the Si oxide is higher than the peak of the concentration distribution of the SiO _2. The high-strength galvannealed steel sheet according to (1), which is located on the surface side of the steel sheet.

(3) The high-strength steel plate is Ni: 0.05 to 2.0% in mass%.
Cu: 0.05-2.0%,
Cr: 0.05-2.0%,
Mo: 0.05-2.0%,
B: 0.0001 to 0.002%,
Ti: 0.001 to 0.1%,
Nb: 0.001 to 0.1%,
V: 0.001 to 0.1%
REM: 0.0001 to 0.1%,
Ca: 0.0001 to 0.1%
The high-strength galvannealed steel sheet according to (1) or (2) above, which contains at least one of the following.

(4) The high-strength galvannealed steel sheet according to any one of (1) to (3), wherein the galvannealed layer further contains Al.
(5) 2 × 10 ⁶ times obtained by performing a fatigue test in accordance with JIS Z 2275 on the first test piece defined in JIS Z 2275 having a parallel part of 30 mm, a plate thickness of 2 mm, and a radius of curvature of 100 mm. The high-strength galvannealed high-galvanized coating according to any one of (1) to (4) above, wherein a fatigue limit ratio, which is a value obtained by dividing time strength by maximum tensile strength, is 0.55 or more steel sheet.
(6) The high-strength alloying melt according to any one of (1) to (5) above, wherein the product of maximum tensile strength (Ts) and elongation (EI) is 21000 (MPa ·%) or more. Galvanized steel sheet.

(7) By mass%
C: 0.07 to 0.25%,
Si: 0.8-2.0%,
Mn: 1.1 to 2.5%
Al: 0.001 to 2.0%,
N: 0.001 to 0.1%
S: 0.0001 to 0.1%,
O: 0.0001 to 0.1%
Is reduced by passing a high-strength steel plate containing Fe and unavoidable impurities through a reduction zone, and then dipped in a plating bath to be pulled up, and then subjected to alloying treatment to continuously melt zinc. A method for producing a high-strength galvannealed steel sheet to be plated,
As the atmosphere of the reduction zone, ₁ to 60% by volume of H ₂ is contained, and the balance consists of one or more of N ₂ , H ₂ O, O ₂ , CO ₂ , CO and inevitable impurities, and the atmosphere The logarithmic log PO ₂ of the partial pressure of oxygen is −0.000034T ² + 0.105T−0.2 [Si%] ² +2.1 [Si%] − 98.8 ≦ log PO ₂ ≦ −0.000038 T ² +0.107 T -90.4 ... (1)
923 ≦ T ≦ 1173 (2)
T: Maximum attained temperature (K) of steel sheet, [Si%]: Si content in steel sheet (mass%)
Reduction in a controlled atmosphere,
A method for producing a high-strength galvannealed steel sheet characterized by causing molten zinc in the plating bath to flow in the plate width direction of the high-strength steel sheet when the high-strength steel sheet is immersed in the plating bath. .

(8) The method for producing a high-strength galvannealed steel sheet according to (7) above, wherein the flow rate of the plating solution is 0.5 to 2.5 m / sec.
(9) The method for producing a high-strength galvannealed steel sheet according to (7) or (8), wherein the alloying treatment is performed at a temperature of 480 ° C. or lower.
(10) The high-strength steel plate is
The cast slab is heated, and the heated cast slab is hot-rolled at an Ar ₃ transformation point or higher, and then wound in a temperature range of 630 ° C. or lower, and then cold-rolled at a reduction rate of 40 to 70% after pickling. Formed by
When reducing the high-strength steel plate,
In the reduction zone, annealing is performed at 750 ° C. or more and 900 ° C. or less, and then cooled to 650 ° C. at 0.1 to 200 ° C./second, and then the average cooling rate between 650 ° C. and 500 ° C. is 3 to 200 ° C./second. It is cooled to (temperature of the plating solution −40) to (temperature of the plating solution +50) ° C. so that the high-strength alloy is formed according to any one of the above (7) to (9) Manufacturing method of hot dip galvanized steel sheet.

  According to the present invention, high fatigue durability can be stably obtained by stably suppressing surface crack formation in a high-strength galvannealed steel sheet. Further, high strength and high workability can be obtained at the same time.

The inventors have intensively studied for the purpose of improving fatigue durability in a high-strength galvannealed steel sheet. As a result, in a steel sheet that includes both a soft phase composed of ferrite and a hard phase composed of retained austenite, martensite, and bainite, by increasing the thickness of the alloy layer formed at the interface portion of the plated layer / steel sheet It has been found that the formation of cracks on the surface can be stably suppressed, and as a result, the fatigue durability can be improved while maintaining the high strength and high workability of the steel sheet. The alloy layer here means a region where the Fe concentration is 20 to 90%.
The reason for this is that the alloy layer (Vickers hardness is about HV300 to 330) is harder than the soft phase of the steel sheet (Vickers hardness is about HV150 to 200). It is considered that the formation of cracks can be suppressed by making the thickness of the alloy layer equal to or greater than the unevenness. In particular, the difference in hardness between soft ferrite and hard bainite structure, retained austenite and martensite structure (Vickers hardness of about HV 300 to 500) is large. The starting point of formation. However, it is possible to suppress deformation of the soft layer during repeated deformation by providing an alloy layer harder than the soft layer on the steel plate surface. As a result, the stress concentration at the interface between the soft tissue and the hard tissue can be relaxed, and the fatigue durability is considered to be improved.

  Specifically, when the thickness of the region where the Fe concentration by GDS is 20 to 90% is 1.2 μm or more at the plating layer / steel plate interface, in the high-strength galvannealed steel plate of the component system described later, Fatigue durability can be improved. The upper limit is not particularly defined, and the plating properties and excellent fatigue durability which are the effects of the present invention are exhibited. However, since it is not economically preferable to set the thickness to 10 μm or more, this is a substantial upper limit.

  This effect is particularly remarkable in a high-strength steel sheet having a hard phase volume ratio of 15% or more. This is because the higher the volume fraction of the hard phase, the higher the strength of the steel sheet, while the fatigue characteristics deteriorate. The hard phase referred to here is a bainite structure, a martensite structure, or a pearlite structure. However, in this steel, Si and Al are added to suppress the formation of carbides such as cementite, and cementite is not included in the bainite structure, or there may be a very small amount even if included. This was also classified as a bainite structure.

  In the hard phase, for example, the volume ratio of retained austenite is 5% or more, and the volume ratio of bainite and martensite is 10% or more in total. The greater the volume fraction of retained austenite, the better the balance between strength and ductility and the better the workability. However, in the present invention, the residual volume ratio is 5% or more as a steel plate excellent in plating property, fatigue durability and workability. However, if improvement in workability is not taken into consideration, ferrite and martensite containing no retained austenite are considered. The fatigue durability improvement by controlling the alloy layer thickness, which is the present method, can also be applied to site steel, ferrite and bainite steel.

  The volume ratio of retained austenite decreases because the decomposition of retained austenite is promoted as the alloying temperature of the plating layer / steel plate increases. As the alloying temperature increases and the decomposition of retained austenite proceeds, fatigue durability, strength, and ductility decrease. For this reason, in the manufacturing method of the steel plate which concerns on this invention, it is preferable that alloying temperature is 480 degrees C or less.

  In addition, in the annealing treatment of the high-strength steel plate performed before the formation of the plating layer, the present inventors keep the oxygen potential of the reduction zone within a predetermined range determined by the highest temperature reached during annealing and the Si concentration in the steel plate. Thus, it has been found that the thickness of the above-described alloy layer can be increased, and that the thickness of the above-described alloy layer can be increased by performing plating while applying a flow in the plate width direction of the steel sheet to the molten Zn in the plating bath.

Specifically, as the atmosphere of the reducing zone, and H ₂ contains 1 to 60 vol%, the remainder N _2, H ₂ O, made O _2, CO _2, CO 1, two or more and unavoidable impurities The logarithm log PO ₂ of the oxygen partial pressure in the atmosphere is controlled by the following equation (1), and the maximum temperature T (K) of the steel sheet is controlled by the following equation (2). In the present invention, all logarithms are shown as common logarithms.
−0.000034T ² + 0.105T−0.2 [Si%] ² +2.1 [Si%] − 98.8 ≦ log PO ₂ ≦ −0.000038 T ² + 0.107T-90.4 (1)
923 ≦ T ≦ 1173 (2)
[Si%]: Si content in the steel sheet (mass%)

The reason why the thickness of the alloy layer can be increased by controlling the oxygen potential is as follows. That is, one or more Si oxides selected from FeSiO ₃ , Fe ₂ SiO ₄ , MnSiO ₃ and Mn ₂ SiO ₄ and SiO ₂ are present in the steel sheet. When logPO ₂ is less than −0.000034T ² + 0.105T−0.2 [Si%] ² +2.1 [Si%] − 98.8, Si contained in the steel sheet diffuses to the steel sheet surface, and the steel sheet surface SiO ₂ is formed on the substrate. Since SiO ₂ has poor wettability with molten zinc, it causes non-plating. For this reason, formation of SiO _{2 on} the steel sheet surface is not preferable.

On the other hand, when logPO ₂ is −0.000034T ² + 0.105T−0.2 [Si%] ² +2.1 [Si%] − 98.8 or more, elements such as Si and Mn are more easily oxidized than Fe. Forms an oxide inside the steel sheet without diffusing into the surface layer of the steel sheet. In particular, by controlling the atmosphere within the above range, the SiO ₂ concentration distribution peak can be positioned inside the Si oxide concentration distribution peak. As a result, it becomes possible to suppress the formation of SiO _{2 on} the steel sheet surface, which has particularly poor wettability with molten zinc. As a result, the plating property is improved, Zn and Fe are easily diffused to each other, and the alloy layer becomes thick. Moreover, since Si and Mn which inhibit alloying are fixed as oxides, alloying is promoted and the alloy layer becomes thick.

Further, at the time of deformation, stress concentrates also around the Si oxide or SiO ₂ formed inside the steel plate, and as a result, the stress concentration on the surface is relaxed and the generation of cracks can be suppressed. In particular, by controlling the atmosphere of the reduction zone within the above range, it is possible to form SiO ₂ more inside the steel plate. Therefore, by setting the SiO ₂ concentration peak inside the Si oxide concentration peak, stress concentration on the steel sheet surface can be alleviated, which is more effective from the viewpoint of improving fatigue durability.
However, as a matter of course, there is a region where Si oxide and SiO ₂ are mixed, but the effect of the present invention can be obtained by positioning the peak of the concentration distribution of SiO ₂ inside the peak of the concentration distribution of Si oxide. It is possible to ensure excellent plating properties and fatigue durability.
Further, depending on the conditions, the SiO ₂ fraction may be very small, but excellent plating properties and fatigue durability, which are the effects of the conditions of the present invention, are ensured.

Also, the reason for limiting the LogPO ₂ below -0.000038T ² + 0.107T-90.4 is to reduce oxides of iron in the reduction zone. If logPO ₂ exceeds −0.000038T ² + 0.107T-90.4, it enters the iron oxidation region, so that an iron oxide film is generated on the surface of the steel sheet, resulting in bluing.

The oxygen potential in the reduction zone is often managed by PH ₂ O / PH ₂ , but as described above, the oxygen potential is directly managed in the present invention. The oxygen potential is managed for the following reasons.

Since FeSiO ₃ , Fe ₂ SiO ₄ , MnSiO ₃ , and Mn ₂ SiO ₄ are stable in a region where the oxygen potential is higher than that of SiO ₂ , FeSiO ₃ , Fe ₂ SiO ₄ , MnSiO ₃ , Mn _In order to obtain a state in which a concentration peak of one or more Si oxides selected from ₂ SiO ₄ exists and a concentration peak of SiO ₂ exists on the inner surface side of the steel sheet, the oxygen potential in the reduction zone, that is, the oxygen on the surface of the steel sheet It is necessary to make the potential larger than the value at which SiO ₂ alone is internally oxidized.

Specifically, since the oxygen potential in the steel decreases from the steel sheet surface toward the inside, at least one selected from FeSiO ₃ , Fe ₂ SiO ₄ , MnSiO ₃ , and Mn ₂ SiO _{4 is} formed on the steel sheet surface or surface side. When the oxygen potential on the steel sheet surface is controlled so that Si oxide is generated, one or more Si oxides selected from FeSiO ₃ , Fe ₂ SiO ₄ , MnSiO ₃ , Mn ₂ SiO ₄ are formed on the steel sheet surface or surface side. SiO ₂ is generated on the inner surface side of the steel plate that has been generated and the oxygen potential has decreased.

On the other hand, when the gas in the atmosphere is H ₂ , H ₂ O, O ₂ , and the balance N ₂ , it is considered that the following equilibrium reaction occurs, and PH ₂ O / PH ₂ is a power of 1/2 of PO ₂ and an equilibrium constant of 1 proportional to / _{K 1.}
H ₂ O = H ₂ + 1 / 2O ₂ : K ₁ = P (H ₂ ) · P (O ₂ ) 1/2 / P (H ₂ O)
However, since the equilibrium constant K ₁ is a variable depending on temperature, when the temperature changes, PH ₂ O / PH ₂ and PO ₂ change separately. That is, even in a region where the ratio of moisture pressure and hydrogen partial pressure, which corresponds to the oxygen potential of the internal oxidation region of Si at a certain temperature range, corresponds to the oxygen potential of the region where iron is oxidized at another temperature range, This is to cope with the oxygen potential of the external oxidation region.

Therefore, even if PH ₂ O / PH ₂ is controlled, the oxide defined in the present invention cannot be generated. In order to generate the oxide defined in the present invention under desired conditions, the PO in the atmosphere _It is necessary to manage ₂ directly.

The reason why H ₂ is limited to 1 to 60% by volume is that if it is less than 1%, the oxide film formed on the surface of the steel sheet cannot be sufficiently reduced, and plating wettability cannot be ensured. This is because the improvement of the action is not seen and the cost increases.

Further, the reason for limiting T to 923K or more is that when T is less than 923K, the oxygen potential of Si being externally oxidized is small, and therefore the oxygen potential in the range where it can be industrially operated becomes an iron oxidation region. This is because SiO ₂ is not generated and the corrosion resistance after coating is not deteriorated. On the other hand, the reason for limiting T to 1173K or less is that annealing at a temperature exceeding 1173K requires a lot of energy and is uneconomical. For the purpose of obtaining the mechanical properties of the steel sheet, it is sufficient that the maximum reached plate temperature is 1153 K or less, as will be described later.

  Further, the higher the atmospheric temperature in the furnace, the easier it is to raise the plate temperature of the steel sheet. However, if the atmospheric temperature is too high, the life of the refractory in the furnace is shortened and the cost is increased.

In the present invention, PO ₂ is operated by introducing one or more of H ₂ O, O ₂ , CO ₂ and CO. In the above-described equilibrium reaction formula, when the temperature is determined, the equilibrium constant is determined, and the oxygen partial pressure, that is, the oxygen potential is determined based on the equilibrium constant. At atmospheric temperatures from 773 K to 1273 K, the gas reaction reaches an equilibrium state in a short time, so that PO ₂ is determined to determine the atmospheric temperature of PH ₂ , PH ₂ O, PCO ₂ and PCO in the furnace.

O ₂ and CO do not need to be consciously introduced. However, when H ₂ O and CO ₂ are introduced into a furnace containing 1% by volume or more of H ₂ at the main annealing temperature, a part of them and H ₂ O ₂ and CO are produced by the equilibrium reaction. The introduction method of H ₂ O and CO ₂ is not particularly limited as long as a necessary amount can be introduced. For example, a method in which a gas in which CO and H ₂ are mixed is burned and the generated H ₂ O and CO ₂ are introduced. , CH ₄ , C ₂ H ₆ , C ₃ H _{8 and} other hydrocarbon gases, and a mixture of hydrocarbons such as LNG, and the generated H ₂ O and CO ₂ are introduced, gasoline, light oil, heavy oil Such as burning a mixture of liquid hydrocarbons and introducing the generated H ₂ O, CO ₂ , burning alcohols such as CH ₃ OH, C ₂ H ₅ OH and mixtures thereof, various organic solvents, Examples include a method of introducing the generated H ₂ O and CO ₂ .

CO only burned, but also conceivable to introduce CO ₂ generated, the annealing temperature, if CO ₂ was introduced into the furnace atmosphere, part is reduced by H _2, CO and H ₂ O is Therefore, there is essentially no difference from the case where H ₂ O and CO ₂ are introduced.

In addition to the method of introducing H ₂ O and CO ₂ generated by combustion, a gas in which CO and H ₂ are mixed, a hydrocarbon gas such as CH ₄ , C ₂ H ₆ , and C ₃ H ₈ , LNG A mixture of hydrocarbons such as gasoline, light oil, heavy oil, etc., a mixture of liquid hydrocarbons, alcohols such as CH ₃ OH and C ₂ H ₅ OH and mixtures thereof, various organic solvents, etc. in an annealing furnace simultaneously with oxygen It is also possible to use a method of introducing H ₂ O and CO ₂ by introducing into the furnace and burning in a furnace.

Such method utilizes N ₂ raising the N ₂ and dew point saturated with water vapor compared to the method of supplying steam, simple and the control is excellent. In addition, since there is no fear of condensation in the pipe, it is possible to save the trouble of heat insulation of the pipe.

In the present invention, the reduction time at the PO ₂ and temperature specified in the claims is not particularly specified, but is preferably 10 seconds to 30 minutes. Increasing the PO ₂ in the reducing furnace, the Atsushi Nobori process, after the LogPO ₂ has passed the region exceeding ^{-0.000038T 2 + 0.107T-90.4, -0.000038T} 2 + 0.107T-90.4 1) selected from FeSiO ₃ , Fe ₂ SiO ₄ , MnSiO ₃ , Mn ₂ SiO ₄ on the target steel plate surface or surface side because the iron oxide film formed first is reduced because it is reduced in the following regions. In order to obtain a steel sheet in which a concentration peak of Si oxide of a seed or more exists and a concentration peak of SiO ₂ exists on the inner surface side of the steel sheet, it is desirable to hold for 10 seconds or more. However, holding for more than 30 minutes is not economically preferable.
However, if the above conditions are satisfied, the whole furnace atmosphere is in the range of −0.000034T ² + 0.105T−0.2 [Si%] ² +2.1 [Si%] − 98.8 ≦ log PO ₂ . It is not necessary to. The purpose of the atmosphere is to form SiO ₂ or Si oxide inside the steel sheet. Since the formed SiO ₂ and Si oxides are difficult to be reduced in the reduction zone atmosphere, once an element that is more easily oxidized than Fe, such as Si or Mn, is converted into SiO ₂ or Si oxide inside the steel plate, the steel plate No SiO ₂ or Si oxide is formed on the surface layer. For this reason, it is not necessary to control the entire furnace atmosphere within the above range. Similarly, once SiO ₂ or Si oxide is formed on the surface of the steel sheet, it is difficult to reduce, so it is important that the furnace atmosphere during heating is within the above range.

Further, if the PO ₂ and temperature in the reducing atmosphere are within the range of the present invention, a normal non-oxidizing furnace type hot dipping method or a hot dipping method using an all radiant tube type annealing furnace can be used. As described in JP-A-55-122865, a method of forming an oxide film on the surface of a steel plate in advance and then annealing and reducing the iron oxide film can be used.

  As a method of forming an iron oxide film, for example, a method of forming an iron oxide film by controlling the combustion air ratio in the oxidation zone to 0.8 to 1.2, or a dew point of the oxidation zone is controlled to 273 K or more and an iron oxide film is formed. Any method of forming can be used.

  The reason for adjusting the combustion air ratio in the range of 0.8 to 1.2 is that a combustion air ratio of 0.8 or more is necessary in order to generate an iron oxide film sufficient to suppress external oxidation of Si. If it is less than 0.8, a sufficient iron oxide film cannot be formed. Further, when the combustion air ratio exceeds 1.2, the iron oxide film formed in the oxidation zone is too thick, and the peeled oxide adheres to the roll and generates appearance defects.

  The reason for controlling the dew point of the oxidation band to 273K or more is that a dew point of 273K or more is necessary to generate an iron oxide film sufficient to suppress external oxidation of Si, and the dew point is less than 273K. This is because an iron oxide film cannot be formed. The upper limit of the dew point is not specified, but it is preferably 373K or less in consideration of the influence on the deterioration of the equipment.

  Since the thickness of the oxide film affects not only the combustion air ratio and dew point, but also the line speed, the ultimate plate temperature, etc., these are controlled appropriately, and the plate is passed under the condition that the thickness of the oxide film is 20 to 200 nm. It is desirable to do.

However, in order to finish the reduction of the generated iron oxide film, the reduction time at PO ₂ and temperature specified in the claims is preferably 20 seconds or more.

In the above manufacturing method, the apparatus for introducing a gas containing 1 to 100% by volume of CO ₂ into the continuous hot dipping equipment and the balance N ₂ , H ₂ O, O ₂ , CO and unavoidable impurities is used as a reduction furnace. be arranged and the CO or hydrocarbon is combusted in a reducing furnace, the CO ₂ containing 1 to 100% by volume, balance N _2, H ₂ O, a gas consisting of O _2, CO and unavoidable impurities This can be achieved by providing a generating device.

In addition, by performing galvanization on the steel plate on which one or more kinds of Si oxides selected from FeSiO ₃ , Fe ₂ SiO ₄ , MnSiO ₃ , Mn ₂ SiO ₄ are formed on the steel plate surface or the surface side, and alloying them, A plating layer containing one or more Si oxides selected from FeSiO ₃ , Fe ₂ SiO ₄ , MnSiO ₃ , and Mn ₂ SiO ₄ can be formed in the plating layer.

  It is necessary to give a flow in the width direction to the molten Zn in the plating bath. The Fe concentration gradient is a value at which fatigue characteristics are improved by controlling the oxygen potential within a range of conditions and applying flow. Zn diffuses from the surface of the steel sheet in the plating bath. When the oxygen potential is controlled, silicate is generated in the vicinity of the surface in the steel sheet. At this time, volume expansion of the oxide occurs. It is thought that fine unevenness | corrugation produces | generates on the steel plate surface before plating by this. For this reason, the diffusion of Zn is promoted by increasing the interface area when Zn is diffused. Further, if there is a flow in the plating bath, the heat transfer coefficient from the plating bath to the steel sheet increases, so that the diffusion interface temperature increases and the diffusion coefficient of Zn increases, thereby promoting diffusion. By combining these, diffusion has already progressed in the plating bath, so the range where the Fe concentration gradient exists is large. On the other hand, in the steel sheet of the present invention with high Si and Mn, the diffusion of Fe into the plating layer during alloying treatment is not as great as in IF steel, and the alloy treatment temperature is ignored ignoring the effect on the strength-ductility balance. Even if it is increased, the range where the Fe concentration gradient exists is not so large.

  As described above, when the flow is applied in the plating bath after controlling the oxygen potential, the range in which the Fe concentration gradient exists is large, and at the same time, a uniform alloy layer can be formed in the width direction. The flow in the width direction generates a flow in the lateral direction using a metal pump when the steel plate is immersed in the snout. This method is known to flow from 0.5 m / s to 1 m / s in order to prevent adhesion of aluminum dross produced in IF steel and aluminum killed steel. In the present invention, since the Al in the plating bath is lower than that of IF steel, the production of aluminum dross is small, so that a metal pump is not usually used. The flow in the width direction is set to 0.5 m / second or more. If the flow is smaller than this, the diffusion of Fe and Zn at the interface cannot be sufficiently promoted, and the thickness of the alloy layer is 1.2 μm or more. It is because it cannot be said. On the other hand, even if the flow is applied at a speed exceeding 2.5 m / sec, the effect is not only saturated but also a significant capital investment is incurred, which is not preferable. However, even if the flow is performed at a flow rate exceeding this value, the fatigue durability, which is the effect of the present invention, can be obtained. Moreover, since it is better that the flow is large, a preferable range is 1.5 m / s to 2.5 m / s.

  Further, when the concentration gradient of Zn and Fe in the thickness direction becomes gentle, the gradient of hardness becomes gentle, so that the stress concentrated on the interface between the plating layer and the steel sheet becomes small. As a result, peeling of the plating layer is suppressed when repeated stress is applied and elastic deformation is performed. At the same time, the alloy layer on the steel sheet surface layer suppresses the deformation of soft ferrite during repeated deformation, thereby suppressing the concentration of deformation at the interface between ferrite and hard structure and the accompanying formation of fatigue cracks. Can greatly contribute to the improvement of fatigue durability.

The above is summarized in Table 1. In particular, when logPO ₂ is controlled within the above range, the molten Zn in the plating bath is flowed in the plate width direction of the steel plate, and the alloying temperature is 480 ° C. or less, the parallel part is 30 mm, the plate thickness is 2 mm, and the radius of curvature. Fatigue that is a value obtained by dividing the 2 × 10 ⁶ time strength obtained by performing a fatigue test in accordance with JIS Z 2275 on the No. 1 test piece defined in JIS Z 2275 with a tensile strength of 100 mm The limit ratio can be stably set to 0.55 or more. Further, the product of the maximum tensile strength (Ts) and the elongation (EI) can be 21000 (MPa ·%) or more.
The shape of the fatigue test piece is 30 mm for the parallel part, 2 mm for the plate thickness, and 100 mm for the radius of curvature. If the radius of curvature is large, the stress concentration factor is large, and easy formation of fatigue cracks occurs. From this, it is because it is not suitable for evaluation of the fatigue durability improvement effect by suppression of fatigue crack formation which is an effect of the present invention.

  Next, the reason for limiting the components in the high-strength steel plate will be described. Hereinafter, the mass% is simply described as%.

  C is an essential element for increasing the strength of a steel sheet by strengthening the structure with martensite or retained austenite. The reason why the content of C is set to 0.07% or more is that when C is less than 0.07%, it is difficult to set the retained austenite volume ratio necessary for increasing strength and improving ductility to 5% or more. is there. On the other hand, the reason why the C content is 0.25% or less is that when C exceeds 0.25%, it is difficult to ensure the strength of the spot weld. However, if mechanical fastening by caulking or bolts is performed, even if it contains C exceeding 0.25%, the effect of the present invention is excellent in plating property, fatigue durability and strength-ductility balance. A high-strength galvannealed steel sheet can be obtained.

  Si is added in an amount of 0.8 to 2.0% as an element that increases the strength without significantly impairing the workability of the steel sheet, particularly the elongation. The reason why the Si content is 0.8% or more is that it is difficult to ensure the required tensile strength when Si is less than 0.8%, and because of the alloying treatment performed immediately after plating. This is because the formation of carbides is remarkably delayed in reheating, and the above-described volume ratio of martensite, bainite and retained austenite are mixed in the ferrite even after cooling to room temperature. The carbide described here indicates cementite or pearlite structure. This is because if a large amount of these exists, austenite will be decomposed, so that it becomes impossible to secure a retained austenite volume ratio of 5% or more. The reason for making the Si content 2.0% or less is that when Si exceeds 2.0%, the effect of increasing the strength is saturated, ductility and weldability are lowered, and plating wettability is impaired. It is. Further, since Si increases the strength of the ferrite by solid solution strengthening, it suppresses the concentration of deformation on the ferrite during repeated deformation, and therefore needs to be added from the viewpoint of improving fatigue durability.

  Mn: Mn is a strengthening element and is effective in increasing the strength of the steel sheet. It also plays an important role in securing retained austenite because it suppresses pearlite transformation. However, if it exceeds 2.5%, the formability of the steel sheet is lowered, so the upper limit was made 2.5%. If the content is less than 1.1%, it becomes difficult to suppress pearlite transformation, plating bath immersion, and subsequent carbide formation during the alloying treatment. Therefore, the lower limit is set to 1.1%.

  Al: Al, like Si, may be added because it remarkably delays the formation of carbides in reheating for alloying performed immediately after plating, and is effective in securing retained austenite. It can also be used as a deoxidizer. In addition, Al may be added because it promotes ferrite formation and improves ductility. However, if it exceeds 2.0%, not only the cost is increased, but also the surface properties are deteriorated and the weldability and plating wettability are impaired, so the content is made 2.0% or less. On the other hand, making the Al content less than 0.001% is economically undesirable because it causes a significant increase in cost.

  N forms coarse nitrides and deteriorates bendability and hole expansibility, and causes blowholes during welding, so the content must be suppressed to 0.01% or less. On the other hand, the lower limit of the N content does not need to be set in particular. However, extremely reducing the N content requires a large amount of cost, so 0.0005% is a practical lower limit from the viewpoint of economy. .

  Since S adversely affects weldability and manufacturability during casting and hot rolling, it is necessary to suppress the content to 0.01% or less. On the other hand, the lower limit of the S content does not need to be set in particular, but extremely reducing the S content requires a large amount of cost, so 0.001% is a practical upper limit from the viewpoint of economy. .

  Since O forms an oxide and deteriorates the moldability, it is necessary to suppress the content to 0.01% or less. On the other hand, the lower limit of the O content does not need to be set in particular. However, extremely reducing the O content requires a large amount of cost, so 0.001% is a practical upper limit from the viewpoint of economy. . In addition, O content here refers to content of O contained in the steel plate after removing the internal oxide contained in a steel plate surface layer, and the oxide contained in a plating layer. Since the steel plate of this invention contains an oxide in any one or both in a steel plate surface layer and a plating layer, O content of a surface layer becomes high compared with the inside of a steel plate. However, since these oxides are present in the plating layer or on the surface layer of the steel sheet, the formability is not adversely affected.

  Further, one or more of Ni, Cu, Cr, Mo, B, Ti, Nb, V, REM (for example, La, Ce), and Ca may be added to the steel containing these as the main components. Even if these are contained, the effects of the present invention are not impaired, and depending on the amount, the corrosion resistance and workability may be improved. Specifically, Ni: 0.05-2.0%, Cu: 0.05-2.0%, Cr: 0.05-2.0%, Mo: 0.05-2.0%, B : 0.0001-0.002%, Ti: 0.001-0.1%, Nb: 0.001-0.1%, V: 0.001-0.1%, REM: 0.0001-0 0.1%, Ca: 0.0001 to 0.1%.

  Next, the alloyed hot-dip galvanized layer will be described. In the present invention, the alloyed hot dip galvanized layer is a plated layer mainly composed of an Fe—Zn alloy in which Fe in steel can diffuse during Zn plating by an alloying reaction. The Fe content is not particularly limited, but if the Fe content in the plating is less than 7% by mass, a soft Zn—Fe alloy is formed on the plating surface to deteriorate the press formability. Since a brittle alloy layer develops too much at the interface and plating adhesion deteriorates, 7 to 15% by mass is appropriate.

  In addition, when performing hot dip galvanization, since Al is added to the plating bath for the purpose of controlling the alloying reaction in the plating bath, 0.05 to 0.5% by mass of Al is contained in the plating. In addition, during the alloying process, the elements added to the steel diffuse simultaneously with the diffusion of Fe, so these elements are also included in the plating.

The steel sheet of the present invention is one of Pb, Sb, Si, Sn, Mg, Mn, Ni, Cr, Co, Ca, Cu, Li, Ti, Be, Bi, and rare earth elements during hot dip galvanizing bath or galvanizing. Alternatively, even if two or more kinds are contained or mixed, the effects of the present invention are not impaired, and depending on the amount, there are cases where the corrosion resistance and workability are improved, and so on. There are no particular restrictions on the amount of alloying hot dip galvanizing, but it is preferably 20 g / m ² or more from the viewpoint of corrosion resistance and 150 g / m ² or less from the viewpoint of economy.

  Next, the reasons for limiting the manufacturing conditions will be described. The slab to be used for hot rolling is not particularly limited as long as it is manufactured with a continuously cast slab or a thin slab caster. It is also suitable for processes such as continuous casting-direct rolling (CC-DR) in which hot rolling is performed immediately after casting.

The hot rolling finishing temperature needs to be at least Ar ₃ from the viewpoint of securing the press formability of the steel sheet. The cooling conditions after hot rolling are not particularly limited, but the winding temperature is preferably 630 ° C. or lower. Winding at a temperature exceeding 630 ° C. is not preferable because the thickness of the oxide formed on the surface of the steel sheet is excessively increased and the pickling property is poor. Although the lower limit is not particularly defined, the effect of the present invention is exhibited. However, since it is technically difficult to wind up at a temperature of room temperature or lower, this is the actual lower limit. Note that rough rolling sheets may be joined to each other during hot rolling to continuously perform finish rolling. Moreover, you may wind up a rough rolling board once.

The hot-rolled steel sheet thus manufactured is pickled. Pickling is important for improving plating properties because it can remove oxides on the surface of the steel sheet. Moreover, pickling may be performed once, or pickling may be performed in a plurality of times. Next, the pickled hot-rolled steel sheet is cold-rolled at a rolling reduction of 40 to 70% and passed through a continuous annealing line or a continuous hot-dip galvanizing line. If the rolling reduction is less than 40%, it is difficult to keep the shape flat. Moreover, since the ductility of the final product becomes poor, this is the lower limit. On the other hand, cold rolling exceeding 70% makes the cold rolling difficult because the cold rolling load becomes too large. 45 to 65% is a more preferable range. The effect of the present invention is exhibited without particularly specifying the number of rolling passes and the rolling reduction for each pass.
In addition, when directly plating a hot-rolled sheet, it is not necessary to perform cold rolling. Alternatively, plating may be performed after passing through box annealing or continuous annealing line.

  When annealing in the reduction zone of the in-line annealing method of continuous hot dip galvanizing equipment, the annealing temperature is in the range of 750 ° C. or more and 900 ° C. or less of ferrite and austenite. If the annealing temperature is less than 750 ° C., it takes too much time to dissolve the carbide formed at the time of hot rolling, and a sufficient amount of austenite cannot be secured. Annealing at a temperature exceeding 900 ° C. is not preferable because the growth of an oxide layer of Si or Mn is remarkable on the surface of the steel strip and plating defects are liable to occur. Excessive high-temperature heating not only is economically undesirable because it leads to an increase in cost, but also induces troubles such as deterioration of the plate shape at the time of high-temperature feeding and reduction of the roll life. Therefore, the upper limit of the maximum heating temperature is set to 900 ° C.

  The steel strip is cooled in the process of being subsequently immersed in the plating bath after annealing. In this case, the cooling rate is from 0.1 to 200 ° C./second on average from the maximum temperature to 650 ° C., and subsequently from 650 ° C. The average cooling rate up to 500 ° C. is 1 to 200 ° C./second. The average of 0.1 to 200 ° C./second up to 650 ° C. is to increase the volume fraction of ferrite in order to improve the workability, and at the same time to increase the C concentration of austenite, thereby lowering its free energy of formation, The purpose is to set the temperature at which site transformation starts to be equal to or lower than the plating bath temperature. In order to make the average cooling rate up to 650 ° C. less than 0.1 ° C./second, it is necessary to lengthen the line length of the continuous hot dip galvanizing equipment, resulting in high costs. 1 ° C / second or more.

  On the other hand, increasing the cooling rate exceeding the average cooling rate of 200 ° C./second up to 650 ° C. requires a large capital investment, leading to high manufacturing costs, so the upper limit should be 200 ° C./second. Is preferred.

  The reason why the average cooling rate from 650 ° C. to the plating bath is 1 to 200 ° C./second is to avoid the transformation of austenite to pearlite during the cooling, and the cooling rate is less than 1 ° C./second. Even if annealing is performed at the temperature specified in the invention and cooling to 650 ° C., formation of pearlite is inevitable. On the other hand, increasing the cooling rate from 650 ° C. to the plating bath by exceeding the average cooling rate of 200 ° C./sec results in high production costs, so the upper limit is preferably 200 ° C./sec.

  In the production of the alloyed hot-dip galvanized steel sheet of the present invention, the hot-dip galvanizing bath used is adjusted so that the Al concentration is 0.01 to 0.5 mass% in terms of the effective Al concentration in the bath. Further, when the alloying temperature is low, the Al concentration is preferably in the range of 0.05 to 0.09%. Here, the effective Al concentration in the plating bath is a value obtained by subtracting the Fe concentration in the bath from the Al concentration in the bath.

When the effective Al concentration in the bath is less than 0.01% by mass, the formation of the Fe—Al—Zn phase that becomes an alloying barrier at the initial stage of plating is insufficient, and a brittle Γ phase can be thickened at the plated steel plate interface during the plating process. For this reason, only an alloyed hot-dip galvanized steel sheet with poor plating film adhesion during processing is obtained, which is not preferable. Addition of Al exceeding 0.5% by mass significantly suppresses the alloying reaction, requires high temperature and long time alloying, and austenite remaining in the steel is transformed into pearlite. This is because it is difficult to achieve both fatigue durability and workability.
The obtained alloyed hot-dip galvanized steel sheet may be subjected to skin pass rolling.

In addition, about the alloying temperature at the time of alloy processing, it is preferable to set it as 480 degrees C or less as mentioned above.
In order to further improve the plating adhesion of the plated steel sheet, the present invention does not depart from the present invention even if the steel sheet is plated with Ni, Cu, Co, or Fe alone or before plating.
In addition, the material of the high-strength steel plate excellent in hydrogen embrittlement resistance of the welded portion of the present invention is generally manufactured through refining, steelmaking, casting, hot rolling, and cold rolling processes, which are ordinary steelmaking processes, Even if manufactured by omitting some or all of them, the effects of the present invention can be obtained as long as the conditions according to the present invention are satisfied.

  Hereinafter, the present invention will be described specifically by way of examples.

A slab having the composition shown in Table 2 was prepared, hot-rolled at an Ar ₃ transformation point or higher, the sheet thickness was 4 mm, wound in a temperature range of 630 ° C. or lower, and then cold pickled at 50% reduction after pickling. By rolling, a high-strength steel plate having a thickness of 2 mm was formed. Then, the plating process was performed on the conditions shown in Table 3 using the continuous hot dip galvanization equipment of the in-line annealing system, and the alloyed hot dip galvanized steel plate was manufactured. The continuous hot-dip galvanizing equipment used a method of reducing and annealing in a reduction zone after heating in a non-oxidizing furnace. The combustion air ratio of the non-oxidizing furnace was adjusted to 1.0 and used as an oxidation zone. Reduction zone is CO and H ₂ The mixed gas by burning generated H ₂ O, fitted with a device for introducing the CO _2, introducing H ₂ O and CO ₂ and H ₂ in N ₂ gas containing 10 vol%. Finally, skin pass rolling was performed on the obtained steel sheet at a rolling reduction of 0.6%.

  Table 4 shows the evaluation results of the plating properties, Table 5 shows the evaluation results of the oxides contained in the plating layer and the steel plate, Table 6 shows the evaluation results of the latter microstructure, and Table 7 shows the evaluation results of the mechanical properties of the steel plate. Are shown respectively.

The PO ₂ in the reduction furnace is the measured values of the hydrogen concentration, water vapor concentration, CO ₂ concentration, CO concentration, and atmospheric temperature in the furnace and the equilibrium reactions H ₂ O = H ₂ + 1 / 2O ₂ , CO ₂ = CO + 1 / 2O _2. The equilibrium constants K ₁ and K ₂ were used.

  The adhesion amount of the plating was measured by a gravimetric method after dissolving the plating with hydrochloric acid containing an inhibitor. The Fe% during plating was obtained by dissolving the plating with hydrochloric acid containing an inhibitor and measuring by ICP. Moreover, the thickness of the area | region where Fe density | concentration becomes 20 to 90% in the interface of a plating layer and a high-strength steel plate was measured by GDS (Glow discharge spectral analysis RSV Analymat 2504 type | mold). The positions different from each sample were measured 5 times in total, and the average value was obtained as the thickness of the region where the Fe concentration was 20 to 90%. Those that did not flow in the plating bath tended to vary in value compared to those that did not flow.

The plating appearance was determined by visually observing the entire length of the passed coil and determining the non-plating area ratio based on the following criteria.
○: No unplated part △: Some unplated part ×: Many unplated parts

  The type of oxide inside the steel plate, the type of oxide in the plating layer, and the type of oxide in the non-plated part were specified by preparing an extracted replica sample and using TEM and EPMA. The extracted replica sample is a method for preparing a sample by dissolving a layer containing an oxide to expose the oxide, depositing a carbon film on the exposed surface, and peeling the deposited film together with the oxide. An oxide containing Si or Mn alone or in combination may be a complex oxide containing other atoms or may contain many defects, but the closest one was found and identified from elemental analysis and structural identification.

When the oxides contained in the steel and the plating layer were identified, these oxides were MnSiO ₃ , Mn ₂ SiO ₄ , SiO ₂ and Al ₂ O ₃ , or in place of Mn in the aforementioned oxides. Some of them contained Fe. The distribution of these oxides can be measured using GDS or CMA. As described above, the Si oxide often exists as a complex oxide containing Mn. From this, the distribution of oxides can be obtained by measuring the element distribution of Si, Mn, and O on the plating layer and the steel sheet surface layer by, for example, GDS or CMA.

If the measurement using GDS is performed, the concentration distribution of Mn, Si and O is measured, and the case where the peak of Mn concentration is on the surface side from the peak of Si concentration is determined by the Si oxide (MnSiO ₃ or Mn ₂ It is assumed that SiO ₄ ) exists on the surface side. When the production conditions of the present invention are satisfied, specifically, when logPO ₂ and temperature are set in the ranges shown by the above formulas (1) and (2) in the reduction zone atmosphere, a peak of Mn concentration exists on the steel sheet surface side. Si oxide was present on the surface side with respect to SiO ₂ . On the other hand, does not satisfy the conditions of the present invention, the peak of the Si concentration is present in the peak at the same position or the surface side of the Mn concentration, or from the peak of the Mn concentration can not be measured, towards the SiO ₂ to the surface side Existed. In addition, the Si or Mn peak mentioned here indicates, for example, a peak at a portion excluding the detected values of Si and Mn components in the steel plate as shown in FIG.

If the measurement using CMA is performed, the oxide distribution can be measured by performing element mapping of Si, Mn, and O on the plating layer and the steel sheet surface. Specifically, element mapping of Si, Mn, and O is performed, and the positions where Si, Mn, and O exist overlap each other, only the positions where Si oxide (MnSiO ₃ or Mn ₂ SiO ₄ ), Si and O exist are present. It overlaps what is referred to as SiO _2. Thereby, the distribution of oxide can be obtained. Measurement may be performed using either GDS or CMA, but GDS is simpler.
As a matter of course, there is a region where Si oxide and SiO ₂ are mixed, but if the Si oxide is observed on the surface side, it is considered that the Si oxide exists on the surface side. It was.

  The thickness of the oxide layer inside the steel plate was measured using SEM. The average oxide content was determined by dissolving the oxide-containing layer and measuring the weight of the undissolved oxide.

  The type and volume ratio of the microstructure of the steel sheet were determined by corroding the steel sheet rolling direction cross section or the rolling direction perpendicular cross section with the Nital reagent and the reagent disclosed in Japanese Patent Application Laid-Open No. 59-219473. Measured by SEM and TEM of 10,000 times. Each sample was observed over 20 fields of view. The volume ratio was specified by obtaining the area ratio of each tissue by the point count method or image analysis.

  Yield stress (YS), tensile strength (TS), and elongation (El) are obtained by cutting a JIS No. 5 specimen from the obtained hot-dip galvanized steel sheet in a direction perpendicular to the rolling direction and conducting a test at room temperature. It was. The yield stress was measured by the 0.2% offset method. A steel sheet with excellent workability was obtained when the strength-ductility balance (TS × El), which is the product of tensile strength and elongation, was 21000 (MPa ×%) or more.

Fatigue durability was evaluated by the fatigue limit ratio. In this specification, the fatigue limit ratio is determined by performing a fatigue test in accordance with JIS Z 2275 on a No. 1 test piece defined in JIS Z 2275 having a parallel part of 30 mm, a plate thickness of 2 mm, and a curvature radius of 100 mm. It is a value obtained by dividing the strength of 2 × 10 ⁶ times obtained by the maximum tensile strength.

Steel plate numbers A1 to A3, B1 to B3, C1, D1 to D3, E1 to E3, F1 to F3, G1, H1 and I1 are within the range defined by the present invention for the chemical components of the steel plate, and the steel plate The production conditions are also within the range defined by the present invention. As a result, as shown in Table 4, the thickness of the region where the Fe concentration was 20 to 90% at the interface between the steel sheet and the plating layer was 1.2 μm or more. Also, the plating property is good, and the Fe concentration contained in the plating layer is also good at 7 to 15% by mass. Further, as shown in Table 5, MnSiO ₃ , Mn ₂ SiO ₄ , and SiO ₂ were observed inside the steel plate and in the plating layer, respectively, but the peak of the concentration of MnSiO ₃ and Mn ₂ SiO _{4 was} the concentration of SiO ₂ . It was located on the plating layer surface side from the peak of. Further, as shown in Table 6, the volume ratio of retained austenite in the steel sheet was 5% or more and the volume ratio of bainite + martensite was 10% or more.

  As a result, as shown in Table 7, these steel sheets have a yield stress of 380 MPa or more, a tensile strength of 600 MPa, a strength-ductility balance of 21000 (MPa ×%) or more, high strength and high workability. showed that. Further, the fatigue limit ratio was 0.60 or more, indicating high fatigue durability.

  On the other hand, steel plate numbers J1 and K1 were within the range defined by the present invention, but the chemical components of the steel plate were outside the range defined by the present invention. For this reason, the plating property deteriorated. For steel plate number K1, the product of tensile maximum strength and elongation was also outside the range specified in the present invention.

  Moreover, since the steel plate numbers A5, B4, C2, D5, E4, and F5 did not provide the flow in the plate width direction in the plating bath, the thickness of the region where the Fe concentration was 20 to 90% became less than 1.0 μm. It was. As a result, as shown in Table 7, the fatigue limit ratio was as low as 0.54 or less.

In addition, the steel plate numbers A9, D9, and F9 had the oxygen potential in the reduction zone lower than the range defined in the present invention. Thus, SiO ₂ is formed on the surface of the steel sheet, plating property is lowered, and the thickness of the region Fe concentration of 20% to 90% became 0.2μm and low value. As a result, as shown in Table 7, the fatigue limit ratio was as low as 0.53 or less.

Steel plates Nos. A-10, D-10, and F10 had an oxygen potential in the reduction zone lower than the range defined in the present invention. Thus, SiO ₂ is formed on the surface of the steel sheet, the plating property was lowered. Further, no flow in the plate width direction was provided in the plating bath. From the above, the thickness of the region where the Fe concentration was 20 to 90% was as low as 0.3 μm. As a result, as shown in Table 7, the fatigue limit ratio was as low as 0.52 or less.

In addition, the steel plate numbers A8, D8, and F8 had an oxygen potential in the reduction zone lower than the range defined in the present invention. Thus, SiO ₂ is formed on the surface of the steel sheet, plating property is lowered, and the thickness of the region Fe concentration of 20% to 90% is equal to or less than 0.7 [mu] m. Further, since the alloying temperature was high, as shown in Table 6, the retained austenite was decomposed into a bainite structure containing pearlite and carbide. As a result, as shown in Table 7, the fatigue limit ratio was as low as 0.49 or less. Further, the product of the maximum tensile strength and the elongation was out of the range defined by the present invention.

In addition, the steel plate numbers A7, B6, D7, and F4 had the oxygen potential in the reduction zone lower than the range defined in the present invention. Thus, SiO ₂ is formed on the surface of the steel sheet, the plating property was lowered. Further, no flow in the plate width direction was provided in the plating bath. From the above, the thickness of the region where the Fe concentration was 20 to 90% was as low as 0.6 μm. Further, since the alloying temperature was high, as shown in Table 6, the retained austenite was decomposed into a bainite structure containing pearlite and carbide. As a result, as shown in Table 7, the fatigue limit ratio was as low as 0.49 or less. Further, the product of the maximum tensile strength and the elongation was out of the range defined by the present invention.

  Further, since steel plate numbers A4, D4, and F4 had high alloying temperatures, as shown in Table 6, the retained austenite was decomposed into a bainite structure containing pearlite and carbides. For this reason, although the thickness of the region where the Fe concentration is 20 to 90% is sufficient to be 2.7 μm or more, the fatigue limit ratio was as low as 0.49 or less as shown in Table 7. Further, the product of the maximum tensile strength and the elongation was out of the range defined by the present invention.

  Steel plate numbers A6, B5, C3, D6, E5, F6, G2, H2, I2, J2, and K2 were higher in oxygen potential than the range specified in the present invention. For this reason, as shown in Table 5, FeO was formed on the surface of the steel sheet, the plating property was lowered, and the thickness of the region where the Fe concentration was 20 to 90% was as low as 0.5 μm or less. As a result, as shown in Table 7, the fatigue limit ratio was as low as 0.54 or less. In addition, for steel plate numbers C3, G2, I2, J2, and K2, the product of the maximum tensile strength and the elongation was out of the range defined by the present invention.

The chart which shows the density distribution of the depth direction of Fe, Zn, Mn, and Si using GDS.

Claims (10)

% By mass
C: 0.07 to 0.25%,
Si: 0.8-2.0%,
Mn: 1.1 to 2.5%
Al: 0.001 to 2.0%,
N: 0.01% or less,
S: 0.01% or less,
O: A high-strength galvanized steel sheet having an alloyed hot-dip galvanized layer containing Fe on a high-strength steel sheet containing 0.01% or less and the balance being Fe and unavoidable impurities. ,
The high-strength steel sheet has a volume ratio of retained austenite of 5% or more, and a total volume ratio of bainite and martensite of 10% or more,
A high-strength galvannealed steel sheet having a thickness of 1.2 μm or more in a region where the Fe concentration by GDS is 20 to 90% at the interface between the galvannealed layer and the high-strength steel sheet . One or more Si oxides selected from FeSiO ₃ , Fe ₂ SiO ₄ , MnSiO ₃ , and Mn ₂ SiO ₄ are present in either one or both of the alloyed hot-dip galvanized layer and the steel sheet, and Either one or both of the plating layer and the steel sheet has SiO ₂ , and the Si oxide concentration distribution peak is closer to the surface side of the galvannealed steel sheet than the SiO ₂ concentration distribution peak. The high-strength galvannealed steel sheet according to claim 1, which is located in The high-strength steel plate is further Ni: 0.05-2.0% by mass,
Cu: 0.05-2.0%,
Cr: 0.05-2.0%,
Mo: 0.05-2.0%,
B: 0.0001 to 0.002%,
Ti: 0.001 to 0.1%,
Nb: 0.001 to 0.1%,
V: 0.001 to 0.1%
REM: 0.0001 to 0.1%,
Ca: 0.0001 to 0.1%
The high-strength galvannealed steel sheet according to claim 1 or 2, characterized by containing at least one of the following.   The high-strength galvannealed steel sheet according to any one of claims 1 to 3, wherein the galvannealed layer further contains Al. 2 × 10 ⁶ times strength required by conducting a fatigue test in accordance with JIS Z 2275 on the No. 1 test piece defined in JIS Z 2275 having a parallel part of 30 mm, a plate thickness of 2 mm, and a radius of curvature of 100 mm. The high-strength galvannealed steel sheet according to any one of claims 1 to 4, wherein a fatigue limit ratio, which is a value obtained by dividing by a tensile maximum strength, is 0.55 or more.   The high-strength alloyed molten zinc according to any one of claims 1 to 5, wherein a product of maximum tensile strength (Ts) and elongation (EI) of the steel sheet is 21000 (MPa ·%) or more. Plated steel sheet. % By mass
C: 0.07 to 0.25%,
Si: 0.8-2.0%,
Mn: 1.1 to 2.5%
Al: 0.001 to 2.0%,
N: 0.001 to 0.1%
S: 0.0001 to 0.1%,
O: 0.0001 to 0.1%
Is reduced by passing a high-strength steel plate containing Fe and unavoidable impurities through a reduction zone, and then dipped in a plating bath to be pulled up, and then subjected to alloying treatment to continuously melt zinc. A method for producing a high-strength galvannealed steel sheet to be plated,
As the atmosphere of the reduction zone, ₁ to 60% by volume of H ₂ is contained, and the balance consists of one or more of N ₂ , H ₂ O, O ₂ , CO ₂ , CO and inevitable impurities, and the atmosphere The logarithmic log PO ₂ of the partial pressure of oxygen is −0.000034T ² + 0.105T−0.2 [Si%] ² +2.1 [Si%] − 98.8 ≦ log PO ₂ ≦ −0.000038 T ² +0.107 T -90.4 ... (1)
923 ≦ T ≦ 1173 (2)
T: Maximum attained temperature (K) of steel sheet, [Si%]: Si content in steel sheet (mass%)
Reduction in a controlled atmosphere,
A method for producing a high-strength galvannealed steel sheet, characterized by causing the plating solution in the plating bath to flow in the plate width direction of the high-strength steel sheet when the high-strength steel sheet is immersed in the plating bath. .   The method for producing a high-strength galvannealed steel sheet according to claim 7, wherein a flow rate of the plating solution is set to 0.5 to 2.5 m / sec.   The said alloying process is performed at the temperature of 480 degrees C or less, The manufacturing method of the high intensity | strength galvannealed steel plate of Claim 7 or 8 characterized by the above-mentioned. The high-strength steel sheet heats the cast slab, hot-rolls the heated cast slab at an Ar ₃ transformation point or higher, winds it up in a temperature range of 630 ° C. or lower, and then pickles after the pickling 40 to 40% Formed by cold rolling at 70%,
When reducing the high-strength steel plate,
In the reduction zone, annealing is performed at 750 ° C. or more and 900 ° C. or less, and then cooled to 650 ° C. at 0.1 to 200 ° C./second, and then the average cooling rate between 650 ° C. and 500 ° C. is 1 to 200 ° C./second. The high-strength alloying melt according to any one of claims 7 to 9, wherein the temperature is cooled to (temperature of the plating solution −40) to (temperature of the plating solution +50) ° C. Manufacturing method of galvanized steel sheet.

Images