Title of Invention	HIGH TENSILE STRENGTH STEEL MATERIAL HAVING EXCELLENT DELAYED FRACTURE RESISTANCE PROPERTY, AND METHOD OF MANUFACTURING THE SAME
Abstract	The invention provides a high tensile strength steel material having a tensile strength of 600 MPa, which is excellent in delayed fracture resistance property, and a method of manufacturing the steel material. As means for this, a steel material contains, in mass percent, C of 0.02 to 0.25%, Si of 0.01 to 0.8%, Mn of 0.5 to 2.0%, Al of 0.005 to 0.1%, N of 0.0005 to 0.008%, P of 0.03% or less, and S of 0.03% or less. In addition, the steel material contains at least one element selected from Mo, Nb, V, and Ti, and contains at least one of Cu, Ni, Cr, W, B, Ca, REM and Mg, as needed. The remainder includes Fe and inevitable impurities. In addition, in the steel material, precipitates having an average grain size of 20 nm or less, which contains at least one of Mo, Nb, V and Ti, are contained in steel in the number of at least 5 per 250000 nm2, and a microstructure includes residual austenite in a volume fraction of 0.5 to 5%. When Ca to be added is specified to be 0.0010% to 0.0020%, it is specified that S is 0.0005% to 0.0020% and O is 0.0008% to 0.0025%. ACR is specified to be 0.2≤ACR(=(Ca-(0.18+130Ca)O)/1.25/S)≤l.0.

Title of Invention

HIGH TENSILE STRENGTH STEEL MATERIAL HAVING EXCELLENT DELAYED FRACTURE RESISTANCE PROPERTY, AND METHOD OF MANUFACTURING THE SAME

Abstract

The invention provides a high tensile strength steel material having a tensile strength of 600 MPa, which is excellent in delayed fracture resistance property, and a method of manufacturing the steel material. As means for this, a steel material contains, in mass percent, C of 0.02 to 0.25%, Si of 0.01 to 0.8%, Mn of 0.5 to 2.0%, Al of 0.005 to 0.1%, N of 0.0005 to 0.008%, P of 0.03% or less, and S of 0.03% or less. In addition, the steel material contains at least one element selected from Mo, Nb, V, and Ti, and contains at least one of Cu, Ni, Cr, W, B, Ca, REM and Mg, as needed. The remainder includes Fe and inevitable impurities. In addition, in the steel material, precipitates having an average grain size of 20 nm or less, which contains at least one of Mo, Nb, V and Ti, are contained in steel in the number of at least 5 per 250000 nm2, and a microstructure includes residual austenite in a volume fraction of 0.5 to 5%. When Ca to be added is specified to be 0.0010% to 0.0020%, it is specified that S is 0.0005% to 0.0020% and O is 0.0008% to 0.0025%. ACR is specified to be 0.2≤ACR(=(Ca-(0.18+130*Ca)*O)/1.25/S)≤l.0.

Full Text	DESCRIPTION HIGH TENSILE STRENGTH STEEL MATERIAL HAVING EXCELLENT DELAYED FRACTURE RESISTANCE PROPERTY, AND METHOD OF MANUFACTURING THE SAME Technical Field The present invention relates to a high tensile strength steel material having an excellent delayed fracture resistance property, and a method of manufacturing the steel material. In particular, the invention relates to a steel material preferable for a high tensile strength steel material that has a tensile strength of 600 MPa or more, and is excellent in delayed fracture resistance property, and a method of manufacturing the steel material. Background Art Recently, in a field using a steel material such as construction industrial machinery, a tank, penstock and a line pipe, a steel material to be used is oriented to be increased in strength, and use environment of a steel material becomes progressively harsher with increase in size of structures as background. However, it is known that such increase in strength of a steel material and increase in harshness of use environment 1 typically increase hydrogen embrittlement sensitivity of the steel material, and for example, in a field of high-strength bolt, a high strength steel material is restrictively used, for example, JIS B 1186 describes that F11T class bolt (with tensile strength of 1100 to 1300 N/mm2) is preferably not used. Therefore, documents described below, that is, patent document 1, patent document 2, patent document 3, patent document 4, and patent document 5 have proposed a method of manufacturing a steel sheet having an excellent hydrogen embrittlement resistance property using various techniques such as optimization of a composition, reinforcement of grain boundaries, refinement of crystal grains, use of hydrogen trap sites, structural morphology control, and fine dispersion of carbides. [Patent document 1] JP-A-3-243745 [Patent document 2] JP-A-2003-73737 [Patent document 3] JP-A-2003-239041 [Patent document 4] JP-A-2003-253376 [Patent document 5] JP-A-2003-321743 Disclosure of the Invention However, even if each of the methods described in the patent documents 1 to 5 is used, when a strength level becomes higher, a delayed fracture resistance property, which is required when a steel material is used in harsh corrosion 2 environment, is hardly obtained. Therefore, a high tensile strength steel material having a more excellent, delayed fracture resistance property particularly in a high level of tensile strength of 900 MPa or more, and a method of manufacturing the high tensile strength steel material have been required so far. The invention was made in the light of such a circumference. That is, an object of the invention is to provide a high tensile strength steel material having an excellent delayed fracture resistance property compared with usual steel materials in a tensile strength of 600 MPa or more, and particularly 900 MPa or more, and provide a method of manufacturing the steel material (note; delayed fracture is known to be induced mainly due to an effect of hydrogen. From a view point of use environment of a steel material, harsher use environment of a steel material generally provides higher sensitivity of hydrogen to brittleness of the steel material. In the application, a property of reducing such sensitivity to delayed fracture of the high strength steel, and improving the delayed fracture resistance property is called "delayed fracture resistance property".) To solve a problem as above, the invention took the following means. That is, delayed fracture occurs as a result of a phenomenon that hydrogen that can diffuse in steel at room temperature, so-called diffusible hydrogen is accumulated in 3 a stress concentration portion, and the amount of the hydrogen reaches to a threshold value of the relevant material. As a measure for preventing this, one specific countermeasure idea for improving the delayed fracture resistance property, that is, means for decreasing the amount of diffusible hydrogen accumulated in the stress concentration portion is considered. The inventors made earnest study to improve the delayed fracture resistance property of a steel material. As a result, they found the following. That is, added amount of Mo, Nb, V or Ti being an element for forming precipitates such as alloy carbides, and a heating rate at a central portion in a thickness direction of a steel material during tempering are specified, thereby precipitates can be finely dispersed, and appropriate amount of residual austenite can be secured. Increase in the amount of trapped diffusible hydrogen due to the precipitates and the residual austenite decreases the amount of diffusible hydrogen accumulated in the stress concentration portion. Thus, in the invention, a high tensile strength steel material can be obtained, which has an excellent delayed fracture resistance property compared with usual materials. Furthermore, the inventor of the application found the following. That is, the added amount of elemental components to be contained, that is, the added amount of S, Ca and 0 is kept in an appropriate range, thereby a composite inclusion of CaS and MnS is made actively usable as a trap site of hydrogen. 4 This further improves the delayed fracture resistance property of the steel material. The invention was made after further investigation based on knowledge obtained as generally described above. That is, the invention provides a high tensile strength steel material having an excellent delayed fracture resistance property and a method of manufacturing the steel material as described below. 1. A high tensile strength steel material having an excellent delayed fracture resistance property contains, in mass percent, C of 0.02 to 0.25%, Si of 0.01.to 0.8%, Mn of 0.5 to 2.0%, Al of 0.005 to 0.1%, N of 0.0005 to 0.008%, P of 0.03% or less, and S of 0.03% or less, and at least one element selected from Mo of 0.01 to 1%, Nb of 0.001 to 0.1%, V of 0.001 to 0.5%, and Ti of 0.001 to 0.1%. The remainder includes Fe and inevitable impurities. In addition, precipitates contained in the steel include at least one of elements selected from Mo, Nb, V and Ti. The precipitates have an average grain size of 20 nm or less. The number of existing precipitates is at least 5 per 250000 nm2. The high tensile strength steel material having an excellent delayed fracture resistance property is characterized by the above. 2. Furthermore, the high tensile strength steel material having an excellent delayed fracture resistance property according to 1 is characterized in that a steel composition 5 contains at least one element among Cu of 2% or less, Ni of 4% or less, Cr of 2% or less, and W of 2% or less, in mass percent. 3. Furthermore, the high tensile strength steel material having an excellent delayed fracture resistance property according to 1 or 2 is characterized in that a steel composition contains at least one element among B of 0.003% or less, Ca of 0. 01% or less, REM of 0.02% or less (note: REM is abbreviation of Rare Earth Metal), and Mg of 0.01% or less. 4. The high tensile strength steel material having an excellent delayed fracture resistance property according to any one of 1 to 3 further contains the following elements: in mass percent, 0.0004≤S≤0.0025%, 0.0010≤Ca≤0.0030%, and 0.0008≤0≤0.0030%; wherein ACR obtained by the following expression satisfies 0.2≤ACR≤1.0. Here, ACR=(Ca-(0.18+130Ca)O)/1.25/S is given, wherein Ca, 0 or S shows the content (mass percent) of each component. 5. A high tensile strength steel material having an excellent delayed fracture resistance property characterized in that the steel material contains, in mass percent, C of 0.02 to 0.25%, Si of 0.01 to 0.8%, Mn of 0.5 to 2.0%, Al of 0.005 to 0.1%, N of 0.0005 to 0.008%, P of 0.03% or less, 0.0004%≤S≤0.0025%, 0.0010%≤Ca≤0.0030%, and 0 . 0008%≤0≤0.0030%, and at least one of elements selected from Mo of 0.01 to 1%, Nb of 0.001 to 0.1%, V of 0.001 to 0.5%, and Ti of 0.001 to 6 0.1%, wherein a value of ACR obtained by the following expression satisfies 0.2≤ACR≤1.0, and the remainder includes Fe and inevitable impurities; in addition, precipitates containing at least one of elements selected from Mo, Nb, V and Ti have an average grain size of 20 nm or less, and the number of existing precipitates is at least 5 per 250000 nm2. Here, ACR=(Ca-(0.18+130Ca)O)/1.25/S is given, wherein Ca, 0 or S shows the content (mass percent) of each component, (note; In the application, ACR is an index showing a crystallization level of Ca based inclusions, which is abbreviation of Atomic Concentration Ratio.) 6. Furthermore, the high tensile,strength steel material having an excellent delayed fracture resistance property according to 5 is characterized in that a steel composition contains at least one element among Cu of 2% or less, Ni of 4% or less, Cr of 2% or less, and W of 2% or less, in mass percent. 7. Furthermore, the high tensile strength steel material having an excellent delayed fracture resistance property according to 5 or 6 is characterized in that a steel composition contains at least one element among B of 0.003% or less, REM of 0.02% or less, and Mg of 0.01% or less, in mass percent. 8. The high tensile strength steel material having an excellent delayed fracture resistance property according to 7 any one of 1 to 6 is characterized in that the steel material includes residual austenite in a volume fraction of 0.5 to 5%. 9. A method of manufacturing the high tensile strength steel material having an excellent delayed fracture resistance property according to any one of 1 to 7, the method includes, a step of quenching the steel material from a temperature of Ar3 transformation temperature to a temperature of 500°C or less, and a step of tempering the steel material while a central portion of the steel material is heated from a tempering start temperature to a predetermined tempering temperature at an average heating rate of l°C/s or more, after the quenching. Best Mode for Carrying Out the Invention [Composition] First, regarding a composition of the invention, the reason for limiting each component is described. Each symbol % showing a chemical composition is mass percent- C: 0.02 to 0.25% C is contained to secure certain tensile strength. However, when C is less than 0.02%, such a containing effect is insufficient. On the other hand, when C is more than 0.25%, a base metal and a weld heat affected zone are degraded in toughness, and weldability is significantly degraded. Therefore, the content of C is limited to be 0.02 to 0.25%. 8 Si: 0.01 to 0.8% Si is contained as a deoxidizing agent in a steel making stage and as an element for improving strength. However, when Si is less than 0.01%, such a containing effect is insufficient. On the other hand, when Si is more than 0.8%, grain boundaries are embrittled, accelerating occurrence of delayed fracture. Therefore, the content of Si is limited to be 0.01 to 0.8%. Mn: 0.5 to 2.0% Mn is contained to secure certain tensile strength. However, when Mn is less than 0.5%, such a containing effect is insufficient. On the other hand, when Mn is more than 2.0%, toughness of a weld heat affected zone is degraded, and weldability is significantly degraded. Therefore, the content of Mn is limited to be 0.5 to 2.0%. Al: 0.005 to 0.1% Al is added as a deoxidizing agent, in addition, has an effect on refinement of crystal grain size. However, when Al is less than 0.005%, such a containing effect is insufficient. On the other hand, when Al is contained more than 0.1%, surface flaws of a steel sheet are easily made. Therefore, the content of Al is limited to be 0.005 to 0.1%. N: 0.0005 to 0.008% N is added because it refines a structure by forming nitrides with Ti or the like and thus improves toughness of the base metal and the weld heat affected zone. When N is added 9 less than 0.0005%, the effect of refining a structure is not sufficiently provided, and on the other hand, when N is added more than 0.008%, the amount of dissolved N is increased, and therefore toughness of the base metal and the weld heat affected zone is degraded. Therefore, the content of N is limited to be 0.0005 to 0.008%. P: 0.03% or less, S: 0.03% or less Each of P and S is an impurity element, and when it is more than 0.03%, sound base metal and sound welding j oint cannot be obtained. Therefore, the content of each of P and S is limited to be 0.03% or less. Here, regarding S, since inclusions of S can be used as trap sites of hydrogen, it is preferably specified to be 0.0004%≤S≤0.0025%. When S is less than 0.0004%, appropriate amount of dispersed inclusions cannot be secured, and the trap sites of hydrogen are decreased, consequently inclusions do not substantially exhibit an effect on delayed fracture resistance. When S is more than 0.0025%, the amount of inclusions is excessivelyincreased and therefore ductile fracture strength is reduced, consequently toughness may be degraded. 0: 0.0008%≤0≤0.0030% 0 is preferably specified to be 0.0008%≤O≤0.0030% since inclusions can be used for trap sites of hydrogen. When 0 is less than 0.0008%, appropriate amount of dispersed inclusions cannot be secured, and the trap sites of hydrogen are decreased, 10 consequently inclusions do not exhibit the effect on delayed fracture resistance as the inclusions. When 0 is more than 0.0030%, the amount of inclusions is excessively increased and therefore ductile fracture strength is reduced, consequently toughness may be degraded. At least one selected from Mo, Nb, V and Ti When the steel material contains at least one of Mo, Nb, V and Ti, the steel material has an effect of trapping diffusible hydrogen and thus improving the delayed fracture resistance property. Therefore, the steel material contains at least one of Mo of 0.01 to 1%, Nb of 0.001 to 0.1%, V of 0.001 to 0.5% and Ti of 0.001 to 0.1%. Hereinafter, description is made on ranges in which Mo, Nb, V and Ti are specified respectively. Mo: 0.01 to 1% Mo has a function of improving hardehability and strength, in addition, traps diffusible hydrogen by forming carbides, thereby improves the delayed fracture resistance property. When Mo is added less than 0.01%, such a containing effect is insufficient, and on the other hand, when it is added more than 1%, economic efficiency is reduced. Therefore, when Mo is added, the content is limited to be 0.01 to 1%. In particular, Mo has a function of increasing tempering softening resistance, and is preferably added 0.2% or more to secure tensile strength of 900 MPa or more. 11 Nb: 0.001 to 0.1% Nb improves strength as a microalloying element, in addition, traps diffusible hydrogen by forming carbides, nitrides, or carbon-nitrides, so that improves the delayed fracture resistance property. When Nb is added less than 0.001%, such an effect is insufficient, and on the other hand, when it is added more than 0.1%, toughness of a weld heat affected zone is degraded. Therefore, when Nb is added, the content is limited to be 0.001 to 0.1%. V: 0.001 to 0.5% V improves strength as a microalloying element, in addition, traps diffusible hydrogen by forming carbides, nitrides, or carbon-nitrides, thereby improves the delayed fracture resistance property. When V is added less than 0.001%, such an effect is insufficient, and on the other hand, when it is added more than 0.5%, toughness of a weld heat affected zone is degraded. Therefore, when V is added, the content is limited to be 0.001 to 0.5%. Ti: 0.001 to 0.1% Ti forms TiN during rolling heating or during welding, thereby inhibits growth of austenite grains, and thereby improves toughness of a base metal and weld heat affected zone, in addition, traps diffusible hydrogen by forming carbides, nitrides, or carbon-nitrides, thereby improves the delayed fracture resistance property. 12 Furthermore, Ti has an effect of trapping diffusible hydrogen by forming a composite precipitate with Mo or Nb, thereby improving the delayed fracture resistance property. However, when Ti is added less than 0.001%, such an effect is insufficient, and on the other hand, when it is added more than 0.1%, toughness of a weld heat affected zone is degraded. Therefore, when Ti is added, the content is limited to be 0.001 to 0.1%. Furthermore, in the invention, the steel material may contain the following components depending on a desired property. That is, components that the steel material may further contain depending on a desired property are as follows. Cu: 2% or less Cu has a function of improving strength by solution hardening and precipitation hardening. However, when the content of Cu exceeds 2%, cracking in hot working tends to occur during heating a steel billet or welding. Therefore, when Cu is added, the content is limited to be 2% or less. Ni: 4% or less Ni has a function of improving toughness and hardenability. However, when the content of Ni exceeds 4%, economic efficiency is reduced. Therefore, when Ni is added, the content is limited to be 4% or less. Cr: 2% or less Cr has a function of improving strength and toughness, 13 and is excellent in high temperature strength property. Therefore, when a steel material is intended to be increased in strength, Cr is actively added, and particularly, Cr of 0.3% or more is preferably added to obtain a property of tensile strength of 900 MPa or more. However, when the content of Cr exceeds 2%, weldability is degraded. Therefore, when Cr is added, the content is limited to be 2% or less. W: 4% or less W has a function of improving strength. However, when the content of W exceeds 2%, weldability is degraded. Therefore, when W is added, the content is limited to be 2% or less. B: 0.003% or less B has a function of improving hardenability. However, when the content of B exceeds 0.003%, toughness is degraded. Therefore, when B is added, the content is limited to be 0.003% or less. Ca: 0.01% or less Ca is an element indispensable for morphology control of sulfide based inclusions. However, when Ca is added more than 0.01%, reduction in cleanliness is caused. Therefore, when Ca is added, the content is limited to be 0.01% or less. Preferably, regarding Ca, since inclusions of Ca can be used as trap sites of hydrogen, it is specified to be 0.0010%≤Ca≤0.0030%. When Ca is less than 0 . 0010%, appropriate 14 amount of dispersed inclusions cannot be secured, and the trap sites of hydrogen are decreased, consequently inclusions do not substantially exhibit an effect on delayed fracture resistance. When Ca is more than 0.0030%, the amount of inclusions is excessively increased and therefore ductile fracture strength is reduced, consequently toughness may be degraded. However, when Ca is specified to be 0.0010≤Ca≤0.0030%, the amount of 0 in steel is specified to be 0.0008≤O≤0.0030%, and ACR obtained by the following expression is specified to be 0.2≤ACR≤1.0. Here, in the expression, ACR=(Ca-(0.18+130Ca)O)/1.25/S, Ca, 0 or S shows the content (mass percent) in steel respectively. ACR is specified to be 0.2≤ACR≤1.0 so that the composite inclusion of CaS and MnS is actively used as the trap site of hydrogen to improve the delayed fracture resistance property. Ca, 0 and S are contained such that ACR satisfies such range, thereby CaS and MnS are prevented from being crystallized as nucleuses respectively, and can be dispersed as fine composite inclusions. As a result, hydrogen is trapped in interfaces between the composite inclusions and a matrix, so that accumulation of hydrogen in interfacial surface of only part of inclusions can be suppressed. Furthermore, alloy carbides are 15 precipitated on surfaces of the composite inclusions in a rapid-heating tempering process, thereby a larger amount of hydrogen are trapped. When ACR is less than 0.2, a nucleus of inclusions is MnS, and the inclusions are extended by rolling and thereby tend to be initial points of delayed fracture, consequently the delayed fracture resistance property is sometimes degraded. When ACR is 1.0 or more, a nucleus of inclusions is CaS, and the inclusions tend to be coarse, and in some cases, the coarse inclusions become initial points of delayed fracture, consequently the delayed fracture resistance property is degraded. More preferably, ACR is in a range of 0.4≤ACR≤0.8. In usual cases, since MnS is extended by rolling, and hydrogen is accumulated in such extended portions, thereby cracks tend to occur, Ca is added so as to satisfy ACR≥1.0, so that S is fixed to perform morphology control of MnS. REM: 0.02% or less REM forms sulfides as REM (0, S) in steel and thus decreases the amount of dissolved S in crystal grain boundaries, so that it improves an SR crack resistance property. However, when REM is added more than 0.02%, REM sulfides are significantly accumulated in a precipitation zone, causing degradation in material. Therefore, when REM is added, added amount is limited to be 0.02% or less. 16 Mg: 0.01% or less Mg is sometimes used as a molten-iron desulfurizing agent. However, when Mg is added more than 0.01%, reduction in cleanliness is caused. Therefore, when Mg is added, added amount is limited to be 0.01% or less. Next, description is made on the reason for limiting a precipitation pattern of precipitates in the invention. First, from a viewpoint of a microstructure of the precipitates, the reason for limiting the precipitation pattern is described below. [Microstructure] In the invention, precipitates containing at least one of elements selected from Mo, Nb, V and Ti have an average grain size of 20 nm or less, and preferably 15 nm or less. The number of precipitates contained in the steel is at least 5 per 250000 nm2, and preferably at least 10 per 250000 nm2. (note; Here, the precipitates typically include a carbide, nitride, carbon-nitride, and compound of them.) The precipitates are observed by a transmission electron microscope by using a sample of a thin film or extraction replica or the like. The grain size is evaluated using a circle-equivalent diameter from image analysis, and the average grain size is, for example, assumed as a simple average value for at least five, optional view fields using precipitates observed in a view field 500 nm square as an object. 17 While the precipitates containing at least one of elements selected from Mo, Nb, V and Ti have an effect of trapping diffusible hydrogen irrespectively of size, when the average grain size is more than 20 nm, lattice matching is reduced, leading to reduction in force of trapping diffusible hydrogen. As a result, in the steel material, the effect of improving the delayed fracture resistance property is reduced. Thus, the average grain size is specified to be 20 nm or less, and preferably 15 nm or less. When density of the precipitates containing at least one of elements selected from Mo, Nb, V and Ti is less than 5 per 250000 nm2, the amount of diffusible hydrogen trapped by the precipitates is decreased, leading to reduction in effect of improving the delayed fracture resistance property. Thus, the precipitates are specified to be contained in a ratio of at least 5 per 250000 nm2 or more, and preferably at least 10 per 250000 nm2. Next, in a viewpoint of the residual austenite, the reason for limiting the precipitation pattern is described below. [Residual austenite] Residual austenite acts as a hydrogen trap site because of high solid solubility of hydrogen, and thereby improves the delayed fracture resistance property. However, such an effect is not sufficient in a volume fraction of residual austenite 18 of less than 0.5%, but strength is reduced in a volume fraction of more than 5%. Therefore, the residual austenite is preferably specified to be in a volume fraction of 0.5 to 5%, and more preferably in a volume fraction of 2 to 4%. The volume fraction of the amount of residual austenite is measured by, for example, quantizing peaks of the lattice constant of austenite using X-ray diffraction. Next, a manufacturing method of the invention is described. In the invention, a steel billet can be manufactured such that the billet can be quenched from the Ar3 transformation temperature or more, and a method of manufacturing a cast billet from molten steel, or a method of manufacturing a steel billet by rolling a cast billet is not particularly specified. Steel ingoted by a converter method, an electric furnace method and the like, or a slab manufactured by continuous casting, an ingot mold method and the like can be used. When a steel billet is manufactured by rolling a cast billet, the cast billet as it is may be started to be subjected to hot rolling without being cooled to the Ar3 transformation temperature or less, or may be started to be subjected to hot rolling after a cast billet that was once cooled is reheated to the Ar3 transformation temperature or more. If rolling is finished at the Ar3 transformation temperature or more, other rolling conditions may not be 19 particularly specified. If rolling is performed at a temperature of the Ar3 transformation temperature or more, the rolling may be performed in a recrystallization range or a non-recrystallization range. In the invention, if quenching is started from a state of an austenite single phase structure at the Ar3 transformation temperature or more, the quenching may be performed directly after hot rolling, or may be performed after reheating a hot-rolled material. As a heating method during tempering, if a required heating rate is achieved, any of methods of induction heating, resistance heating, infrared radiation heating, atmospheric heating and the like can be used. Next, description is made on a manufacturing condition preferable for manufacturing steel in the invention. The invention can be applied to steel materials in various forms such as a steel sheet, shape steel, and rod steel. In the manufacturing condition, temperature is specified with temperature at a central portion of the steel material, which is a center in thickness in the steel sheet, a center in thickness in a region, to which properties according to the invention are added, in the shape steel, and a center in a radial direction in the rod steel. However, since the neighborhood of the central portion is subjected to substantially the same temperature history, the central portion is not limited to the 20 center itself. A manufacturing condition preferable for manufacturing the steel of the invention is described below from a viewpoint of quenching and tempering. A quenching condition in the invention is as follows. To secure strength and toughness of a base metal, quenching is performed from a temperature of the Ar3 transformation temperature or more to a temperature of 500°C or less. In the quenching, cooling is performed at a rate of 0.5°C/sec or more, and preferably l°C/sec or more. These are specified to complete transformation from austenite to martensite or bainite to reinforce a base metal. While an expression for obtaining the Ar3 transformation temperature (°C) is not particularly specified in the invention, for example, Ar3=910-310C-80Mn-20Cu-15Cr-55Ni-80Mo is assumed. In the expression, each elemental symbol shows the content (mass percent) in steel. A tempering condition in the invention is as follows. During tempering, an average heating rate is set to be l°C/sec or more, and preferably set to be 2°C/sec or more from a tempering start temperature to a predetermined tempering temperature. In the case that steel is temporarily cooled to room temperature due to reheating quenching, the average heating rate is also set to be l°C/sec or more, and preferably set to be 2°C/sec or more during tempering. 21 Behavior of formation or growth of precipitates formed during tempering, including, alloy carbides, alloy nitrides, alloy carbon-nitrides and the like is affected by a heating rate during tempering, and when the average heating rate is also set to be l°C/sec or more, and preferably set to be 2°C/sec or more, fine dispersion of precipitates is achieved. When the rate is less than l°C/sec, since C is diffused into grain boundaries or lath interfaces before carbides or carbon-nitrides precipitate, only coarse carbides or carbon-nitrides can be obtained, consequently an effect of finely dispersing carbides or carbon-nitrides to be as trap sites of hydrogen is not obtained. Furthermore, in tempering, when a temperature range where a heating rate at 600°C or more is at least 10°C/sec is included, an alloy element is substituted for Fe in dispersedly precipitated cementite, which preferably accelerates precipitation of fine alloy carbides. When a steel material is increased in strength to have a tensile strength of 900 MPa or more, it is preferable for obtaining a well-balanced property of high strength and high toughness that tempering temperature is set to be in a range of 450 to 550°C. Furthermore, for a heating process during tempering, it is enough that a predetermined average heating rate is obtained, and either of a linear temperature history, and a temperature 22 history in which temperature is retained during heating may be used, that is, a temperature history is not particularly specified. Holding time at tempering temperature is desirably 60 sec or less to prevent degradation in productivity, or degradation in delayed fracture resistance property due to coarsening of precipitates. Regarding a cooling rate after tempering, it is desirable that an average cooling rate is set to be 0.05°C/sec or more from the tempering temperature to 200°C to prevent coarsening of precipitates during cooling. According to the above conditions, since the amount of trapped diffusible hydrogen due to the precipitates is increased, the amount of diffusible hydrogen accumulated in a stress concentration portion is decreased, consequently the delayed fracture resistance property is improved compared with that of usual steel materials. [Example] Effectiveness of the invention is described using an example. Steel A to steel P and Steel Q to steel U of chemical composition shown in Tables 1 and 4 were ingoted and casted into slabs, then the slabs were heated in a heating furnace and then rolled into steel sheets. After rolling, successively, the steel sheets were directly quenched, and then 23 subjected to tempering using a solenoid-type induction heating apparatus. An average heating rate at a central portion in thickness was controlled by using threading speed of a steel sheet. When a steel sheet was held at the tempering temperature, the steel sheet was heated while being reciprocated, so that it was held within a variation range of ±5°C. As cooling after heating, air cooling was used. Temperature such as tempering temperature or quenching temperature at a central portion in thickness was obtained by heat transfer calculation from a result of sequential temperature measurement of a surface using a radiation thermometer. Table 2 shows manufacturing conditions of the steel sheets, average grain size of precipitates, density of the precipitates, and volume fractions of residual austenite, and Table 3 shows yield strength, tensile strength, fracture transition temperature (vTrs), and amount of critical diffusible hydrogen. For the size and density of the precipitates, precipitates extracted by using an extraction replica were photographed using a transmission electron microscope, then average was obtained for five, optional view fields using precipitates observed in a view field 500 nm square as an object. Grain size was evaluated using a circle-equivalent diameter 24 from image analysis. The volume fraction of residual austenite was measured by quantizing peaks of the lattice constant of austenite using X-ray diffraction. The yield strength and the tensile strength were measured using full-thicknes.s tensile test pieces, and the toughness was evaluated by vTrs obtained by a Charpy impact test using test pieces sampled from central portions in thickness. Furthermore, the amount of critical diffusible hydrogen was defined as maximum amount of diffusible hydrogen at which delayed fracture did not occur within 100 hr under constant load of 90% of tensile strength, and a round-bar tensile test piece with circular notch was used as a test piece, and the amount of diffusible hydrogen was measured by gas chromatography method. An objective value of the amount of critical diffusible hydrogen was set to be at least 0.2 ppm by mass for a steel type having a tensile strength of 1200 MP or more, and set to be at least 0.3 ppm by mass for a steel type having a tensile strength of less than 1200 MP. 25 CM 00 Table 3 No. Steeltype Thickness(mm) Yield strength(Mpa) Tensilestrength(MPa) vTrs at centralportion inthickness(°C) Amount ofcriticaldiffusiblehydrogen(mass ppm) Remarks 1 A 10 595 672 -120 2.35 Example of the invention 2 B 25 601 685 -126 1.69 Example of the invention 3 C 25 821 870 -91 1.33 Example of the invention 4 D 25 1023 1046 -83 1.01 Example of the invention 5 E 25 1011 1039 -88 0.89 Example of the invention 6 F 12 1098 1120 -71 0.75 Example of the invention 7 G 25 1067 1097 -75 0.69 Example of the invention 8 H 50 1011 1034 -76 0.66 Example of the invention 9 I 12 1352 1378 -59 0.69 Example of the invention 10 J 25 1335 1350 -55 0.53 Example of the invention 11 K 50 1295 1311 -51 0.52 Example of the invention 12 L 25 1492 1522 -39 0.48 Example of the Invention 13 G 6 1292 1310 -68 0.66 Example of the invention 14 I 12 1413 1423 -55 0.63 Example of the invention 15 J 25 1398 1411 -51 0.50 Example of the invention 16 K 60 1326 1342 •43 0.50 Example of the invention 17 M 25 815 869 -67 0.26 Comparative example 18 N 25 1000 1019 -56 0.19 Comparative example 19 0 25 1093 1112 -43 0.26" Comparative example 20 P 25 1308 1368 -17 0.15 Comparative example 21 A 10 541 619 -135 0.26 Comparative example 22 B 25 517 591 -145 0.29 Comparative example 23 C 25 810 862 -65 0.24' Comparative example 24 D 25 1011 1036 -52 0.23' Comparative example 25 E 25 1005 1029 -51 0.15' Comparative example 26 F 12 1121 1136 -43 0.19 Comparative example 27 G 25 1083 1103 -38 0.16' Comparative example 28 H 50 1011 1028 -36 0.09' Comparative example 29 I 12 1351 1369 -29 0.14' Comparative example 30 J 25 1332 1362 -24 0.11 Comparative example 31 K 50 1287 1305 -26 0.16 Comparative example 32 L 25 1453 1516 -18 0.05 Comparative example 33 Q 25 970 1180 -98 2.56 Example of the invention 34 R 30 1000 1210 -88 2.10 Example of the invention 35 S 35 1150 1350 -75 1.48 Example of the invention 36 S 35 1215 1388 -77 1.85 Example of the invention 37 T 50 1250 1480 -78 1.44 Example of the invention 38 T 50 1300 1450 -78 1.99 Example of the invention 39 U 60 1320 1460 -86 1.56 Example of the invention Note A mark * shows the value is out of the range of the invention. 29 o m As clear from Table 3, in steel sheets Nos. 1 to 16 manufactured by the method of the invention (examples of the invention), in which the chemical composition, manufacturing method, precipitation pattern of precipitates, or volume fraction of residual austenite is within a range of the invention, high amount of critical diffusible hydrogen was able to be obtained. Furthermore, in steel sheets Nos. 33 to 39 (examples of the invention), in which ACR is within a range of the invention, comparatively higher amount of critical diffusible hydrogen was able to be obtained. On the contrary, in comparative steel sheets Nos. 17 to 32 (comparative examples), the amount of critical diffusible hydrogen is out of the objective range. Hereinafter, the comparative examples are individually described. In steel sheets Nos. 17 to 20, in which each composition is out of the range of the invention, both of the density of precipitates and the volume fraction of residual austenite are out of the range of the invention, and the amount of critical diffusible hydrogen does notreach to the objective value. In a steel sheet No. 21, in which direct quenching start temperature is out of the range of the invention, both of the density of precipitates and the volume fraction of residual austenite are out of the range of the invention, and the amount of critical diffusible hydrogen does not reach to the objective value. 31 In a steel sheet No. 22, in which direct quenching stop temperature is out of the range of the invention, both of the density of precipitates and the volume fraction of residual austenite are out of the range of the invention, and the amount of critical diffusible hydrogen does not reach to the objective value. In steel sheets Nos. 23 to 32, in which each average heating rate at a central portion of a steel material from a tempering start temperature to a predetermined tempering temperature is out of the range of the invention, numeral values of any two among the average grain size of precipitates, density of the precipitates, and volume fraction of residual austenite are out of the range of the invention, and the amount of critical diffusible hydrogen does not reach to the objective value. Industrial Applicability According to the invention, a high tensile strength steel material having an extremely excellent, delayed fracture resistance property, of which tensile strength is 600 MPa or more, and particularly 900 MPa or more, can be manufactured, which is industrially extremely useful. 32 Claims 1. A high tensile strength steel material having an excellent delayed fracture resistance property, comprising: elements of, in mass percent, C of 0.02 to 0.25%, Si of 0.01 to 0.8%, Mn of 0.5 to 2.0%, Al of 0. 005 to 0.1%, N of 0.0005 to 0.008%, P of 0.03% or less, and S of 0.03% or less, and at least one element selected from, in mass percent, Mo of 0.01 to 1%, Nb of 0.001 to 0.1%, V of 0.001 to 0.5%, and Ti of 0.001 to 0.1%, and the remainder being Fe and inevitable impurities, wherein precipitates contained in steel include at least one of elements selected from Mo, Nb, V and Ti, an average grain size of the precipitates is 20 nm or less, and the number of existing precipitates is at least 5 per 250000 nm2. 2. The high tensile strength steel material having an excellent delayed fracture resistance property according to claim 1: Wherein the steel composition further contains at least one element among Cu of 2% or less, Ni of 4% or less, Cr of 2% or less, and W of 2% or less, in mass percent. 3. The high tensile strength steel material having an excellent 33 delayed fracture resistance property according to claim 1 or 2: wherein the steel composition further contains at least one element among B of 0.003% or less, Ca of 0.01% or less, REM of 0.02% or less, and Mg of 0.01% or less, in mass percent. 4. The high tensile strength steel material having an excellent delayed fracture resistance property according to any one of claims 1 to 3: wherein the high tensile strength steel material further contains the elements of 0.0004≤S≤0.0025%, 0.0010≤Ca≤0.0030%, and 0.0008≤0≤0.0030% in mass percent; and ACR obtained by the following expression satisfies 0.2≤ACR≤1.0, here, ACR=(Ca-(0.18+130Ca)O) /1.25/S is given, wherein Ca, 0 or S shows the content (mass percent) of each component. 5. A high tensile strength steel material having an excellent delayed fracture resistance property, comprising: elements of, in mass percent, C of 0.02 to 0.25%, Si of 0.01 to 0.8%, Mn of 0.5 to 2.0%, Al of 0.005 to 0.1%, N of 0.0005 to 0.008%, P of 0.03% or less, 0.0004%≤S≤0.0025%, 0.0010%≤Ca≤0.0030%, and 0.0008%≤O≤0.0030%, and at least one of elements selected from Mo of 0.01 to 1%, 34 Nb of 0.001 to 0.1%, V of 0.001 to 0.5%, and Ti of 0.001 to 0.1%, in mass percent, and a value of ACR obtained by the following expression satisfies 0.2≤ACR≤1.0, and the remainder including Fe and inevitable impurities, and precipitates contained in steel include at least one of elements selected from Mo, Nb, V and Ti, an average grain size of the precipitates is 20 nm or less, and the number of existing precipitates is at least 5 per 250000 nm2, here ACR=(Ca-(0.18 + 130Ca)O)/1.25/S is given, wherein Ca, 0 or S is the content (mass percent) of each component. 6. The high tensile strength steel material having an excellent delayed fracture resistance property according to clam 5, further comprising: a steel composition contained in steel containing at least one element among Cu of 2% or less, Ni of 4% or less, Cr of 2% or less, and W of 2% or less, in mass percent. 7. The high tensile.strength steel material having an excellent delayed fracture resistance property according to claim 5 or 35 6: wherein a steel composition contains at least one element among B of 0.003% or less, REM of 0.02% or less, and Mg of 0.01% or less, in mass percent. 8 . The high tensile strength steel material having an excellent delayed fracture resistance property according to any one of claims 1 to 7; wherein the steel material includes residual austenite in a volume fraction of 0.5 to 5% in a microstructure. 9. A method of manufacturing the high tensile strength steel material having an excellent delayed fracture resistance property according to any one of claims 1 to 7, comprising: a step of quenching the steel material from a temperature of Ar3 transformation temperature to a temperature of 500°C or less, and a step of tempering the steel material while a central portion of the steel material is heated from a tempering start temperature to a predetermined tempering temperature at an average heating rate of l°C/s or more, after the quenching. 36 The invention provides a high tensile strength steel material having a tensile strength of 600 MPa, which is excellent in delayed fracture resistance property, and a method of manufacturing the steel material. As means for this, a steel material contains, in mass percent, C of 0.02 to 0.25%, Si of 0.01 to 0.8%, Mn of 0.5 to 2.0%, Al of 0.005 to 0.1%, N of 0.0005 to 0.008%, P of 0.03% or less, and S of 0.03% or less. In addition, the steel material contains at least one element selected from Mo, Nb, V, and Ti, and contains at least one of Cu, Ni, Cr, W, B, Ca, REM and Mg, as needed. The remainder includes Fe and inevitable impurities. In addition, in the steel material, precipitates having an average grain size of 20 nm or less, which contains at least one of Mo, Nb, V and Ti, are contained in steel in the number of at least 5 per 250000 nm2, and a microstructure includes residual austenite in a volume fraction of 0.5 to 5%. When Ca to be added is specified to be 0.0010% to 0.0020%, it is specified that S is 0.0005% to 0.0020% and O is 0.0008% to 0.0025%. ACR is specified to be 0.2≤ACR(=(Ca-(0.18+130Ca)O)/1.25/S)≤l.0.

Full Text

DESCRIPTION
HIGH TENSILE STRENGTH STEEL MATERIAL HAVING EXCELLENT DELAYED
FRACTURE RESISTANCE PROPERTY, AND METHOD OF MANUFACTURING THE
SAME
Technical Field
The present invention relates to a high tensile strength
steel material having an excellent delayed fracture resistance
property, and a method of manufacturing the steel material.
In particular, the invention relates to a steel material
preferable for a high tensile strength steel material that has
a tensile strength of 600 MPa or more, and is excellent in
delayed fracture resistance property, and a method of
manufacturing the steel material.
Background Art
Recently, in a field using a steel material such as
construction industrial machinery, a tank, penstock and a line
pipe, a steel material to be used is oriented to be increased
in strength, and use environment of a steel material becomes
progressively harsher with increase in size of structures as
background.
However, it is known that such increase in strength of
a steel material and increase in harshness of use environment
1

typically increase hydrogen embrittlement sensitivity of the
steel material, and for example, in a field of high-strength
bolt, a high strength steel material is restrictively used,
for example, JIS B 1186 describes that F11T class bolt (with
tensile strength of 1100 to 1300 N/mm2) is preferably not used.
Therefore, documents described below, that is, patent
document 1, patent document 2, patent document 3, patent
document 4, and patent document 5 have proposed a method of
manufacturing a steel sheet having an excellent hydrogen
embrittlement resistance property using various techniques
such as optimization of a composition, reinforcement of grain
boundaries, refinement of crystal grains, use of hydrogen trap
sites, structural morphology control, and fine dispersion of
carbides.
[Patent document 1] JP-A-3-243745
[Patent document 2] JP-A-2003-73737
[Patent document 3] JP-A-2003-239041
[Patent document 4] JP-A-2003-253376
[Patent document 5] JP-A-2003-321743
Disclosure of the Invention
However, even if each of the methods described in the
patent documents 1 to 5 is used, when a strength level becomes
higher, a delayed fracture resistance property, which is
required when a steel material is used in harsh corrosion
2

environment, is hardly obtained. Therefore, a high tensile
strength steel material having a more excellent, delayed
fracture resistance property particularly in a high level of
tensile strength of 900 MPa or more, and a method of
manufacturing the high tensile strength steel material have
been required so far.
The invention was made in the light of such a
circumference. That is, an object of the invention is to
provide a high tensile strength steel material having an
excellent delayed fracture resistance property compared with
usual steel materials in a tensile strength of 600 MPa or more,
and particularly 900 MPa or more, and provide a method of
manufacturing the steel material (note; delayed fracture is
known to be induced mainly due to an effect of hydrogen. From
a view point of use environment of a steel material, harsher
use environment of a steel material generally provides higher
sensitivity of hydrogen to brittleness of the steel material.
In the application, a property of reducing such sensitivity
to delayed fracture of the high strength steel, and improving
the delayed fracture resistance property is called "delayed
fracture resistance property".)
To solve a problem as above, the invention took the
following means. That is, delayed fracture occurs as a result
of a phenomenon that hydrogen that can diffuse in steel at room
temperature, so-called diffusible hydrogen is accumulated in
3

a stress concentration portion, and the amount of the hydrogen
reaches to a threshold value of the relevant material. As a
measure for preventing this, one specific countermeasure idea
for improving the delayed fracture resistance property, that
is, means for decreasing the amount of diffusible hydrogen
accumulated in the stress concentration portion is considered.
The inventors made earnest study to improve the delayed
fracture resistance property of a steel material. As a result,
they found the following. That is, added amount of Mo, Nb,
V or Ti being an element for forming precipitates such as alloy
carbides, and a heating rate at a central portion in a thickness
direction of a steel material during tempering are specified,
thereby precipitates can be finely dispersed, and appropriate
amount of residual austenite can be secured. Increase in the
amount of trapped diffusible hydrogen due to the precipitates
and the residual austenite decreases the amount of diffusible
hydrogen accumulated in the stress concentration portion.
Thus, in the invention, a high tensile strength steel material
can be obtained, which has an excellent delayed fracture
resistance property compared with usual materials.
Furthermore, the inventor of the application found the
following. That is, the added amount of elemental components
to be contained, that is, the added amount of S, Ca and 0 is
kept in an appropriate range, thereby a composite inclusion
of CaS and MnS is made actively usable as a trap site of hydrogen.
4

This further improves the delayed fracture resistance property
of the steel material.
The invention was made after further investigation based
on knowledge obtained as generally described above. That is,
the invention provides a high tensile strength steel material
having an excellent delayed fracture resistance property and
a method of manufacturing the steel material as described
below.
1. A high tensile strength steel material having an
excellent delayed fracture resistance property contains, in
mass percent, C of 0.02 to 0.25%, Si of 0.01.to 0.8%, Mn of
0.5 to 2.0%, Al of 0.005 to 0.1%, N of 0.0005 to 0.008%, P of
0.03% or less, and S of 0.03% or less, and at least one element
selected from Mo of 0.01 to 1%, Nb of 0.001 to 0.1%, V of 0.001
to 0.5%, and Ti of 0.001 to 0.1%. The remainder includes Fe
and inevitable impurities. In addition, precipitates
contained in the steel include at least one of elements selected
from Mo, Nb, V and Ti. The precipitates have an average grain
size of 20 nm or less. The number of existing precipitates
is at least 5 per 250000 nm2. The high tensile strength steel
material having an excellent delayed fracture resistance
property is characterized by the above.
2. Furthermore, the high tensile strength steel material
having an excellent delayed fracture resistance property
according to 1 is characterized in that a steel composition
5

contains at least one element among Cu of 2% or less, Ni of
4% or less, Cr of 2% or less, and W of 2% or less, in mass percent.
3. Furthermore, the high tensile strength steel material
having an excellent delayed fracture resistance property
according to 1 or 2 is characterized in that a steel composition
contains at least one element among B of 0.003% or less, Ca
of 0. 01% or less, REM of 0.02% or less (note: REM is abbreviation
of Rare Earth Metal), and Mg of 0.01% or less.
4. The high tensile strength steel material having an
excellent delayed fracture resistance property according to
any one of 1 to 3 further contains the following elements:
in mass percent, 0.0004≤S≤0.0025%, 0.0010≤Ca≤0.0030%,
and 0.0008≤0≤0.0030%; wherein ACR obtained by the following
expression satisfies 0.2≤ACR≤1.0. Here,
ACR=(Ca-(0.18+130*Ca)*O)/1.25/S is given,
wherein Ca, 0 or S shows the content (mass percent) of
each component.
5. A high tensile strength steel material having an
excellent delayed fracture resistance property characterized
in that the steel material contains, in mass percent, C of 0.02
to 0.25%, Si of 0.01 to 0.8%, Mn of 0.5 to 2.0%, Al of 0.005
to 0.1%, N of 0.0005 to 0.008%, P of 0.03% or less,
0.0004%≤S≤0.0025%, 0.0010%≤Ca≤0.0030%, and 0 . 0008%≤0≤0.0030%,
and at least one of elements selected from Mo of 0.01 to 1%,
Nb of 0.001 to 0.1%, V of 0.001 to 0.5%, and Ti of 0.001 to
6

0.1%, wherein a value of ACR obtained by the following
expression satisfies 0.2≤ACR≤1.0, and the remainder includes
Fe and inevitable impurities; in addition, precipitates
containing at least one of elements selected from Mo, Nb, V
and Ti have an average grain size of 20 nm or less, and the
number of existing precipitates is at least 5 per 250000 nm2.
Here,
ACR=(Ca-(0.18+130*Ca)*O)/1.25/S is given,
wherein Ca, 0 or S shows the content (mass percent) of
each component,
(note; In the application, ACR is an index showing a
crystallization level of Ca based inclusions, which is
abbreviation of Atomic Concentration Ratio.)
6. Furthermore, the high tensile,strength steel material
having an excellent delayed fracture resistance property
according to 5 is characterized in that a steel composition
contains at least one element among Cu of 2% or less, Ni of
4% or less, Cr of 2% or less, and W of 2% or less, in mass percent.
7. Furthermore, the high tensile strength steel material
having an excellent delayed fracture resistance property
according to 5 or 6 is characterized in that a steel composition
contains at least one element among B of 0.003% or less, REM
of 0.02% or less, and Mg of 0.01% or less, in mass percent.
8. The high tensile strength steel material having an
excellent delayed fracture resistance property according to
7

any one of 1 to 6 is characterized in that the steel material
includes residual austenite in a volume fraction of 0.5 to 5%.
9. A method of manufacturing the high tensile strength
steel material having an excellent delayed fracture resistance
property according to any one of 1 to 7, the method includes,
a step of quenching the steel material from a temperature
of Ar3 transformation temperature to a temperature of 500°C
or less, and
a step of tempering the steel material while a central
portion of the steel material is heated from a tempering start
temperature to a predetermined tempering temperature at an
average heating rate of l°C/s or more, after the quenching.
Best Mode for Carrying Out the Invention
[Composition]
First, regarding a composition of the invention, the
reason for limiting each component is described. Each symbol %
showing a chemical composition is mass percent-
C: 0.02 to 0.25%
C is contained to secure certain tensile strength.
However, when C is less than 0.02%, such a containing effect
is insufficient. On the other hand, when C is more than 0.25%,
a base metal and a weld heat affected zone are degraded in
toughness, and weldability is significantly degraded.
Therefore, the content of C is limited to be 0.02 to 0.25%.
8

Si: 0.01 to 0.8%
Si is contained as a deoxidizing agent in a steel making
stage and as an element for improving strength. However, when
Si is less than 0.01%, such a containing effect is insufficient.
On the other hand, when Si is more than 0.8%, grain boundaries
are embrittled, accelerating occurrence of delayed fracture.
Therefore, the content of Si is limited to be 0.01 to 0.8%.
Mn: 0.5 to 2.0%
Mn is contained to secure certain tensile strength.
However, when Mn is less than 0.5%, such a containing effect
is insufficient. On the other hand, when Mn is more than 2.0%,
toughness of a weld heat affected zone is degraded, and
weldability is significantly degraded. Therefore, the
content of Mn is limited to be 0.5 to 2.0%.
Al: 0.005 to 0.1%
Al is added as a deoxidizing agent, in addition, has an
effect on refinement of crystal grain size. However, when Al
is less than 0.005%, such a containing effect is insufficient.
On the other hand, when Al is contained more than 0.1%, surface
flaws of a steel sheet are easily made. Therefore, the content
of Al is limited to be 0.005 to 0.1%.
N: 0.0005 to 0.008%
N is added because it refines a structure by forming
nitrides with Ti or the like and thus improves toughness of
the base metal and the weld heat affected zone. When N is added
9

less than 0.0005%, the effect of refining a structure is not
sufficiently provided, and on the other hand, when N is added
more than 0.008%, the amount of dissolved N is increased, and
therefore toughness of the base metal and the weld heat affected
zone is degraded. Therefore, the content of N is limited to
be 0.0005 to 0.008%.
P: 0.03% or less, S: 0.03% or less
Each of P and S is an impurity element, and when it is
more than 0.03%, sound base metal and sound welding j oint cannot
be obtained. Therefore, the content of each of P and S is
limited to be 0.03% or less. Here, regarding S, since
inclusions of S can be used as trap sites of hydrogen, it is
preferably specified to be 0.0004%≤S≤0.0025%. When S is less
than 0.0004%, appropriate amount of dispersed inclusions
cannot be secured, and the trap sites of hydrogen are decreased,
consequently inclusions do not substantially exhibit an effect
on delayed fracture resistance. When S is more than 0.0025%,
the amount of inclusions is excessivelyincreased and therefore
ductile fracture strength is reduced, consequently toughness
may be degraded.
0: 0.0008%≤0≤0.0030%
0 is preferably specified to be 0.0008%≤O≤0.0030% since
inclusions can be used for trap sites of hydrogen. When 0 is
less than 0.0008%, appropriate amount of dispersed inclusions
cannot be secured, and the trap sites of hydrogen are decreased,
10

consequently inclusions do not exhibit the effect on delayed
fracture resistance as the inclusions. When 0 is more than
0.0030%, the amount of inclusions is excessively increased and
therefore ductile fracture strength is reduced, consequently
toughness may be degraded.
At least one selected from Mo, Nb, V and Ti
When the steel material contains at least one of Mo, Nb,
V and Ti, the steel material has an effect of trapping
diffusible hydrogen and thus improving the delayed fracture
resistance property. Therefore, the steel material contains
at least one of Mo of 0.01 to 1%, Nb of 0.001 to 0.1%, V of
0.001 to 0.5% and Ti of 0.001 to 0.1%.
Hereinafter, description is made on ranges in which Mo,
Nb, V and Ti are specified respectively.
Mo: 0.01 to 1%
Mo has a function of improving hardehability and strength,
in addition, traps diffusible hydrogen by forming carbides,
thereby improves the delayed fracture resistance property.
When Mo is added less than 0.01%, such a containing effect is
insufficient, and on the other hand, when it is added more than
1%, economic efficiency is reduced. Therefore, when Mo is
added, the content is limited to be 0.01 to 1%. In particular,
Mo has a function of increasing tempering softening resistance,
and is preferably added 0.2% or more to secure tensile strength
of 900 MPa or more.
11

Nb: 0.001 to 0.1%
Nb improves strength as a microalloying element, in
addition, traps diffusible hydrogen by forming carbides,
nitrides, or carbon-nitrides, so that improves the delayed
fracture resistance property. When Nb is added less than
0.001%, such an effect is insufficient, and on the other hand,
when it is added more than 0.1%, toughness of a weld heat
affected zone is degraded. Therefore, when Nb is added, the
content is limited to be 0.001 to 0.1%.
V: 0.001 to 0.5%
V improves strength as a microalloying element, in
addition, traps diffusible hydrogen by forming carbides,
nitrides, or carbon-nitrides, thereby improves the delayed
fracture resistance property. When V is added less than 0.001%,
such an effect is insufficient, and on the other hand, when
it is added more than 0.5%, toughness of a weld heat affected
zone is degraded. Therefore, when V is added, the content is
limited to be 0.001 to 0.5%.
Ti: 0.001 to 0.1%
Ti forms TiN during rolling heating or during welding,
thereby inhibits growth of austenite grains, and thereby
improves toughness of a base metal and weld heat affected zone,
in addition, traps diffusible hydrogen by forming carbides,
nitrides, or carbon-nitrides, thereby improves the delayed
fracture resistance property.
12

Furthermore, Ti has an effect of trapping diffusible
hydrogen by forming a composite precipitate with Mo or Nb,
thereby improving the delayed fracture resistance property.
However, when Ti is added less than 0.001%, such an effect is
insufficient, and on the other hand, when it is added more than
0.1%, toughness of a weld heat affected zone is degraded.
Therefore, when Ti is added, the content is limited to be 0.001
to 0.1%.
Furthermore, in the invention, the steel material may
contain the following components depending on a desired
property. That is, components that the steel material may
further contain depending on a desired property are as follows.
Cu: 2% or less
Cu has a function of improving strength by solution
hardening and precipitation hardening. However, when the
content of Cu exceeds 2%, cracking in hot working tends to occur
during heating a steel billet or welding. Therefore, when Cu
is added, the content is limited to be 2% or less.
Ni: 4% or less
Ni has a function of improving toughness and
hardenability. However, when the content of Ni exceeds 4%,
economic efficiency is reduced. Therefore, when Ni is added,
the content is limited to be 4% or less.
Cr: 2% or less
Cr has a function of improving strength and toughness,
13

and is excellent in high temperature strength property.
Therefore, when a steel material is intended to be increased
in strength, Cr is actively added, and particularly, Cr of 0.3%
or more is preferably added to obtain a property of tensile
strength of 900 MPa or more. However, when the content of Cr
exceeds 2%, weldability is degraded. Therefore, when Cr is
added, the content is limited to be 2% or less.
W: 4% or less
W has a function of improving strength. However, when
the content of W exceeds 2%, weldability is degraded.
Therefore, when W is added, the content is limited to be 2%
or less.
B: 0.003% or less
B has a function of improving hardenability. However,
when the content of B exceeds 0.003%, toughness is degraded.
Therefore, when B is added, the content is limited to be 0.003%
or less.
Ca: 0.01% or less
Ca is an element indispensable for morphology control
of sulfide based inclusions. However, when Ca is added more
than 0.01%, reduction in cleanliness is caused. Therefore,
when Ca is added, the content is limited to be 0.01% or less.
Preferably, regarding Ca, since inclusions of Ca can be
used as trap sites of hydrogen, it is specified to be
0.0010%≤Ca≤0.0030%. When Ca is less than 0 . 0010%, appropriate
14

amount of dispersed inclusions cannot be secured, and the trap
sites of hydrogen are decreased, consequently inclusions do
not substantially exhibit an effect on delayed fracture
resistance.
When Ca is more than 0.0030%, the amount of inclusions
is excessively increased and therefore ductile fracture
strength is reduced, consequently toughness may be degraded.
However, when Ca is specified to be 0.0010≤Ca≤0.0030%,
the amount of 0 in steel is specified to be 0.0008≤O≤0.0030%,
and ACR obtained by the following expression is specified to
be 0.2≤ACR≤1.0.
Here, in the expression,
ACR=(Ca-(0.18+130*Ca)*O)/1.25/S, Ca, 0 or S shows the content
(mass percent) in steel respectively.
ACR is specified to be 0.2≤ACR≤1.0 so that the composite
inclusion of CaS and MnS is actively used as the trap site of
hydrogen to improve the delayed fracture resistance property.
Ca, 0 and S are contained such that ACR satisfies such range,
thereby CaS and MnS are prevented from being crystallized as
nucleuses respectively, and can be dispersed as fine composite
inclusions.
As a result, hydrogen is trapped in interfaces between
the composite inclusions and a matrix, so that accumulation
of hydrogen in interfacial surface of only part of inclusions
can be suppressed. Furthermore, alloy carbides are
15

precipitated on surfaces of the composite inclusions in a
rapid-heating tempering process, thereby a larger amount of
hydrogen are trapped. When ACR is less than 0.2, a nucleus
of inclusions is MnS, and the inclusions are extended by rolling
and thereby tend to be initial points of delayed fracture,
consequently the delayed fracture resistance property is
sometimes degraded.
When ACR is 1.0 or more, a nucleus of inclusions is CaS,
and the inclusions tend to be coarse, and in some cases, the
coarse inclusions become initial points of delayed fracture,
consequently the delayed fracture resistance property is
degraded.
More preferably, ACR is in a range of 0.4≤ACR≤0.8.
In usual cases, since MnS is extended by rolling, and
hydrogen is accumulated in such extended portions, thereby
cracks tend to occur, Ca is added so as to satisfy ACR≥1.0,
so that S is fixed to perform morphology control of MnS.
REM: 0.02% or less
REM forms sulfides as REM (0, S) in steel and thus
decreases the amount of dissolved S in crystal grain boundaries,
so that it improves an SR crack resistance property. However,
when REM is added more than 0.02%, REM sulfides are
significantly accumulated in a precipitation zone, causing
degradation in material. Therefore, when REM is added, added
amount is limited to be 0.02% or less.
16

Mg: 0.01% or less
Mg is sometimes used as a molten-iron desulfurizing agent.
However, when Mg is added more than 0.01%, reduction in
cleanliness is caused. Therefore, when Mg is added, added
amount is limited to be 0.01% or less.
Next, description is made on the reason for limiting a
precipitation pattern of precipitates in the invention. First,
from a viewpoint of a microstructure of the precipitates, the
reason for limiting the precipitation pattern is described
below.
[Microstructure] In the invention, precipitates containing
at least one of elements selected from Mo, Nb, V and Ti have
an average grain size of 20 nm or less, and preferably 15 nm
or less. The number of precipitates contained in the steel
is at least 5 per 250000 nm2, and preferably at least 10 per
250000 nm2. (note; Here, the precipitates typically include
a carbide, nitride, carbon-nitride, and compound of them.)
The precipitates are observed by a transmission electron
microscope by using a sample of a thin film or extraction
replica or the like. The grain size is evaluated using a
circle-equivalent diameter from image analysis, and the
average grain size is, for example, assumed as a simple average
value for at least five, optional view fields using
precipitates observed in a view field 500 nm square as an
object.
17

While the precipitates containing at least one of
elements selected from Mo, Nb, V and Ti have an effect of
trapping diffusible hydrogen irrespectively of size, when the
average grain size is more than 20 nm, lattice matching is
reduced, leading to reduction in force of trapping diffusible
hydrogen. As a result, in the steel material, the effect of
improving the delayed fracture resistance property is reduced.
Thus, the average grain size is specified to be 20 nm or less,
and preferably 15 nm or less.
When density of the precipitates containing at least one
of elements selected from Mo, Nb, V and Ti is less than 5 per
250000 nm2, the amount of diffusible hydrogen trapped by the
precipitates is decreased, leading to reduction in effect of
improving the delayed fracture resistance property. Thus, the
precipitates are specified to be contained in a ratio of at
least 5 per 250000 nm2 or more, and preferably at least 10 per
250000 nm2.
Next, in a viewpoint of the residual austenite, the
reason for limiting the precipitation pattern is described
below.
[Residual austenite]
Residual austenite acts as a hydrogen trap site because
of high solid solubility of hydrogen, and thereby improves the
delayed fracture resistance property. However, such an effect
is not sufficient in a volume fraction of residual austenite
18

of less than 0.5%, but strength is reduced in a volume fraction
of more than 5%. Therefore, the residual austenite is
preferably specified to be in a volume fraction of 0.5 to 5%,
and more preferably in a volume fraction of 2 to 4%.
The volume fraction of the amount of residual austenite
is measured by, for example, quantizing peaks of the lattice
constant of austenite using X-ray diffraction.
Next, a manufacturing method of the invention is
described.
In the invention, a steel billet can be manufactured such
that the billet can be quenched from the Ar3 transformation
temperature or more, and a method of manufacturing a cast billet
from molten steel, or a method of manufacturing a steel billet
by rolling a cast billet is not particularly specified. Steel
ingoted by a converter method, an electric furnace method and
the like, or a slab manufactured by continuous casting, an ingot
mold method and the like can be used.
When a steel billet is manufactured by rolling a cast
billet, the cast billet as it is may be started to be subjected
to hot rolling without being cooled to the Ar3 transformation
temperature or less, or may be started to be subjected to hot
rolling after a cast billet that was once cooled is reheated
to the Ar3 transformation temperature or more.
If rolling is finished at the Ar3 transformation
temperature or more, other rolling conditions may not be
19

particularly specified. If rolling is performed at a
temperature of the Ar3 transformation temperature or more, the
rolling may be performed in a recrystallization range or a
non-recrystallization range.
In the invention, if quenching is started from a state
of an austenite single phase structure at the Ar3 transformation
temperature or more, the quenching may be performed directly
after hot rolling, or may be performed after reheating a
hot-rolled material.
As a heating method during tempering, if a required
heating rate is achieved, any of methods of induction heating,
resistance heating, infrared radiation heating, atmospheric
heating and the like can be used.
Next, description is made on a manufacturing condition
preferable for manufacturing steel in the invention. The
invention can be applied to steel materials in various forms
such as a steel sheet, shape steel, and rod steel. In the
manufacturing condition, temperature is specified with
temperature at a central portion of the steel material, which
is a center in thickness in the steel sheet, a center in
thickness in a region, to which properties according to the
invention are added, in the shape steel, and a center in a radial
direction in the rod steel. However, since the neighborhood
of the central portion is subjected to substantially the same
temperature history, the central portion is not limited to the
20

center itself.
A manufacturing condition preferable for manufacturing
the steel of the invention is described below from a viewpoint
of quenching and tempering.
A quenching condition in the invention is as follows.
To secure strength and toughness of a base metal,
quenching is performed from a temperature of the Ar3
transformation temperature or more to a temperature of 500°C
or less. In the quenching, cooling is performed at a rate of
0.5°C/sec or more, and preferably l°C/sec or more.
These are specified to complete transformation from
austenite to martensite or bainite to reinforce a base metal.
While an expression for obtaining the Ar3 transformation
temperature (°C) is not particularly specified in the invention,
for example, Ar3=910-310C-80Mn-20Cu-15Cr-55Ni-80Mo is assumed.
In the expression, each elemental symbol shows the content
(mass percent) in steel.
A tempering condition in the invention is as follows.
During tempering, an average heating rate is set to be
l°C/sec or more, and preferably set to be 2°C/sec or more from
a tempering start temperature to a predetermined tempering
temperature. In the case that steel is temporarily cooled to
room temperature due to reheating quenching, the average
heating rate is also set to be l°C/sec or more, and preferably
set to be 2°C/sec or more during tempering.
21

Behavior of formation or growth of precipitates formed
during tempering, including, alloy carbides, alloy nitrides,
alloy carbon-nitrides and the like is affected by a heating
rate during tempering, and when the average heating rate is
also set to be l°C/sec or more, and preferably set to be 2°C/sec
or more, fine dispersion of precipitates is achieved.
When the rate is less than l°C/sec, since C is diffused
into grain boundaries or lath interfaces before carbides or
carbon-nitrides precipitate, only coarse carbides or
carbon-nitrides can be obtained, consequently an effect of
finely dispersing carbides or carbon-nitrides to be as trap
sites of hydrogen is not obtained.
Furthermore, in tempering, when a temperature range
where a heating rate at 600°C or more is at least 10°C/sec is
included, an alloy element is substituted for Fe in dispersedly
precipitated cementite, which preferably accelerates
precipitation of fine alloy carbides.
When a steel material is increased in strength to have
a tensile strength of 900 MPa or more, it is preferable for
obtaining a well-balanced property of high strength and high
toughness that tempering temperature is set to be in a range
of 450 to 550°C.
Furthermore, for a heating process during tempering, it
is enough that a predetermined average heating rate is obtained,
and either of a linear temperature history, and a temperature
22

history in which temperature is retained during heating may
be used, that is, a temperature history is not particularly
specified.
Holding time at tempering temperature is desirably 60
sec or less to prevent degradation in productivity, or
degradation in delayed fracture resistance property due to
coarsening of precipitates.
Regarding a cooling rate after tempering, it is desirable
that an average cooling rate is set to be 0.05°C/sec or more
from the tempering temperature to 200°C to prevent coarsening
of precipitates during cooling.
According to the above conditions, since the amount of
trapped diffusible hydrogen due to the precipitates is
increased, the amount of diffusible hydrogen accumulated in
a stress concentration portion is decreased, consequently the
delayed fracture resistance property is improved compared with
that of usual steel materials.
[Example]
Effectiveness of the invention is described using an
example. Steel A to steel P and Steel Q to steel U of chemical
composition shown in Tables 1 and 4 were ingoted and casted
into slabs, then the slabs were heated in a heating furnace
and then rolled into steel sheets. After rolling,
successively, the steel sheets were directly quenched, and then
23

subjected to tempering using a solenoid-type induction heating
apparatus.
An average heating rate at a central portion in thickness
was controlled by using threading speed of a steel sheet. When
a steel sheet was held at the tempering temperature, the steel
sheet was heated while being reciprocated, so that it was held
within a variation range of ±5°C.
As cooling after heating, air cooling was used.
Temperature such as tempering temperature or quenching
temperature at a central portion in thickness was obtained by
heat transfer calculation from a result of sequential
temperature measurement of a surface using a radiation
thermometer.
Table 2 shows manufacturing conditions of the steel
sheets, average grain size of precipitates, density of the
precipitates, and volume fractions of residual austenite, and
Table 3 shows yield strength, tensile strength, fracture
transition temperature (vTrs), and amount of critical
diffusible hydrogen.
For the size and density of the precipitates,
precipitates extracted by using an extraction replica were
photographed using a transmission electron microscope, then
average was obtained for five, optional view fields using
precipitates observed in a view field 500 nm square as an object.
Grain size was evaluated using a circle-equivalent diameter
24

from image analysis.
The volume fraction of residual austenite was measured
by quantizing peaks of the lattice constant of austenite using
X-ray diffraction.
The yield strength and the tensile strength were measured
using full-thicknes.s tensile test pieces, and the toughness
was evaluated by vTrs obtained by a Charpy impact test using
test pieces sampled from central portions in thickness.
Furthermore, the amount of critical diffusible hydrogen
was defined as maximum amount of diffusible hydrogen at which
delayed fracture did not occur within 100 hr under constant
load of 90% of tensile strength, and a round-bar tensile test
piece with circular notch was used as a test piece, and the
amount of diffusible hydrogen was measured by gas
chromatography method.
An objective value of the amount of critical diffusible
hydrogen was set to be at least 0.2 ppm by mass for a steel
type having a tensile strength of 1200 MP or more, and set to
be at least 0.3 ppm by mass for a steel type having a tensile
strength of less than 1200 MP.
25

CM

00

Table 3
No. Steeltype Thickness(mm) Yield strength(Mpa) Tensilestrength(MPa) vTrs at centralportion inthickness(°C) Amount ofcriticaldiffusiblehydrogen(mass ppm) Remarks
1 A 10 595 672 -120 2.35 Example of the invention
2 B 25 601 685 -126 1.69 Example of the invention
3 C 25 821 870 -91 1.33 Example of the invention
4 D 25 1023 1046 -83 1.01 Example of the invention
5 E 25 1011 1039 -88 0.89 Example of the invention
6 F 12 1098 1120 -71 0.75 Example of the invention
7 G 25 1067 1097 -75 0.69 Example of the invention
8 H 50 1011 1034 -76 0.66 Example of the invention
9 I 12 1352 1378 -59 0.69 Example of the invention
10 J 25 1335 1350 -55 0.53 Example of the invention
11 K 50 1295 1311 -51 0.52 Example of the invention
12 L 25 1492 1522 -39 0.48 Example of the Invention
13 G 6 1292 1310 -68 0.66 Example of the invention
14 I 12 1413 1423 -55 0.63 Example of the invention
15 J 25 1398 1411 -51 0.50 Example of the invention
16 K 60 1326 1342 •43 0.50 Example of the invention
17 M 25 815 869 -67 0.26 Comparative example
18 N 25 1000 1019 -56 0.19 Comparative example
19 0 25 1093 1112 -43 0.26" Comparative example
20 P 25 1308 1368 -17 0.15 Comparative example
21 A 10 541 619 -135 0.26 Comparative example
22 B 25 517 591 -145 0.29 Comparative example
23 C 25 810 862 -65 0.24' Comparative example
24 D 25 1011 1036 -52 0.23' Comparative example
25 E 25 1005 1029 -51 0.15' Comparative example
26 F 12 1121 1136 -43 0.19 Comparative example
27 G 25 1083 1103 -38 0.16' Comparative example
28 H 50 1011 1028 -36 0.09' Comparative example
29 I 12 1351 1369 -29 0.14' Comparative example
30 J 25 1332 1362 -24 0.11 Comparative example
31 K 50 1287 1305 -26 0.16 Comparative example
32 L 25 1453 1516 -18 0.05 Comparative example
33 Q 25 970 1180 -98 2.56 Example of the invention
34 R 30 1000 1210 -88 2.10 Example of the invention
35 S 35 1150 1350 -75 1.48 Example of the invention
36 S 35 1215 1388 -77 1.85 Example of the invention
37 T 50 1250 1480 -78 1.44 Example of the invention
38 T 50 1300 1450 -78 1.99 Example of the invention
39 U 60 1320 1460 -86 1.56 Example of the invention
Note A mark * shows the value is out of the range of the invention.
29

o
m

As clear from Table 3, in steel sheets Nos. 1 to 16
manufactured by the method of the invention (examples of the
invention), in which the chemical composition, manufacturing
method, precipitation pattern of precipitates, or volume
fraction of residual austenite is within a range of the
invention, high amount of critical diffusible hydrogen was able
to be obtained. Furthermore, in steel sheets Nos. 33 to 39
(examples of the invention), in which ACR is within a range
of the invention, comparatively higher amount of critical
diffusible hydrogen was able to be obtained.
On the contrary, in comparative steel sheets Nos. 17 to
32 (comparative examples), the amount of critical diffusible
hydrogen is out of the objective range. Hereinafter, the
comparative examples are individually described.
In steel sheets Nos. 17 to 20, in which each composition
is out of the range of the invention, both of the density of
precipitates and the volume fraction of residual austenite are
out of the range of the invention, and the amount of critical
diffusible hydrogen does notreach to the objective value.
In a steel sheet No. 21, in which direct quenching start
temperature is out of the range of the invention, both of the
density of precipitates and the volume fraction of residual
austenite are out of the range of the invention, and the amount
of critical diffusible hydrogen does not reach to the objective
value.
31

In a steel sheet No. 22, in which direct quenching stop
temperature is out of the range of the invention, both of the
density of precipitates and the volume fraction of residual
austenite are out of the range of the invention, and the amount
of critical diffusible hydrogen does not reach to the objective
value.
In steel sheets Nos. 23 to 32, in which each average
heating rate at a central portion of a steel material from a
tempering start temperature to a predetermined tempering
temperature is out of the range of the invention, numeral values
of any two among the average grain size of precipitates, density
of the precipitates, and volume fraction of residual austenite
are out of the range of the invention, and the amount of critical
diffusible hydrogen does not reach to the objective value.
Industrial Applicability
According to the invention, a high tensile strength steel
material having an extremely excellent, delayed fracture
resistance property, of which tensile strength is 600 MPa or
more, and particularly 900 MPa or more, can be manufactured,
which is industrially extremely useful.
32

Claims
1. A high tensile strength steel material having an excellent
delayed fracture resistance property, comprising:
elements of, in mass percent, C of 0.02 to 0.25%, Si of
0.01 to 0.8%, Mn of 0.5 to 2.0%, Al of 0. 005 to 0.1%, N of 0.0005
to 0.008%, P of 0.03% or less, and S of 0.03% or less, and
at least one element selected from, in mass percent, Mo
of 0.01 to 1%, Nb of 0.001 to 0.1%, V of 0.001 to 0.5%, and
Ti of 0.001 to 0.1%, and
the remainder being Fe and inevitable impurities,
wherein precipitates contained in steel include at least
one of elements selected from Mo, Nb, V and Ti,
an average grain size of the precipitates is 20 nm or
less, and
the number of existing precipitates is at least 5 per
250000 nm2.
2. The high tensile strength steel material having an excellent
delayed fracture resistance property according to claim 1:
Wherein the steel composition further contains at least
one element among Cu of 2% or less, Ni of 4% or less, Cr of
2% or less, and W of 2% or less, in mass percent.
3. The high tensile strength steel material having an excellent
33

delayed fracture resistance property according to claim 1 or
2:
wherein the steel composition further contains at least
one element among B of 0.003% or less, Ca of 0.01% or less,
REM of 0.02% or less, and Mg of 0.01% or less, in mass percent.
4. The high tensile strength steel material having an excellent
delayed fracture resistance property according to any one of
claims 1 to 3:
wherein the high tensile strength steel material further
contains the elements of 0.0004≤S≤0.0025%, 0.0010≤Ca≤0.0030%,
and 0.0008≤0≤0.0030% in mass percent; and
ACR obtained by the following expression satisfies
0.2≤ACR≤1.0, here,
ACR=(Ca-(0.18+130*Ca)*O) /1.25/S is given,
wherein Ca, 0 or S shows the content (mass percent) of
each component.
5. A high tensile strength steel material having an excellent
delayed fracture resistance property, comprising:
elements of, in mass percent, C of 0.02 to 0.25%, Si of
0.01 to 0.8%, Mn of 0.5 to 2.0%, Al of 0.005 to 0.1%, N of 0.0005
to 0.008%, P of 0.03% or less, 0.0004%≤S≤0.0025%,
0.0010%≤Ca≤0.0030%, and 0.0008%≤O≤0.0030%, and
at least one of elements selected from Mo of 0.01 to 1%,
34

Nb of 0.001 to 0.1%, V of 0.001 to 0.5%, and Ti of 0.001 to
0.1%, in mass percent, and
a value of ACR obtained by the following expression
satisfies 0.2≤ACR≤1.0, and
the remainder including Fe and inevitable impurities,
and
precipitates contained in steel include at least one of
elements selected from Mo, Nb, V and Ti,
an average grain size of the precipitates is 20 nm or
less, and
the number of existing precipitates is at least 5 per
250000 nm2, here
ACR=(Ca-(0.18 + 130*Ca)*O)/1.25/S is given,
wherein Ca, 0 or S is the content (mass percent) of each
component.
6. The high tensile strength steel material having an excellent
delayed fracture resistance property according to clam 5,
further comprising:
a steel composition contained in steel containing at
least one element among Cu of 2% or less, Ni of 4% or less,
Cr of 2% or less, and W of 2% or less, in mass percent.
7. The high tensile.strength steel material having an excellent
delayed fracture resistance property according to claim 5 or
35

6:
wherein a steel composition contains at least one element
among B of 0.003% or less, REM of 0.02% or less, and Mg of 0.01%
or less, in mass percent.
8 . The high tensile strength steel material having an excellent
delayed fracture resistance property according to any one of
claims 1 to 7;
wherein the steel material includes residual austenite
in a volume fraction of 0.5 to 5% in a microstructure.
9. A method of manufacturing the high tensile strength steel
material having an excellent delayed fracture resistance
property according to any one of claims 1 to 7, comprising:
a step of quenching the steel material from a temperature
of Ar3 transformation temperature to a temperature of 500°C
or less, and
a step of tempering the steel material while a central
portion of the steel material is heated from a tempering start
temperature to a predetermined tempering temperature at an
average heating rate of l°C/s or more, after the quenching.

36

The invention provides a high tensile strength steel
material having a tensile strength of 600 MPa, which is
excellent in delayed fracture resistance property, and a method
of manufacturing the steel material. As means for this, a steel
material contains, in mass percent, C of 0.02 to 0.25%, Si of
0.01 to 0.8%, Mn of 0.5 to 2.0%, Al of 0.005 to 0.1%, N of 0.0005
to 0.008%, P of 0.03% or less, and S of 0.03% or less. In
addition, the steel material contains at least one element
selected from Mo, Nb, V, and Ti, and contains at least one of
Cu, Ni, Cr, W, B, Ca, REM and Mg, as needed. The remainder
includes Fe and inevitable impurities. In addition, in the
steel material, precipitates having an average grain size of
20 nm or less, which contains at least one of Mo, Nb, V and
Ti, are contained in steel in the number of at least 5 per 250000
nm2, and a microstructure includes residual austenite in a
volume fraction of 0.5 to 5%. When Ca to be added is specified
to be 0.0010% to 0.0020%, it is specified that S is 0.0005%
to 0.0020% and O is 0.0008% to 0.0025%. ACR is specified to
be 0.2≤ACR(=(Ca-(0.18+130*Ca)*O)/1.25/S)≤l.0.

Documents:

02708-kolnp-2007-abstract.pdf

02708-kolnp-2007-claims.pdf

02708-kolnp-2007-correspondence others 1.1.pdf

02708-kolnp-2007-correspondence others 1.2.pdf

02708-kolnp-2007-correspondence others 1.3.pdf

02708-kolnp-2007-correspondence others.pdf

02708-kolnp-2007-description complete.pdf

02708-kolnp-2007-form 1.pdf

02708-kolnp-2007-form 18.pdf

02708-kolnp-2007-form 2.pdf

02708-kolnp-2007-form 3.pdf

02708-kolnp-2007-form 5.pdf

02708-kolnp-2007-gpa.pdf

02708-kolnp-2007-pct request form.pdf

02708-kolnp-2007-priority document.pdf

02708-kolnp-2007-translated copy of priority document.pdf

2708-KOLNP-2007-(20-03-2012)-ABSTRACT.pdf

2708-KOLNP-2007-(20-03-2012)-CLAIMS.pdf

2708-KOLNP-2007-(20-03-2012)-DESCRIPTION (COMPLETE).pdf

2708-KOLNP-2007-(20-03-2012)-EXAMINATION REPORT REPLY RECIEVED.PDF

2708-KOLNP-2007-(20-03-2012)-FORM-1.pdf

2708-KOLNP-2007-(20-03-2012)-FORM-2.pdf

2708-KOLNP-2007-(20-03-2012)-FORM-3.pdf

2708-KOLNP-2007-(20-03-2012)-OTHERS.pdf

2708-KOLNP-2007-(20-03-2012)-PETITION UNDER RULE 137.pdf

2708-KOLNP-2007-CORRESPONDENCE 1.1.pdf

2708-KOLNP-2007-CORRESPONDENCE 1.2.pdf

2708-KOLNP-2007-FORM 13.pdf

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Patent Number

252236

Indian Patent Application Number

2708/KOLNP/2007

PG Journal Number

18/2012

Publication Date

04-May-2012

Grant Date

02-May-2012

Date of Filing

23-Jul-2007

Name of Patentee

JFE STEEL CORPORATION

Applicant Address

2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO

Inventors:

#	Inventor's Name	Inventor's Address
1	AKIHIDE NAGAO	C/O. INTELLECTUAL PROPERTY DEPARTMENT JFE STEEL CORPORATION, 2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO 100-0011
2	KENJI OI	C/O. INTELLECTUAL PROPERTY DEPARTMENT JFE STEEL CORPORATION, 2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO 100-0011
3	KENJI HAYASHI	C/O. INTELLECTUAL PROPERTY DEPARTMENT JFE STEEL CORPORATION, 2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO 100-0011

PCT International Classification Number

C22C 38/00

PCT International Application Number

PCT/JP06/311157

PCT International Filing date

2006-05-29

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2006-145407	2006-05-25	Japan
2	2005-157275	2005-05-30	Japan