JP4610500B2 - Ultra high strength steel excellent in workability and delayed fracture resistance and method for producing the same - Google Patents

Description

  The present invention relates to an ultra-high strength steel excellent in workability and delayed fracture resistance, and in particular, has an excellent balance with ductility despite having a tensile strength of about 1200 MPa or more, and is also resistant to delay. It relates to ultra high strength steel with good fracture characteristics. The ultra high strength steel of the present invention is suitably used for, for example, building materials, automobile structural parts, reinforcing members, and the like.

  In recent years, as demands for earthquake resistance performance of buildings, weight reduction of automobiles, collision safety, and the like have increased, for example, the application of ultra-high strength steel sheets exceeding a tensile strength of 780 MPa has been expanded. In addition, with the widespread use of the recycling business, attempts have been actively made to develop high-strength steel by reusing Cu, which has been impossible to remove until now.

Against this background, the applicant of the present application has previously proposed a technique relating to Cu-added high-strength steel (Patent Document 1). Here, high-strength steel with outstanding balance between strength and ductility is disclosed by dispersing and precipitating nanometer-level Cu (nano Cu) in a high dislocation density martensite structure (tempered martensite). is doing. According to Patent Document 1, a steel having a tensile strength of about 1000 MPa or more and an excellent balance with ductility (total elongation characteristics) can be obtained.
JP 2005-264176 A

  There is an increasing demand for tensile strength, and for example, there is a need to provide ultra-high strength steel that is excellent in balance with ductility even at a tensile strength of about 1200 MPa class. On the other hand, when the strength increases, delayed fracture tends to occur. 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. It is a phenomenon, and the time to failure (delayed failure time) becomes shorter as the stress is larger and the amount of hydrogen is larger.

  However, in Patent Document 1 described above, nothing is taken into consideration for prevention of delayed fracture.

  The present invention has been made in view of the above circumstances, and the object thereof is excellent in balance with ductility in spite of having a tensile strength of about 1200 MPa class, and also has improved delayed fracture resistance. It is an object of the present invention to provide an ultrahigh strength steel and a method for producing the same.

  The ultra-high-strength steel excellent in workability and delayed fracture resistance according to the present invention, which has been able to solve the above-described problems, is composed of steel in mass%, C: 0.1 to 1.0%, Si: 2% or less (excluding 0%), Mn: 0.5 to 3%, Cu: 1.5 to 5%, balance: Fe and inevitable impurities are satisfied, and the average grain size of the prior austenite is 7 μm or less The structure contains tempered martensite as a main component, Cu particles having an average particle diameter of 1.5 to 50 nm are dispersed in the structure, and is measured by an XAFS (X-ray absorption Fine Structure) method. The peak height of 8.98 keV in the vicinity of the fluorescent X-ray spectrum K absorption edge is summarized in the range of 0.340 to 0.38 in normalized fluorescence yield.

  The other ultra-high strength steel excellent in workability and delayed fracture resistance according to the present invention that has solved the above-mentioned problems, the component in the steel is mass%, C: more than 0.3% to 1.0 %, Si: 2% or less (excluding 0%), Mn: 0.5 to 3%, Cu: 1.5 to 5%, balance: Fe and inevitable impurities are satisfied, and the average grain size of the prior austenite is 10 μm or less, the structure mainly contains tempered martensite, Cu particles having an average particle diameter of 1.5 to 50 nm are dispersed in the structure, and a fluorescent X-ray spectrum of Cu by the XAFS method. Has a gist that the peak height of 8.98 keV in the vicinity of the K absorption edge is in the range of 0.340 to 0.38 in normalized fluorescence yield.

Further, a method for producing an ultra-high strength steel excellent in workability and delayed fracture resistance according to the present invention that has solved the above problems is a method for producing the ultra-high strength steel, wherein It includes a step (a) of rolling steel that satisfies the components, a step (b) of quenching after rolling, and a step (c) of aging after quenching, and the step (b) is 825 ° C. or higher and 850 ° C. Including the step (b-1) of quenching at a heating temperature of less than 850 ° C. or less and a step of quenching at a heating temperature of 850 ° C. or more and 900 ° C. or less (b-2), wherein the step (c) is 400 It has a gist that it includes a step of aging a temperature of ˜600 ° C. within a time range defined by the following formula (1).
{(768-20.3 × [Cu])-T} / (4.9 × [Cu] +46.2) ≦ ln (t) ≦ {(705-7 × [Cu])-T} / (1.1 × [Cu] + 35.5) ... (1)
In the formula, [Cu] is the Cu content (% by mass),
t is the aging time (min),
T is an aging temperature (° C.).

  Since the ultra high strength steel of the present invention is configured as described above, it has an excellent balance with ductility in spite of having a tensile strength of about 1200 MPa class, and also has improved delayed fracture resistance. It was possible to provide the ultra-high strength steel obtained.

  The present inventor has repeatedly studied on the basis of the nano Cu technology described in Patent Document 1 described above in order to develop an ultra-high strength steel having an excellent balance between tensile strength and ductility and enhanced delayed fracture resistance. It was. Specifically, in order to ensure the desired delayed fracture resistance, the structure of nano Cu is changed to a structure (face-centered cubic lattice, fcc) in which the hydrogen trap sites that cause delayed fracture are sufficiently enhanced. The idea is to increase the proportion of non-matching interfaces (interfaces where there is no continuity of the crystal lattice of the iron matrix and nano Cu particles) and to refine the average grain size of the prior austenite (former γ). Based on the study. As a result, it is possible to obtain a steel suitable for delayed fracture resistance by controlling the heating process of the quenching treatment after rolling and the aging process after quenching to a predetermined range. Such a steel is obtained by the XAFS method. When the fluorescent X-ray spectrum of Cu was measured, it was found that the peak height of 8.98 keV in the vicinity of the K absorption edge satisfied a predetermined range, and the present invention was completed.

  In this specification, “ultra high strength” means that the tensile strength (TS) is about 1200 MPa or more (preferably 1300 MPa or more, more preferably 1350 MPa or more).

  The index of “workability” is the product (TS × El) of TS and El (total elongation), and TS × El is 17000 or more (preferably 18000 or more) when TS is a level of about 1200 to 1350 MPa. On the other hand, when TS is at a level of about 1350 MPa or more, it means that TS × El is 15000 or more (preferably 15500 or more).

  Further, in this specification, “excellent in delayed fracture resistance” means that the amount of delayed fracture hydrogen measured by the method described in Examples below is about 0.20 ppm or more (preferably 0.30 ppm or more). It means that there is.

  Hereinafter, the ultra high strength steel of the present invention will be described.

  As described above, in the present invention, the balance between strength and ductility is achieved by dispersing and precipitating nanometer-level Cu (nano Cu) in tempered martensite, and fluorescent X-rays measured by the XAFS method. The delayed fracture resistance is improved by controlling the peak height of 8.98 keV in the vicinity of the spectrum K absorption edge to a predetermined range and controlling the average grain size of the prior austenite to a predetermined range.

  In the present invention, the structure mainly contains tempered martensite.

  Here, “consisting mainly of tempered martensite” means that the ratio (area ratio) of tempered martensite to the entire structure is about 85% or more and substantially does not contain pro-eutectoid ferrite. . By using tempered martensite with a high dislocation density as the parent phase structure, and dispersing and precipitating nano Cu, which will be described later, in the parent phase structure, strength improvement (reinforcement by carbide and dislocation strengthening) and nano Strength improvement by Cu is effectively exhibited, and the balance between strength and ductility is remarkably increased. Furthermore, in the present invention, the generation of pro-eutectoid ferrite is suppressed in order to improve delayed fracture resistance. This is because when pro-eutectoid ferrite is generated, deformation during stress loading tends to concentrate on pro-eutectoid ferrite, so that delayed fracture is likely to occur. The amount of pro-eutectoid ferrite is preferably as small as possible, and is preferably 5 area% at most, and most preferably 0 area%. The higher the area ratio of tempered martensite, the better. For example, it is preferably 90% or more, and more preferably 95% or more. Examples of the structure (remainder) other than tempered martensite include bainite and retained austenite.

  In the present invention, Cu particles having an average particle diameter of 1.5 to 50 nm are dispersed in the above-described structure, and thereby, the strength improving action by nano Cu is effectively exhibited. If the average particle size of the Cu particles is out of the above range, the desired balance between strength and ductility cannot be ensured. The lower limit of the average particle diameter of the Cu particles is preferably 2.0 nm, and the upper limit thereof is preferably 40 nm, and more preferably 30 nm or less. In particular, in consideration of improvement in delayed fracture resistance, it is recommended that the thickness is 2.5 nm or more and 20 nm or less.

  The average particle diameter of Cu particles is measured as follows using a three-dimensional atom probe field ion microscope (3DAP, manufactured by CAMECA) according to the cross-sectional shape of the steel.

  A needle-like sample (tip radius of curvature <100 nm) is prepared from a position of t / 4 (t = plate thickness) in the case of a plate material, and 4 / D (D = diameter) in the case of a wire rod or steel bar, and is about 10 nm × 10 nm. Ions are collected from a region of × 100 nm, and a spatial distribution map of Cu ions is created. In the above distribution map, an area where Cu is concentrated (area where the density of dots corresponding to Cu ions is high) is regarded as Cu particles, and the particle diameter of Cu particles is observed. Diameter ”. The method for measuring the Cu particles is, for example, M.M. K. It is described in documents such as “Atom Probe Tomography” by Miller (Kluwer Academic, 2000).

In this specification, “Cu particles are dispersed” means that, for example, about 20 to 200 Cu particles having the above particle diameter exist in the observation field of view 9 × 10 ⁻²³ m ³ . Means that.

  In the ultra high strength steel of the present invention, the average grain size of prior austenite is 7 μm or less (when C is contained in an amount of 0.1 to 1.0%) or 10 μm or less (C is contained in an amount of more than 0.3% to 1.0%). In the case of containing). Delayed fracture often occurs from the grain boundaries of the prior austenite. Therefore, the delayed fracture resistance can be improved by reducing the grain size of the prior austenite as described above. Here, the reason why the upper limit of the average grain size of the prior austenite differs depending on the range of the amount of C contained in the steel is that variation in the average grain size of the prior austenite is taken into consideration. Since the delayed fracture occurs from the weakest part of the structure, if there is a variation in the grain size of the prior austenite, it is preferable to define the maximum grain size of the prior austenite. However, since it is difficult to measure the maximum grain size of prior austenite, for convenience, the delayed fracture resistance is controlled by the average grain size of prior austenite. In the case of steel (C: 0.1 to 1.0%) containing a low C content (generally, C: 0.3% or less) that is likely to occur, the upper limit of the average grain size of prior austenite is reduced to 7 μm or less, The ratio of coarse old austenite was suppressed as much as possible.

  The smaller the average particle size of the prior austenite, the better. When it contains 0.1 to 1.0% of C, it is preferably 5.0 μm or less, and more preferably 3.0 μm or less. On the other hand, when it contains more than 0.3% to 1.0% of C, it is preferably 7 μm or less, more preferably 5.0 μm or less, and further preferably 3.0 μm or less.

  The average particle size of prior austenite is measured as follows.

  After performing quenching and aging treatment based on the method specified in JIS G0551, a test piece (size: exposed area of about 10 mm × 10 mm) whose surface was polished and corroded with an alcoholic solution of picric acid was subjected to an optical microscope. A photograph is taken while observing at a magnification of 400 times using the. For 10 visual fields (1.35 mm × 1.80 mm / field), perform image analysis using “Image-Pro Plus” manufactured by Media Cybernetics, and measure the particle size of the prior austenite observed in the visual field. The average value of 10 observation fields is defined as “average grain size of prior austenite”.

  Furthermore, in the ultra-high strength steel of the present invention, when the fluorescent X-ray spectrum of Cu is measured by the XAFS method, the peak height of 8.98 keV in the vicinity of the K absorption edge is 0.340-0 in terms of the normalized fluorescence yield. Within the range of .38. As a result, an ultra-high strength steel having an excellent balance between strength and ductility and enhanced delayed fracture resistance can be obtained.

  Here, the XAFS method will be described.

  XAFS is an abbreviation for X-ray Absorption Fine Structure (X-ray absorption fine structure), and is a kind of state analysis by X-ray absorption spectroscopy. In general, when the absorption coefficient of a material is measured while increasing the X-ray energy by step scanning using a spectroscopic crystal, the absorption coefficient of the material decreases corresponding to the increase of the X-ray energy, but the interaction is large. It increases rapidly in the region. This X-ray energy region is called an X-ray absorption edge. Here, a phenomenon such as a part of photoelectrons generated by X-ray absorption colliding with adjacent atoms and causing interference with a part of scattered photoelectrons is observed, and the X-ray absorption coefficient is modulated. Appears as a fine structure. For this reason, it is known that information on the microscopic structure of atoms can be obtained by dispersing the fine structure on the absorption coefficient appearing in this region. A region around ± 50 eV in the vicinity of the X-ray absorption edge is called XANES (X-ray absorption near edge structure, X-ray absorption edge fine structure), and a region where there is a structure that slowly vibrates over about 1000 eV on the higher energy side. Is called EXAFS (Extended X-ray abstraction Fine Structure). From XANES, information on the symmetry of the arrangement of atoms and the electronic state is obtained, and from EXAFS, information on the radial distribution and coordination number around the atoms is obtained.

  The present inventor pays attention to the fact that the hydrogen trapping capacity, which is an index of delayed fracture resistance, increases with the increase in the fcc structure of the Cu particles, and measures the fcc structure of the Cu particles based on the XAFS method. I made it. As described above, the hydrogen trapping capability increases with an increase in the non-matching interface between the iron matrix and the nano Cu particles. The ratio of the non-matching interface increases the fcc structure in which the crystal structure of the Cu particles is stable. This is because it increases with this.

  Details of the measurement method by the XAFS method will be described with reference to FIG. Here, No. of Table 2 of the Example mentioned later is shown. 1 (example of the present invention).

  First, using the BL38B1XAFS experimental measuring device of the industrial dedicated beamline (SUNBEAM) of the SPring-8 Large Synchrotron Radiation Research Center, High Brightness Optical Science Research Center, near the K absorption edge of Cu at room temperature by fluorescence method A fluorescent X-ray (Kα-ray) spectrum of (XANES portion) was measured. For the measurement, a Si (III) crystal spectrometer was used. While the energy was shifted by step scanning before and after the K absorption edge of Cu, Cu Kα fluorescent lines generated at each energy point were detected by a 7-element SDD detector.

  Next, in order to calculate the spectral intensity (peak height) of 8.98 keV in the XANES portion, it was corrected to “normalized fluorescence yield”. The correction is performed by fitting portions corresponding to background absorption before and after the K absorption edge of Cu with a polynomial function, subtracting them from the raw spectrum, and then normalizing the jump amount (edge jump) of the entire absorption edge to 1. It was.

  The result is shown in FIG.

  As shown in FIG. The “standardized fluorescence yield” of No. 1 is 0.365, which satisfies the range of the present invention (0.340 to 0.38), and therefore has excellent delayed fracture resistance (Examples described later) See Table 2).

  In order to ensure the desired delayed fracture resistance and strength, the normalized fluorescence yield calculated as described above needs to be in the range of 0.340 to 0.38. If it is less than 0.340, since the hydrogen trapping ability is small, the delayed fracture resistance is deteriorated. On the other hand, if it exceeds 0.38, the average particle diameter of the nano Cu particles is increased and the strength is lowered (Examples described later). See). The normalized fluorescence yield is preferably 0.345 or more and 0.370 or less, and more preferably 0.350 or more and 0.360 or less.

  Next, components in the steel of the steel of the present invention will be described. All the components in steel are expressed in mass%.

C: 0.1 to 1.0%
C is an element necessary for ensuring a desired strength by introducing high-density dislocations during martensite transformation to produce tempered martensite and uniformly dispersing nano Cu particles in the aging process. In order to exhibit such an action effectively, 0.1% or more of C is added. However, even if added excessively, the above action is saturated and economically useless, so the upper limit of C was made 1.0%. C is preferably 0.13% or more and 0.80% or less, and more preferably 0.15% or more and 0.60% or less. In order to obtain an extremely high strength steel of about 1300 to 1400 MPa, it is preferable that C is more than 0.3%.

Si: 2% or less (excluding 0%)
Si is an element effective for deoxidation and solid solution strengthening. In order to effectively exhibit such an action, it is preferable to add 0.01% or more of Si, and more preferably 0.02% or more. However, if Si is added excessively, the toughness deteriorates, so the upper limit is made 2%. The upper limit of Si is preferably 1.8%, and more preferably 1.5%.

Mn: 0.5 to 3%
Mn is an essential element for securing the hardenability of steel and obtaining a martensite structure. In order to effectively exhibit such an action, 0.5% or more of Mn is added. However, even if Mn is added in excess of 3%, the above action is saturated and it is economically wasteful, so the upper limit was made 3%. Mn is preferably 0.6% or more and 2.0% or less, and more preferably 0.7% or more and 1.5% or less.

Cu: 1.5 to 5%
Cu is an extremely important element for dispersing desired nano Cu particles. When the addition amount of Cu is less than 1.5%, the amount of deposited nano Cu becomes insufficient, and a desired effect cannot be obtained. On the other hand, even if Cu is added excessively in excess of 5%, the action of nano-Cu is saturated and economically useless, so the upper limit of Cu is set to 5%. Cu is preferably 1.8% or more and 4% or less, and more preferably 2.0% or more and 3.5% or less.

  The steel of the present invention contains the above components, and the balance: Fe and inevitable impurities.

  For example, it is preferable to suppress P to 0.08% or less and S to 0.01% or less because the toughness and workability of P and S, which are unavoidable impurities, deteriorate as the content increases.

  Further, sol.Al and N, which are inevitable impurities, are preferably suppressed to 0.1% or less and 0.007% or less, respectively.

  Next, a method for producing the above-described ultra high strength steel of the present invention will be described.

The production method of the present invention includes a step (a) of rolling the steel satisfying the above-mentioned components in steel, a step (b) of quenching after rolling, and a step (c) of aging after quenching, The step (a) includes a step of performing finish rolling at a temperature _{equal to} or higher than the _Ar3 transformation point, and the step (b) is a step (b-1) of quenching at a heating temperature of 825 ° C. or higher and lower than 850 ° C., or 850 Including a step (b-2) of performing a step of quenching twice or more at a heating temperature of not less than 900 ° C. and not more than 900 ° C., wherein the step (c) is performed at a temperature of 400 to 600 ° C. for a time determined by the following equation (1): The method includes a step of aging in the range.
{(768-20.3 × [Cu])-T} / (4.9 × [Cu] +46.2) ≦ ln (t) ≦ {(705-7 × [Cu])-T} / (1.1 × [Cu] + 35.5) ... (1)
In the formula, [Cu] is the Cu content (% by mass),
t is the aging time (min),
T is an aging temperature (° C.).

  First, after steel containing a predetermined component is cast, hot rolling is performed (step (a)).

  The heating temperature is not particularly limited and is, for example, in the range of about 1100 to 1300 ° C.

The finish rolling step is important for securing desired workability and delayed fracture resistance, and it is preferable to perform finish rolling at a temperature equal to or higher than the Ar ₃ transformation point.

  Cool after finish rolling. In the present invention, as will be described in detail later, mainly in the quenching step (step (b)) and aging step (step (c)) after hot rolling, to ensure the desired martensite, The heat history (cooling rate, cooling stop temperature, etc.) after hot rolling is not particularly limited. For example, a temperature up to about 200 ° C. (cooling stop temperature) is an average cooling rate of about 0.5 ° C./sec or more. It is preferable to cool with.

  After the above hot rolling, pickling or cold rolling may be performed as necessary. Although a cold rolling rate is not specifically limited, For example, it is preferable to exist in the range of about 20 to 70%.

  Next, a quenching process is performed (process (b)).

  In the quenching step (b), the step (austenite treatment) shown in the following (b-1) or (b-2) is performed. As a result, the average grain size of the prior austenite can be refined, and a large amount of desired tempered martensite is generated, so that the delayed fracture resistance is improved. The range of the heating temperature (quenching temperature) of the austenitizing treatment is mainly different between the step (b-1) and the step (b-2), and any pattern is formed according to the set heating temperature. However, in consideration of work efficiency and the like, it is preferable to select the step (b-1).

(B-1): Method of quenching at a heating temperature of 825 ° C. or more and less than 850 ° C. When the above heating temperature is less than 825 ° C., pro-eutectoid ferrite is formed and delayed fracture resistance is lowered, while 850 ° C. or more. In this case, the average grain size of the prior austenite becomes coarse (see the examples described later). The heating temperature is preferably 830 ° C. or higher and 845 ° C. or lower. The heating time is preferably about 10 minutes to 2 hours.

  As for the cooling condition after heating, it is preferable to rapidly cool the temperature up to about 250 ° C. at an average cooling rate of about 10 to 200 ° C./sec from the viewpoint of securing martensite of a predetermined area.

(B-2): Method of performing the step of quenching at a heating temperature of 850 ° C. or more and 900 ° C. or less twice or more When the heating temperature of the austenitizing treatment is set higher than the step (b-1), From the viewpoint of refining the prior austenite crystal grains, the quenching step is performed twice or more. Specifically, at a heating temperature of 850 ° C. or higher and 900 ° C. or lower (preferably 850 ° C. or higher and 880 ° C. or lower), after holding for about 1 to 10 minutes, the temperature up to about 250 ° C. is about 10 to 200 ° C./sec. It is preferable to perform the quenching process of rapidly cooling at an average cooling rate of 2 times or more. When the heating temperature is less than 850 ° C., there is a possibility that the heating will not be performed uniformly. On the other hand, when the heating temperature exceeds 900 ° C., the crystal grains of the prior austenite may not be refined. Further, if the above quenching treatment is not repeated twice or more, there is a problem that crystal grains of the prior austenite are not refined. The higher the number of quenching treatments, the better. The upper limit is not particularly limited, but is preferably 5 times in actual operation.

  The heating temperature in each quenching process may be the same or different as long as the above range is satisfied. For example, as shown in the examples described later, the heating temperature during the first quenching process may be as high as 880 ° C., and the heating temperature during the second quenching process may be as low as 850 ° C.

  Next, an aging treatment is performed (step (c)). Before performing the aging treatment, cold working such as cold rolling may be performed as necessary.

Specifically, the aging treatment is performed at a temperature of 400 to 600 ° C. within a time range determined by the following expression (1).
{(768-20.3 × [Cu])-T} / (4.9 × [Cu] +46.2) ≦ ln (t) ≦ {(705-7 × [Cu])-T} / (1.1 × [Cu] + 35.5) ... (1)
In the formula, [Cu] is the Cu content (% by mass),
t is the aging time (min),
T is an aging temperature (° C.).

  Here, the Cu particles are uniformly and finely dispersed at the nanometer level in the martensite structure obtained by the above-described method, and the martensite structure is appropriately tempered to obtain tempered martensite. Processing is in progress.

  The aging temperature (T) is 400 to 600 ° C. If it is less than 400 degreeC, precipitation of nano Cu will become inadequate and a favorable balance of strength-ductility will not be obtained. On the other hand, when aging is performed at over 600 ° C., the precipitated Cu particles are extremely coarsened, and the martensite structure is excessively tempered, resulting in a significant decrease in strength. The lower limit of the aging temperature is preferably 420 ° C., while the upper limit thereof is preferably 550 ° C. and more preferably 520 ° C. or less.

  The aging time (t) is performed within the range represented by the above formula (1). The above formula (1) is to control the precipitation rate of Cu particles to prevent coarsening, and to increase the hydrogen trapping capability and improve the delayed fracture resistance, so that the optimum aging time (t) is expressed as the aging temperature ( T) and the Cu content ([Cu]), which are set through many basic experiments by the present inventors.

When the aging time is less than the lower limit of the above formula (1), the hydrogen trap ability is lowered, the fluorescence yield calculated as described above is also below the predetermined range, and the delayed fracture resistance is deteriorated. On the other hand, when the upper limit of the above formula (1) is exceeded, the Cu particles become coarse, a desired intensity cannot be obtained, and the fluorescence yield also exceeds a predetermined range. The aging time preferably satisfies the following formula (2), and more preferably satisfies the following formula (3).
{(768-20.3 × [Cu])-T} / (3.9 × [Cu] +43.2) ≦ ln (t) ≦ {(705-7 × [Cu])-T} / (1.1 × [Cu] + 35.5) ... (2)
{(768-20.3 × [Cu])-T} / (3.9 × [Cu] +43.2) ≦ ln (t) ≦ {(715-7 × [Cu])-T} / (1.1 × [Cu] + 45.5) ... (3)

  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.

  First, steel materials A to E having the composition shown in Table 1 (the balance is Fe and inevitable impurities) were melted, heated to 1200 ° C., and hot-rolled at a finish rolling temperature of 950 ° C. Among the steel materials A to E, A, B and E are examples satisfying the components in steel defined in the present invention, C is a comparative example having a low Cu content, and D is a comparative example not containing Cu. .

  Next, quenching and aging treatment were performed under the conditions shown in Table 2.

  Detailed quenching conditions are as follows.

(Nos. 1-2, 4, 6-16 in Table 2)
These are examples in which quenching was performed in the above-described step (b-1). The samples were heated at various temperatures shown in Table 2, held for 30 minutes, and then cooled with water.

(No. 5 in Table 2)
No. 5 is an example in which quenching was performed in the step (b-2) described above. First, as shown in Table 2, it was heated to 880 ° C., held for 30 minutes, and then cooled with water (first quenching treatment). Next, as shown in Table 2, it was heated to 850 ° C., held for 30 minutes in the same manner as the first quenching process, and then cooled with water (second quenching process).

(No. 3 in Table 2)
No. No. 3 was an example in which the quenching process was not performed, and an aging treatment was performed immediately after hot rolling.

  Using each specimen thus obtained, the average particle size of Cu particles, the average particle size of prior austenite, and the normalized fluorescence yield were measured based on the above-described method, and as follows. The tissue and each property were measured.

(1) Method for observing the structure The structure excluding the ferrite structure is parallel to the rolling direction at a position of t / 4 (t = plate thickness) in the case of a plate material and D / 4 (diameter of the cross section) in the case of a wire rod or steel bar. The surface structure was observed with an optical microscope (magnification 1500 times), and the area ratio was measured.

  For the ferrite structure, the above surface was polished and etched with a nital solution, and then observed with an optical microscope (a magnification of 1500 times), and the area ratio was measured.

(2) Tensile strength and elongation A JIS No. 5 test piece was sampled from a cross section perpendicular to the rolling direction and subjected to a tensile test, and the tensile strength (TS) and elongation [total elongation (El)] were measured. The crosshead speed in the tensile test was 1 mm / sec.

Here, TS ≧ 1200 MPa and El ≧ 10.0% are regarded as acceptable. “TS × El”, which is an index of workability, is determined as follows according to the level of TS.
When TS is 1200 to 1350 MPa, TS × El ≧ 17000 is passed.
When TS is 1350 MPa or more, TS × El ≧ 15000 is passed.

(3) Delayed fracture resistance The test piece shown in Fig. 2 is prepared, and the SSRT test (Slow Strain Rate Test) is performed under the following hydrogen charge conditions. Measurement was performed as follows.

(Hydrogen charge condition)
Electrolytic solution: H ₂ SO ₄ aqueous solution (containing 0.01 mol / L of KSCN, pH = 3)
Electrolytic current density: 4 to 10 mA / cm ²
Precharge time: 16 hours Continuous charge during SSRT

(SSRT condition)
Crosshead speed: 2 μm / min
(Strain rate: 1 × 10 ⁻⁶ s ⁻¹ )

(Measurement of hydrogen content)
The amount of hydrogen after the hydrogen charge was large when an ultra-sensitive gas analyzer UG-240APN manufactured by Hitachi Tokyo Electron Co., Ltd. was assembled with an E410-7101 type infrared image furnace manufactured by Vacuum Riko Co., Ltd. as a temperature raising mechanism for the sample. It measured using atmospheric pressure ionization mass spectrometry (Atmospheric Pressure Ionization Mass Spectrometer, API-MS). Specifically, Ar gas having a flow rate of 8000 mL / min was used as a carrier gas, and the mixture was heated from room temperature to 200 ° C. at a rate of temperature increase of 12 ° C./min. .

(Measurement of delayed fracture hydrogen content)
Next, the amount of hydrogen (hydrogen charge amount) is variously changed by changing the electrolytic current density, and the ratio (TS1 / TS0) of the tensile strength (TS0) before hydrogen charging and the tensile strength (TS1) after hydrogen charging is 0. The amount of hydrogen that was .6 was determined, and this amount of hydrogen was defined as the amount of delayed fracture hydrogen.

  A test piece with a large amount of delayed fracture hydrogen means that it easily absorbs hydrogen harmful to delayed fracture resistance. Here, a test piece having a delayed fracture hydrogen amount of 0.20 ppm or more was defined as an example of the present invention (pass).

  These results are also shown in Table 2. In the column of the base material in Table 2, M means a tempered martensite structure, F means a ferrite structure, and P means a pearlite structure. For example, in Table 2, “M” means that tempered martensite is 100% by area and ferrite is 0%. In Table 2, examples that deviate from the requirements defined in the present invention are underlined.

  In Table 2, No. 1, 5, 6, 8, 13, 16, and 17 are all examples of the present invention that satisfy the requirements defined in the present invention, have high strength, and excellent workability and delayed fracture resistance. Yes.

  On the other hand, in the following comparative examples, the delayed fracture resistance decreased for the following reasons. In addition, No. in which TS significantly decreased. Nos. 3, 7, 10, 11, 14, and TS are high but El and TS × El are low. No. 15 did not perform a delayed fracture test.

  No. Since No. 2 had a high quenching temperature, the grain size of the prior austenite became coarse.

  No. In No. 3, since no quenching treatment was performed, the structure after hot rolling (mixed structure of ferrite and pearlite) remained as it was, and the desired tempered martensite structure was not obtained. As a result, the tensile strength was also significantly reduced.

  No. Since No. 4 had a low quenching temperature, about 10% of ferrite was generated in the steel in addition to tempered martensite.

  No. In No. 7, since the aging treatment was performed at a low temperature for a short time, the Cu particles were refined and the desired fluorescence yield was not obtained. Also, the tensile strength was significantly reduced.

  No. In No. 9, since the aging time was short, the Cu particles were refined and the desired fluorescence yield was not obtained.

  No. In No. 10, since the aging treatment was performed for a long time, the Cu particles were coarsened, and the desired fluorescence yield was not obtained. Also, the tensile strength was significantly reduced.

  No. No. 11 was subjected to an aging treatment at a high temperature for a long time, so that the Cu particles were coarsened and a desired fluorescence yield could not be obtained. Also, the tensile strength was significantly reduced.

  No. Since No. 12 had a high quenching temperature, the prior austenite grain size became coarse and the delayed fracture resistance deteriorated. Moreover, the workability also decreased.

  No. 14 is an example in which the steel material C having a low Cu content was used, and only a short-term aging treatment was performed. The Cu particles were excessively refined, the average grain size of the prior austenite was coarsened, and the desired fluorescence yield was obtained. It was not obtained. Also, the tensile strength was significantly reduced.

  No. 15 is an example using a steel material D to which no Cu is added. Here, since the aging treatment was performed at a low temperature, the desired tempered martensite was generated and a predetermined strength was ensured, but the elongation was significantly reduced. Therefore, measurement of fluorescence yield and delayed destruction test were not performed.

  No. No. 18 is an example in which the quenching temperature is high, and the average grain size of the prior austenite has increased.

  No. In No. 19, since the aging treatment was performed only for a short time, the desired fluorescence yield could not be obtained.

FIG. 1 shows No. 1 in Table 2 of the examples. It is a graph which shows the relationship between the fluorescence yield normalized and photon energy about 1 (invention example). FIG. 2 is a schematic plan view showing a delayed fracture test piece used in the example.

Claims (3)

The component in steel is mass%,
C: 0.1 to 1.0%
Si: 2% or less (excluding 0%),
Mn: 0.5-3%,
Cu: 1.5 to 5%,
Balance: Fe and inevitable impurities are satisfied,
The average particle size of the prior austenite is 7 μm or less,
The structure contains a ratio of tempered martensite to the entire structure of 85 area% or more, and restricts pro-eutectoid ferrite to 5 area% or less (including 0 area%) ,
In the structure, Cu particles having an average particle size of 1.5 to 50 nm are dispersed,
When the X-ray absorption fine structure (XAFS) method was used to measure the fluorescent X-ray spectrum of Cu, the peak height of 8.98 keV near the K absorption edge was 0.340 to 0.38 in terms of normalized fluorescence yield. Ultra high strength steel with excellent workability and delayed fracture resistance, characterized by being in the range. The component in steel is mass%,
C: more than 0.3% to 1.0%,
Si: 2% or less (excluding 0%),
Mn: 0.5-3%,
Cu: 1.5 to 5%,
Balance: Fe and inevitable impurities are satisfied,
The average particle size of the prior austenite is 10 μm or less,
The structure contains a ratio of tempered martensite to the entire structure of 85 area% or more, and restricts pro-eutectoid ferrite to 5 area% or less (including 0 area%) ,
In the structure, Cu particles having an average particle size of 1.5 to 50 nm are dispersed,
When the X-ray absorption fine structure (XAFS) method was used to measure the fluorescent X-ray spectrum of Cu, the peak height of 8.98 keV near the K absorption edge was 0.340 to 0.38 in terms of normalized fluorescence yield. Ultra high strength steel with excellent workability and delayed fracture resistance, characterized by being in the range. A method for producing the ultra high strength steel according to claim 1 or 2,
Rolling the steel satisfying the components in the steel (a),
A step (b) of quenching after rolling;
And (c) aging after quenching,
In the step (b), the step (b-1) of quenching at a heating temperature of 825 ° C. or more and less than 850 ° C. or the step of quenching at a heating temperature of 850 ° C. or more and 900 ° C. or less (b-2) )
The step (c) includes a step of aging a temperature of 400 to 600 ° C. within a time range defined by the following formula (1), and has an ultrahigh strength excellent in workability and delayed fracture resistance Steel manufacturing method.
{(768-20.3 × [Cu])-T} / (4.9 × [Cu] +46.2) ≦ ln (t) ≦ {(705-7 × [Cu])-T} / (1.1 × [Cu] + 35.5)
... (1)
In the formula, [Cu] is the Cu content (% by mass),
t is the aging time (min),
T is an aging temperature (° C.).

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