JP4684002B2 - Ultra high strength thin steel sheet with excellent hydrogen embrittlement resistance - Google Patents

Description

  The present invention relates to an ultra-high-strength thin steel sheet having excellent hydrogen embrittlement resistance. In particular, the tensile strength of 1180 MPa or more is a problem caused by hydrogen embrittlement caused by hydrogen embrittlement such as cracking and delayed fracture. The present invention relates to a suppressed ultra high strength thin steel sheet.

  When a high-strength part constituting an automobile, industrial machine, or the like is obtained by press forming or bending, the steel sheet used for the processing is required to have excellent strength and ductility. In recent years, the need for ultra-high-strength steel sheets of 1180 MPa or more has increased with the further weight reduction of automobiles, and TRIP (TRansformation Induced Plasticity) steel sheets have attracted attention as steel sheets that meet these needs. ing.

  The TRIP steel sheet has a retained austenite structure, and when deformed at a temperature equal to or higher than the martensite transformation start temperature (Ms point), the retained austenite (residual γ) is transformed into martensite by stress, resulting in a large elongation. Steel plate. There are several types, for example, TRIP type composite structure steel (TPF steel) containing polygonal ferrite as a parent phase and containing retained austenite; TRIP type tempered martens containing tempered martensite as a parent phase and containing retained austenite. Sight steel (TAM steel); TRIP type bainite steel (TBF steel) containing bainitic ferrite as a parent phase and containing retained austenite is known. Among these, TBF steel has been known for a long time (for example, Non-Patent Document 1 etc.), and high strength is easily obtained by hard bainitic ferrite, and there is a boundary between lath-shaped bainitic ferrite in the structure. In addition, fine retained austenite is easily formed, and such a structure form has a feature of providing very excellent elongation. Furthermore, TBF steel also has a manufacturing merit that it can be easily manufactured by a single heat treatment (continuous annealing process or plating process).

  However, in the ultra-high strength region of 1180 MPa class or higher, it is known that the TRIP steel plate as well as other high-strength steel materials has a new problem of delayed fracture due to hydrogen embrittlement. Delayed fracture is a high-strength steel in which hydrogen generated from a corrosive environment or atmosphere diffuses into defects such as dislocations, vacancies, and grain boundaries, embrittles the material, and breaks when stress is applied. This is a phenomenon, and as a result, it causes adverse effects such as a decrease in the ductility and toughness of the metal material.

  In high strength steels that have been widely used for applications such as bolts, PC steel wires, and line pipes, hydrogen embrittlement (pickling brittleness, plating brittleness, delayed fracture) due to hydrogen intrusion into the steel when the tensile strength exceeds 980 MPa Etc.) is widely known to occur. Therefore, most of the techniques for improving the hydrogen embrittlement resistance are directed to the steel materials for the bolts and the like. For example, Non-Patent Document 2 reports that if a metal structure is mainly tempered martensite and an element showing temper softening resistance such as Cr, Mo, V is added, it is effective in improving delayed fracture resistance. . This is a technology that suppresses fracture by shifting the delayed fracture mode from grain boundaries to intragranular fracture by depositing alloy carbides and utilizing them as hydrogen trap sites.

  By the way, in the case of a thin steel plate, conventionally, from the viewpoint of workability and weldability, a steel plate having a thickness of 780 MPa or more is not often used. There was no active measure against hydrogen embrittlement because it was not regarded as a problem. Recently, however, as mentioned above, due to the necessity of reducing the weight of automobiles and improving collision safety, reinforcing materials such as bumpers and impact beams and seat rails have been required to have higher strength. Therefore, since the demand for ultra-high strength steel sheets of 980 MPa or more is increasing, it is necessary to surely improve the hydrogen embrittlement resistance of the ultra-high strength steel sheets.

  In order to improve the hydrogen embrittlement resistance of the ultra-high strength steel sheet, it may be possible to divert the technology related to the bolt steel and the like. For example, in the case of Non-Patent Document 2, the C amount is 0.4% or more. In addition, since it contains a large amount of alloy elements, if the technique of this document is applied to a thin steel plate, it becomes impossible to ensure the workability and weldability required for the thin steel plate. Moreover, since precipitation heat treatment of several hours or more is required for precipitation of alloy carbide, there is also a problem in manufacturability. Therefore, it is necessary to establish a unique technique to improve the hydrogen embrittlement resistance of the thin steel sheet.

  So far, as a technique for improving the hydrogen embrittlement resistance of a steel sheet, Patent Document 1 has proposed that hydrogen defects can be suppressed if an oxide mainly composed of Ti and Mg is present. However, this technology is intended for thick steel plates, and is considered for delayed fracture after high heat input welding, but is used in automobile parts and the like manufactured using thin steel plates (for example, corrosive environments). ) Is not fully considered. Patent Document 2 discloses a mutual relationship among Mg oxide, sulfide, composite crystallized product or composite precipitate dispersion form (standard deviation or average particle size from average particle size), volume fraction of retained austenite, and steel plate strength. It is shown that if the relationship is controlled, ductility and delayed fracture resistance after forming can be improved at the same time. However, it is difficult to improve the hydrogen embrittlement resistance in an environment where hydrogen is generated and exists due to corrosion of the steel sheet only by the trap effect by controlling the morphology of the precipitate.

In Non-Patent Document 3 and Non-Patent Document 4, the hydrogen embrittlement characteristics of TRIP steel are examined. Among them, the amount of hydrogen storage in TBF steel is particularly large, and the fracture surface of TBF steel is observed. It is shown that the pseudo-cleavage destruction due to is suppressed. However, the delayed fracture characteristics of the TBF steel reported in this document is about 1000 seconds at most until the occurrence of cracking by the cathodic charge test, taking into account the harsh usage environment for a long time such as automobile parts. It ’s hard to say. In addition, the heat treatment conditions in the above document have a problem that the production efficiency of the actual machine is poor because the heating temperature is set high, and the development of a new TBF steel with excellent production efficiency is eagerly desired. ing.
JP-A-11-293383 Japanese Patent Laid-Open No. 2003-166035 NISSHIN STEEL TECHNICAL REPORT (Nissin Steel Engineering Report), No. 43, Dec. 1980, p.1-10 “New Developments in Elucidation of Delayed Fracture” (Iron Japan Society, published in January 1997) p.111-120 Tomohiko Kitajo, 5 others, "Hydrogen embrittlement of ultra-high strength low alloy TRIP steel (1st report: Hydrogen storage properties and ductility)" p.17-18 Tomohiko Kitajima, 5 others, “Effect of austempering temperature on hydrogen embrittlement of ultra-high strength low alloy TRIP steel”, CAMP-ISIJ, 2003, Vol. 16, p.568

  The present invention has been made in view of the above circumstances, and its purpose is to prevent hydrogen embrittlement in an ultrahigh strength region where the tensile strength is 1180 MPa or more without impairing the excellent ductility characteristic of the TRIP steel sheet. An object of the present invention is to provide a TRIP thin steel sheet that can significantly increase the thickness.

The ultra-high strength thin steel sheet having excellent hydrogen embrittlement resistance according to the present invention is C: 0.10 to 0.25% (meaning of mass%, the same applies to the component composition), Si: 1.0 to 3. 0%, Mn: 1.0 to 3.5%, P: 0.15% or less, S: 0.02% or less, Al: 1.5% or less (excluding 0%), the balance being iron And inevitable impurities,
It has an area ratio of 1% or more of retained austenite with respect to the whole structure,
The average axial ratio (major axis / minor axis) of the residual austenite crystal grains is 5 or more,
The average minor axis length of the residual austenite crystal grains is 1 μm or less, and the nearest neighbor distance between the residual austenite crystal grains is 1 μm or less;
Further, there is a characteristic in that the tensile strength is 1180 MPa or more (hereinafter sometimes referred to as “the steel plate 1 of the present invention”).

Another ultra-high strength thin steel sheet excellent in hydrogen embrittlement resistance according to the present invention is C: 0.10 to 0.25%, Si: 1.0 to 3.0%, Mn: 1.0 to 3 0.5%, P: 0.15% or less, S: 0.02% or less, Al: 0.5% or less (not including 0%), the balance being made of iron and inevitable impurities,
It has an area ratio of 1% or more of retained austenite with respect to the whole structure,
The average axial ratio (major axis / minor axis) of the residual austenite crystal grains is 5 or more,
The average minor axis length of the residual austenite crystal grains is 1 μm or less, and the nearest neighbor distance between the residual austenite crystal grains is 1 μm or less;
Further, there is a characteristic in that the tensile strength is 1180 MPa or more (hereinafter sometimes referred to as “the steel plate 2 of the present invention”).

The ultra-high strength thin steel sheet of the present invention is an area ratio with respect to the entire structure,
Bainitic ferrite and martensite total 80% or more,
It is preferable that ferrite and pearlite satisfy a total of 9% or less (including 0%).

  Moreover, the ultra-high strength thin steel sheet of the present invention further includes Cu: 0.003-0.5% and / or Ni: 0.003-1.0%, Ti and / or V in total 0.003-1. 0.0%, Mo: 1.0% or less (not including 0%), Nb: 0.1% or less (not including 0%), B: 0.0002 to 0.01%, and Ca: 0 One or more selected from the group consisting of .0005 to 0.005%, Mg: 0.0005 to 0.01%, and REM: 0.0005 to 0.01% may be included.

  According to the present invention, an ultra-high strength steel sheet having a tensile strength of 1180 MPa or more with improved hydrogen embrittlement resistance by detoxifying hydrogen entering from the outside can be produced with high productivity, such as delayed fracture. As ultra-high-strength parts that are extremely unlikely to occur, for example, reinforcing materials such as bumpers and impact beams, and automobile parts such as seat rails, pillars, reinforcements, and members can be provided.

  In the case of tempered martensite steel or martensite + ferritic steel that has been generally adopted as a high-strength steel material, delayed fracture due to hydrogen is caused by accumulation of hydrogen at the prior austenite grain boundaries, etc. In order to reduce the susceptibility to delayed fracture, hydrogen trap sites such as carbides are dispersed evenly and finely, and hydrogen is trapped in the part to diffuse hydrogen concentration. Has been considered as a general solution. However, even if a large number of carbides or the like are dispersed as hydrogen trap sites in this way, the delayed capability due to hydrogen cannot be sufficiently suppressed due to the limited trapping capability.

  Therefore, the present inventors focused on improving the hydrogen trapping ability of the steel sheet, in particular, in order to achieve higher hydrogen embrittlement resistance (delayed fracture resistance) that fully considers the use environment in the thin steel sheet, We examined specific means for that.

As a result, while ensuring 1% or more of retained austenite, as the form of the retained austenite,
-Average axial ratio of retained austenite crystal grains (major axis / minor axis): 5 or more,
・ The average minor axis length of residual austenite crystal grains: 1 μm or less, and ・ The closest distance between residual austenite crystal grains: 1 μm or less, if controlled so that all of the alloy elements are not added excessively The inventors have found that the hydrogen embrittlement resistance of a high-strength steel sheet can be sufficiently improved, and have arrived at the present invention. Hereinafter, the form of retained austenite in the present invention will be described in detail.

<Average axis ratio of residual austenite crystal grains (major axis / minor axis): 5 or more>
Conventionally, retained austenite has been thought to have an adverse effect on hydrogen embrittlement resistance and fatigue. Although it has an adverse effect on embrittlement characteristics and fatigue, it has been found that if the shape of the retained austenite is lath, the hydrogen trapping capability is sufficiently greater than that of carbide.

  FIG. 1 shows an average axial ratio of residual austenite grains measured by a method described later, and a hydrogen embrittlement risk index (which is a method shown in the examples described later), which is an index of hydrogen embrittlement resistance. FIG. 1 shows that the average axis ratio (major axis / minor axis) of the retained austenite crystal grains is particularly 5 or more. It can be seen that the hydrogen embrittlement risk index decreases rapidly. This is because the residual austenite crystal grains have a high average axial ratio of 5 or more, so that the hydrogen absorptive ability inherent in retained austenite is sufficiently exerted, and the hydrogen trapping capability is overwhelmingly larger than that of carbide, so-called atmospheric corrosion. This is thought to be because the hydrogen that intrudes in is made substantially harmless, and the hydrogen embrittlement resistance is remarkably improved. The average axial ratio of the retained austenite is preferably 10 or more, more preferably 15 or more.

  On the other hand, the upper limit of the average axial ratio is not particularly defined from the viewpoint of enhancing the hydrogen embrittlement resistance. However, in order to effectively exhibit the TRIP effect, a certain thickness of retained austenite is necessary. Considering this, the upper limit is preferably 30 and more preferably 20 or less.

<Average minor axis length of residual austenite crystal grains: 1 μm or less>
In the present invention, it is effective for improving the hydrogen embrittlement resistance that the lath-like retained austenite is finely dispersed. Specifically, the lath-like retained austenite crystal grains are 1 μm or less (sub- It was found that the resistance to hydrogen embrittlement can be surely improved by dispersing (micron order) material. This is presumably because the surface area (interface) of the retained austenite crystal grains increases and the hydrogen trapping ability increases when a large number of fine retained austenite crystal grains with a short average minor axis length are dispersed. The average short axis length of the residual austenite crystal grains is preferably 0.5 μm or less, more preferably 0.25 μm or less.

  In the present invention, as described above, by controlling the average minor axis length together with the average axial ratio of the retained austenite crystal grains, the fine lath-like austenite of the present invention can be used even when residual austenite having the same volume ratio is present. The hydrogen trapping capability of can be overwhelmingly larger than that in the case of dispersing the carbide, and hydrogen that enters due to atmospheric corrosion can be made substantially harmless.

<The nearest neighbor distance between residual austenite crystal grains: 1 μm or less>
In the present invention, it has been found that the hydrogen embrittlement resistance can be further improved by controlling the nearest neighbor distance between residual austenite crystal grains. Specifically, it has been found that if the nearest neighbor distance between the residual austenite crystal grains is 1 μm or less, the hydrogen embrittlement resistance can be reliably improved. This is because the formation of a state in which a large number of the fine lath-like retained austenite is dispersed in close proximity, the propagation of fracture (cracks) is suppressed, and a structure having high resistance to fracture is obtained. It is thought that it is. The nearest neighbor distance between residual austenite crystal grains is preferably 0.8 μm or less, more preferably 0.5 μm or less.

  The residual austenite not only greatly contributes to the improvement of hydrogen embrittlement resistance as described above, but is also useful to improve the total elongation as is generally known, preferably 2% or more, more preferably 3 % Should be present. On the other hand, if a large amount of retained austenite is present, the desired ultra-high strength cannot be ensured, so the upper limit is recommended to be 15% (more preferably 10%).

From the viewpoint of the stability of the retained austenite, the C concentration ( _CγR ) in the retained austenite is recommended to be 0.8% or more. Further, if this _CγR is controlled to 0.8% or more, the elongation and the like can be effectively increased. Preferably it is 1.0% or more, More preferably, it is 1.2% or more. The higher C _γR is more preferable, but the upper limit that can be adjusted is considered to be approximately 1.6% in actual operation.

The said retained austenite means the area | region observed as a FCC phase (face centered cubic lattice) by the FE-SEM / EBSP method mentioned later. As a specific example of the measurement by EBSP, as in the case of observation of the bainitic ferrite and martensite, an arbitrary measurement area (about 50 × 50 μm, The measurement interval may be 0.1 μm). Incidentally, when polishing up to the measurement surface, electrolytic polishing is performed in order to prevent transformation of retained austenite. Next, using a “FE-SEM equipped with an EBSP detector” (details will be described later), the sample set in the lens barrel of the SEM is irradiated with an electron beam. Take an EBSP image projected on the screen with a high-sensitivity camera (VE-1000-SIT, manufactured by Dage-MTI Inc.) and capture it as an image on a computer. Then, image analysis is performed by a computer, and an FCC phase determined by comparison with a simulation pattern using a known crystal system [in the case of retained austenite, FCC phase (face-centered cubic lattice)] is color-mapped. The area ratio of the region mapped in this manner is obtained, and this is defined as “area ratio of residual austenite”. Note that the OIM (Orientation Imaging Microscopy ^™ ) system of TexSEM Laboratories Inc. was used as hardware and software for the above analysis.

  Moreover, the measuring method of the average axial ratio of the said retained austenite crystal grain, the average minor axis length, and the nearest distance between the retained austenite crystal grains is as follows. First, the average axis ratio of the residual austenite crystal grains is observed with a TEM (Transmission Electron Microscope) (magnification 15,000 times), and the major axis and the minor axis of the remaining austenite crystal grains exist in three arbitrarily selected visual fields. The axial ratio was determined by measurement, and the average value was calculated as the average axial ratio. The average minor axis length of residual austenite crystal grains was determined by calculating the average value of minor axes measured as described above. Moreover, the nearest neighbor distance between the residual austenite crystal grains was observed with TEM (magnification: 15,000 times) and aligned in the major axis direction as shown in FIG. [Thus, the distance shown in FIG. 2 (b) is not the nearest neighbor distance] The nearest neighbor distance of the residual austenite crystal grains was measured, and the nearest neighbor distance of the three fields of view was averaged.

  In order to reduce the starting point of grain boundary fracture in the steel sheet, to reliably reduce the diffusible hydrogen concentration in the steel sheet to the detoxification level, and to easily ensure ultra-high strength, the base phase of the steel sheet is made from a high-strength steel material. It is preferable to use a two-phase structure of bainitic ferrite and martensite, rather than a martensite single-phase structure that is generally adopted in the present invention.

  In the case of the above-described martensite single phase structure, carbide (for example, film-like cementite) precipitates at the grain boundaries and is likely to cause grain boundary fracture, whereas the two-phase structure of bainitic ferrite and martensite is used. For example, since the bainitic ferrite is hard, the strength of the entire structure can be easily increased as in the case of the martensite single phase structure, and moreover, a large number of hydrogen is trapped on this dislocation, Hydrogen embrittlement resistance can also be improved. In addition, the presence of the bainitic ferrite and residual austenite, which will be described later, can prevent the formation of carbides that are the starting point of grain boundary fracture, and the lath-like residual at the boundary of the lath-like bainitic ferrite. There is also a merit that austenite is easily generated and a very excellent elongation can be obtained.

  In order to effectively exhibit such an action, the total area ratio of bainitic ferrite and martensite is preferably 80% or more, more preferably 85% or more, and still more preferably 90%. That's it. On the other hand, the upper limit can be determined by balance with other structures (residual austenite), and when the ferrite structure or the like is not contained, the upper limit is controlled to 99%.

  The bainitic ferrite in the present invention is a plate-like ferrite and means a substructure having a high dislocation density, and a polygonal ferrite having a substructure with no or very few dislocations, The SEM observation clearly distinguishes as follows.

  The area ratio of the bainitic ferrite structure is obtained as follows. That is, a steel plate is corroded with nital, and an arbitrary measurement area (about 50 × 50 μm) in a plane parallel to the rolling surface at a position of a thickness of 1/4 is observed with a SEM (Scanning Electron Microscope) (magnification: (1500 times).

  Bainitic ferrite is dark gray in the SEM photograph (in the case of SEM, bainitic ferrite may not be distinguished from retained austenite and martensite in some cases), but polygonal ferrite is black in the SEM photograph. It has a square shape and does not contain retained austenite or martensite.

  The SEM used in the present invention is a “high-resolution FE-SEM (EB Emission Type Scanning Electron Microscope, manufactured by Philips, XL30S-FEG) equipped with an EBSP (Electron Back Scatter Diffraction Pattern) detector”. There is a merit that the processed region can be simultaneously analyzed on the spot by the EBSP detector. The EBSP method will be briefly described here. The EBSP determines the crystal orientation of the electron beam incident position by making an electron beam incident on the sample surface and analyzing the Kikuchi pattern obtained from the reflected electrons generated at this time. If the electron beam is scanned two-dimensionally on the sample surface and the crystal orientation is measured at every predetermined pitch, the orientation distribution on the sample surface can be measured. According to this EBSP observation, there is an advantage that textures in the plate thickness direction, which are determined to be the same in normal microscope observation and have different crystal orientation differences, can be identified by color tone differences.

  The steel sheet of the present invention may be composed only of the above structure (that is, a mixed structure of bainitic ferrite + martensite and retained austenite), but as long as the other structure is not impaired as long as the effect of the present invention is not impaired. It may have ferrite (herein, “ferrite” means polygonal ferrite, ie, ferrite having no or very low dislocation density) and pearlite. These are structures that can inevitably remain in the production process of the present invention. However, the smaller the structure, the better. In the present invention, it is suppressed to 9% or less. Preferably it is less than 5%, more preferably less than 3%.

  As described above, the present invention is particularly characterized in that the amount of retained austenite and its form are controlled, and in this way, a steel sheet that easily controls the amount of retained austenite and its form and exhibits specified strength is obtained. It is necessary to control the component composition as described below.

<C: 0.10 to 0.25%>
C is necessary to ensure high strength of 1180 MPa or more. Further, a sufficient amount of C is contained in the austenite phase and is an important element for allowing a desired austenite phase to remain even at room temperature. In the present invention, it is contained in an amount of 0.10% or more. Preferably it is 0.12% or more, more preferably 0.15% or more. However, from the viewpoint of ensuring corrosion resistance and weldability, the C content is suppressed to 0.25% or less in the present invention. Preferably it is 0.23% or less.

<Si: 1.0-3.0%>
Si is an important element that effectively suppresses the decomposition of retained austenite and the formation of carbides. It is also a substitutional solid solution strengthening element effective to sufficiently harden the material. In order to effectively exhibit such an action, it is necessary to contain 1.0% or more. Preferably it is 1.2% or more, More preferably, it is 1.5% or more. However, if the amount of Si is excessive, scale formation by hot rolling becomes prominent, and the cost for removing scratches is high, which is economically undesirable. Preferably it is 2.5% or less, More preferably, it is 2.0% or less.

<Mn: 1.0 to 3.5%>
Mn is an element necessary for stabilizing austenite and obtaining desired retained austenite. In order to exhibit such an action effectively, it is necessary to contain 1.0% or more. Preferably it is 1.2% or more, More preferably, it is 1.5% or more. On the other hand, when the amount of Mn becomes excessive, segregation becomes prominent and workability may deteriorate, so 3.5% is made the upper limit. Preferably it is 3.0% or less.

<P: 0.15% or less (excluding 0%)>
P is an element that promotes grain boundary fracture due to grain boundary segregation, so a lower value is desirable, and its upper limit is 0.15%. Preferably it is 0.1% or less, more preferably 0.05% or less.

<S: 0.02% or less (excluding 0%)>
S is an element that promotes hydrogen absorption of the steel sheet in a corrosive environment, so a lower value is desirable, and its upper limit is 0.02%.

<Al: 1.5% or less (not including 0%)> (in the case of the steel sheet 1 of the present invention)
<Al: 0.5% or less (0% not included)> (In the case of the steel sheet 2 of the present invention)
Al may be added in an amount of 0.01% or more for deoxidation. Further, Al is an element having not only a deoxidizing action but also a corrosion resistance improving action and a hydrogen embrittlement resistance improving action.

  As a mechanism of the above-mentioned corrosion resistance improving action, specifically, the effect of the corrosion resistance improvement of the base metal itself and the generated rust caused by the atmospheric corrosion can be considered, but it is estimated that the effect of the latter generated rust is particularly large. The reason is that the generated rust is denser and more protective than ordinary iron rust, so that atmospheric corrosion is suppressed, and as a result, the amount of hydrogen generated by the atmospheric corrosion is reduced, resulting in hydrogen embrittlement, that is, delay. It is thought that destruction is effectively suppressed.

  In addition, the details of the mechanism of improving the hydrogen embrittlement resistance property of Al are unknown, but it is difficult for hydrogen to penetrate into steel due to the concentration of Al on the steel sheet surface, and the hydrogen in steel. It is presumed that the diffusion rate of hydrogen decreases, hydrogen migration becomes difficult, and hydrogen embrittlement hardly occurs. Furthermore, it is considered that the addition of Al increases the stability of the lath-like retained austenite, which contributes to the improvement of hydrogen embrittlement resistance.

  In order to effectively exhibit such an effect of improving the corrosion resistance and hydrogen embrittlement resistance of Al, the Al content is 0.02% or more, preferably 0.2% or more, more preferably 0.5% or more. It is good to do.

However, while suppressing the increase and enlarging of inclusions such as alumina to ensure workability, ensuring the production of fine retained austenite, further suppressing corrosion starting from Al-containing inclusions, and manufacturing costs In order to suppress the increase, it is necessary to suppress the Al amount to 1.5% or less. From a manufacturing point of view, it is preferable to adjust so that A ₃ point is 1000 ° C. or less.

  On the other hand, when the Al content is increased as described above, inclusions such as alumina are increased and workability is deteriorated. Therefore, the inclusions such as alumina are sufficiently suppressed, and a steel sheet having better workability is obtained. , Al content is suppressed to 0.5% or less. Preferably it is 0.3% or less, More preferably, it is 0.1% or less.

  The contained elements specified in the present invention are as described above, and the remaining component is substantially Fe, but 0.001% or less as an inevitable impurity brought into the steel depending on the situation of raw materials, materials, manufacturing equipment, etc. As a matter of course, it is allowed to contain other elements as described below within a range that does not adversely affect the operation of the present invention. It is.

<Cu: 0.003-0.5% and / or Ni: 0.003-1.0%>
By containing Cu and / or Ni, generation of hydrogen that causes hydrogen embrittlement can be sufficiently suppressed, and penetration of the generated hydrogen into the steel sheet can be suppressed. As a result, the diffusible hydrogen concentration in the steel sheet can be sufficiently reduced to the detoxification level due to a synergistic effect with the improvement of the hydrogen trap ability of the steel sheet by the above structure control.

  Specifically, Cu and Ni have the effect of improving the corrosion resistance of the steel material itself and sufficiently suppressing hydrogen generation due to corrosion of the steel sheet. These elements also have the effect of promoting the generation of iron oxide: α-FeOOH, which is said to be thermodynamically stable and protective among rust generated in the atmosphere. By promoting, the penetration of the generated hydrogen into the steel sheet can be suppressed, and the hydrogen embrittlement resistance can be sufficiently enhanced in a severe corrosive environment. This effect is easily manifested particularly by the coexistence of Cu and Ni.

  In order to exhibit the said effect, when making it contain Cu, it is necessary to set it as 0.003% or more. Preferably it is 0.05% or more, More preferably, it is 0.1% or more. Moreover, when it contains Ni, it is necessary to set it as 0.003% or more. Preferably it is 0.05% or more, More preferably, it is 0.1% or more.

  Note that if both elements are contained excessively, the workability is lowered, so that Cu is suppressed to 0.5% or less, and Ni is suppressed to 1.0% or less.

<Ti and / or V: 0.003 to 1.0% in total>
Ti, like Cu and Ni, has an effect of promoting the generation of protective rust. The protective rust has a very beneficial effect of suppressing the production of β-FeOOH which is generated particularly in a chloride environment and adversely affects the corrosion resistance (resulting in hydrogen embrittlement resistance). The formation of such a protective rust is promoted particularly by the combined addition of Ti and V (or Zr). Ti is an element that imparts very excellent corrosion resistance, and also has the advantage of cleaning steel.

  V is an element that is effective in improving the resistance to hydrogen embrittlement by coexisting with Ti as described above, and also effective in increasing the strength and grain size of the steel sheet.

  In order to fully exhibit the effects of Ti and / or V, it is preferable to contain 0.003% or more (more preferably 0.01% or more) in total. In particular, from the viewpoint of improving the hydrogen embrittlement resistance, it is preferable to add more than 0.03% of Ti, more preferably 0.05% or more of Ti. On the other hand, even if Ti is added excessively, the effect is saturated, which is economically undesirable. If V is added excessively, the precipitation of carbonitride increases and the workability and resistance to hydrogen embrittlement deteriorate. Invite. Therefore, it is preferable to add Ti and / or V within a total range of 1.0% or less. More preferably, it is 0.5% or less.

<Zr: 0.003-1.0%>
Zr is an element effective for increasing the strength and refining of the steel sheet, and has the effect of coexisting with Ti and improving the resistance to hydrogen embrittlement. In order to exhibit such an effect effectively, it is preferable to contain 0.003% or more of Zr. On the other hand, if Zr is contained excessively, the precipitation of carbonitrides increases and the workability and hydrogen embrittlement resistance deteriorate, so it is preferable to add within 1.0% or less.

<Mo: 1.0% or less (excluding 0%)>
Mo has the effect of stabilizing austenite and securing retained austenite, suppressing hydrogen intrusion and improving hydrogen embrittlement resistance. It is also an effective element for enhancing the hardenability of the steel sheet. In addition, it has the effect of strengthening grain boundaries and suppressing hydrogen embrittlement. In order to effectively exhibit such an action, it is recommended to contain Mo by 0.005% or more. More preferably, it is 0.1% or more. However, even if the amount of Mo exceeds 1.0%, the above effect is saturated and it is economically useless. Preferably it is 0.8% or less, More preferably, it is 0.5% or less.

<Nb: 0.1% or less (excluding 0%)>
Nb is an element that is very effective for increasing the strength of the steel sheet and refining the structure, and the effect is sufficiently exerted particularly by the combined addition with Mo. In order to exert such effects, it is recommended to contain 0.005% or more. More preferably, it is 0.01% or more. However, even if Nb is contained excessively, these effects are saturated and economically useless, so the content is suppressed to 0.1% or less. Preferably it is 0.08% or less.

<B: 0.0002 to 0.01%>
B is an element effective for increasing the strength of the steel sheet, and 0.0002% or more (more preferably 0.0005% or more) is preferably contained in order to exert the effect. On the other hand, when B is contained excessively, the hot workability deteriorates, so that it is preferably contained in the range of 0.01% or less (more preferably 0.005% or less).

<Ca: 0.0005 to 0.005%,
Mg: 0.0005 to 0.01%, and REM: 0.0005 to 0.01%
One or more selected from the group consisting of>
Ca, Mg, and REM (rare earth elements) are effective elements for suppressing the increase of the hydrogen ion concentration in the interface atmosphere accompanying the corrosion of the steel sheet surface, that is, for suppressing the decrease in pH and enhancing the corrosion resistance of the steel sheet. It is also effective for controlling the form of sulfides in steel and improving workability. In order to fully exhibit the effect, the content is 0.0005% or more in any of Ca, Mg, and REM. It is preferable. On the other hand, since workability deteriorates if contained excessively, Ca is preferably 0.005% or less, and Mg and REM are preferably suppressed to 0.01% or less.

  Although the present invention does not define the production conditions, in order to form the above-described structure exhibiting ultrahigh strength and excellent hydrogen embrittlement resistance using a steel material satisfying the above component composition, It is recommended that the finishing temperature be a supercooled austenite region temperature at which ferrite is not generated and be as low as possible. This is because the austenite of the hot-rolled steel sheet can be refined by performing finish rolling at the temperature, and as a result, the structure of the final product becomes fine.

In addition, it is recommended to perform heat treatment in the following manner after hot rolling or after cold rolling performed thereafter. That is, the steel satisfying the chemical composition from 10 to 1800 seconds at a temperature (T1) of the _{A 3} point ~ _{(A 3} point + 50 ℃) (t1) after heating and holding, 3 ° C. / s or more average cooling rate mentioned above ( It is recommended to cool to a temperature (T2) between Ms point and 100 ° C.) to Bs point and to heat and hold in this temperature range for 60 to 1800 seconds (t2).

Or the T1 exceeds _{(A 3} point + 50 ° C.), the t1 exceeds 1800 seconds, lead to grain growth of the austenite, since formability (stretch flangeability) is undesirably poor. On the other hand, the T1 becomes lower than the temperature of the _three points A, not predetermined bainitic ferrite structure can not be obtained. Further, when t1 is less than 10 seconds, austenitization is not sufficiently performed, and cementite and other alloy carbides remain, which is not preferable. The t1 is preferably 30 seconds to 600 seconds, more preferably 60 seconds to 400 seconds.

  Then, the steel sheet is cooled at an average cooling rate of 3 ° C./s or more in order to avoid the formation of a pearlite structure by avoiding the pearlite transformation region. It is recommended that the average cooling rate be as large as possible, preferably 5 ° C./s or higher, more preferably 10 ° C./s or higher.

  Next, after rapidly cooling from the (Ms point−100 ° C.) to the Bs point at the above speed, a predetermined structure can be introduced by isothermal transformation. When the heating and holding temperature (T2) here exceeds the Bs point, a large amount of pearlite that is undesirable for the present invention is generated, and a bainitic ferrite structure cannot be sufficiently secured. On the other hand, if the T2 is lower than (Ms point−100 ° C.), the retained austenite decreases, which is not preferable.

  On the other hand, when the heating and holding time (t2) exceeds 1800 seconds, the dislocation density of the bainitic ferrite decreases and the amount of trapped hydrogen decreases, and a predetermined retained austenite cannot be obtained. On the other hand, even if the t2 is less than 60 seconds, a predetermined bainitic ferrite structure cannot be obtained. Preferably, t2 is 90 seconds to 1200 seconds, more preferably 120 seconds to 600 seconds. The cooling method after heating and holding is not particularly limited, and air cooling, rapid cooling, air-water cooling, and the like can be performed.

  In consideration of actual operation, it is easy to perform the annealing treatment using a continuous annealing facility or a batch annealing facility. Moreover, when plating a cold-rolled sheet to make hot dip galvanizing, the plating conditions may be set so as to satisfy the heat treatment conditions, and the heat treatment may be performed in the plating step.

Moreover, the hot-rolling process (the cold-rolling process as needed) before performing the continuous annealing process mentioned above is not specifically limited, Usually, the conditions implemented can be selected suitably and can be employ | adopted. Specifically, as the above hot rolling process, for example, after completion of hot rolling at _three or more points of Ar, conditions such as cooling at an average cooling rate of about 30 ° C./s and winding at a temperature of about 500 to 600 ° C. are adopted. Can do. Moreover, when the shape after hot rolling is bad, cold rolling may be performed for the purpose of shape correction. Here, the cold rolling rate is recommended to be 1 to 70%. This is because cold rolling exceeding a cold rolling rate of 70% increases the rolling load and makes rolling difficult.

  The present invention is intended for thin steel sheets, but the product form is not particularly limited, and in addition to steel sheets obtained by hot rolling and steel sheets obtained by further cold rolling, hot rolling Or after performing cold rolling, annealing may be performed, and then chemical conversion treatment may be performed, or plating by hot dipping, electroplating, vapor deposition, etc., various types of coating, paint base treatment, organic coating treatment, and the like may be performed.

  As the type of plating, any of general zinc plating, aluminum plating, and the like may be used. The plating method may be either hot-dip plating or electroplating, and may be further subjected to alloying heat treatment after plating, or may be subjected to multilayer plating. Moreover, you may give a film lamination process on a non-plated steel plate or a plated steel plate.

  When performing the above-mentioned coating, chemical conversion treatment such as phosphate treatment or electrodeposition coating may be performed according to various applications. A known resin can be used for the paint, and an epoxy resin, a fluorine-containing resin, a silicon acrylic resin, a polyurethane resin, an acrylic resin, a polyester resin, a phenol resin, an alkyd resin, a melamine resin, or the like can be used together with a known curing agent. Is possible. In particular, from the viewpoint of corrosion resistance, use of an epoxy resin, a fluorine-containing resin, or a silicon acrylic resin is recommended. In addition, known additives added to the paint, such as coloring pigments, coupling agents, leveling agents, sensitizers, antioxidants, ultraviolet stabilizers, flame retardants, and the like may be added.

  The form of the paint is not particularly limited, and can be appropriately selected according to the use such as solvent-based paint, powder paint, water-based paint, water-dispersed paint, and electrodeposition paint. In order to form a desired coating layer on a steel material using the coating material, a known method such as a dipping method, a roll coater method, a spray method, or a curtain flow coater method may be used. The thickness of the coating layer may be a known appropriate value depending on the application.

  The ultra-high-strength steel sheet of the present invention can be applied not only to automotive strength parts such as bumpers, door impact beams, pillars, reinforcements, and members of automobiles such as members, but also to indoor parts such as seat rails. . Parts obtained by forming and processing in this manner also have sufficient material properties (strength) and exhibit excellent hydrogen embrittlement resistance.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. It is also possible to implement, and they are all included in the technical scope of the present invention.

  Test steel No. 1 composed of the components shown in Table 1 After A to R were melted in vacuum and made into an experimental slab, the surface scale was removed by pickling after obtaining a hot-rolled steel plate with a thickness of 3.2 mm according to the following process (hot rolling → cold rolling → continuous annealing). Then, cold rolling was performed until the thickness became 1.2 mm.

<Hot rolling process> Start temperature (SRT): Hold at 1150-1250 ° C for 30 minutes
Finishing temperature (FDT): 850 ℃
Cooling rate: 40 ° C / s
Winding temperature: 550 ℃
<Cold rolling process> Cold rolling rate: 50%
For <continuous annealing process> Each sample steels, after holding for 120 seconds at _{A 3} point + 30 ° C., rapidly cooled at an average cooling rate of 20 ° C. / s to the To ° C. in Table 2 (air), at the the To ° C. 240 Held for 2 seconds. Thereafter, it was cooled with air to room temperature.

  In Table 2, No. 12, as a comparative example, in order to produce martensitic steel, which is a conventional high strength steel, the steel sheet after cold rolling was heated to 830 ° C. and held for 5 minutes, then water quenched and tempered at 300 ° C. for 10 minutes. . No. In No. 13, the cold-rolled steel sheet was heated to 800 ° C. and held for 120 seconds, then cooled to 350 ° C. at an average cooling rate of 20 ° C./s, and held at that temperature for 240 seconds.

  The metal structure, tensile strength (TS), elongation [total elongation (El)], and hydrogen embrittlement resistance (hydrogen embrittlement risk index) of each steel sheet thus obtained were examined in the following manner. It was.

[Observation of metal structure]
Observe and photograph an arbitrary measurement area (approximately 50 μm x 50 μm, measurement interval is 0.1 μm) in the plane parallel to the rolling surface at the position of the product thickness ¼, bainitic ferrite (BF) and martens The area ratio of the site (M) and the area ratio of residual austenite (residual γ) were measured according to the methods described above. And it measured similarly in the 2 visual fields selected arbitrarily, and calculated | required the average value. Further, other structures (ferrite, pearlite, etc.) were obtained by subtracting the area ratio occupied by the above structure from the total structure (100%). Further, the average axial ratio of the residual austenite crystal grains is measured according to the above-mentioned method, and those having an average axial ratio of 5 or more satisfy the requirement of the present invention (◯), and those having an average axial ratio of less than 5 are the requirements of the present invention. It was evaluated as not satisfying (×).

[Measurement of tensile strength (TS) and elongation (El)]
The tensile test was performed using a JIS No. 5 test piece, and the tensile strength (TS) and elongation (El) were measured. The strain rate in the tensile test was 1 mm / sec. In the present invention, a steel sheet having a tensile strength measured by the above method of 1180 MPa or more was evaluated as having an elongation of 8% or more as “excellent in elongation”.

[Evaluation of hydrogen embrittlement resistance]
Using a flat plate test piece having a thickness of 1.2 mm, a low strain rate tensile test method (SSRT) with a strain rate of 1 × 10 ⁻⁴ / sec was performed, and a hydrogen embrittlement risk index ( %) To evaluate hydrogen embrittlement resistance.
Hydrogen embrittlement risk index (%) = 100 × (1−E1 / E0)

Here, E0 indicates the elongation at break of the test piece in a state that substantially does not contain hydrogen in the steel, and E1 indicates breakage of the steel material (test piece) electrochemically charged with hydrogen in sulfuric acid. It shows the growth of time. The hydrogen charge is performed by immersing a steel material (test piece) in a mixed solution of H ₂ SO ₄ (0.5 mol / L) and KSCN (0.01 mol / L) at room temperature and a constant current (100 A / m ^2). ).

  If the hydrogen embrittlement risk index exceeds 50%, there is a risk of causing hydrogen embrittlement during use. Therefore, in the present invention, 50% or less was evaluated as having excellent hydrogen embrittlement resistance. These results are shown in Table 2.

[Evaluation of weldability]
No. which is a typical steel type. 1 and No. 11 was subjected to a weldability test. In the test, test pieces were prepared according to JISZ 3136 and JISZ 3137 using a test material having a thickness of 1.2 mm, spot-welded under the following conditions, and then a shear tensile test (maximum load at 20 mm / min tensile speed). ) And a cross tensile test (a tensile speed was measured at a maximum speed of 20 mm / min) to determine a shear tensile strength (TSS) and a cross tensile strength (CTS). And it evaluated that the ductility ratio (CTS / TSS) represented by ratio of the said shear tensile strength (TSS) and cross tensile strength (CTS) was 0.2 or more was excellent in weldability. As a result, no. No. 11 (conventional steel) has a ductility ratio of 0.19. The ductility ratio of No. 1 (developed steel) was 0.22 and excellent in weldability.

<Spot welding conditions>
・ Initial pressurization time: 60 cycles / 60 Hz, applied pressure 450 kgf (4.4 kN)
-Energizing time: 1 cycle / 60Hz
・ Welding current: 8.5 kA

  The following can be considered from Tables 1 and 2 (the following No. indicates the experiment No. in Table 2).

  No. satisfying the requirements defined in the present invention. Nos. 1 to 10 and 14 to 18 show excellent hydrogen embrittlement resistance while being super high strength steel plates of 1180 MPa or more. Moreover, since the elongation which should be comprised as a TRIP steel plate is also favorable, and also having the outstanding weldability, the optimal steel plate is obtained as a reinforcement part etc. of the motor vehicle exposed to an atmospheric corrosive atmosphere.

  On the other hand, No. which does not satisfy the provisions of the present invention. Each of 11 to 13 and 19 has the following problems.

  That is, No. 11 is an example using the steel type K having an excessive amount of C, but does not have sufficient weldability.

  No. No. 12 is an example of obtaining martensitic steel, which is a conventional high-strength steel, using a steel type L having an insufficient amount of Si. However, since there is almost no retained austenite, the resistance to hydrogen embrittlement is poor. ing.

  No. No. 13 uses a steel material that satisfies the component composition defined in the present invention, but because it was not manufactured under the recommended conditions, the obtained steel plate was a conventional TRIP steel plate. That is, the retained austenite did not satisfy the average axial ratio defined in the present invention and was agglomerated, and the matrix did not have a two-phase structure of bainitic ferrite and martensite, resulting in insufficient strength.

  No. No. 19 exceeds the amount of Al defined as the steel sheet 1 of the present invention, so that a predetermined amount of retained austenite can be secured, but the retained austenite does not satisfy the average axial ratio defined in the present invention, and the desired mother Since it does not become a phase and further includes inclusions such as AlN, it is inferior in hydrogen embrittlement resistance.

  Next, parts were formed using the steel type symbols A and D in Table 1 above and a comparative steel plate (a conventional high-tensile steel plate of 590 MPa class), and as shown below, a puncture resistance test and an impact resistance test The performance (crush resistance and impact resistance) as a molded product was examined.

[Pressure resistance test]
First, parts (test body, hat channel parts) 1 as shown in FIG. 3 were prepared using the steel type symbols A and D of Table 1 and the comparative steel sheet, respectively, and the crushability test was performed as follows. . That is, spot welding was performed at a pitch of 35 mm as shown in FIG. 3 by applying a current 0.5 kA lower than the dust generation current from an electrode having a tip diameter of 6 mm to the spot welding position 2 of the component shown in FIG. And as shown in FIG. 4, the metal mold | die 3 was pressed from the upper direction center part of the component 1, and the maximum load was calculated | required. Absorbed energy was determined from the area of the load-displacement diagram. The results are shown in Table 3.

  From Table 3, the part (test body) created using the steel plate of the present invention shows a higher load than when a conventional steel plate with low strength is used, and the absorbed energy is also high, so it has an excellent pressure resistance. It turns out that it has destructiveness.

[Impact resistance test]
Parts (test body, hat channel parts) 4 as shown in FIG. 5 were prepared using steel sheets of steel type symbols A and D in Table 1 and comparative steel sheets, respectively, and an impact resistance test was performed as follows. FIG. 6 is a cross-sectional view taken along line AA of the component 4 in FIG. In the impact resistance test, after spot welding is performed at the spot welding position 5 of the part 4 as in the case of the above-mentioned fracture resistance test, the part 4 is set on the base 7 as schematically shown in FIG. The falling energy (mass: 110 kg) 6 was dropped from the position of 11 m in height from above 4, and the absorbed energy until the part 4 was deformed 40 mm (the height direction contracted) was determined. The results are shown in Table 4.

  From Table 4, it can be seen that the part (test body) prepared using the steel sheet of the present invention has higher absorbed energy than the case of using a conventional steel sheet having low strength and has excellent impact resistance characteristics. .

  For reference, a TEM observation photograph of the test piece obtained in this example is shown. FIG. 9 is a TEM observation photograph example (magnification 15,000 times), and FIG. 9 is an enlarged TEM observation photograph example (magnification 60,000 times) of a part of the photograph shown in FIG. Thus, the microstructure of the ultra-high-strength steel sheet of the present invention is a state in which retained austenite (in FIGS. 8 and 9, bar-like black portions) is finely dispersed, and the shape of the retained austenite is defined by the present invention. It can be seen that the lath shape meets the requirements. On the other hand, FIG. 13 is a TEM observation photograph of FIG. Residual austenite (slightly round black portion in FIG. 10) is present in 13 ultra high strength steel sheets, but it is understood that the austenite is a massive austenite that does not satisfy the provisions of the present invention.

It is a graph which shows the relationship between the average axial ratio of a retained austenite crystal grain, and a hydrogen embrittlement risk index. It is the figure which showed typically the nearest neighbor distance between residual austenite crystal grains. It is a general-view perspective view of the components used for the pressure-resistant fracture test in an Example. It is the side view which showed typically the mode of the pressure-proof fracture test in an Example. It is a general | schematic perspective view of the components used for the impact-resistant characteristic test in an Example. It is AA sectional drawing in the said FIG. It is the side view which showed typically the mode of the impact-resistant characteristic test in an Example. No. of an Example. 1 is an example of a TEM observation photograph (magnification: 15,000 times) in No. 1 (example of the present invention). No. of an Example. 1 is an example of a TEM observation photograph (magnification: 60,000 times) in 1 (invention example). No. of an Example. 13 is a TEM observation photograph example (magnification: 15,000 times) in No. 13 (comparative example).

Explanation of symbols

1 Pressure fracture test parts (test specimen)
2,5 Spot welding position 3 Mold 4 Impact resistance test parts (test body)
6 Falling weight 7 (For impact resistance test)

Claims (7)

% By mass
C: 0.10 to 0.25%,
Si: 1.5 to 3.0%,
Mn: 1.0 to 3.5%
P: 0.15% or less,
S: 0.02% or less,
Al: 1.5% or less (excluding 0%)
And the balance consists of iron and inevitable impurities,
The area ratio with respect to the whole structure includes both bainitic ferrite and martensite, and is 80% or more in total, and ferrite and pearlite satisfy 9% or less (including 0%) in total,
It has an area ratio of 1% or more of retained austenite with respect to the whole structure,
The average axial ratio (major axis / minor axis) of the residual austenite crystal grains is 5 or more,
The average minor axis length of the residual austenite crystal grains is 1 μm or less, and the nearest neighbor distance between the residual austenite crystal grains is 1 μm or less;
Furthermore, an ultra-high strength thin steel sheet having excellent hydrogen embrittlement resistance, wherein the tensile strength is 1180 MPa or more. % By mass
C: 0.10 to 0.25%,
Si: 1.5 to 3.0%,
Mn: 1.0 to 3.5%
P: 0.15% or less,
S: 0.02% or less,
Al: 0.5% or less (excluding 0%)
And the balance consists of iron and inevitable impurities,
The area ratio with respect to the whole structure includes both bainitic ferrite and martensite, and is 80% or more in total, and ferrite and pearlite satisfy 9% or less (including 0%) in total,
It has an area ratio of 1% or more of retained austenite with respect to the whole structure,
The average axial ratio (major axis / minor axis) of the residual austenite crystal grains is 5 or more,
The average minor axis length of the residual austenite crystal grains is 1 μm or less, and the nearest neighbor distance between the residual austenite crystal grains is 1 μm or less;
Furthermore, an ultra-high strength thin steel sheet having excellent hydrogen embrittlement resistance, wherein the tensile strength is 1180 MPa or more. Furthermore, in mass%,
Cu: 0.003-0.5% and / or Ni: 0.003-1.0%
The ultra-high-strength thin steel sheet according to claim 1 or 2 . Furthermore, in mass%,
The ultra high strength thin steel sheet according to any one of claims 1 to 3 , comprising 0.003 to 1.0% of Ti and / or V in total. Furthermore, in mass%,
Mo: 1.0% or less (excluding 0%),
Nb: 0.1% or less (excluding 0%)
The ultra-high-strength thin steel sheet according to any one of claims 1 to 4 . Furthermore, in mass%,
B: The ultra-high-strength thin steel sheet according to any one of claims 1 to 5 , comprising 0.0002 to 0.01%. Furthermore, in mass%,
Ca: 0.0005 to 0.005%,
Mg: 0.0005 to 0.01%, and REM: 0.0005 to 0.01%
The ultra-high strength thin steel sheet according to any one of claims 1 to 6 , comprising at least one selected from the group consisting of: