High-strength low-alloy steel excellent in high-pressure hydrogen environment embrittlement resistance characteristics and method for producing the same

Abstract

An object of the present invention is to provide at a low cost a low-alloy steel having a high strength and excellent high-pressure hydrogen environment embrittlement resistance characteristics under a high-pressure hydrogen environment. The invention is a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics, which has a composition comprising C: 0.10 to 0.20% by mass, Si: 0.10 to 0.40% by mass, Mn: 0.50 to 1.20% by mass, Ni: 0.75 to 1.75% by mass, Cr: 0.20 to 0.80% by mass, Cu: 0.10 to 0.50% by mass, Mo: 0.10 to 1.00% by mass, V: 0.01 to 0.10% by mass, B: 0.0005 to 0.005% by mass and N: 0.01% by mass or less, and further comprising one or two of Nb: 0.01 to 0.10% by mass and Ti: 0.005 to 0.050% by mass, with the balance consisting of Fe and unavoidable impurities.

Claims

1. A method for producing a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics, the method comprising: melting an alloy steel material having a composition comprising C: 0.10 to 0.20% by mass, Si: 0.10 to 0.40% by mass, Mn: 0.50 to 1.20% by mass, Ni: 0.75 to 1.75% by mass, Cr: 0.20 to 0.80% by mass, Cu: 0.10 to 0.50% by mass, Mo: 0.10 to 1.00% by mass, V: 0.01 to 0.10% by mass, B: 0.0005 to 0.005% by mass and N: 0.01% by mass or less, and further comprising one or two of Nb: 0.01 to 0.10% by mass and Ti: 0.005 to 0.050% by mass, with the balance consisting of Fe and unavoidable impurities to form a steel ingot; subjecting the steel ingot to hot-working to provide a hot-worked material; after the hot-working, performing normalizing at 1,000 C. to 1,100 C. to homogenize a structure, wherein the normalizing is performed by heating the hot-worked material at 1,000 C. to 1,100 C. and then cooling; after the normalizing, performing quenching from the temperature range of 880 C. to 900 C. to impart an optimum crystal grain size, wherein the quenching is performed by heating to 880 C. to 900 C. and then cooling; and after the quenching, performing tempering at 560 C. to 580 C. to impart an optimum tensile strength, wherein the tempering is performed by heating to 560 C. to 580 C.

2. A method for producing a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics according to claim 1, wherein the composition comprises C: 0.10 to 0.20% by mass, Si: 0.10 to 0.40% by mass, Mn: 0.50 to 1.20% by mass, Ni: 0.75 to 1.75% by mass, Cr: 0.20 to 0.80% by mass, Cu: 0.10 to 0.50% by mass, Mo: 0.10 to 1.00% by mass, V: 0.01 to 0.10% by mass, B: 0.0005 to 0.005% by mass and N: 0.01% by mass or less, and further comprises Nb: 0.01 to 0.10% by mass and Ti: 0.005 to 0.050% by mass, with the balance consisting of Fe and unavoidable impurities.

3. A method for producing a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics according to claim 1, wherein the composition comprises C: 0.10 to 0.20% by mass, Si: 0.10 to 0.40% by mass, Mn: 0. 50 to 1.20% by mass, Ni: 0.75 to 1.75% by mass, Cr: 0.20 to 0.80% by mass, Cu: 0.10 to 0.50% by mass, Mo: 0.10 to 1.00% by mass, V: 0.01 to 0.10% by mass, B: 0.0005 to 0.005% by mass and N: 0.01% by mass or less, and further comprises Ti: 0.005 to 0.050% by mass, with the balance consisting of Fe and unavoidable impurities.

4. A method for producing a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics according to claim 1, wherein the composition further comprises Ti: 0.012 to 0.032% by mass.

5. A method for producing a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics according to claim 1, wherein the composition further comprises Ti: 0.032 to 0.050% by mass.

6. A method for producing a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics, the method consisting of: melting an alloy steel material having a composition comprising C: 0.10 to 0.20% by mass, Si: 0.10 to 0.40% by mass, Mn: 0.50 to 1.20% by mass, Ni: 0.75 to 1.75% by mass, Cr: 0.20 to 0.80% by mass, Cu: 0.10 to 0.50% by mass, Mo: 0.10 to 1.00% by mass, V: 0.01 to 0.10% by mass, B: 0.0005 to 0.005% by mass and N: 0.01% by mass or less, and further comprising one or two of Nb: 0.01 to 0.10% by mass and Ti: 0.005 to 0.050% by mass, with the balance consisting of Fe and unavoidable impurities to form a steel ingot; subjecting the steel ingot to hot-working to provide a hot-worked material; after the hot-working, performing normalizing at 1,000 C. to 1,100 C. to homogenize a structure, wherein the normalizing is performed by heating the hot-worked material at 1,000 C. to 1,100 C. and then cooling; after the normalizing, performing quenching from the temperature range of 880 C. to 900 C. to impart an optimum crystal grain size, wherein the quenching is performed by heating to 880 C. to 900 C. and then cooling; and after the quenching, performing tempering at 560 C. to 580 C. to impart an optimum tensile strength, wherein the tempering is performed by heating to 560 C. to 580 C.

7. A method for producing a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics according to claim 6, wherein the composition comprises C: 0.10 to 0.20% by mass, Si: 0.10 to 0.40% by mass, Mn: 0.50 to 1.20% by mass, Ni: 0.75 to 1.75% by mass, Cr: 0.20 to 0.80% by mass, Cu: 0.10 to 0.50% by mass, Mo: 0.10 to 1.00% by mass, V: 0.01 to 0.10% by mass, B: 0.0005 to 0.005% by mass and N: 0.01% by mass or less, and further comprises Nb: 0.01 to 0.10% by mass and Ti: 0.005 to 0.050% by mass, with the balance consisting of Fe and unavoidable impurities.

8. A method for producing a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics according to claim 6, wherein the composition comprises C: 0.10 to 0.20% by mass, Si: 0.10 to 0.40% by mass, Mn: 0. 50 to 1.20% by mass, Ni: 0.75 to 1.75% by mass, Cr: 0.20 to 0.80% by mass, Cu: 0.10 to 0.50% by mass, Mo: 0.10 to 1.00% by mass, V: 0.01 to 0.10% by mass, B: 0.0005 to 0.005% by mass and N: 0.01% by mass or less, and further comprises Ti: 0.005 to 0.050% by mass, with the balance consisting of Fe and unavoidable impurities.

9. A method for producing a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics according to claim 6, wherein the composition further comprises Ti: 0.012 to 0.032% by mass.

10. A method for producing a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics according to claim 6, wherein the composition further comprises Ti: 0.032 to 0.050% by mass.

11. A method for producing a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics according to claim 1, wherein Al is not present in the composition of the alloy steel material.

12. A method for producing a high-strength low-alloy steel having high-pressure hydrogen environment embrittlement resistance characteristics according to claim 6, wherein Al is not present in the composition of the alloy steel material.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a graph showing relationship between tensile strength in the air and relative reduction of area (a ratio of reduction of area in hydrogen of 45 MPa and reduction of area in the air) of invention steels and comparative steels in Examples.

(2) FIG. 2 is a graph showing relationship between the tensile strength in the air and reduction of area of invention steels and comparative steels in Examples.

(3) FIG. 3 is a graph showing relationship between a crystal grain size number and the relative reduction of area of invention steels and comparative steels in Examples.

(4) FIG. 4 is a graph showing relationship between an average grain size and the relative reduction of area of invention steels and comparative steels in Examples.

(5) FIGS. 5(a) and 5(b) are views showing a fracture surface of a tensile test piece in hydrogen of 45 MPa of invention steel 6 in Examples, and FIG. 5(c) is a view showing a fracture surface of a tensile test piece in hydrogen of 45 MPa of comparative steel 1.

MODE FOR CARRYING OUT THE INVENTION

(6) The limited ranges of the components and the like in the invention will be described below in detail. The following component contents are all represented by mass percentage.

(7) C (Carbon): 0.10 to 0.20%

(8) C is a component effective for improving the strength of the steel, and in order to secure the strength as a steel for welding, the lower limit value thereof is decided to be 0.10%. The excessive inclusion thereof extremely deteriorates weldability of the steel, so that the upper limit value thereof is taken as 0.20%. Preferably, the lower limit is 0.14%, and the upper limit is 0.16%.

(9) Si (Silicon): 0.10 to 0.40%

(10) Si is a component necessary for securing the strength of a base material, deoxidation and the like, and in order to obtain the effects thereof, the lower limit value thereof is taken as 0.10%. However, the excessive inclusion thereof causes a decrease in toughness of a welded part, so that the upper limit value thereof is taken as 0.40%. Preferably, the lower limit is 0.18%, and the upper limit is 0.32%.

(11) Mn (Manganese): 0.50 to 1.20%

(12) Mn is a component effective for strengthening of the steel, and the lower limit value thereof is decided to be 0.50%. However, the excessive inclusion thereof causes a decrease in toughness or a crack of a welded part, so that the upper limit value thereof is taken as 1.20%. Preferably, the lower limit is 0.80%, and the upper limit is 0.84%.

(13) Cr (Chromium): 0.20 to 0.80%

(14) Cr improves the strength of the steel, but the excessive inclusion thereof deteriorates weldability. Accordingly, the lower limit value thereof is taken as 0.200%, and the upper limit value thereof is taken as 0.80%. Preferably, the lower limit is 0.47%, and the upper limit is 0.57%.

(15) Ni (Nickel): 0.75 to 1.75%

(16) Ni is an element effective for improving the strength and hardenability of the steel, but too much Ni causes deterioration of hydrogen environment embrittlement resistance characteristics. Accordingly, the lower limit value thereof is taken as 0.75%, and the upper limit value thereof is taken as 1.75% herein. Preferably, the lower limit is 0.70%, and the upper limit is 1.55%.

(17) Cu (Copper): 0.10 to 0.50%

(18) Cu improves the strength of the steel, but the excessive inclusion thereof increases crack susceptibility at the time of welding. Accordingly, the lower limit value thereof is taken as 0.10%, and the upper limit value thereof is taken as 0.50%. Preferably, the lower limit is 0.20%, and the upper limit is 0.40%. More preferably, the lower limit is 0.31%, and the upper limit is 0.33%.

(19) Mo (Molybdenum): 0.10 to 1.00%

(20) Mo is an element effective for strengthening of the steel, but the excessive inclusion thereof deteriorates weldability, and causes an increase in cost. Accordingly, the lower limit value thereof is taken as 0.10%, and the upper limit value thereof is taken as 1.00%. Preferably, the lower limit is 0.45%, and the upper limit is 0.55%.

(21) V (Vanadium): 0.01 to 0.10%

(22) V is an element important to secure the strength of the steel, but too much has an adverse effect on toughness. Accordingly, the lower limit value thereof is taken as 0.01%, and the upper limit value thereof is taken as 0.10%. Preferably, the lower limit is 0.04%, and the upper limit is 0.06%.

(23) B (Boron): 0.0005 to 0.005%

(24) B is an element effective for strengthening of the steel and also effective for improvement of hardenability, so that the lower limit value thereof is taken as 0.0005%. On the other hand, the excessive inclusion thereof causes a reduction in weldability, so that the upper limit value thereof is taken as 0.005%. Preferably, the upper limit is 0.002%.

(25) N (Nitrogen): 0.01% or Less

(26) When N exceeds 0.01%, solid solution N increases to cause a decrease in toughness of a welded part. Accordingly, the upper limit value thereof is taken as 0.01%.

(27) Nb (Niobium): 0.01 to 0.10%

(28) Ti (Titanium): 0.005 to 0.050%

(29) Nb and Ti are elements effective for grain refining of the steel, so that one or two thereof are allowed to be contained. However, less than 0.01% of Nb or less than 0.005% of Ti results in a failure to obtain the sufficient function. Accordingly, the lower limit value of Nb is decided to be 0.01%, and the lower limit value of Ti is decided to be 0.005%. Incidentally, when one component is contained in an amount of the lower limit or more, the other component may be contained as an impurity in an amount of less than the lower limit. On the other hand, the excessive inclusion of Nb results in saturation of the effect, and moreover, causes a reduction in weldability, so that the upper limit value thereof is decided to be 0.10%. Further, the excessive inclusion of Ti causes a decrease in toughness due to excessive deposition of TiC, so that the upper limit value thereof is decided to be 0.05%. Preferably, the lower limit of Nb is 0.02% and the upper limit thereof is 0.06%, and the lower limit of Ti is 0.01% and the upper limit thereof is 0.04%.

(30) Balance: Fe and Unavoidable Impurities

(31) In the high-strength low-alloy steel of the invention, the balance consists of Fe and unavoidable impurities. The unavoidable impurities include P and S.

(32) P (Phosphorus): 0.005% or Less

(33) In terms of preventing deterioration in hot-workability, it is preferable that the content of P is as small as possible. Taking industrial efficiency into account, the upper limit value thereof is taken as 0.005%.

(34) S (Sulfur): 0.002% or Less

(35) In terms of preventing deterioration in hot-workability and a decrease in toughness, it is preferable that the content of S is as small as possible. Taking industrial efficiency into account, the upper limit value thereof is taken as 0.002%.

(36) Crystal Grain Size Number: 8.4 or more

(37) The crystal grain size number was measured by a comparison method based on a ferrite crystal grain size test method for steels specified in JIS G 0552. The grain size after heat treatment is preferably 8.4 or more. The hydrogen environment embrittlement resistance characteristics excellent compared to those of conventional steels can be exhibited by adjusting the grain size to 8.4 or more. In the case of less than 8.4, the grain size is equal to or smaller than that of conventional steels, and improvement of the hydrogen environment embrittlement resistance characteristics cannot be expected.

(38) Tensile Strength: 900 to 950 MPa

(39) As a target strength, the tensile strength in the air after heat treatment is taken as 900 MPa or more. However, exceeding 950 MPa results in an increase insusceptibility to hydrogen environment embrittlement, so that the upper limit is taken as 950 MPa. Incidentally, this tensile strength is the strength at room temperature.

(40) As heat treatment conditions to the alloy steel having the above-described composition, the following conditions are shown.

(41) Normalizing Temperature: 1,000 C. to 1,100 C.

(42) In order to remove strain at the time of forging, the normalizing temperature is decided to be 1,000 C. to 1,100 C.

(43) Quenching Temperature: 880 to 900 C.

(44) In order to impart the optimum crystal grain size, the quenching temperature is decided to be 880 to 900 C.

(45) Tempering Temperature: 560 C. to 580 C.

(46) In order to impart the optimum tensile strength at room temperature in the air, the tempering temperature is decided to be 560 C. to 580 C.

(47) One embodiment of the invention will be described below.

(48) Alloy steel raw materials adjusted to the composition of the invention are melted to obtain an ingot. A method for melting the alloy steel raw materials is not particularly limited as the invention, and the ingot can be obtained by a conventional method.

(49) The ingot can be subjected to hot-working (hot rolling, hot forging or the like) by a conventional method, and conditions and the like in the hot-working are not particularly limited as the invention.

(50) After the hot-working, suitably, normalizing is performed to a hot-worked material to homogenize a structure. The normalizing can be performed, for example, by heating at 1,100 C. for two hours, followed by furnace cooling.

(51) Further, a quenching-tempering treatment can be performed as heat treatment.

(52) Quenching can be performed by heating, for example, to 880 to 900 C. and rapid cooling. After the quenching, tempering in which heating is performed can be performed at 560 to 580 C., for example. In the tempering, it is preferable to adjust the tempering parameter represented by T (logt+20)10.sup.3 for the tempering temperature T (K) and time t (hr.) within the range of 18.0 to 18.5.

(53) In the invention steel, the tensile strength in the air can be set to 900 to 950 MPa, and the crystal grain size can be adjusted to a grain size number of 8.4 or more in the comparison method of JIS G 0552 (the ferrite crystal grain size test method for steels), by heat treatment. The low-alloy high-strength steel shows an excellent reduction of area and excellent elongation characteristics even in a hydrogen atmosphere of 45 MPa.

EXAMPLES

(54) Examples of the invention will be described in detail below.

(55) A material under test having a composition (the balance was the other unavoidable impurities) shown in Table 1 was melted in a vacuum induction melting furnace to prepare a 50 kg round steel ingot, the thickness of which was adjusted to 35 mm by hot forging. In this test, heat treatment was performed at a thickness of 35 mm after hot forging as a production method. Incidentally, the Ti amount in example Nos. 1 and 2 and the Nb amount in example Nos. 3 and 4 are less than the analytical lower limit (Ti<0.0005%, Nb<0.01%).

(56) The normalizing temperature in invention steels 1 to 7 was 950 C., the quenching temperature was from 880 C. to 900 C., and the tempering was performed at 580 C. The tempering temperature T (K) and time t (h) were adjusted, and the tempering parameter represented by T(logt+20)10.sup.3 was varied within the range of 17.3 to 18.7, thereby adjusting the tensile strength in the air to the range of 900 to 950 MPa.

(57) The quenching temperature in comparative steel 1 was 920 C., and tempering was performed at 600 C. Incidentally, the tempering time was adjusted as 11 hours and 50 minutes, 34 hours, and 97 hours and 30 minutes.

(58) The normalizing temperature in comparative steel 2 was 1,200 C., and the quenching temperature was 950 C. Tempering was performed at 660 C. for 6 hours.

(59) The normalizing temperature in comparative steel 3 was 900 C., and the quenching temperature was 840 C. Tempering was performed at 600 C. for 35 hours.

(60) TABLE-US-00001 TABLE 1 Material Under Low-Alloy Steel Composition (mass %) Test No. C Si Mn P S Cr Mo Ni V Invention 1 0.15 0.26 0.84 <0.003 0.002 0.53 0.52 0.75 0.05 Steel 2 0.14 0.25 0.84 <0.003 0.002 0.53 0.52 0.76 0.05 3 0.14 0.25 0.84 <0.003 0.002 0.53 0.52 0.76 0.05 4 0.15 0.25 0.84 <0.003 0.001 0.53 0.52 0.76 0.05 5 0.15 0.24 0.85 <0.003 0.002 0.53 0.53 0.75 0.05 6 0.16 0.24 0.83 <0.003 0.002 0.53 0.51 1.02 0.05 7 0.15 0.25 0.84 <0.003 0.002 0.53 0.52 1.52 0.05 Comparative 1 0.15 0.23 0.97 0.006 <0.001 0.50 0.51 1.45 0.04 Steel 2 0.13 0.04 0.56 0.006 0.003 2.47 1.08 0.17 0.29 3 0.24 0.26 0.41 0.01 0.007 1.78 0.40 3.69 0.13 Material Under Low-Alloy Steel Composition (mass %) Remarks Test No. B Cu Nb N Ti Al Fe (Alloy Name) Invention 1 0.0011 0.31 0.031 0.0072 bal. Steel 2 0.0011 0.31 0.054 0.0072 bal. 3 0.0011 0.32 0.0074 0.012 bal. 4 0.001 0.32 0.0076 0.032 bal. 5 0.0009 0.32 0.036 0.0069 0.014 bal. 6 0.0011 0.31 0.029 0.0069 0.013 bal. 7 0.0009 0.31 0.029 0.0070 0.013 bal. Comparative 1 0.0009 0.23 bal. SHY685NSF Steel 2 0.0007 0.07 0.024 0.01 0.01 bal. F22V 3 0.008 <0.005 bal. 3.5NiCrMoV

(61) After the heat treatment, the test material was processed to a smooth bar tensile test specimen specified in JIS Z 2201, No. 14. A tensile test in hydrogen was performed under a hydrogen environment of 45 MPa using a high-pressure hydrogen environment fatigue tester. The tensile test was performed under conditions of ordinary temperature and a stroke rate of 0.0015 mm/s. The crystal grain size was measured on the basis of the comparison method specified in JIS G 0552.

(62) The relationship between the tensile strength in the air and the relative reduction of area (the ratio of reduction of area in hydrogen of 45 MPa and reduction of area in the air) of invention steels 1 to 7 and comparative steels 1 to 3 is shown in FIG. 1. The relative reduction of area of the invention steels showed a large reduction of area even when compared to the other kind of steels within 900 to 950 MPa as the target strength range. This shows that the invention steels have a higher strength than the comparative steels and are excellent in susceptibility to hydrogen environment embrittlement.

(63) The relationship between the tensile strength in the air and the reduction of area of invention steels 1 to 7 and comparative steels 1 to 3 is shown in FIG. 2. The invention steels showed a larger value than the conventional steels, also in the absolute value of the reduction of area.

(64) The relationship between the grain size number and the relative reduction of area of invention steels 1 to 7 and comparative steels 1 to 3 is shown in FIG. 3, and the relationship between the average grain size and the relative reduction of area of invention steels 1 to 7 and comparative steels 1 to 3 is shown in FIG. 4. The invention steels are approximately equivalent to or smaller than the comparative steel 1 in the grain size, and larger in the relative reduction of area. It is conceivable that the effect of grain refining due to the addition of Nb and Ti has been exerted.

(65) Views showing a fracture surface of a tensile test piece of invention steel 6 in hydrogen of 45 MPa, which has been observed under a scanning electron microscope (SEM), are shown in FIGS. 5(a) and 5(b). An observed view of a fracture surface of comparative steel 1 after the tensile test in hydrogen of 45 MPa is also shown in FIG. 5(c), for comparison. In comparative steel 1, a quasi-cleavage fracture surface is observed in the whole fracture surface. Compared with this, in invention steel 6, fine dimples having a diameter of 1 m or less are observed. It is therefore conceivable that a ductile fracture behavior has occurred also under the hydrogen environment of 45 MPa.

(66) The invention has been described based on the above-described embodiments and examples as described above. However, the invention is not intended to be limited to the description of the above-described embodiments and examples, and appropriate changes are of course possible without departing from the scope of the invention.

(67) Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The invention is based on Japanese Patent Application No. 2008-125838 filed on May 13, 2008, the contents of which are herein incorporated by reference.

INDUSTRIAL APPLICABILITY

(68) According to the invention, as a main advantage thereof, it becomes possible to prepare a high-pressure hydrogen pressure vessel at a lower cost than an austenitic stainless steel, as described above. Further, the strength is higher than that of a conventional steel, and susceptibility to hydrogen environment embrittlement is small, so that the design pressure can be increased, or the design thickness can be thinned. Furthermore, as a subordinate advantage, the amount of hydrogen loaded can be increased by an increase in the design pressure. In addition, the production cost of the container can be deceased by a decrease in the thickness of the container.