Heat resisting steel and steam turbine rotor shaft

Abstract: Disclosed is a heat resisting steel whose metal structure is entirely martensite phase produced by tempering after quenching. The steel comprises, by weight, 0.05 to 0.20% C, not more than 0.15% Si, not more than 1.5% Mn, not more than 1.0% Ni, 8.5 to 13.0% Cr, not more than 3.50% Mo, not more than 3.5% W, 0.05 to 0.30% V, 0.01 to 0.20% Nb, not more than 5.0% Co, 0.001 to 0.020% boron, 0.005 to 0.040% nitrogen, 0.0005 to 0.0050% oxygen and 0.00001 to 0.0002% hydrogen. The steel has preferably not more than 10 of the Cr equivalent. The steel has 10 kgf/mm 2 or more of 100000 hours creep rupture strength at 650°C.

Description: BACKGROUND OF THE INVENTION The present invention relates to a high strength heat resisting steel of a high temperature steam turbine in a thermal power plant of ultra supercritical pressure and a steam turbine rotor which is made of the heat resisting steel. In recent years, with regard to thermal power generation plants, considerable attentions have been payed to operating those under high temperature and high pressure in the view point of improving efficiency thereof, wherein it is intended to raise steam temperature of steam turbines up to 600°C from the highest steam temperature of 566°C at present, finally up to 650°C. In order to raise the steam temperature, a heat resisting material is required, which is excellent in high temperature strength than conventional ferritic heat resisting steel. Austenitic heat resisting alloys are hardly applied to such use since they are inferior in thermal fatigue strength due to a large thermal expansion coefficient and expensive in production cost, while some of them are excellent in high temperature strength. Thus, recently there have been proposed many new ferritic heat resisting steels which are improved in high temperature strength, for example, in JP-A-62-103345, JP-A-62-60845, JP-A-60-165360, JP-A-60-165359, JP-A-60-165358, JP-A-63-89644, JP-A-62-297436, JP-A-62-297435, JP-A-61-231139 and JP-A-61-69948 to all of which one of the present inventors participated. Among those ferritic heat resisting steels, it is believed that a steel disclosed in JP-A-62-103345 has the highest strength. There have been also proposed other heat resisting steels in JP-A-57-207161 and JP-B2-57-25629, which are objects to be improved by the present invention. The present inventors further proposed another heat resisting steel as shown in JP-A-4-147948. However, in order to achieve the ultimate steam temperature of 650°C, those alloys mentioned above are not fully satisfactory, thus it has been desired to develop an available ferritic heat resisting steel having high strength at high temperature. The heat resisting steel taught in above JP-A-4-147948 is generally satisfactory. But, it has been found that, while the steel of JP'948 has high strength at high temperature on the average, there is a large variance in high temperature strength and low temperature toughness thereof. It is required to provide a rotor material which has 100000 hours creep rupture strength of not less than 10 kgf/mm 2 at 650°C in order to realize a thermal power plant of ultra supercritical pressure which is operated under the ultimate steam temperature of 650°C. The rotor material is also required to be excellent in toughness property and brittleness resistance property in the view point of keeping safety against brittle fracture. SUMMARY OF THE INVENTION An object of the present invention is to provide a heat resisting steel and a steam turbine rotor shaft which are more excellent in high temperature strength than those conventional. The present inventors reviewed conventional alloys and studied an optimum amount of respective additive elements in a heat resisting steel in order to further strengthen those. As a result thereof, it was found that the heat resisting steel can be considerably improved by positively adding a comparatively larger amount of Co than that in similar conventional alloys and further adding a larger amount of W (tungsten) than that in the above conventional alloys together with Mo attaching more importance to W than Mo. Such remarkable effect is primarily owing to synergism by W and Co. The inventors further found that the heat resisting steel can have stably high strength at high temperature and high toughness at low temperature by controlling the respective amounts of B (boron), nitrogen, oxygen and hydrogen within an appropriate range. The present invention is also based on this new recognition. According to a first aspect of the invention, there is provided a heat resisting steel excellent in high temperature strength, whose metal structure is entirely martensite phase produced by tempering or reheating treatment after quenching, and which comprises, by weight, 0.05 to 0.20% C, not more than 0.10% Si, 0.35 to 0.85% Mn, not more than 1.0% Ni, 8.5 to 13.0% Cr, not more than 3.5% Mo, preferably from 0.05 to less than 0.50% or from more than 0.5 to not more than 3.5%, 1.0 to 3.5% W, 0.05 to 0.30% V, 0.01 to 0.20% Nb, 2.0 to 5.0% Co, 0.001 to 0.020% boron, 0.005 to 0.040% nitrogen, not more than 0.010% oxygen and not more than 0.00020% hydrogen. The component elements are preferably controlled such that the heat resisting steel has the Cr equivalent of not more than 8.5, where the Cr equivalent is defined by weight as follows: "Cr equivalent = - 40 x C - 30 x N - 2 x Mn - 4 x Ni + Cr + 6 x Si + 4 x Mo + 1.5 W + 11 x V + 5 x Nb - 2 x Co" According to a second aspect of the invention, there is provided a steam turbine rotor shaft which is made of the heat resisting martensitic steel mentioned above. According to a third aspect of the invention, there is provided a heat resisting steel whose metal structure is entirely martensite phase produced by tempering after quenching, and which comprises, by weight, 0.08 to 0.16% C, not more than 0.10% Si, 0.35 to 0.85% Mn, 0.20 to 0.80% Ni, 10.0 to 12.0% Cr, 0.05 to 0.50% Mo, 2.0 to 3.0% W, 0.10 to 0.30% V, 0.03 to 0.13% Nb, 2.0 to 3.5% Co, 0.004 to 0.017% boron, 0.010 to 0.030% nitrogen, 0.0005 to 0.0035% oxygen and 0.00001 to 0.00015% hydrogen. The Cr equivalent thereof is preferably controlled to not more than 8.5. According to a fourth aspect of the invention, there is provided a rotor shaft which is made of the heat resisting ferritic steel mentioned in the above paragraph of the third aspect and which can be utilized in a thermal power plant of ultra supercritical pressure which is operated under a steam temperature of not less than 610°C. According to a fifth aspect of the invention, there is provided a rotor shaft which is made of the heat resisting ferritic steels mentioned in the above paragraphs of the first and the third aspects and which has 100000 hours creep rupture strength of not less than 10 kgf /mm 2 at 650°C. According to a sixth aspect of the invention, there is provided a heat treatment method for a steam turbine rotor shaft, which comprises the steps of: quenching a starting material of said rotor shaft from a temperature of 1000 to 1100°C; tempering, i.e. reheating the quenched material optionally followed by secondary tempering or reheating; forming a center hole in the tempered material along the axis thereof; and further tempering the material provided with said center hole. According to a seventh aspect of the invention, the above heat resisting steels comprise boron and nitrogen in a total amount of not more than 0.050%, respectively, wherein a ratio of N/B is 1 to 5, where "N" is nitrogen and "B" is boron. According to an eighth aspect of the invention, there is provided a steam turbine rotor shaft which is made of the heat resisting steel mentioned in the above paragraph of the seventh aspect. According to a ninth aspect of the invention, the above heat resisting steel mentioned in the paragraph of the third aspect comprise boron and nitrogen in a total amount of not more than 0.035%, wherein a ratio of N/B is 1 to 5, where "N" is nitrogen and "B" is boron. According to a tenth aspect of the invention, there is provided a steam turbine rotor shaft which is made of the heat resisting steel mentioned in the above paragraph of the first, third or seventh aspects and which is operated under a steam temperature of not less than 610°C. According to an eleventh aspect of the invention, the above heat resisting steel mentioned in the paragraph of the first, third or seventh aspects has 100000 hours creep rupture strength of not less than 10 kgf/mm 2 at 650°C and the impact absorption energy of not less than 2 kgf-m at 20°C after heating for 1000 hours at 650°C. According to a twelfth aspect of the invention, there is provided a steam turbine rotor shaft which is made of the heat resisting steel mentioned in the above paragraph of the eleventh aspect. The respective heat resisting steels mentioned in the above paragraphs of the first, third, seventh, ninth and eleventh aspects may comprise, by weight, not more than 0.2% in the aggregate of at least one element selected from Ca, Ti, Zr, Ta, Hf, Mg and rare earth elements. Summarizing, the invention relates to a heat resisting steel whose metal structure is entirely martensite phase produced by tempering, i.e. reheating treatment, after quenching, and which comprises, by weight, 0.05 to 0.20% C, not more than 0.10% Si, 0.35% to 0.85% Mn, not more than 1.0% Ni, 8.5 to 13.0% Cr, not more than 3.50% Mo, not more than 3.5% W, 0.05 to 0.30% V, 0.01 to 0.20% Nb, 2.0 to 5.0% Co, 0.001 to 0.020% B (boron), 0.005 to 0.040% N (nitrogen), not more than 0.010% O (oxygen), not more than 0.00020% H (hydrogen), preferably at least one element selected from Ti, Zr, Hf in an amount of not more than 0.5% in the aggregate, more preferably at least one element selected from Ca, Ti, Zr, Ta, Hf, Mg, Al, and rare earth elements in an amount of not more than 0.2% in the aggregate, balance Fe and unavoidable impurities. Conveniently the heat resisting steel comprises, by weight, 0.08 to 0.16% C, not more than 0.10% Si, 0.35% to 0.85% Mn, 0.20 to 0.80% Ni, 10.0 to 12.0% Cr, 0.05 to 0.50% Mo, 2.0 to 3.0% W, 0.10 to 0.30% V, 0.03 to 0.13% Nb, 2.0 to 3.5% Co, 0.004 to 0.017% B, 0.010 to 0.030% N, 0.0005 to 0.0035% O and 0.00001 to 0.00015% H, preferably at least one element selected from Ti, Zr, Hf in an amount of not more than 0.5% in the aggregate, more preferably at least one element selected from Ca, Ti, Zr, Ta, Hf, Mg, Al, and rare earth elements in an amount of not more than 0.2% in the aggregate, balance Fe and unavoidable impurities. The heat resisting steel advantageously comprises, by weight, 0.09 to 0.14% C, not more than 0.06% Si, 0.35 to 0.65% Mn, 0.4 to 0.6% Ni, 10.5 to 11.5% Cr, 0.55 to 0.85% Mo or 1.2 to 2.5% Mo, 0.5 to 1.0% W in case of 1.2 to 2.5% Mo or 1.6 to 3.0% W in case of less than 1.2% Mo; 0.15 to 0.25% V, 0.04 to 0.10% Nb, 2.2 to 3.1% Co, 0.006 to 0.013% B, 0.015 to 0.025% N, 0.0005 to 0.002% O, 0.00001 to 0.0001% H, preferably at least one element selected from Ti, Zr, Hf in an amount of not more than 0.5% in the aggregate, more preferably at least one element selected from Ca, Ti, Zr, Ta, Hf, Mg, Al, and rare earth elements in an amount of not more than 0.2% in the aggregate, balance Fe and unavoidable impurities. With the above-mentioned heat resisting steels a total amount of B and N is not more than 0.050% and preferably 0.015 to 0.035% by weight and a ratio of N/B is 1 to 5. In a preferred composition the heat resisting steel according to the invention has in weight percent a Cr equivalent, i.e. - 40 x C - 30 x N - 2 x Mn - 4 x Ni + Cr + 6 x Si + 4 x Mo + 1.5 x W + 11 x V + 5 x Nb - 2 x Co, of not more than 10, preferably of not more than 8.5 and most preferably of not more than 7.5. The heat resisting steel according to the invention has 100000 hours creep rupture strenght of not less than 98 N/mm 2 (10 kgf/mm 2 ) at 650°C and an impact absorption energy of not less than 19.6 Nm (2 kgf-m) at 20°C after heating for 1000 hours at 650°C. A steam turbine rotor shaft which is used in a steam turbine operated under a steam temperature of 610°C to 650°C is advantageously made of one of the above-mentioned heat resisting steels. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a graph which shows the effect of boron on 100000 hours creep rupture strength at 650°C; Fig. 2 shows a graph which shows the effect of boron on impact absorption energy at 20°C; Fig. 3 shows a graph which shows the effect of nitrogen on 100000 hours creep rupture strength at 650°C; Fig. 4 shows a graph which shows the effect of nitrogen on impact absorption energy at 20 C; Fig. 5 shows a graph which shows the effect of hydrogen on impact absorption energy at 20°C; Fig. 6 shows a graph which shows the effect of oxygen on 100000 hours creep rupture strength at 650°C; Fig. 7 shows a graph which shows the effect of oxygen on impact absorption energy at 20°C; and Fig. 8 shows a perspective view of a steam turbine rotor shaft according to the invention. DETAILED DESCRIPTION OF THE INVENTION Ten types of known alloys disclosed in the above raised document of from JP-A-62-103345 to JP-A-61-69948 do not comprise Co or comprise only not more than 1% Co. Conventionally, it has been generally believed that a much additive amount of Co is inappropriate for tungsten containing steels which are liable to be deteriorated especially in ductility, since the Charpy impact value of steel may be deteriorated by Co according to a general knowledge. But, according to researches made by the present inventors, it was found that there is no such unfavorable tendency caused by additive Co and that, in contrast, high temperature strength and toughness are significantly improved by addition of not less than 2.0% Co. Thus, in the invention steel, it is possible to considerably improve high temperature strength thereof by adding 2.1% Co. An alloy disclosed in JP-A-57-207161 comprises 0.5 to 2.0% Mo, 1.0 to 2.5% W, 0.3 to 2.0% Co, in which Mo and W are regarded as identically important alloying elements, and Co is controlled to a comparatively low amount. In contrast, the invention steels comprise a lower amount of Mo than the Mo amount range of JP'161 alloy, in which W is regarded as rather important and high temperature strength is further improved by synergism of higher amounts of additive W and Co. JP-A-57-25629 teaches a material for a combustion chamber of an internal combustion engine, especially a casting material which is directed to improving thermal fatigue resistance property thereof. Thus, in the material of JP'629, Si is positively added in a range of 0.2 to 3.0% as an effective deoxidizer and also in order to improve fluidity of molten metal during casting and oxidation property in high temperature. The material is different from the invention alloys with regard to those chemical compositions and applications. The invention alloys are quite different from the material of JP'629 in the point that, in the invention alloys, Si is a detrimental element and must be restricted to not more than 0.15%. JP-A-57-25629 also teaches that Mo, W, Nb, V and Ti are identical to one another as alloying elements with regard to those effects, thus the material may comprise at least one of those elements. Contrasting, in the invention alloys, since Mo, W, Nb and V have different functions, respectively, it is necessary for the alloys to comprise all of those elements. This means that the technical idea of the invention is quite different from that of JP'629. With respect to such difference in the alloy compositions of the JP'629 material and the invention alloys, the former has the maximum creep rupture strength of 12.5 kgf/mm 2 for 100 hours at 700°C, whereas the latter have that of not lower than 15 kgf/mm 2 thereby it has been realized to improve alloy strength by the invention. Further, in the case where the invention steel comprises controlled amounts of 0.001 to 0.020% boron, 0.005 to 0.040% nitrogen, 0.0005 to 0.0050% oxygen and 0.00001 to 0.00020% hydrogen, it is possible to obtain 100000 hours creep rupture strength of not less than 10 kgf/mm 2 at 650°C which is required to the rotor shaft of the ultra supercritical pressure turbine. By such control in the chemical composition, the invention steel can have high toughness in low temperature of impact absorption energy of 2 kgf-m at 20°C even after embrittlement treatment for 1000 hours at 650°C. In the invention steel, high temperature strength and low temperature toughness can be raised by adding at least one of carbide forming elements such as Ti, Zr, Hf and so on in amount or aggregation amount of not more than 0.5% and at least one of Ca, Mg, Al and rare earth elements including La, Ce, Y and so on in amount or aggregation amount of not more than 0.2%. Especially, not more than 0.2% Ti and not more than 0.2% Hf are preferable. The followings are reasons why the specified amount range of the respective alloying elements is preferred. Carbon (C) is an indispensable for the invention steel in order to keep quenching property and raise high temperature strength by precipitating M 23 C 6 type carbides during tempering treatment. While the invention steel requires at least 0.05% carbon, in the case of exceeding 0.20% carbon, an excess amount of M 23 C 6 type carbides are precipitated thereby the matrix is deteriorated in strength so as to reduce high temperature strength of steel in a long time use. Thus, carbon is limited to an amount range of 0.05 to 0.20%, preferably 0.08 to 0.16% and more desirably 0.09 to 0.14%. Mn is necessary for the invention steel in order to restrain formation of the 6-ferrite phase and promote precipitation of M 23 C 6 type carbides. An excess amount of more than 1.5% Mn deteriorates oxidation resistance and brittleness resistance properties of the steel. The preferred amount range of Mn is 0.35 to 0.85%, preferably 0.35 to 0.65%. Ni restrains formation of the 6-ferrite phase and raises toughness of the invention steel. More than 1.0% Ni deteriorates the steel in creep rupture strength. Thus, Ni is limited to an amount of not more than 1.0%, preferably 0.2 to 0.8% and more desirably 0.4 to 0.6%. Cr is indispensable for the invention steel in order to provide with oxidation resistance and precipitate M 23 C 6 type carbides so as to raise high temperature strength. While the invention steel requires at least 8.5% Cr, in the case of exceeding 13% Cr, the 6-ferrite phase is formed thereby the steel is deteriorated in high temperature strength and toughness. Thus, Cr is limited to an amount range of 8.5 to 13.0%, preferably 10.0 to 12.0% and more desirably 10.5 to 11.5%. Mo promotes fine precipitation of M 23 C 6 type carbides while preventing aggregation thereof. Thus, it is effective to maintain high temperature strength of the invention steel for a long time. However, in the case of exceeding 3.50% Mo, the 6-ferrite phase is liable to be formed, therefore Mo is limited to an amount of not more than 3.5%, preferably 0.15 to 0.25% or more than 0.5 to not more than 3.5% and more desirably 0.55 to 0.85% or 1.2 to 2.5%. Tungsten (W) more effectively restrains M 23 C 6 type carbides to aggregate to become coarse than Mo and is effective for improving high temperature strength of the steel since tungsten dissolves in the matrix to strengthen it. While the invention steel requires not more than 3.5% W, in the case of exceeding 3.5% W, the 6-ferrite phase and the Laves phase (Fe 2 W) are liable to be formed thereby the steel is deteriorated in high temperature strength. Thus, tungsten is limited to an amount of not more than 3.5%, preferably 0.5 to 1.0% in the case of the Mo amount of 1.2 to 2.5%, 1.6 to 3.0% in the case of the Mo amount of less than 1.2%, and more desirably 2.0 to 2.8%. Vanadium (V) is effective for precipitating carbo-nitrides thereof in the steel matrix to raise high temperature strength. While the invention steel requires at least 0.05% V, in the case of exceeding 0.3% V, carbon is excessively fixed by V and precipitates of M 23 C 6 type carbides are reduced in amount to deteriorate high temperature strength of the steel. Thus, vanadium is limited to an amount range of 0.05 to 0.3%, preferably 0.10 to 0.30% and more desirably 0.15 to 0.25%. Nb forms NbC to refine crystal grains of the steel, and a part thereof is dissolved in the matrix when quenched and precipitated during tempering to raise high temperature strength. While the invention steel requires at least 0.01% V, in the case of exceeding 0.20% Nb, is excessively fixed by Nb and precipitates of M 23 C 6 type carbides are reduced in amount to deteriorate high temperature strength of the steel. Thus, Nb is limited to an amount range of 0.01 to 0.20%, preferably 0.03 to 0.13% and more desirably 0.04 to 0.10%. Co is an important alloying element by which the invention steel is characterized in distinguishing it from conventional steels and significantly improved in high temperature strength of the steel. It is believed that such effect is probably owing to a cooperative action of Co and tungsten with respect to the particular chemical composition of the invention steel comprising not less than 1.6% tungsten. In order to more clearly realize such Co effect, the invention steel comprises at least 2.0%. On the other hand, in the case of an excess amount of Co, the invention steel is deteriorated in ductility and caused to become expensive in the production cost. Thus, Co is limited up to 5.0%, preferably 2.1 to 3.5% and more desirably 2.2 to 3.1%. Nitrogen (N) is effective for precipitating vanadium nitrides and raising high temperature strength of the steel in the form of solid solution by so called the "IS effect" in cooperation with Mo and tungsten, the IS effect being of an interaction between an interstitial solvent element and a substitution type solvent element. While the invention steel requires at least 0.005% nitrogen, in the case of exceeding 0.04% nitrogen, the steel is deteriorated in ductility and toughness. Thus, nitrogen is limited to an amount range of 0.005 to 0.04%, preferably 0.01 to 0.03% and more desirably 0.015 to 0.025%. Si is a detrimental element, which promotes formation of the Laves phase and deteriorates the steel in toughness due to grainboundary segregation thereof and so on. Thus, Si is limited to an amount of not more than 0.10% and preferably not more than 0.06%. While Si is usually added in the steel as a deoxidizer, in the case where the steel is deoxidized under vacuum, it is not added thereto. In the latter case, the steel comprises not more than 0.01% Si, preferably 0.005 to 0.06%. Boron (B) has the grain boundary strengthening effect and the carbide dispersion strengthening effect in the steel so as to raise high temperature strength, the latter effect being owing to that boron produce precipitates of M 23 (CB) 6 which are more stable in high temperature than M 23 C 6 type carbides and which prevent carbides to aggregate and be coarsened. While at least 0.001% B is effective for obtaining such effects, in the case of exceeding 0.020% B, the steel is deteriorated in weldability, forging ability and low temperature toughness. Thus, boron is limited to an amount range of 0.001 to 0.020%, preferably not less than 0.002%, more preferably 0.004 to 0.017% and more desirably 0.006 to 0.013%. Boron and nitrogen are closely connected with each other. It is preferred to control amounts thereof such that the amount ratio "N/B" is 1 to 5 and the aggregation thereof is not more than 0.050%. Especially, with regard to the aggregation amount, it is noted that, in the case of not less than 0.010% boron or less than 0.015% nitrogen, not more than 0.050% is preferred, and in the case of less than 0.010% boron or not less than 0.015% nitrogen, not more than 0.040% is preferred. The aggregation amount is more preferably not less than 0.015% and further desirably 0.015 to 0.035%. The solubility of oxygen in steel is at most 0.001%, but actually steel comprises an excess amount of oxygen to form nonmetallic compounds including MnO-SiO2. While oxygen has an effect of preventing coarsening of crystal grains of steel, an excess amount thereof deteriorates the invention steel in creep rupture strength and rupture toughness. Thus, oxygen is limited up to 0.010%, preferably 0.0050%, more preferably 0.0005 to 0.0035% and more desirably 0.0005 to 0.0020%. Hydrogen exists in steel as an interstitial solvent because of the small atomic radius. Further, while it has been well known that hydrogen is responsible for formation of defects in steel, such as white spots, it can not be completely eliminated from steel by the current industrial technology. Since an excess amount of more than 0.00020% hydrogen deteriorates the invention steel in creep rupture strength and rupture toughness, hydrogen is limited up to 0.0002%, preferably 0.00001 to 0.00015% and more preferably 0.00001 to 0.00010%. Regarding the Cr equivalent, if it is more than 10, the detrimental 6-ferrite phase, which deteriorates the steel in low temperature toughness, brittleness resistance property and fatigue strength, is precipitated in the steel, thus it is limited to not more than 10, preferably not more than 8.5 and more preferably not more than 7.5. The invention rotor shaft is produced by the following steps: casting an ingot from a molten metal of the invention steel which is melted in an electric furnace or by the electro-slag remelting method (ESR); forging the ingot; heating the forged product up to 900°C to 1150°C; quenching the forged product after heating in a cooling rate of 50°C/hour to 600°C/hour at the central region of the product; tempering the quenched product at 500°C to 700°C (: a primary tempering) optionally followed by secondary tempering at 600°C to 750°C; forming a center hole in the tempered product along the axis thereof; and further tempering the product provided with the center hole (: a final tempering). The tempering is conducted at not lower than 200°C, preferably 500°C to 700°C. The final tempering is conducted at a temperature higher than that of the first tempering and lower than that of the optional tempering. Especially, the invention steel and the invention rotor shaft can have high strength and high toughness by the quenching cooling rate of 50°C/hour to 600°C/hour at the central region of the product to be processed. EXAMPLE Example 1 The alloys having the chemical compositions shown in Table 1 were melted by a vacuum induction melting method, respectively. They were cast to ingots each having a weight of 50 kg and forged to produce rectangular bars each having a cross sectional dimension of 30mm x 90mm. The forged products were subjected to a heat treatment, respectively, which corresponds to that of the central region of an actual large steam turbine rotor. Examples No. 1 to 17 were subjected to quenching treatment at a cooling rate of 100°C/hour after keeping at 1050°C for 5 hours, a first tempering treatment of 570°C for 20 hours, a secondary tempering treatment of 710°C for 20 hours, and a ternary tempering treatment of 680°C for 20 hours. Example No. 21 was subjected to quenching treatment at a cooling rate of 100°C/hour after keeping at 1050°C for 5 hours, a first tempering treatment of 570°C for 20 hours, and a secondary tempering treatment of 670°C for 20 hours. Specimens were taken from the above heat treated materials, respectively, and subjected to the creep rupture test at 650°C and 700°C, The test results were evaluated by means of the Larson-Miller method to determine 100000 hours creep rupture strength at 650°C with regard to the respective specimens. With respect to the impact test, the above heat treated materials were subjected to an embrittlement treatment at 650°C for 1000 hours, respectively, and thereafter V-notch Charpy test specimens were taken from them in accordance with JIS Z 2202 No. 4. The specimens were subjected to the V-notch Charpy test at 20°C and an impact absorption energy was determined with regard to the respective specimens. In Table 1, Examples No. 1, 11, 14 and 17 are of the invention steel, No. 2 to 5, 12, 13, 15 and 16 are of the comparative steel, and No. 21 is of a conventional rotor material which has been widely used in the current turbines. Table 2 shows the 100000 hours creep rupture strength at 650°C and the impact absorption energy of the respective Examples. The invention steel Examples No. 1, 11, 14 and 17 have 11.5 to 12.7 kgf/mm 2 of 100000 hours creep rupture strength at 650°C which are remarkably excellent and about three times of the conventional material of No.21. Further, Examples No. 1, 11, 14 and 17 of the invention steel have 2.5 to 3.2 kgf-m (at 20°C) of toughness which are generally equal to or greater than the conventional material. It is believed that the invention steel is enough applicable to a rotor of the ultra supercritical pressure steam turbine which is operated under the ultimate steam temperature of 650°C. Figs. 1 to 8 show the test results of mechanical properties of the Examples. From those drawings, the following can be recognized. While additive boron deteriorates the toughness (Fig. 2), it remarkably raises the creep rupture strength (Fig. 1). By adding not less than 0.001% boron, not less than 10 kgf/mm 2 of 100000 hours creep rupture strength at 650°C can be obtained. However, an excess amount of boron deteriorates the toughness, especially more than 0.02% of boron makes the impact absorption energy less than 2 kgf-m. While nitrogen in the steels deteriorates the toughness (Fig. 4), around 0.02% nitrogen remarkably raises the creep rupture strength (Fig. 3). By adding 0.005 to 0.04% nitrogen, not less than 10 kgf/mm 2 of 100000 hours creep rupture strength at 650°C can be obtained. An increase of hydrogen deteriorates the toughness (Fig. 5). If hydrogen is in an amount of more than 0.0002%, it is impossible to keep not less than 10 kgf/mm 2 of 100000 hours creep rupture strength at 650°C and not less than 2 kgf-m of impact absorption energy. An increase of oxygen deteriorates the creep rupture strength and the toughness (Figs. 6 and 7). If oxygen is in an amount of not less than 0.005%, it is impossible to keep not less than 10 kgf/mm 2 of 100000 hours creep rupture strength at 650°C. Example 2 A material which has the chemical composition of Example No. 17 shown in Table 1 was melted in an electric furnace. An ingot from the melt was forged to obtain an electrode bar. Subsequently the electrode bar was subjected to the electro-slag remelting process. The obtained product from the electro-slag remelting process was forged at 1150°C to produce an article of a rotor shape which has a maximum diameter of about 900 mm and a length of 4500 mm and thereafter subjected to rough machining. The thus obtained product was subjected to heat treatments of quenching and thrice tempering which are the same conditions as those in Example 1. In order for dehydrogenation, the ternary tempering was conducted after forming a center hole having a diameter of 90 mm in the product just after the secondary tempering treatment. Regarding Example No. 17, Table 1 shows the result of chemical analysis of the central portion of the product having the rotor shaft shape which was already subjected to the above heat treatments. Table 2 shows the results of the creep rupture test and the V-notch Charpy test with regard to the product having the rotor shaft shape. The results are approximately identical to those of the invention steel in embodiment 1. From the Example, it was proved that the invention steel is applicable to a rotor of a large turbine without any problems on fabricability. As will be apparent from the above, according to the invention steel, when it is applied to a rotor shaft of an ultra supercritical pressure steam turbine, the steam temperature thereof can be raised up to about 650°C thereby the thermal efficiency in a thermal power plant will be remarkably improved.

Claims: A heat resisting steel whose metal structure is entirely martensite phase produced by tempering after quenching comprising, by weight, 0.05 to 0.20% C, not more than 0.10% Si, 0.35% to 0.85% Mn, not more than 1.0% Ni, 8.5 to 13.0% Cr, not more than 3.50% Mo, not more than 3.5% W, 0.05 to 0.30% V, 0.01 to 0.20% Nb, 2.0 to 5.0% Co, 0.001 to 0.020% B (boron), 0.005 to 0.040% N (nitrogen), not more than 0.010% O (oxygen), not more than 0.00020% H (hydrogen), preferably at least one element selected from Ti, Zr, Hf in an amount of not more than 0.5% in the aggregate, more preferably at least one element selected from Ca, Ti, Zr, Ta, Hf, Mg, Al, and rare earth elements in an amount of not more than 0.2% in the aggregate, balance Fe and unavoidable impurities. The heat resisting steel according claim 1 comprising, by weight, 0.08 to 0.16% C, not more than 0.10% Si, 0.35% to 0.85% Mn, 0.20 to 0.80% Ni, 10.0 to 12.0% Cr, 0.05 to 0.50% Mo, 2.0 to 3.0% W, 0.10 to 0.30% V, 0.03 to 0.13% Nb, 2.0 to 3.5% Co, 0.004 to 0.017% B, 0.010 to 0.030% N, 0.0005 to 0.0035% O and 0.00001 to 0.00015% H, preferably at least one element selected from Ti, Zr, Hf in an amount of not more than 0.5% in the aggregate, more preferably at least one element selected from Ca, Ti, Zr, Ta, Hf, Mg, Al, and rare earth elements in an amount of not more than 0.2% in the aggregate, balance Fe and unavoidable impurities. The heat resisting steel according to claim 1 comprising, by weight, 0.09 to 0.14% C, not more than 0.06% Si, 0.35 to 0.65% Mn, 0.4 to 0.6% Ni, 10.5 to 11.5% Cr, 0.55 to 0.85% Mo or 1.2 to 2.5% Mo, 0.5 to 1.0% W in case of 1.2 to 2.5% Mo or 1.6 to 3.0% W in case of less than 1.2% Mo; 0.15 to 0.25% V, 0.04 to 0.10% Nb, 2.2 to 3.1% Co, 0.006 to 0.013% B, 0.015 to 0.025% N, 0.0005 to 0.002% O, 0.00001 to 0.0001% H, preferably at least one element selected from Ti, Zr, Hf in amount of not more than 0.5% in the aggregate, more preferably at least one element selected from Ca, Ti, Zr, Ta, Hf, Mg, Al, and rare earth elements in an amount of not more than 0.2% in the aggregate, balance Fe and unavoidable impurities. The heat resisting steel according to any one of the preceding claims, wherein a total amount of B and N is up to 0.050% by weight and a ratio of N/B is 1 to 5. The heat resisting steel according to claim 4, wherein the total amount of B and N is 0.015 to 0.035% by weight. The heat resisting steel according to any one of the preceding claims which has in weight percent a Cr equivalent, i.e. - 40 x C - 30 x N - 2 x Mn - 4 x Ni + Cr + 6 x Si + 4 x Mo + 1.5 x W + 11 x V + 5 x Nb - 2 x Co, up to 10, preferably up to 8.5 and most preferably up to 7.5. The heat resisting steel according to one of the preceding claims which has 100000 hours creep rupture strength of not less than 98 N/mm 2 (10 kgf/mm 2 ) at 650°C and the impact absorption energy of not less than 19.6 Nm (2 kgf-m) at 20°C after heating for 1000 hours at 650°C. A steam turbine rotor shaft made of a heat resisting steel according to one of the preceding claims, which shaft is used in a steam turbine operated under a steam temperature of 610°C to 650°C. A heat treatment method for a steam turbine rotor shaft according to claim 8 comprising the following steps: quenching a starting material of said rotor shaft from a temperature of 900°C to 1150°C, preferably of 1000°C to 1100°C, primarily tempering the quenched material optionally followed by secondary tempering; forming a center hole in the tempered material along the axis thereof; and finally tempering the material provided with said center hole. The method according to claim 9, wherein the starting material is an ingot cast from a melting of the heat resisting steel melted in an electric furnace or by electro-slag remelting, which ingot is subsequently forged. The method according to the claim 9 or 10, wherein quenching is conducted with a cooling rate of 50°C/h to 600°C/h at the central region of the material. The method according to one of the claims 9 to 11, wherein the primary tempering is conducted at 500°C to 700°C, while the optional secondary tempering is conducted at 600°C to 750°C. The method according to one of the claims 9 to 12, wherein the final tempering is conducted at a temperature higher than that of the first tempering and lower than that of the optional tempering. The method according to one of the claims 9 to 13, wherein the final tempering is conducted at a temperature not lower than 200°C, preferably at 500°C to 700°C.

Inventors: FUJITA TOSHIO, FUKUI YUTAKA, HARADA YASUHIRO, HIDAKA KISHIO, KANEKO RYOICHI, MORISADA NORIO, NAKAMURA SHIGEYOSHI, SHIGA MASAO, SHIMIZU NOBUO, TANAKA YASUHIKO, WATANABE YASUO, YAMADA NORIO, FUJITA, TOSHIO, FUKUI, YUTAKA, HARADA, YASUHIRO, HIDAKA, KISHIO, KANEKO, RYOICHI, MORISADA, NORIO, NAKAMURA, SHIGEYOSHI, SHIGA, MASAO, SHIMIZU, NOBUO, TANAKA, YASUHIKO, WATANABE, YASUO, YAMADA, NORIO
Applicants: HITACHI LTD, JAPAN STEEL WORKS LTD, HITACHI, LTD., THE JAPAN STEEL WORKS, LTD.
Application year: 1997
Main classification: C22C38
IPC codes: C22C38, C21D9, F01D5