Annealed steel material and method for manufacturing the same

Abstract

The present invention provides an annealed steel material having a composition containing, in mass %, 0.28≤C≤0.42, 0.01≤Si≤1.50, 0.20≤Mn≤1.20, 4.80≤Cr≤6.00, 0.80≤Mo≤3.20, 0.40≤V≤1.20, and 0.002≤N≤0.080, with the balance being Fe and unavoidable impurities; in which the annealed steel material has a cross-sectional size of a thickness of 200 mm or more and a width of 250 mm or more, and a hardness of 100 HRB or less; and in which a diameter of a largest ferritic grain observed in a microstructure is 120 μm or less in terms of a perfect circle equivalent, an area ratio of carbides is 3.0% or more and less than 10.5%, and an average particle diameter of the carbides is 0.18 μm or more and 0.29 μm or less.

Claims

1. An annealed steel material having a composition consisting of, in mass %: 0.28≤C<0.42, 0.01≤Si≤1.50, 0.20≤Mn≤1.20, 4.80≤Cr≤6.00, 0.80≤Mo≤3.20, 0.40≤V≤1.20, and 0.002≤N≤0.080, with a balance being Fe and unavoidable impurities, and optionally, Cu≤1.00, Ni≤1.50, B≤0.0050, W≤5.00, Co≤4.00, Nb≤0.100, Ta≤0.100, Ti≤0.100, Zr≤0.100, Al≤1.50, S≤0.200, Ca≤0.2000, Se≤0.50, Te≤0.100, Bi≤0.50, and Pb≤0.50, wherein the annealed steel material has: a cross-sectional size of a thickness of 200 min or more and a width of 250 mm or more; and a hardness of 100 HRB or less, wherein, when a cross-section of the annealed steel material is polished, corroded with an acid to expose a metallic structure, and observed with an optical microscope, a diameter of a largest ferritic gain observed in the metallic structure in a state after annealing is 120 μm or less in terms of a perfect circle equivalent, an area ratio of carbides is 3.0% or more and less than 10.5%, in which the area ratio is obtained by an equation of Area ratio (%)=100xs/A from a total area “s” of carbides present in a cumulative area A of plural visual fields observed in 5,000 magnifications, the cumulative area A of the plural visual fields being in a range from 4,000 μm.sup.2 to 5,000 μm.sup.2, and an average particle diameter of the carbides is 0.18 μm or more and 0.29 μm or less, in which when an average area C=s/n is calculated from the total area “s” of the carbides and a total number “n” of the carbides, the average particle diameter of the carbides is a diameter of an assumed perfect circle having an area of C, and wherein the carbides are spherical carbides uniformly dispersed, and the metallic structure is in the state after the annealing and before quenching.

2. The annealed steel material according to claim 1, wherein the composition comprises, in mass %, at least one of: 0.30≤Cu≤1.00, and 0.30≤Ni≤1.50.

3. The annealed steel material according to claim 1, wherein the composition comprises, in mass %: 0.0001<B≤0.0050.

4. The annealed steel material according to claim 1, wherein the composition comprises, in mass %, at least one of: 0.30<W≤5.00, and 0.30<Co≤4.00.

5. The annealed steel material according to claim 1, wherein the composition comprises, in mass %, at least one of: 0.004<Nb≤0.100, 0.004<Ta≤0.100, 0.004<Ti≤0.100, and 0.004<Zr≤0.100.

6. The annealed steel material according to claim 1, wherein the composition comprises, in mass %: 0.10<Al≤1.50.

7. The annealed steel material according to claim 1, wherein the composition comprises, in mass %, at least one of: 0.008<S≤0.200, 0.0005<Ca≤0.2000, 0.03<Se≤0.50, 0.005<Te≤0.100, 0.01<Bi≤0.50, and 0.03<Pb≤0.50.

8. A method for manufacturing the annealed steel material described in claim 1, the method comprising performing a plural times of an annealing treatment on a steel material, wherein the annealing treatment comprises heating the steel material to a temperature exceeding [Ac3 transformation point −20° C.] and [Ac3 transformation point +60° C.] or lower.

9. The annealed steel material according to claim 1, wherein the area ratio of carbides is in a range front 3.2% to 10.0%.

10. The annealed steel material according to claim 1, wherein the composition comprises, in mass %: 0.03≤Si≤1.20.

11. The annealed steel material according to claim 1, wherein the composition comprises, in mass %: 1.00≤Mo≤3.10.

12. The annealed steel material according to claim 1, wherein the composition comprises, in mass %: 0.48≤V≤1.10.

13. The annealed steel material according to claim 1, wherein the composition comprises, in mass %, 0.41≤V≤1.00.

14. The annealed steel material according to claim 1, wherein the composition comprises, in mass %, 0.60≤Ni≤1.50.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a graph showing the relationship between an impact value of quenched then tempered condition and austenitic grain size.

(2) FIG. 2 is a micrograph showing the microstructure of a die having cracks generated in an early stage.

(3) FIGS. 3A to 3D are micrographs showing the microstructures of a steel material changing by annealing and quenching.

(4) FIGS. 4A to 4D are micrographs showing the microstructures of a steel material under annealing conditions different from those in FIGS. 3A to 3D.

(5) FIGS. 5A to 5D are micrographs showing the microstructures of a steel material under annealing conditions different from those in FIGS. 3A to 3D and 4A to 4D.

(6) FIG. 6 is a graph showing the relationship between a size of carbide and Si content.

(7) FIG. 7 is a graph showing the relationship between an area ratio of carbide and Mo content.

(8) FIG. 8 is a graph showing the relationship between the largest ferritic grain size and a thickness of a steel material in an annealed steel material manufactured under the conventional annealing conditions.

(9) FIG. 9 is a micrograph showing the microstructure of the conventional annealed steel material.

MODES FOR CARRYING OUT THE INVENTION

(10) A method for creating the structure of the present invention is described below. FIGS. 3A to 3D are micrographs showing the state that the microstructure of JIS SKD61 material changes by annealing and quenching. FIG. 3A shows a microstructure of the steel material before annealing, which has been subjected to a heating at 1,240° C. simulating a hot plastic working, followed by being cooled to room temperature and then subjected to an intermediate heat treatment of being heated to 680° C. that is lower than Ac1 transformation point. FIG. 3B shows a microstructure after the steel material in the state of FIG. 3A is annealed one time at 900° C. that exceeds Ac3 transformation point (cooled from 900° C. to 600° C. in a rate of 15° C./hr). The microstructure of FIG. 3B is in a soft state in which spheroidized carbides are dispersed in a matrix of ferrite. It is observed in FIG. 3B the state where the influence of coarse prior microstructure (FIG. 3A) clearly remains, fine ferritic grains are present in a dotted line shape in the vicinity of the grain boundary, and columnar coarse ferritic grains extend toward the inside of coarse grains from the grain boundary. The coarse ferritic grains have a diameter exceeding 120 μm when its area is converted to a perfect circle by image processing. FIG. 3C shows a quenched microstructure obtained by heating the annealed material of FIG. 3B to 1,030° C., maintaining the annealed material for 1 hour at this temperature and rapidly cooling to form martensite. FIG. 3D is an enlarged view of a square section surrounded by a solid line in the vicinity of the center of visual field of FIG. 3C. The broken line in FIG. 3C is the prior austenitic grain boundary. In other words, FIG. 3D is an enlarged view of a cross point of the prior austenitic grain boundary. Fine grains are interspersed in the prior austenitic grain boundary of the quenched microstructure, and its average grain size (diameter in terms of a perfect circle equivalent) is small as 35 μm or less. On the other hand, fine grains are also interspersed in the coarse prior austenitic grains in an isolated island state. When an area of a region obtained by removing the grain boundary and fine grains from one coarse grain is converted to a perfect circle, the diameter of the coarse prior austenitic grain exceeds 100 μm.

(11) FIGS. 4A to 4D show the case where the same experiments as in FIGS. 3A to 3D were conducted except that the annealing treatment at 900° C. was repeated three times in total. FIG. 4A shows a microstructure of the steel material before annealing, and does not basically differ from FIG. 3A. FIG. 4B shows a microstructure after the steel material in the state of FIG. 4A is repeatedly subjected to the annealing treatment at 900° C. three times in total. The microstructure of FIG. 4B clearly differs from that of FIG. 3B and is a graded fine grain structure of fine ferritic matrix, and the diameter of the ferritic grain is small as less than 100 μm. FIGS. 4C and 4D show a quenched microstructure obtained by heating the annealed steel material having such a fine ferritic structure to 1,030° C., maintaining the annealed steel material for 1 hour and rapidly cooling to form martensite. The quenched microstructure shown in FIGS. 4C and 4D differs from the case of FIGS. 3C and 3D, and is a graded fine grain microstructure. The average grain size is small as 35 m or less, and such coarse grains as exceeding 100 μm are not present. Thus, FIGS. 4C and 4D show extremely desirable state as the quenched microstructure.

(12) FIGS. 5A to 5D shows the case where the same experiments as in FIGS. 4A to 4D were conducted except that the annealing temperature was changed to 860° C. FIG. 5A shows a microstructure of the steel material before annealing, and does not basically differ from FIG. 3A and FIG. 4A. FIG. 5B shows a microstructure after the steel material in the state of FIG. 5A is repeatedly subjected to an annealing treatment at 860° C. three times in total. The annealed microstructure shown in FIG. 5B, however, does not almost change from FIG. 5A before annealing. The annealed microstructure quite differs from FIG. 3B and FIG. 4B, and there is an impression that a matrix seems to be martensite or bainite tempered at high temperature, rather than ferrite. FIGS. 5C and 5D show a quenched structure obtained by heating the coarse annealed steel material of FIG. 5B to 1,030° C., maintaining the annealed steel material at 1 hour and rapidly cooling to form martensite. FIG. 5D is an enlarged view of a square section surrounded by a solid line in the vicinity of the center of the visual field of FIG. 5C. The broken line in FIG. 5C is the prior austenitic grain boundary. In other words, FIG. 5D is an enlarged view of a cross point of the prior austenitic grain boundary. Fine grains are interspersed in the prior austenitic grain boundary of the quenched microstructure, and its average grain size is small as 35 μm or less. On the other hand, fine grains are also interspersed in the coarse prior austenitic grains in an isolated island state. When an area of a region obtained by removing the grain boundary and fine grains from one coarse grain is converted to a perfect circle, the diameter of the coarse prior austenitic grains exceeds 100 μm. Rather, the diameter does not almost differ from very large grain size before annealing.

(13) As described above, even though the grains before annealing (structure after hot plastic working) are coarse, if the largest ferritic grain size observed in the annealed steel material is made 120 μm or less by repeating an annealing treatment in a temperature region just around Ac3 transformation point or exceeding Ac3 transformation point several times, coarse austenitic grains exceeding 100 μm can be suppressed from being generated at quenching temperature.

(14) The size of fine grains (interspersed so as to surround coarse grains) observed in the quenched structures of FIGS. 2 to 5D above was 35 μm or less. However, the size of fine grains varies depending on the state of the annealed microstructure and the quenching conditions, and the size of “35 μm or less” is merely one example. The size of fine grains may be 55 μm or less or 75 μm or less. It is important that the size of coarse grains observed in the quenched microstructure does not exceed 100 μm in order to secure an impact value required in a die and the like.

(15) In addition, highly reliable reasoning became possible to the position that coarse grains are not generated “at all times” and “in the whole sites in a cross-section of a die”. Specifically, the part at which coarse grains are generated at quenching is the “coarse grain part at hot plastic working”. There are two pertinent parts. One is the vicinity of the center of a material having large cross-section, and the other is a dead metal zone (a site at which a temperature decreases due to the contact with a tool and deformation becomes very small due to the superposition with a large friction coefficient) in a surface side of the material. Particularly, it is difficult to predict the place of a material on which the dead metal zone is to be generated. For this reason, it is also difficult to predict the place on which coarse grain part is to be generated at quenching. Furthermore, in many cases, a part is cut out of a material having a large cross-section to manufacture a die. In this case, it appears that if the dead metal zone or the vicinity of the center of a material is accidentally cut, coarse grains are generated at quenching.

(16) So far as inhomogeneity of the microstructure is unavoidably present in a hot plastic worked material, repeating an annealing treatment at a temperature in the vicinity of Ac3 transformation point several times is an essential requirement to stably obtain the fine grain structure at quenching.

(17) The annealing temperature is set [Ac3 transformation point −20° C.]<annealing temperature≤[Ac3 transformation point +60° C.]. In the case where the annealing temperature is excessive low, the phenomenon shown in FIGS. 5A to 5D is easy to be developed. In the case where the annealing temperature is excessively high, the amount of insoluble carbides (insoluble carbides serving as nuclei when carbides are spheroidized) decreases, making it difficult to perform softening and thus, a cooling rate to a predetermined temperature (e.g., 600° C.) must make smaller. This is inefficient. In the case of JIS SKD61 material, the annealing temperature is desirably 880° C. to 930° C.

(18) Steels with lower Si content or higher Mn content than that of JIS SKD61 steel have a low Ac3 transformation point. Therefore, the annealing temperature of these steels is preferably 830° C. to 910° C. The Ac3 transformation point intended in the present invention is a value in the case of heating in a rate of 100° C./hr to 200° C./hr.

(19) In manufacturing the annealed steel material of the present invention, the recommendable number of the annealing treatment conducted in the above-mentioned temperature region is 2 to 5. The number of the annealing treatment must be increased as the initial structure is coarser. In the case where the number of the annealing treatment is excessively small, the phenomenon shown in FIGS. 3A to 3D is easy to be developed. On the other hand, excessive number of annealing treatment saturates the effect of refinement but leads to an increase in processing cost.

(20) Sufficient effect (coarse austenitic grains exceeding 100 μm are not generated at quenching temperature) may be obtained even though the number of the annealing treatment is 2, depending on the structure state before annealing. However, to stably develop the effect, the number of the annealing treatment is preferably 3 or more.

(21) The annealed steel material of the present invention can be applied to a steel material having a component system suitable for use in a die or parts for injection molding of plastics, molding and processing of rubbers, molding of carbon fiber reinforced plastics (CFRP), various casting, warm forging or hot forging, hot stamping and the like, in addition to that for the above-discussed die-casting die.

(22) The reason for limiting each chemical component in the present invention is described below. The amount of each chemical component is expressed in mass %.

(23) 0.28≤C<0.42

(24) In the case of C<0.28, hardness required as a die is difficult to be stably achieved when quenching rate is low and tempering temperature is high. Furthermore, in the case of C<0.28, the amount of insoluble VC pinning austenitic grain boundary at quenching is excessively small, and austenitic grains cannot be maintained in fine state. In the case of 0.42≤C, the amount of coarse carbides increases, which act as the crack initiation point. As a result, an impact value is decreased. Furthermore, in the case of 0.42≤C, weldability is deteriorated. The C content is preferably 0.29≤C≤0.41, and more preferably 0.30≤C≤0.40, from the standpoint of excellent balance in various properties.

(25) 0.01≤Si≤1.50

(26) In the case of Si<0.01, machinability when machining is remarkably deteriorated. In the case of 1.50<Si, heat conductivity is greatly decreased. Furthermore, in the case of 1.50<Si, Ac3 transformation point is excessively high, heating temperature for an annealing must be increased, and much time is required for heating to the annealing temperature and cooling to the completion temperature. As a result, production efficiency is deteriorated. Furthermore, in the case of 1.50<Si, carbides become too large, and the effect of suppressing grain growth of austenite phase at quenching is insufficient. The Si content is preferably 0.02≤Si≤1.35, and more preferably 0.03≤Si≤1.20, from the standpoint of excellent balance in various properties.

(27) When the amount of Si increases, carbides in the annealed steel material enlarge. This tendency is shown in FIG. 6.

(28) The material of FIG. 6 had main components of 0.38C-0.45Mn-5.20Cr-1.19Mo-0.91V-0.020N, and the amount of Si was changed in the basic components. The material underwent an annealing treatment of heating to 915° C. from room temperature and then cooling to 600° C. in a rate of 15° C./hr. An average size of spherical carbides uniformly dispersed in the annealed structure was obtained by image processing. FIG. 6 shows the relationship between the average size and Si content. A part of those carbides remains as insoluble carbides when quenching, and suppresses grain growth of austenitic grains due to the dispersion thereof.

(29) The effect of suppressing grain growth is greatly influenced by a size of carbides. When an area ratio of carbides is the same, small-sized carbides have stronger effect of suppressing grain growth of austenite. Therefore, in the case where the amount of Si is excessive and a size of carbides is too large, grain growth of austenite at quenching cannot be suppressed. For this reason, it is important to specify the upper limit of the Si content.

(30) 0.20≤Mn≤1.20

(31) In the case of Mn<0.20, hardenability during quenching is insufficient, leading to the decrease in impact value due to the mixing of bainite. In the case of 1.20<Mn, annealing property is remarkably deteriorated, and the heat treatment for softening is complicated and requires much time, leading to an increase in production costs. Furthermore, in the case of 1.20<Mn, thermal conductivity is also greatly deteriorated. The Mn content is preferably 0.25≤Mn≤1.10, and more preferably 0.35≤Mn≤1.00, from the standpoint of excellent balance in various properties.

(32) 4.80≤Cr≤6.00

(33) In the case of Cr<4.80, hardenability during quenching and corrosion resistance are not sufficient. In a large die for die-casting or hot forging, the die must be completely quenched up to the inside thereof at which quenching rate is small (fully martensitic structure) to secure a high impact value. However, this requirement cannot be satisfied in the case of Cr<4.80 because hardenability during quenching is not sufficient. Furthermore, in the case of Cr<4.80, annealing property is remarkably deteriorated, and satisfactory annealing property required as a material for a die for die-casting or hot forging cannot be achieved.

(34) On the other hand, in the case of 6.00<Cr, softening resistance and thermal conductivity are greatly deteriorated. In a die for die-casting or hot forging, high softening resistance is required such that strength is not deteriorated even when the die is brought into contact with a high temperature material to be worked and heated. This requirement cannot be satisfied in the case of 6.00<Cr. Also, high thermal conductivity required for the reduction of thermal fatigue of a die cannot be satisfied in the case of 6.00<Cr.

(35) Many prior arts generally describe a wide Cr content such as “1 to 8%”. However, for the reasons described above, the present invention specifies narrow range of 4.80≤Cr≤6.00 that matches the actual working conditions of a die. The Cr content is preferably 4.90≤Cr≤5.90, and more preferably 5.00≤Cr≤5.85, from the standpoint of excellent balance in various properties.

(36) 0.80≤Mo≤3.20

(37) In the case of Mo<0.80, Mo cannot sufficiently contribute to secondary hardening, and in the case where tempering temperature is high, it is difficult to stably achieve high hardness. In the case of 3.20<Mo, annealing property is remarkably deteriorated. Furthermore, in the case of 3.20<Mo, fracture toughness is remarkably deteriorated, and cracking of a die is a concern. In the case of 3.20<Mo, material cost also remarkably increases. Furthermore, in the case of 3.20<Mo, Ac3 transformation point is excessively high and thus, heating temperature for an annealing treatment must be increased. As a result, much time is required for heating to the annealing temperature and cooling to the completion temperature, leading to a deterioration of production efficiency. The Mo content is preferably 0.90≤Mo≤3.15, and more preferably 1.00≤Mo≤3.10, from the standpoint of excellent balance in various properties.

(38) When the amount of Mo increases, the amount of carbides in an annealed material also increases. This tendency is shown in FIG. 7. The material of FIG. 7 had main components of 0.38C-0.95Si-0.46Mn-5.22Cr-0.92V-0.019N, and the amount of Mo was changed in the basic components. The material underwent an annealing treatment of heating to 915° C. from room temperature and then cooling to 600° C. in a rate of 15° C./hr. An area ratio of spherical carbides uniformly dispersed in the annealed structure was obtained by image processing. FIG. 7 shows the relationship between the area ratio and Mo content. A part of those carbides remains as insoluble carbides when quenching, and suppresses grain growth of austenite phase due to the dispersion thereof.

(39) The effect of suppressing grain growth is also greatly influenced by an area ratio of carbides. When carbides have the same size, carbides having larger area ratio have stronger effect of suppressing grain growth of austenite. Therefore, larger amount of Mo is preferred from the standpoint of maintaining fine grains. On the other hand, if a component system is prepared for increasing the area ratio of carbides, coarse carbides of 5 μm or more are easy to be formed when solidifying, which remarkably deteriorates an impact value. For this reason, it is important to specify the upper limit of the Mo content in order to maintain fine grains and to avoid the generation of too much coarse carbides.

(40) 0.40≤V≤1.20

(41) In the case of V<0.40, VC at quenching temperature is decreased. As a result, the effect of suppressing the coarsening of austenitic grains is poor. In the case of 1.20<V, the effect of maintaining fine grains is saturated, but cost increases. Furthermore, in the case of 1.20<V, the amount of coarse carbides of 5 μm or more (formed when solidifying) increases, which act as the crack initiation point. As a result, an impact value is deteriorated. The V content is preferably 0.44≤V≤1.15, and more preferably 0.48≤V≤1.10, from the standpoint of excellent balance in various properties.

(42) 0.002≤N≤0.080 In the case of N<0.002, VC at quenching temperature is decreased. As a result, the effect of suppressing the coarsening of austenitic grains is poor. Similar to C, Mo and V, N greatly affects insoluble VC amount at quenching temperature, and in the case of considering austenite grain size at quenching, N is an important element that cannot be ignored.

(43) On the other hand, in the case of 0.080<N, the time and cost for refining required in N addition are increased, leading to an increase of material cost. Furthermore, in the case of 0.080<N, the amount of coarse nitrides increases, which act as the crack initiation point. As a result, toughness is deteriorated. The N content is preferably 0.005≤N≤0.060, and more preferably 0.008≤N≤0.045, from the standpoint of excellent balance in various properties.

(44) Cross-Sectional Size: Thickness of 200 mm or More and Width of 250 mm or More

(45) The annealed steel material of the present invention is mainly used in a large die, and therefore has a large cross-sectional size. One of the characteristics of the present invention is that coarse ferritic grains having a diameter exceeding 120 μm in terms of a perfect circle equivalent are not present even though a size of cross-section is large.

(46) FIG. 8 shows an influence of the thickness of an annealed steel material affecting the maximum ferritic grain size of the annealed steel material. This annealed steel material was manufactured by a conventional process different from the manufacturing method of the present invention. According to FIG. 8, although the width W of the annealed steel material affects the ferritic grain size, the thickness H of the steel material greatly affects the ferritic grain size. The thickness H of 200 mm or more and the width W of 250 mm or more are required to manufacture a large die, but the largest ferritic grain size exceeds 120 μm in this region. FIG. 9 shows one example of the case, and shows the structure of an annealed steel material having both thickness H and width W of 500 mm or more. The components of this steel material are 0.34C-0.09Si-1.04Mn-5.11Cr-1.83Mo-0.52V-0.015N.

(47) The present invention overcomes the above-described problem that cannot be achieved by a conventional technique (the problem that austenitic grains are coarsened at quenching) by controlling the largest ferritic grain size to 120 μm or less in an annealed steel material having a cross-sectional size of thickness of 200 mm or more and width of 250 mm or more.

(48) The directions of “thickness” and “width” mean directions perpendicular to the direction in which length has finally elongated when a material is subjected to hot plastic processing (so-called “fiber direction”). Of the two perpendicular directions, smaller direction is defined as “thickness” and larger direction is defined as “width”. Even in the case where a steel material is cut out of very large material or long material and a fiber direction is unclear, the fiber direction can be judged from the microstructure. Specifically, a direction of segregation, distribution of inclusions, elongation direction of inclusions, and the like are evaluated.

(49) Hardness: 100 HRB or Less

(50) The annealed steel material of the present invention is to be subjected to a machining in a later stage, and is therefore required to be softened up to machinable state. For this reason, the present invention specifies the hardness to be 100 HRB or less.

(51) Area Ratio of Carbides: 3.0% or More and Less than 10.5%

(52) Average Grain Size of Carbides: 0.18 μm or More and 0.29 μm or Less

(53) As noted above, a part of carbides remains as insoluble carbides at quenching temperature, and suppresses grain growth of austenitic grains due to the dispersion thereof. To achieve this effect, an average grain size of carbides in the annealed structure is controlled to 0.18 μm or more. On the other hand, coarse carbides become a factor of deteriorating an impact value. Therefore, the upper limit of the average grain size is set to 0.29 μm. The average grain size of carbides is preferably 0.185 μm or more and 0.280 μm or less.

(54) Larger area ratio of carbides provides large effect of suppressing grain growth. However, in the case where the area ratio of carbides is excessively large, coarse carbides are easy to be formed, which becomes a factor of deteriorating an impact value. For this reason, the area ratio of carbides is controlled to 3.0% or more and less than 10.5%. The area ratio of carbides is preferably 3.2% or more and 10.0% or less.

(55) Chemical Components: Cu and Ni

(56) In order to improve hardenability during quenching, at least one element of Cu and Ni may be contained in amounts of, in mass %:

(57) 0.30≤Cu≤1.00, and

(58) 0.30≤Ni≤1.50.

(59) In the case where the amounts of those elements are excessively large, annealing property is deteriorated and thermal conductivity is also deteriorated. Furthermore, in the case where the amount of Cu exceeds 1.00%, cracking during hot plastic working becomes a problem.

(60) Chemical Component: B

(61) Addition of B is also effective as an improvement for hardenability during quenching. Specifically, B may be contained in an amount of:

(62) 0.0001<B≤0.0050.

(63) When B forms BN, the effect of improving hardenability during quenching is lost. Therefore, B is required to be present alone in a steel. Specifically, N is made to form a nitride with an element having strong affinity with N rather than B, so as to avoid B bonding to N. Examples of such an element include Nb, Ta, Ti and Zr. Those elements have the effect of fixing N even though they are present in the level of impurities, but those elements may sometimes be added in the amounts described below depending on the amount of N. Even though B bonds to N in a steel to form BN, if excessive B is present alone in a steel, the excessive B enhances hardenability during quenching.

(64) B is also effective to improve machinability. The improvement in machinability can be achieved by forming BN. BN has properties similar to those of graphite, and decreases cutting resistance and simultaneously improves chip breakability. In the case where B and BN are present in a steel, hardenability during quenching and machinability are simultaneously improved.

(65) Chemical Components: W and Co

(66) W and Co are optionally added to secure strength without increasing the amount of C. W increases the strength due to the precipitation of carbides. Co increases the strength due to solid-solution in a matrix, and simultaneously contributes to precipitation hardening through the change of carbide form.

(67) Specifically, at least one element of W and Co may be contained in amounts of, in mass %:

(68) 0.30<W≤5.00, and

(69) 0.30<Co≤4.00.

(70) Each element in an amount exceeding the predetermined amount leads to saturation of properties and remarkable increase in cost.

(71) Chemical Components: Nb, Ta, Ti and Zr

(72) When the heating temperature for quenching increases and/or the heating time for quenching is prolonged by unexpected facility troubles or the like, the deterioration of various properties due to the coarsening of grains is a concern. For such an occasion, Nb, Ta, Ti and/or Zr can be optionally added to form fine precipitates, whereby the coarsening of austenitic grains at quenching can be suppressed. Specifically, at least one element of Nb, Ta, Ti and Zr may be contained in amounts of, in mass %:

(73) 0.004<Nb≤0.100,

(74) 0.004<Ta≤0.100,

(75) 0.004<Ti≤0.100, and

(76) 0.004<Zr≤0.100.

(77) In the case where the amount of each element exceeds the predetermined amount, carbides, nitrides or oxides are excessively formed, leading to the deteriorations in the impact value and mirror polishability.

(78) Chemical Component: Al

(79) Al that forms AlN by bonding to N may be added in order to suppress growth of austenitic grains at quenching. Al has a high affinity with N and accelerates the penetration of N into a steel. Therefore, when a steel material containing Al is subjected to a nitriding treatment, surface hardness is liable to increase. Use of a steel material containing Al is effective for a die to which a nitriding treatment for higher wear resistance is performed. Specifically, Al may be contained in an amount of, in mass %:

(80) 0.10<Al≤1.50.

(81) However, the amount of Al exceeding the predetermined amount leads to the deterioration in thermal conductivity and toughness.

(82) Chemical Components: S, Ca, Se, Te, Bi, and Pb

(83) Die-casting die has very complicated shape, and therefore is required to have good machinability. Practical machinability is exhibited in the Si content in the level of the steel of the present invention. For further improvement in machinability, free-cutting elements may be added. Specifically, at least one element of S, Ca, Se, Te, Bi, and Pb may be contained in amounts of, in mass %:

(84) 0.008<S≤0.200,

(85) 0.0005<Ca≤0.2000,

(86) 0.03<Se≤0.50,

(87) 0.005<Te≤0.100,

(88) 0.01<Bi≤0.50, and

(89) 0.03<Pb≤0.50.

(90) The amount of each element exceeding the predetermined amount leads to the saturation of machinability, the deterioration in hot workability, and the deteriorations in the impact value and mirror polishability.

EXAMPLES

(91) Steel materials were obtained from 19 kinds (A to S) of steels shown in Table 1 below by changing annealing conditions. Ac3 transformation point, hardness (HRB) after annealing, largest ferritic grain size, area ratio and average grain size of carbides, largest prior austenitic grain size after quenching, and impact value after tempering of those steel materials obtained were examined.

(92) The annealed steel material of the present invention is assumed to be used as a material for a large die for die-casting or hot forging. In such a use, a narrow range of 4.80≤Cr≤6.00 (mass %) is essential from the standpoints of hardenability during quenching, softening resistance and thermal conductivity. Therefore, in conformity with the actual situation, the effect was verified based on steel materials containing 4.80≤Cr≤6.00. In Table 1, steels A to N, R and S are that the amount of each element added is within the range of the present invention. On the other hand, steels O, P and Q are that the amount of at least one element added is outside the range of the present invention.

(93) TABLE-US-00001 TABLE 1 Chemical components (mass %, a remainder being Fe) Steel C Si Mn Cr Mo V N Others A 0.39 0.93 0.45 5.19 1.19 0.87 0.019 B 0.35 0.48 0.71 5.53 1.26 0.58 0.019 C 0.36 0.08 0.46 5.37 1.21 0.57 0.021 D 0.35 0.28 0.82 5.75 2.46 0.53 0.020 E 0.35 0.27 1.12 5.51 2.51 0.56 0.019 F 0.34 0.03 0.59 5.54 3.02 0.93 0.018 G 0.38 0.07 0.81 5.78 1.60 0.79 0.021 H 0.31 0.19 0.22 5.85 0.92 0.48 0.003 0.58Cu I 0.28 0.70 0.35 5.96 0.83 1.09 0.008 0.96Ni J 0.30 1.20 0.99 4.83 0.92 1.01 0.044 1.26W K 0.41 0.59 0.90 5.02 1.81 0.41 0.068 0.98Co L 0.40 1.12 1.18 5.11 1.44 0.62 0.031 0.03Nb M 0.37 0.82 1.09 5.54 2.03 0.70 0.056 0.12S N 0.33 1.33 0.65 5.83 2.75 1.17 0.013 0.41Cu, 0.60Ni O 0.26 1.01 0.46 5.21 1.20 0.36 0.019 P 0.48 1.08 0.44 5.20 3.36 1.42 0.021 Q 0.35 0.27 1.54 4.84 2.06 0.60 0.022 R 0.38 0.38 0.40 4.91 1.05 0.81 0.020 0.07Ti, 0.005B S 0.39 1.02 0.77 5.22 1.24 0.97 0.013 0.25Al

(94) The steel materials used for the evaluation were prepared as follows. Each steel having a chemical composition shown in Table 1 was melted, cast in an ingot of 2 tons, and then maintained at 1,240° C. for 24 hours for homogenization treatment. The steel material was formed into a rectangular cross-section having a width of 450 mm and a height (thickness) of 200 mm by forging. The steel material forged was tempered by maintaining at 760° C. for 8 hours as an intermediate heat treatment.

(95) Test piece for measurement of Ac3 transformation point, a small block (for heat treatment test) of 10 mm×10 mm×20 mm and a square bar (for impact test piece) of 11 mm×11 mm×55 mm were prepared from the central part (top side of original ingot before forging) of the tempered material. Those were subjected to 3 heat treatment tests having different annealing conditions. If a block having a size of 450 mm width×200 mm thickness is directly used in a test for investigating structure change through the annealing treatment, a large-scale apparatus is required for the test. Therefore, the test was efficiently conducted with the small block above by introducing a technique to give “thermal history simulating a material with a large cross-section”. Of course, because the test gives thermal history exactly simulating a material with a large cross-section, the phenomenon occurred in the actual material with a large cross-section is reproduced.
Heat treatment test 1(Annealing one time at [Ac3 transformation point −20° C.]<Annealing temperature≤[Ac3 transformation point +60° C.])

(96) First, Ac3 transformation point was judged from dimensional change of a test piece during heating from room temperature to 1,100° C. in a rate of 200° C./hr. Next, the small block of 10 mm×10 mm×20 mm was annealed. Prior to the annealing treatment, the small block was heated at 1,240° C. for 1 hour simulating a hot working in an actual production to coarsen grains, and then cooled to room temperature. Thereafter, the small block was annealed. The annealing treatment was steps of heating the steel material (small block) to [Ac3 transformation point −20° C.]<Annealing temperature≤[Ac3 transformation point +60° C.], maintaining at the annealing temperature for 2 hours, cooling to 600° C. in a rate of 20° C./hr, and then naturally cooling. The number of the annealing treatment was only one. After annealing, HRB hardness was measured and then, after etching with an acid, the largest ferritic grain size (perfect circle equivalent diameter), area ratio of carbides, and average particle diameter of carbides were evaluated. The largest ferritic grain size (perfect circle equivalent diameter) was obtained by the method described above.

(97) After completion of the quantification of the annealed microstructure, the annealed steel material was subjected to a quenching of heating to 1,030° C., maintaining at 1,030° C. for 1 hour, and then rapid cooling. The quenched steel material was etched with an acid to expose the grain boundary of prior austenitic grains of 1,030° C., the largest prior austenitic grain was selected, and its perfect circle equivalent diameter was obtained. The perfect circle equivalent diameter of the largest prior austenitic grain was obtained in the same procedure as in the largest ferritic grain size.

(98) The square bar (for impact test piece) of 11 mm×11 mm×55 mm was also subjected to 1,240° C. heating (simulating forging working), annealing and quenching under the same conditions as in the small block, and then, subjected to several times of tempering at 580° C. to 600° C., thereby adjusting hardness to 46HRC. The impact value of the adjusted material was evaluated at room temperature.

(99) The results obtained are shown in Table 2 below.

(100) TABLE-US-00002 TABLE 2 Largest ferritie Largest grain Carbide austenitie Impact size of Average grain size value Annealing annealed Area particle after after Steel Ac3 Annealing −Ac3 material ratio diameter quenching tempering material Steel (° C.) (° C.) (° C.) HRB (μm) (%) (μm) (μm) (J/cm.sup.2) Comp. 01 A 890 915 25 91 168 5.9 0.24 213 25 Ex. 02 B 883 900 17 91 172 5.1 0.23 197 23 03 C 856 900 44 90 161 5.2 0.21 183 23 04 D 851 900 49 91 177 7.0 0.23 224 21 05 E 862 900 38 89 181 7.3 0.24 191 23 06 F 859 900 41 91 173 8.0 0.19 202 22 07 G 861 900 39 91 167 4.6 0.20 215 24 08 H 880 900 20 89 174 3.3 0.21 187 25 09 I 857 900 43 90 173 3.2 0.25 206 22 10 J 888 915 27 87 180 4.2 0.26 212 21 11 K 874 900 26 89 175 6.7 0.23 190 23 12 L 876 900 24 92 174 7.0 0.25 203 23 13 M 872 900 28 90 162 5.5 0.22 205 22 14 N 897 915 18 94 163 5.0 0.27 182 24 15 O 891 915 24 89 171 4.1 0.22 201 16 16 P 901 915 14 93 173 10.6 0.24 243 11 17 Q 853 900 47 111 291 4.9 0.24 276 13 18 R 853 900 47 90 170 6.0 0.23 203 23 19 S 891 915 24 90 165 6.1 0.25 192 24

(101) In the steel materials 01 to 19 (Comparative Examples) shown in Table 2, the heating temperature when annealing was 14 to 49° C. higher than Ac3 transformation point. Regarding the hardness of the annealed steel materials, only the steel material 17 (steel Q) had a hardiness of 111 HRB outside the requirement (100 HRB or less) of the present invention. The steel material 17 has very good hardenability during quenching and due to this, has poor annealing property. Therefore, the steel material 17 had a mixed structure in which the vicinity of the grain boundary of coarse grains softened (the structure was ferrite and spherical carbide) and the inside of coarse grains was hard (the structure was bainite and martensite).

(102) The structure of each of the annealed steel materials 01 to 19 was coarse, and the largest ferritic grain size present on the observation surface did not satisfy 120 μm or less that is the requirement of the present invention. The annealed state of the annealed steel materials 01 to 19 was the microstructure like FIG. 3B, and there remained strongly the influence of coarse grains formed when heating at 1,240° C. simulating a hot working. The annealed steel materials 01 to 19 satisfied the requirement of the area ratio of carbides required in the present invention, except for the steel material 16. All of the annealed steel materials 01 to 19 satisfied the requirement of the average particle diameter of carbides required in the present invention.

(103) The microstructure of the steel materials after quenching was coarse similar to the microstructure after annealing. The largest prior austenitic grain size present on the observation surface did not satisfy 100 μm or less that is intended in the present invention. The quenched state of the quenched steel materials 01 to 19 was the microstructure like FIGS. 3C and 3D, and fine grains were interspersed in the grain boundary of coarse grains. Thus, because the structure was coarse, none of the steel materials showed an impact value exceeding 25 J/cm.sup.2 that is conventionally required as a die. In the steel material 16 containing large amount of carbide forming elements, coarse carbides of 5 μm or more are liable to be densely formed, which remain to serve as the origin of fracture. Therefore, the steel material 16 had a particularly low impact value. The steel materials 01 to 19 shown in Table 2 had low levels of impact value. Therefore, if dies are actually manufactured from those steel materials, the fracture of the dies in an early stage is a concern.

(104) As demonstrated above, even though the chemical compositions and annealing temperature are within the scope of the present invention, the annealed microstructure specified in the present invention cannot be obtained by one-time annealing treatment, and therefore the structure and impact value after quenching are also not desirable state.
Heat treatment test 2(Annealing three times at [Ac3 transformation point −20° C.]<Annealing temperature≤[Ac3 transformation point +60° C.])

(105) The case where the chemical compositions and annealing temperature are within the scope of the present invention and the annealing treatment is repeated three times in total was verified. To the steel materials, the heating at 1,240° C. was conducted one time, the annealing treatment was conducted at the same temperature as in the case of Heat treatment test 1 three times, and the quenching at 1,030° C. was conducted. The conditions other than the number of the annealing treatment were the same as in the case of Heat treatment test 1. The results obtained are shown in Table 3 below.

(106) TABLE-US-00003 TABLE 3 Largest ferritie Largest grain Carbide austenitie Impact size of Average grain size value Annealing annealed Area particle after after Steel Ac3 Annealing −Ac3 material ratio diameter quenching tempering material Steel (° C.) (° C.) (° C.) HRB (μm) (%) (μm) (μm) (J/cm.sup.2) Ex. 21 A 890 915 25 89 24 6.7 0.25 23 56 22 B 883 900 17 88 63 5.8 0.24 56 53 23 C 856 900 44 87 59 5.4 0.21 52 55 24 D 851 900 49 87 66 7.9 0.24 52 52 25 E 862 900 38 87 65 8.2 0.24 53 53 26 F 859 900 41 88 31 8.7 0.21 24 53 27 G 861 900 39 87 30 5.3 0.21 26 58 28 H 880 900 20 86 92 4.3 0.22 73 55 29 I 857 900 43 86 25 4.1 0.25 24 52 30 J 888 915 27 88 25 4.6 0.27 23 51 31 K 874 900 26 87 98 7.3 0.25 72 55 32 L 876 900 24 90 28 7.3 0.26 25 53 33 M 872 900 28 89 24 5.6 0.23 24 54 34 N 897 915 18 90 24 5.3 0.28 22 54 Comp. 35 O 891 915 24 86 32 4.5 0.23 201 15 Ex. 36 P 901 915 14 91 26 10.9 0.26 25 13 37 Q 853 900 47 109 235 5.8 0.24 228 17 Ex. 38 R 853 900 47 89 41 6.2 0.24 37 53 39 S 891 915 24 89 36 6.4 0.25 31 53

(107) As shown in Table 3, regarding the hardness of annealed steel materials, only the steel material 37 had a hardness of 109 HRB outside the requirement of the present invention. The steel material 37 had a mixed structure in which the vicinity of the grain boundary of coarse grains softened (the microstructure was ferrite and spherical carbides) and the inside of the coarse grains was hard (the microstructure was bainite and martensite), similar to the case of the steel material 17. The steel material 37 had a spread softened region and somewhat decreased hardness as compared with the case of the steel material 17, but this hardness still has a problem in machinability when forming into a die shape.

(108) The microstructure of each of the annealed steel materials 21 to 39 other than the steel material 37 was fine, and the largest ferritic grain size satisfied 120 μm or less that is the requirement of the present invention. The annealed state of the annealed steel materials 21 to 39 other than the steel material 37 was the microstructure like FIG. 4B, and there remained no influence of coarse grains formed when heating at 1,240° C. simulating a hot working. The annealed steel materials 21 to 39 other than the steel material 37 satisfied the requirement of the area ratio of carbides required in the present invention. All of the annealed steel materials 21 to 39 satisfied the requirement of the average particle diameter of carbides required in the present invention.

(109) Regarding the largest prior austenitic grain size after quenching, the steel materials 35 and 37 did not satisfy 100 μm or less that is intended in the present invention. The steel material 35 had a small amount of carbides suppressing movement of austenitic grain boundary at quenching temperature, and as a result, grains grown. The steel material 37 received the influence of the coarse particles in the annealed state in which the softening was not sufficient.

(110) The quenched state of the steel materials 21 to 39 other than the steel materials 35 and 37 was the microstructure like FIGS. 4C and 4D, and the entire surface was fine-grained. Thus, because the structure was fine, the steel materials 21 to 39 other than the steel materials 35 and 37 achieved, after tempering, an impact value exceeding 25 J/cm.sup.2 that is conventionally required as a die. If dies are actually manufactured from those steel materials, it is expected that the dies do not fracture in an early stage. However, in the steel material 36 containing a large amount of carbide forming elements, coarse carbides of 5 μm or more are liable to be densely formed, which remain and serve as the origin of fracture. Therefore, the steel material 36 had a low impact value even though grains were fine.

(111) As demonstrated above, in order to maintain austenitic grains at quenching temperature in a fine state, the annealed state must be soft and fine and many carbides must be dispersed at quenching. In the case where the chemical compositions and annealing temperature are within the scope of the present invention as in the steel materials 21 to 34, 38 and 39 (Examples), the annealed microstructure specified in the present invention can be obtained by performing a plural times of annealing treatment, and as a result, the desirable microstructure and impact value after quenching can be achieved.
Heat treatment test 3(Annealing three times at annealing temperature≤[Ac3 transformation point −20° C.])

(112) The case where the heating temperature at annealing is [Ac3 transformation point −20° C.] or lower was verified. The annealing condition of this test deviated from the scope of the present invention. The test was conducted to confirm that even though the chemical compositions of a steel material are within the scope of the present invention, sufficient effect cannot be achieved if the annealing condition is not appropriate.

(113) In the steel materials 41 to 56 (Comparative Examples) shown in Table 4, the steels A to N, R and S shown in Table 1 were used. Those steels have chemical compositions within the scope of the present invention. The steel materials 41 to 56 were heated at 1,240° C. for 1 hour simulating a hot working, and then repeatedly subjected to an annealing treatment three times in total. The respective annealing treatment was steps of heating the steel material to an annealing temperature of [Ac3 transformation point −20° C.] or lower, maintaining at the annealing temperature for 2 hours, cooling to 600° C. in a rate of 20° C./hr, and then naturally cooling. The annealed steel materials were evaluated in accordance with the verification described in Table 2.

(114) The square bar (for impact test piece) of 11 mm×11 mm×55 mm was subjected to a heating at 1,240° C. simulating a hot working one time, annealing treatments at an annealing temperature≤[Ac3 transformation point −20° C.] three times, a quenching at 1,030° C., and then a tempering to adjust the hardness to 46HRC. The impact value of the adjusted material was evaluated in accordance with the verification described in Table 2.

(115) The results obtained are shown in Table 4 below.

(116) TABLE-US-00004 TABLE 4 Largest ferritie Largest grain Carbide austenitie Impact size of Average grain size value Annealing annealed Area particle after after Steel Ac3 Annealing −Ac3 material ratio diameter quenching tempering material Steel (° C.) (° C.) (° C.) HRB (μm) (%) (μm) (μm) (J/cm.sup.2) Comp. 41 A 890 860 −30 89 220 5.5 0.21 207 23 Ex. 42 B 883 850 −33 90 209 4.7 0.20 214 21 43 C 856 830 −26 90 214 4.9 0.19 196 22 44 D 851 820 −31 89 236 6.6 0.21 222 22 45 E 862 830 −32 88 231 7.0 0.22 227 22 46 F 859 820 −39 90 217 7.2 0.17 210 19 47 G 861 820 −41 91 223 4.1 0.18 192 23 48 H 880 840 −40 88 205 3.1 0.20 190 21 49 I 857 820 −37 89 212 2.9 0.22 223 18 50 J 888 850 −38 86 198 3.9 0.23 206 24 51 K 874 840 −34 88 218 6.5 0.21 211 23 52 L 876 840 −36 91 216 6.9 0.24 215 23 53 M 872 840 −32 90 197 5.1 0.20 204 22 54 N 897 860 −37 93 203 4.8 0.24 201 23 55 R 853 820 −33 91 211 5.8 0.22 210 22 56 S 891 860 −31 92 202 5.7 0.23 196 22

(117) As shown in Table 4, the annealing temperature was 26° C. to 41° C. lower than Ac3 transformation point. All of the annealed steel materials 41 to 56 had a hardness of 100 HRB or less. However, any of these steel materials had a coarse microstructure in the annealed state, and the largest ferritic grain present on the observation surface did not satisfy 120 μm or less that is the requirement of the present invention. The annealed state of the annealed steel materials 41 to 56 was the microstructure like FIG. 5B, and there remained strongly the influence of coarse grains formed when heating at 1,240° C. simulating a hot working. Because the heating temperature at annealing was lower than Ac3 transformation point, the microstructure of the steel material annealed was basically similar to high temperature-tempered martensite, and only the vicinity of the grain boundary, which had been austenitized exceeding Ac1 transformation point, transformed into ferrite and spherical carbides. The area ratio and size of the carbides were smaller than those in the case where the annealing temperature exceeds Ac3 transformation point. Specifically, the area ratio of the carbides in the steel material 49 was lower than 3.0% that is the lower limit of the area ratio in the present invention, and the average particle diameter of the carbides in the steel material 46 is lower than 0.18 μm that is the lower limit of the average particle diameter in the present invention.

(118) The microstructure of the steel material after quenching was coarse similar to the structure after annealing. In all steel materials 41 to 56, the largest prior austenitic grain size present on the observation surface did not satisfy 100 μm or less that is intended in the present invention. The quenched state of the quenched steel materials 41 to 56 was the microstructure like FIGS. 5A to 5D, and fine grains were interspersed in the grain boundary of coarse grains. Thus, due to such a coarse structure, none of the steel materials 41 to 56 showed an impact value exceeding 25 J/cm.sup.2 that is conventionally required as a die after tempering. Therefore, if dies are actually manufactured from these steel materials, the fracture of the dies in an early stage is a concern. As described above, even though the chemical compositions are within the scope of the present invention, unless the annealing conditions are appropriate, the annealed structure specified in the present invention cannot be obtained. Accordingly, it could be confirmed that unless the annealing conditions are appropriate, the structure and impact value after quenching are not in the desirable state.

(119) Examples of the present invention have been described in detail above, but those examples are merely exemplified embodiments. The annealed steel material of the present invention is suitable for use in dies and parts for injection molding of plastics, molding and processing of rubbers, molding of CFRP, various castings, warm working, hot forging, hot stamp, and the like. The annealed steel material of the present invention can be combined with surface modification (shot blast, sand blast, nitriding, PVD treatment, CVD treatment, plating, etc.). Furthermore, the annealed steel material of the present invention can be formed into a rod shape or a wire shape and used for welding repair of a main body or parts of a die. The present invention can be applied to a die or parts manufactured by additive manufacturing of a plate or a powder. The present invention can be carried out in an embodiment to which various modifications have been added in scope that does not deviate from the gist thereof.

(120) The present application is based on Japanese Patent Application No. 2017-063911 filed on Mar. 28, 2017 and Japanese Patent Application No. 2018-003470 filed on Jan. 12, 2018, which contents are incorporated herein by reference.