Patent Grant
7531129
This invention relates to a stainless steel, having good mechanical properties (strength, ductility) and corrosion resistance in a high-pressure hydrogen gas environment, and further having good stress corrosion cracking resistance in an environment in which the chloride ion exists, for example in a seashore environment. This invention relates also to a container or piping for high-pressure hydrogen gas, or an accessory part or device belonging thereto, which is made of the steel. These containers and so forth include structural equipment members, especially cylinders, piping and valves for fuel cells for vehicles or hydrogen gas stations, for example, which are exposed to a high-pressure hydrogen gas environment.
Fuel cell-powered vehicles depend on electric power from hydrogen and oxygen as fuels and have attracted attention as the next-generation clean vehicles, which do not emit such hazardous substances as carbon dioxide [CO2], nitrogen oxide [NOx] and sulfur oxide [SOx], unlike the current conventional gasoline engine vehicles or diesel engine vehicles. In Japan, the introduction of 5 million such vehicles prior to 2020 is planned under the leadership of the Japanese Ministry of Economy, Trade and Industry.
At present, the greatest problems to be solved before the practical use of these fuel cell-powered vehicles are how to generate the fuel, i.e., hydrogen, and how to store it. Various research and development work is going on at the present time.
Typical methods are loading a hydrogen gas cylinder into the vehicle, generating hydrogen by reforming methanol or gasoline in a reformer carried on the vehicle, and installing a hydrogen storage alloy with hydrogen adsorbed therein in the vehicle.
While each of these methods has its merits and demerits, fuel cell-powered vehicles carrying a hydrogen gas cylinder, were first put on the world market by Japan in December 2002 (Heisei 14), and several of them are already in use as official cars by the Japanese Ministry of Land, Infrastructure and Transport and so on.
However, while the current fuel cell-powdered vehicles are already performing close to the standard of gasoline-driven private cars with a maximum speed of about 150 km/hr and power of about 100 horsepower, the maximum range is less than 300 km due to the limited cylinder size, and this problem has prevented them from coming into wide use.
The method for installing a reformer, which uses methanol or gasoline as a fuel, still has some problems; for example, methanol is toxic and the gasoline needs to be desulphurized. Also an expensive catalyst is required at the present time and, further, the reforming efficiency is unsatisfactory, hence the CO2 emission reducing effect does not justify the increase in cost.
The method which uses a hydrogen storage alloy has technological problems. For example the hydrogen storage alloy is very expensive, and excessive time is required for hydrogen absorption, which corresponds to fuel charging, and the hydrogen storage alloy deteriorates by repeating absorption and releasing hydrogen. Therefore the great deal of time is still required before this method can be put into practical use.
With the background discussed above, various research and development work is being encouraged in Japan in order to improve the performance of the fuel cell-powered vehicles carrying a high-pressure gas cylinder, and also reduce the cost of its production. In order to popularize the so-called next-generation clean vehicles, it is necessary to overcome the following problems.
The range of the fuel cell-powered vehicles should be increased. The infrastructure for example, the hydrogen stations necessary for the popularization of the car should be prepared. And the technology to improve the safety in handling of hydrogen should be developed.
A trial calculation indicates that, in order to extend the range of the vehicle to 500 km, for instance, the hydrogen gas pressure in the cylinder to be carried on the vehicle should be increased from the current level of 35 MPa to a higher level of 70 MPa. Further, hydrogen gas stations become necessary instead of the existing gasoline stations and, accordingly, the generation, transportation and storage of high-pressure hydrogen gas, as well as rapid charging (feeding to vehicles) thereof, become necessary.
Since hydrogen gas is flammable, close attention should be paid in handling it. As for the interaction between hydrogen gas under very high pressure exceeding 50 MPa in particular, and the structural equipment members, there are a number of points that remain unclear, hence it is imperative that the technology for the safe utilization of equipment be established.
The material used in the high-pressure hydrogen gas equipment in the fuel cell-powered vehicles commercialized in 2002 (Heisei 14) is an austenitic stainless steel, i.e., JIS SUS 316 type material, whose reliability has been widely recognized in the art. This is because this steel has better hydrogen embrittlement insusceptibility, in an environment of up to 35 MPa hydrogen than other structural steels such as JIS STS 480 type carbon steel and SUS 304 type stainless steel, and also is excellent in workability and weldability, and the technology of its utilization has been established.
However, in using this SUS 316 steel as piping for high-pressure hydrogen gas, whose gas pressure has been increased from 35 MPa to 70 MPa, the outer diameter of the pipe should be increased to 34.7 mm, the inner diameter to 20 mm (pipe wall thickness 7.35 mm), for instance, as compared with the conventional outer diameter of 26.2 mm and the inner diameter of 20 mm (wall thickness 3.1 mm). Thus, the piping cannot endure unless the pipe wall thickness is increased twice or more and the weight three times. Therefore, a marked increase in on-board equipment weight and in size of gas stations will be inevitable, presenting serious obstacles to practical use.
It is known that cold working increases the strength of austenitic stainless steel. Therefore it is possible to avoid the increase in the pipe wall thickness by increasing the strength with such cold working as drawing and rolling.
High-level strength can be obtained by such cold working. However the ductility and toughness markedly decrease and, further, an anisotropy problem may arise due to such working. In addition, it has been made clear that cold-worked austenitic stainless steel shows a marked increase in hydrogen embrittlement susceptibility in a high-pressure hydrogen gas environment, and it has been found that, considering the safety in handling high-pressure hydrogen gas, cold working cannot be employed for increasing pipe strength.
As for the method of strengthening austenitic stainless steel, the so-called solid solution hardening method, in which a large amount of nitrogen [N], as a solid solution element is used, is known from Japanese Patent Laid-open (JP Kokai) Nos. H05-65601 and H07-188863. Further, in JP Kokai No. H05-98391, there is proposed a precipitation hardening method, which comprises causing precipitation of carbides and/or nitrides. However, these conventional strengthening technologies inevitably decrease ductility and toughness and, in particular, cause an increase in anisotropy in toughness, possibly leading to the same problem as in the cold working when the pipes are used in a high-pressure hydrogen gas environment.
Furthermore, in JP Kokai No. H06-128699 and JP Kokai No. H07-26350, there are proposed stainless steels, in which corrosion resistance is improved by adding a large amount of nitrogen [N]. However, these steels do not have characteristics to cope with a high-pressure hydrogen gas environment; hence it is not easy to secure the safety for the same reasons as mentioned above.
Hydrogen gas stations may be located in seashore regions. Vehicles may also be exposed to a salt-containing environment while running or parking. Therefore, the material to be used for hydrogen gas storage containers is also required to be free of any fear of stress corrosion cracking due to the chloride ion.
One of the means for improving the stress corrosion cracking resistance of stainless steel is increasing Cr content. However, merely increasing the Cr content causes precipitation of large amounts of Cr nitrides and the sigma phase. Therefore, such steel cannot have the characteristics required for steel materials for high-pressure hydrogen gas.
The containers and piping for high-pressure hydrogen and accessory parts or devices that belong thereto are often manufactured by welding. The welded joints also have the following problems. Namely, a decrease in strength occur in the weld metal of the joints due to melting and solidification, and in the welding heat affected zone due to heat cycles in welding. This decrease in the strength in the welding heat affected zone can be prevented by carrying out appropriate heat treatment after welding. However, the weld metal has a coarse solidification structure, and, therefore, the strength thereof cannot be improved by mere post-welding heat treatment.
The first objective of the present invention is to provide a high-strength stainless steel, having not only superior mechanical properties and corrosion resistance in a high-pressure hydrogen gas environment, but also improved stress corrosion cracking resistance.
The second objective of the invention is to provide containers, piping and other parts or devices for high-pressure hydrogen gas, which are manufactured from the above-mentioned stainless steel.
The third objective of the invention is to provide such containers, piping and other parts or devices as mentioned above which have welded joint(s) with improved characteristics.
Next, findings that have led to completion of the invention will be described.
The present inventors conducted various investigations concerning the influences of the chemical composition and metallurgical structure (microstructure) of each of the various materials on the mechanical properties and corrosion resistance in a high-pressure hydrogen gas environment. In particular, in an attempt to improve the stress corrosion cracking resistance in a chloride ion-containing environment, they investigated an austenitic stainless steel having a Cr content of 22% or higher. As a result, the inventors obtained the following findings.
1) In conventional austenitic stainless steel having a Cr content exceeding 22%, CrN and Cr2N precipitate and also the sigma phase precipitates in large amounts, which cause a marked decrease in ductility and toughness. However, when a proper balance is maintained among Mn, Ni, Cr and N, even such a steel can acquire good mechanical properties and good resistance to stress corrosion cracking, due to the chloride ion in seashore areas for example.
2) As is generally known, solid solution hardening with N is most effective for increasing the strength of the conventional austenitic stainless steel. With the increasing of the addition of N, the strength increases but the ductility and toughness decrease, and, at the same time, the anisotropy becomes significant. However, by properly selecting constituent elements such as Mn, Cr, Ni and C and properly adjusting the contents thereof, it becomes possible to prevent the ductility and toughness from decreasing and, further, to solve the anisotropy problem.
3) When N is added to the conventional austenitic stainless steel at a level exceeding the solubility limit, Cr nitrides such as CrN and Cr2N are formed. Insofar as they are finely dispersed, these nitrides contribute to increasing the strength. Coarse nitrides, however, not only deteriorate the ductility and toughness but also increase the hydrogen embrittlement susceptibility.
4) This is due to nitrides such as CrN and Cr2N are hexagonal in crystal structure and poor in coherency with the matrix lattice of the austenite phase and, therefore, readily aggregate and become coarser. However, when V is added to the steel containing adequately selected alloying elements, such as Ni and Cr, at adjusted content levels, V can be contained in the Cr nitrides. Even when remaining hexagonal in a crystal structure, such nitrides are improved in coherency with the austenite phase matrix lattice and become difficult to coarsen. Further, V-containing Cr nitrides are converted at least partly to the cubic system nitrides. These cubic system nitrides have good coherency with the matrix phase and can be precipitated in a finely dispersed state. To sum up, when V is contained in the steel, Cr nitrides can be finely dispersed even if they are hexagonal in a crystal structure and, further, after conversion of part thereof to cubic system nitrides, the fine dispersion becomes more certain.
5) The strength, ductility and toughness and, further, hydrogen embrittlement insusceptibility of the austenitic stainless steel vary considerably according to different states of dispersion due to the differences in the crystal structure of Cr nitrides as mentioned above.
6) It is generally known that when the grain size in austenitic stainless steel is reduced, the proof stress increases, but, at the same time, the ductility decreases. However, the steel, wherein N is added and the alloying elements, such as Mn, Cr, Ni and C are properly selected and the contents thereof are adequately adjusted, have not only high strength but also high ductility.
7) The strength of the base metal can be increased by a high Mn content that increase the solubility of N, by adding V and N at respective adequate levels and by carrying out an appropriate heat treatment. Since the weld metal of the welded joint has a coarse solidification structure as mentioned above, the strength thereof will not be improved by the conventional heat treatment following welding. However, by specifying the relation between Nieq and Creq in the weld metal, it becomes possible to improve not only its strength but also other mechanical properties and the hydrogen embrittlement resistance.
The present invention has been completed based on the above findings and the gist thereof consists in the stainless steel defined below under [1] and the containers and the like defined below under [2] and [3]. In the subsequent description, the “%” indicating the content of each component means “% by mass”.
(1) A stainless steel for a high-pressure hydrogen gas characterized in that the steel consists of C: not more than 0.02%, Si: not more than 1.0%, Mn: 3 to 30%, Cr: more than 22% but not more than 30%, Ni: 17 to 30%, V: 0.001 to 1.0%, N, 0.10 to 0.50% and Al: not more than 0.10%, and the balance Fe and impurities, wherein, among the impurities, P is not more than 0.030%, S is not more than 0.005%, and Ti, Zr and Hf are not more than 0.01% respectively, and further characterized in that the contents of Cr, Mn and N satisfy the following relationship [1]:
5Cr+3.4Mn≦500N [1]
wherein the symbols of the elements represent the contents of the respective elements (% by mass).
This stainless steel may contain at least one element selected from at least one group out of the following first to third group:
The first group of elements;
Mo: 0.3 to 3.0%, W: 0.3 to 6.0%, Nb: 0.001 to 0.20%, and Ta: 0.001 to 0.40%.
The second group of elements;
B: 0.0001 to 0.020%, Cu: 0.3 to 5.0%, and Co: 0.3 to 10.0%.
The third group of elements;
Mg: 0.0001 to 0.0050%, Ca: 0.0001 to 0.0050%, La: 0.0001 to 0.20%, Ce: 0.0001 to 0.20%, Y: 0.0001 to 0.40%, Sm: 0.0001 to 0.40%, Pr: 0.0001 to 0.40%, and Nd: 0.0001 to 0.50%.
Further, it is desirable that this stainless steel has at least one of the following characteristics [a] to [d] in its microstructure:
[a] The mean austenite grain size is not greater than 20 μm;
[b] Fine nitride precipitates of not greater than 0.5 μm are dispersed in an amount of not less than 0.01% by volume;
[c] The fine nitride precipitates of not greater than 0.5 μm contain not less than 10 mass % of V within them;
[d] The fine nitride precipitates of not greater than 0.5 μm are face-centered cubic in crystal structure.
(2) A container, piping or accessory part or device for a high-pressure hydrogen gas that is made of the stainless steel defined above under (1).
The container includes cylinders, tanks and other storage vessels, the piping includes pipes connecting such containers to each other or connecting such containers to other parts or devices, and the accessory part or device includes valves and other parts or devices belonging to the containers or piping.
(3) A container, piping or accessory part or device for a high-pressure hydrogen gas which is made of the stainless steel defined in above (1), characterized in that the weld metal of the welded joint thereof consists of C: not more than 0.02%, Si: not more than 1.0%, Mn: 3 to 30%, Cr: more than 22% but not more than 30%, Ni: 8 to 30%, V: 0.001 to 1.0%, Mo: 0 to 3.0%, W: 0 to 6.0%, N, 0.1 to 0.5%, Al: not more than 0.10%, and each of Ti, Nb, Zr, Hf and Ta: 0 to 0.01%, and the balance Fe and impurities, among the impurities, P is not more than 0.030% and S is not more than 0.005%, and that the following relationship [2] is satisfied:
−11≦Nieq−1.1×Creq≦−8 [2]
where
Nieq=Ni+30×(C+N)−0.5×Mn [3]
and
Creq=Cr+Mo+1.5×Si [4].
In the above formulas [3] and [4], the symbols of the elements represent the contents of the respective elements (% by mass).
The above-mentioned weld metal may contain at least one element selected from the second group of elements and the third group of elements as defined above.
1. Stainless Steel of the Present Invention
The effects of the components constituting the austenitic stainless steel of the present invention and the grounds for restriction of the contents thereof will be described below in detail.
C: not more than 0.02%
The Cr content in the steel of the present invention is high so that the high corrosion resistance, in particular the good stress corrosion cracking resistance, can be obtained. In such a high Cr steel, the tendency for M23C6 type carbides [M: Cr, Mo, Fe, etc.] to be formed is pronounced, hence there is a tendency toward a decrease in toughness. For preventing these carbides from precipitating, it is necessary to reduce C to 0.02% or below. Although the C content is desirably as low as possible, an extreme reduction of C content causes an increase in cost of refining. Practically, it is desirably not lower than 0.0001%.
Si: not more than 1.0%
Si is known to be an element effective in improving the corrosion resistance in certain environments. When its content is high, however, it may form intermetallic compounds with Ni, Cr and so on or promote the formation of such intermetallic compounds as the sigma phase, possibly causing marked deterioration in hot workability. Therefore, the Si content should be not more than 1.0%. More preferably, it is not more than 0.5%. The Si content is desirably as low as possible but, considering the cost of refining, it is desirably not less than 0.001%.
Mn: 3 to 30%
Mn is an inexpensive austenite-stabilizing element. In the steel of the present invention, Mn contributes toward increasing the strength and improving the ductility and toughness, when appropriately combined with Cr, Ni, N and so forth. Therefore, Mn is caused to be contained in the steel at a level of not lower than 3%. At levels exceeding 30%, however, the hot workability and/or atmospheric corrosion resistance may decrease in some instances. Therefore, 3 to 30% is the proper content. A more desirable Mn content is 5 to 22%.
Cr: more than 22% but not more than 30%
Cr is an essential component to serve as an element improving the corrosion resistance in a high-pressure hydrogen gas environment and the stress corrosion cracking resistance in the environment containing chloride ion. For producing these effects, a content thereof exceeding 22% is necessary. When Cr exceeds 30%, however, nitrides such as CrN and Cr2N and M23C6 type carbides, which are injurious to the ductility and toughness, tend to be formed in large amounts. Therefore, the proper content of Cr is more than 22% but not more than 30%.
Ni: 17 to 30%
Ni is added as an austenite-stabilizing element. In the steel of the present invention, it contributes toward increasing the strength and improving the ductility and toughness when appropriately combined with Cr, Mn, N and so forth. In particular when the Cr and Mn contents are high, it is necessary to prevent sigma phase formation by increasing the Ni content. Therefore, the Ni content should be not less than 17%. At levels exceeding 30%, however, the increment in effect is small and increases in material cost will result. Therefore, 17 to 30% is the proper content.
V: 0.001 to 1.0%
In the steel of the present invention, V improves the coherency of hexagonal Cr nitrides with the matrix phase, prevents them from becoming coarser and, further, promotes the formation of cubic Cr nitrides, thus greatly contributing toward increasing the strength, improving the ductility, toughness and the hydrogen embrittlement resistance. For producing these effects, a content of not less than 0.001% is necessary. On the other hand, when the content exceeds 1.0%, the increment in effect is small but the material cost increases. Therefore, the upper limit is set at 1.0%. The V content desirable for an increase in yield of cubic Cr nitrides is 0.05 to 1.0%, most desirably 0.1 to 1.0%.
N, 0.10 to 0.50%
N is the most important element for solid solution hardening, and, in the respective proper content ranges of Mn, Cr, Ni, C and so forth, it contributes toward increasing the strength and at the same time prevents the formation of intermetallic compounds such as the sigma phase, and thus contributes toward improving the toughness. For these purposes, a content of not lower than 0.10% is necessary. When N exceeds 0.50%, however, the formation of coarse hexagonal nitrides, such as CrN and Cr2N, becomes inevitable. Therefore, the proper content is 0.10 to 0.50%. Meanwhile, when the balance among Mn, Cr and N in the steel of the present invention satisfies the relationship [1] given below, both high strength and high ductility features can be embodied in the most balanced manner. In the formula [1], the symbols of the elements represent the contents of the respective elements (% by mass).
5Cr+3.4Mn≦500N [1]
The coefficients given to Cr and Mn in the above formula [1] were obtained from the contributions of Cr and Mn to the solubility limit of N and from the tendency toward sigma phase formation.
Al: not more than 0.10%
Al is an element important as a deoxidizer but the content thereof in excess of 0.10% promotes the formation of intermetallic compounds such as the sigma phase. Therefore, such content is undesirable for the balance between strength and toughness as intended by the present invention. For securing the deoxidizing effect, a content of not lower than 0.001% is desirable.
An embodiment of the steel of the present invention comprises the above-mentioned components, with the balance being Fe and impurities. The restrictions to be imposed on some specific elements among the impurities will be described herein later.
Another embodiment of the steel of the present invention further comprises at least one element selected from at least one group among the first to the third group described below.
The elements belonging to the first group are Mo, W, Nb and Ta. These are substantially equivalent in their effect of promoting the formation and stabilization of cubic nitrides. The grounds for restrictions of the respective contents are as follows.
Mo: 0.3 to 3.0%, W: 0.3 to 6.0%
Mo and W are effective in stabilizing cubic nitrides and serve also as solid solution hardening elements. Therefore, one or both may be added according to need. They are effective at levels of not lower than 0.3% respectively. At excessively high addition levels, however, austenite becomes unstable. Therefore, when they are added, it is recommended that their contents should be 0.3 to 3.0% and 0.3 to 6.0% respectively.
Nb: 0.001 to 0.20%, Ta: 0.001 to 0.40%
Nb and Ta, like V, form cubic nitrides and, therefore, one or both of them may be added according to need. The effect becomes significant at respective levels not lower than 0.001%. At excessively high addition levels, however, austenite becomes unstable. Therefore, when they are added, it is recommended that their contents should be not more than 0.20% and 0.40% respectively.
The elements belonging to the second group are B, Cu and Co. These contribute toward improving the strength of the steel of the present invention. The grounds for restrictions of the respective contents are as follows.
B: 0.0001 to 0.020%
B makes the precipitate and austenite crystal grain size finer and increases the strength. Therefore, it can be added according to need. Such effects are produced at levels of not lower than 0.0001%. On the other hand, an excessive content may result in the formation of low melting point compounds, leading to deterioration of hot workability. Therefore, the upper limit is set at 0.020%.
Cu: 0.3 to 5.0%, Co: 0.3 to 10.0%
Cu and Co are austenite-stabilizing elements. When appropriately combined with Mn, Ni, Cr and C in the steel of the present invention, they contribute toward further increasing the strength. Therefore, one or both of them can be added at levels of not lower than 0.3% respectively according to need. Considering the balance between the effect and the material cost, however, the upper limits of their contents are set at 5.0% and 10.0% respectively.
The elements belonging to the third group are Mg, Ca, La, Ce, Y, Sm, Pr and Nd. The effects of these and the grounds for restrictions of the respective contents are as described below.
In the composition range of the steel of the present invention, Mg and Ca, and La, Ce, Y, Sm, Pr and Nd among the transition metals have the ability to prevent cracking upon solidification in the step of casting, and have the effect of preventing a decrease in ductility due to hydrogen embrittlement after a long period of use. Therefore, one or more of them may be contained in the steel according to need. Each produces its effect at levels of not lower than 0.0001%. However, at excessively high content levels, each reduces the hot workability. Therefore, the upper limit is set at 0.0050% for each of Mg and Ca, 0.20% for each of La and Ce, 0.40% for each of Y, Sm and Pr, and 0.50% for Nd.
Now, the restrictions as to impurities are described. In the stainless steel of the present invention, restrictions are imposed upon P, S, Ti, Zr and Hf among the impurities as follows.
P: not more than 0.030%; S: not more than 0.005%
Both of P and S are elements adversely affecting the toughness and other properties of the steel. Therefore, their content is preferably as low as possible. However, at their levels not higher than 0.030% and 0.005% respectively, no significant deterioration in characteristics of the steel of the present invention is observed.
Ti, Zr, and Hf: not more than 0.01% respectively
Ti, Zr and Hf, like V, form cubic nitrides. However, these form nitrides in preference to V in a higher temperature range and, therefore, they inhibit the formation of V-based nitrides. In addition, the nitrides of Ti, Zr and Hf are not good in coherency with the austenite matrix, so that they themselves tend to aggregate and become coarse and are less effective in improving the strength. Therefore, their contents are restricted to 0.01% or below respectively.
5Cr+3.4Mn≦500N
The contents of Cr, Mn and N are required to satisfy the above relationship (relationship [1]) because when the relationship [1] is satisfied, namely when Pmcn2≦0, the tensile strength of the steel becomes high and the elongation increases, as shown in
The stainless steel of the present invention is used as hot-worked or after one or more steps of heat treatment at a temperature between 700 and 1,200° C. The desirable metallurgical structure can be obtained even as hot-worked, depending on the heating temperature during hot working and/or the cooling conditions after hot working. When the above heat treatment is carried out after hot working or after various processing treatments subsequent to hot working, the desirable structure mentioned below can be obtained with more certainty.
It is desirable that the austenitic stainless steel of the present invention be structured as follows.
(a) Mean austenite grain size is not greater than 20 μm:
Generally, as the crystal grain size decreases, the strength, in particular the yield strength (0.2% proof stress) increases but the ductility and toughness conversely decrease. However, as shown in
(b) Fine nitrides of not greater than 0.5 μm are dispersed in an amount of not less than 0.01% by volume:
When N is added in large amounts to the conventional SUS 310 type high-Cr austenitic stainless steels containing 23 to 25% of Cr, nitrides such as CrN and Cr2N are formed. So long as these nitrides precipitate in a fine state of not greater than 0.5 μm, they contribute toward increasing the strength of the steels. However, the Cr nitrides formed in the steel, to which merely a large amount of N is added, are hexagonal and poor in coherency with the austenite matrix, as described above. Therefore, the Cr nitrides tend to aggregate and become coarse and, after coarsening, they cause decreases in ductility and toughness.
The coherency, so referred to above, is a matching ability between nitrides and austenite due to the differences in the crystal structure and the lattice constant. When the structure and the lattice constant are identical, the coherency becomes best. Therefore, when utilizing nitrides in the steel of the present invention, it is desirable that nitrides in a fine state of not greater than 0.5 μm be precipitated and dispersed in an amount of not less than 0.01% by volume.
The nitride size is evaluated herein in terms of the maximum diameter after conversion of the sectional shapes of nitrides to equivalent circles.
(c) The fine nitrides of not greater than 0.5 μm contain not less than 10% by mass of V within them:
When N is added in large amounts to the conventional high-Cr austenitic stainless steels, the nitrides such as CrN and Cr2N generally occur in a most stable state. These nitrides are not good in the coherency with the matrix, so that they tend to aggregate and become coarse. However, as V is dissolved as a solid-solution in the nitrides, the lattice constants of the nitrides vary gradually, even when the Cr nitrides remain hexagonal, with the result that the coherency with the austenite matrix is improved; thus, V contributes to improvements in strength and toughness. For producing these effects, the content of V in the nitrides is desirably not less than 10% by mass.
(d) The fine nitrides of not greater than 0.5 μm are face-centered cubic in crystal structure:
When the nitrides have the same face-centered cubic crystal structure as the austenite matrix, the nitrides precipitate coherently with the austenite matrix and will hardly aggregate to become coarse. Therefore, it is desirable that at least part of the Cr nitrides have the face-centered cubic crystal structure.
As shown in Example described hereinafter, the austenitic stainless steel of the invention is not only high in strength but is also excellent in ductility and toughness. In addition, its hydrogen embrittlement susceptibility is low even in a high-pressure hydrogen environment. Therefore, this steel is very useful as a material for the manufacture of containers, piping, and accessory parts or devices for high-pressure hydrogen gas. The term “high-pressure hydrogen gas”, as used herein, means hydrogen gas under a pressure of not lower than 50 MPa, in particular not lower than 70 MPa.
2. Containers and so Forth According to the Present Invention
The containers and so forth, according to the present invention include containers, piping, and accessory parts and devices belonging thereto, which are manufactured from the stainless steel mentioned above and to be used for high-pressure hydrogen gas. In cases where the containers and so forth contain one or more welded joints, the weld metal desirably has the chemical composition described hereinabove. Hereinafter, the components of weld metal, by which the welded joints are characterized, will be described.
C: not more than 0.02%
When C content exceeds 0.02%, carbides are formed and the ductility and toughness of the weld metal are thereby markedly decreased. Therefore, the C content is not higher than 0.02% and desirably is as low as possible.
Si: not more than 1.0%
Si is an element necessary as a deoxidizer. However, it forms intermetallic compounds in the weld metal and thereby deteriorates the toughness. Therefore, its content should be not higher than 1.0% and is desirably as low as possible. A desirable Si content level is not higher than 0.5%, more desirably, not higher than 0.2%. The lower limit may be the impurity level.
Mn: 3 to 30%
Mn is effective as an element for increasing the solubility of N and thereby preventing N from being released during welding. For obtaining such effects, a content of not lower than 3% is required. On the other hand, when welding materials are manufactured, from the viewpoint of hot workability in the processing into rods or wires, its content is desirably low; hence the upper limit is set at 30%. Amore desirable upper limit is 25%.
Cr: more than 22% but not more than 30%
Cr is an element necessary for improving the corrosion resistance in a high-pressure gas environment and, further, for securing the stress corrosion cracking resistance. For obtaining such effects, a content exceeding 22% is required in the weld metal as well as the base metal. However, when Cr becomes excessive, such mechanical properties as toughness and workability may deteriorate, hence the upper limit is set at 30%.
Ni: 8 to 30%
Ni is an element necessary for stabilizing the austenite phase in the weld metal. For producing this effect, a content of not lower than 8% is necessary. However, the content of 30% is sufficient to obtain such an effect, and a higher content unfavorably causes an increase in welding material cost.
V: 0.001 to 1.0%
In the weld metal, V produces the following effects on the condition that Nieq and Creq satisfy the relationship [2] given hereinabove. Thus, within the range, in which the relationship given in [2] is satisfied, when the mode of solidification of the weld metal is such that primary crystals is δ ferrite phase and the austenite phase appears from the eutectic reaction in the middle and later stages of solidification, the concentration of V in the remaining liquid phase is inhibited. Therefore, V does not segregate among the primary crystal dendrite branches. As a result, V efficiently combines with N in the process of solidification to form fine VN, therefore it becomes possible to prevent toughness deterioration. This effect becomes significant at a level of not lower than 0.001%. However, when it exists at an excessive level, exceeding 1.0%, the effect saturates and only the disadvantage of higher production cost becomes significant.
Mo: 0 to 3.0%, W: 0 to 6.0%
Mo and W are elements which are effective in improving the strength and corrosion resistance of the weld metal, and may be added according to need. When Mo and W are added at excessive levels, they segregate and cause a decrease in ductility. When they are added, the upper content limit should be set at 3.0% for Mo and at 6.0% for W.
N: 0.1 to 0.5%
N is necessary for securing the strength of the weld metal. N dissolves as a solid solution in the weld metal and contributes to strengthening and, at the same time, combines with V to form fine nitrides and thus contributes to precipitation hardening. At levels lower than 0.1%, these effects are weak. On the other hand, an excessive addition of N will bring about welding defects, such as blowholes; hence the upper content limit is set at 0.5%.
Al: not more than 0.1%
Al is an element effective as a deoxidizing element. However it combines with N to form nitrides and thereby weakens the effects of the addition of N. Therefore, it is recommended that the Al content not be more than 0.1%. A desirable content is not more than 0.05%, more desirably not more than 0.02%.
Ti, Nb, Zr, Hf and Ta: 0 to 0.01% respectively
These elements form fine nitrides in the process of solidification of the weld metal and thus contribute to strength improvement. Therefore, they may be added according to need. When they are added at excessive levels, however, they may cause the formation of coarse nitrides, not only failing to contribute to strength improvement but also deteriorating the toughness. Therefore, when they are added, it is recommended that the content of each not be higher than 0.01%. When they are added, the content of each is desirably not lower than 0.001%.
P: not more than 0.030%
P is an unfavorable impurity deteriorating the toughness of the weld metal. Its content should not be more than 0.030% and is desirably as low as possible.
S: not more than 0.005%
S is a very harmful element segregating at grain boundaries in the weld metal and thereby weakening the bonding strength among grains and deteriorating the weldability, hence it is necessary to set an upper limit. Its content should not be more than 0.005%, and is desirably as low as possible.
The weld metal is required to satisfy the condition specified by the elationship [2]. The relationship [2] is the following:
−11≦Nieq−1.1×Creq <−8 [2]
where
Nieq=Ni+30×(C+N)−0.5×Mn [3]
and
Creq=Cr+Mo+1.5×Si [4].
First, when Nieq−1.1×Creq≦−8, the solidification segregation of V is weakened and it becomes possible for fine VN to precipitate upon only post-welding heat treatment. This is because the solidification mode becomes such that primary crystals form δ ferrite phase and the austenite phase is formed by the eutectic reaction in the middle and later stages of solidification, so that the concentration of V in the remaining liquid phase and the segregation of V among dendrite branches can be prevented.
On the other hand, the low temperature toughness and hydrogen embrittlement resistance characteristics of the weld metal are improved by satisfying the condition −11≦Nieq−1.1×Creq. When this condition is satisfied, the hydrogen cracking susceptibility after solidification and cooling of the weld metal decreases and, at the same time, the amount of δ ferrite, which is brittle at low temperatures, is reduced, whereby good low temperature toughness can be secured.
The above weld metal may contain at least one element selected from the above-mentioned second group elements and third group elements. The effects of these elements and the grounds for restrictions on the contents thereof are as described above, referring to the stainless steel of the present invention.
Regarding the welded joints of the containers and so forth, according to the present invention, it is only necessary that the composition of the weld metal resulting from melting and mixing of the base metal and welding material should satisfy the requirements described above. Practically, it is necessary to select the welding material according to the composition of the base metal. The base metal dilution rate, which is defined as the proportion of the base metal composition in the composition of the weld metal, depends on the method of welding. In the case of TIG and MIG welding, it is about 5 to 30% and, in the case of submerged arc welding, it is about 40 to 60%. Therefore, when the base metal composition is given, the composition of the welding material can be selected by making calculations so that the weld metal composition may fall within the ranges mentioned above, considering the base metal dilution rate. After welding, aging heat treatment is carried out at 550 to 700° C. for about 30 to 100 hours, thereby high-strength welded joints with a tensile strength of not lower than 800 MPa can be obtained.
The following examples illustrate the effects of the present invention more specifically.
Chemical compositions (% by mass) of austenitic stainless steels according to the present invention are shown in Table 1, and those of conventional steels and steels for comparison are shown in Table 2. For indicating whether each chemical composition satisfies the relationship [1] or not, the values of “Pmcn2=5Cr+3.4Mn−500N” are also given. When Pmcn2 is not larger than 0 (zero), the relationship [1], namely “5Cr+3.4Mn≦500N”, is satisfied.
The steels having the respective compositions specified in Table 1 and Table 2 were melted by using a 150-kg vacuum induction-melting furnace, and made into ingots. The ingots were then soaked at 1,200° C. for 4 hours, and hot-forged at 1,000° C. or above to produce plates, 25 mm in thickness and 100 mm in width. The plates were then subjected to a solution treatment for 1 hour at 1,000° C., followed by water-cooling. The plates were used for test specimens.
The steels of the present invention all showed an austenitic single-phase structure as shown in
Specimens for tensile test (diameter: 4 mm, GL: 20 mm), specimens for tensile test in a hydrogen gas environment (diameter: 2.54 mm, GL: 30 mm), 2V-notched specimens for Charpy impact test (10 mm×10 mm×55 mm) and 0.25U-notched specimens (2 mm×10 mm×75 mm) for the four-point bent stress corrosion cracking test were cut out from the plate mentioned above. The tensile test was carried out at room temperature, and Charpy impact test at 0° C. The tensile test in a hydrogen gas environment was carried out at room temperature in a high-pressure (75 MPa) hydrogen gas environment at a strain rate of 1×10−4/s. Comparisons were made in performance characteristics with the conventional steels and steels for comparison.
The stress corrosion cracking test was carried out for 72 hours of immersion in vapor-saturated synthetic seawater at 90° C., under a stress load of 1.0 σy, and judgments were made as to the occurrence or nonoccurrence of cracking. The results are shown in Table 3, Table 4 and
For the steels No. 1 to 20 of the present invention, the TS (tensile strength) at room temperature is 1 GPa or higher, the YS (yield strength) is 600 MPa or higher, and the elongation is 30% or higher. In addition, the toughness (vEo: absorbed energy) is 50 J or higher. Thus, they are very high in strength and high in ductility and in toughness. Further, the hydrogen embrittlement susceptibility, which was evaluated based on the ductility in the tensile test in a hydrogen gas environment, is very small. Furthermore, the stress corrosion cracking resistance is good.
The steels for comparison, namely No. G to Y, on the contrary, do not satisfy the range requirements in accordance with the present invention with respect to the content of at least one component or the Pmcn2 value. These are not satisfactory in any one of the features including strength, ductility, toughness and hydrogen embrittlement resistance.
As shown in
In
As shown in the figures, it is possible to further improve either the strength or the toughness by employing the metallurgical structure defined herein.
Base metals [M1 and M2], having the respective chemical compositions specified in Table 5, were melted in a 50-kg vacuum high-frequency furnace and then forged to produce 25-mm-thick plates, which were subjected to heat treatment by maintaining at 1,000° C. for 1 hour, followed by water cooling. The plates were used for test specimens. Similarly, alloys W1, W2, Y1 and Y2, having the respective chemical composition specified in Table 5, were melted in a 50-kg vacuum high-frequency furnace and then worked into wires with an outer diameter of 2 mm to produce welding materials. For weldability evaluation, welded joints were made in the manner mentioned below and subjected to evaluation tests.
The plates (25 mm thick, 100 mm wide, 200 mm long) were provided with a V groove with an angle of 20 degrees on one side. Pairs of such plates identical in composition were butted against each other, and welded joints were produced by multilayer welding in the grooves by the TIG welding using welding materials shown in Table 5, in combinations with the base metals as shown in Table 6 and Table 7. The welding conditions were as follows:
Welding current; 130 A,
Welding voltage; 12 V,
Welding speed; 15 cm/min.
Tensile test specimens, having a parallel portion with an outer diameter of 6 mm and a length of 30 mm, and having the weld metal in the middle of the parallel portion, and test specimens for a tensile test in a hydrogen gas environment, having a parallel portion with an outer diameter of 2.54 mm and a length of 30 mm, and having the weld metal in the middle of the parallel portion, were respectively taken from the above welded joints in the direction perpendicular to the weld line. Further, Charpy impact test specimens of “10×10×55 mm”, having a 2-mm-deep V notch in the middle of the weld metal, were also taken in the direction perpendicular to the weld line.
Tensile test was carried out at room temperature, and the Charpy impact test at −60° C., and the welded joints were then evaluated for strength and toughness. The tensile tests in a hydrogen gas environment were carried out at room temperature in a high-pressure, 75 MPa, hydrogen gas environment at a strain rate of 1×10−4/s.
In evaluating the results, the tensile strength was judged to be successful when it was not lower than 800 MPa, the toughness to be successful when the Charpy absorbed energy was not lower than 20 J, and the hydrogen embrittlement resistance to be successful when the ratio of the elongation at rupture in the tensile test in the hydrogen gas environment to that in the tensile test in the air was not lower than 0.8. The results are shown in Table 7, wherein the mark “◯” means “successful”.
As is evident from Table 7, the joints A1 to A4, in which the weld metal meets the requirement of the present invention, are above the criteria given hereinabove in all the aspects of tensile strength, toughness and Charpy absorbed energy. As for the hydrogen embrittlement resistance, the ratios of the elongation at rupture in the tensile test in the hydrogen gas environment to that in tensile test in the air were not lower than 0.8. Thus, these joints not only have high strength but also show superior toughness and hydrogen embrittlement resistance.
On the contrary, the joints B1 and B2, in which the relationship [2] given hereinabove is not satisfied, even though the contents of the respective elements are within the respective ranges defined herein, did not acquire good toughness or hydrogen embrittlement resistance, while they have high strength, since, in the most important late stage of solidification, other nuclei for solidification appear from the liquid phase and other solid phase grows around those nuclei.
The austenitic stainless steel of the present invention has superior mechanical properties and corrosion resistance, for instance, hydrogen cracking resistance, and also is excellent in stress corrosion cracking resistance. This steel is very useful as a material for containers or devices for handling high-pressure hydrogen gas, mainly cylinders for fuel cell-powered vehicles, hydrogen storage vessels for hydrogen gas stations or the like.
The containers and so forth, according to the invention, are suited for use as piping, containers and the like for high-pressure hydrogen gas, since even when they have a welded joint or joints, the weld metal is excellent in low temperature toughness and the hydrogen embrittlement resistance and high in strength.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2003-079120 | Mar 2003 | JP | national |
This application is a continuation of International Patent Application No. PCT/JP2004/003797 filed Mar. 19, 2004. This PCT Application was not in English as published under PCT Article 21(2).
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| Number | Date | Country | |
|---|---|---|---|
| 20050178478 A1 | Aug 2005 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2004/003797 | Mar 2004 | US |
| Child | 11108099 | US |
