WO2016039429A1 - Austenitic stainless steel sheet which is not susceptible to diffusion bonding - Google Patents
Austenitic stainless steel sheet which is not susceptible to diffusion bonding Download PDFInfo
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- WO2016039429A1 WO2016039429A1 PCT/JP2015/075766 JP2015075766W WO2016039429A1 WO 2016039429 A1 WO2016039429 A1 WO 2016039429A1 JP 2015075766 W JP2015075766 W JP 2015075766W WO 2016039429 A1 WO2016039429 A1 WO 2016039429A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
- C25F1/06—Iron or steel
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
Definitions
- the present invention relates to an austenitic stainless steel sheet that is difficult to be diffusion bonded.
- Austenitic stainless steel is used for heat-resistant parts such as exhaust gaskets for automobiles and motorcycles that require high heat resistance. From the viewpoint of improving fuel consumption, exhaust temperatures are increasing year by year, and these heat-resistant components may be exposed to high temperatures of 700 ° C. or higher. At such a high temperature, in addition to softening of the material, there is a problem that it joins with surrounding parts. This is a phenomenon called diffusion junction in which atoms in contact with each other diffuse.
- Patent Document 1 proposes a ferritic stainless steel that is difficult to be diffusion bonded by adding 3 to 10% Al and forming an Al 2 O 3 film.
- ferritic stainless steel cannot provide sufficient high-temperature strength as an exhaust system gasket. Further, as disclosed in Patent Document 1, when a large amount of Al is added, inclusions made of AlN are easily generated, and a thin part such as a gasket has a remarkable adverse effect on fatigue characteristics.
- An object of the present invention is to provide industrially stable austenitic stainless steel that is difficult to be diffusion bonded even at high temperatures in order to solve the problems of the prior art.
- the present inventors considered that the diffusion bondability is greatly influenced by the surface film of the steel sheet, and investigated and examined the relationship between the composition and thickness of the film and the structure of the film constituent material and the diffusion bondability. As a result, it is effective to suppress diffusion bonding by reducing the amount of Fe in the film and concentrating the amount of Si present as SiO 2 in the film and increasing the thickness of the Si-concentrated layer. I found out.
- SiO 2 in the film on the surface of the austenitic stainless steel is hard to disappear even at a high temperature as compared with Cr 2 O 3 which is a general stainless steel film, it has an effect of suppressing bonding.
- Fe is present in a large amount in the base material of austenitic stainless steel, it can be present in the vicinity of the bonding interface as an Fe oxide.
- the Fe oxide easily disappears in the diffusion bonding process as compared with the above-described SiO 2 and Cr 2 O 3 . For this reason, when a large amount of Fe is present in the vicinity of the bonding interface, even if SiO 2 in the surface film is concentrated, it is difficult to suppress the diffusion of Fe, and the effect of suppressing the bonding is insufficient. It becomes. Therefore, it is important to reduce Fe in the surface coating and concentrate Si present as SiO 2 .
- FIG. 1 shows the relationship between the heat treatment temperature (° C.), the maximum Si amount (mass%) in the coating on the stainless steel surface after the heat treatment, and the Si concentrated layer thickness (nm).
- This experiment was performed using a heat treatment furnace in a mixed gas atmosphere (dew point: -50 ° C.) containing N 2 : 90 vol% and H 2 : 10 vol% and changing various temperatures.
- dew point -50 ° C.
- N 2 90 vol%
- H 2 10 vol%
- the heat treatment conditions are specifically the treatment temperature, the atmosphere, and the dew point.
- the treatment temperature is a temperature after soaking for a certain time in a heat treatment furnace set to a predetermined temperature, and specifically, is the same as the set temperature of the heat treatment furnace.
- FIG. 2 shows the relationship between the current density during electrolytic treatment (mA / cm 2 ) and the maximum amount of Si (mass%) in the coating on the stainless steel surface.
- the inventors have found that an austenitic stainless steel sheet capable of achieving the object of the present invention can be provided industrially stably at a specific current density because the amount of Si in the film is very large.
- the present invention has been made based on the above findings, and the gist thereof is as follows.
- An austenitic stainless steel sheet having a film formed on at least a part of its surface The chemical composition of the austenitic stainless steel sheet is mass%, C: 0.01% or more and 0.10% or less, Si: 0.2% or more and 2.0% or less, Mn: 1.5% or less, Mo: 1.0% or less, Cr: 15.0% to 22.0%, Ni: 4.5% or more and 10.0% or less, Cu: 1.0% or less, Nb: 0.30% or less, N: 0.01% or more and 0.15% or less, The balance is Fe and inevitable impurities,
- the film includes a Si-concentrated layer having a maximum Si amount in a range from the surface layer to 10 nm of 10.0% or more and a maximum Fe amount of 8.5% or less, An austenitic stainless steel sheet in which the thickness of the Si-concentrated layer is 5 nm or more and is difficult to be diffusion bonded.
- the chemical composition of the steel sheet of the present invention is the chemical composition necessary for obtaining an austenitic stainless steel sheet, heat resistance such as high-temperature strength, and chemical composition necessary for obtaining a high Si film. In addition, it is stipulated. Specifically, it is as follows. However,% means the mass%.
- C 0.01% or more and 0.10% or less
- C is an element that contributes to high strength at high temperatures by solid solution strengthening or precipitation strengthening. Therefore, C is contained in an amount of 0.01% or more. Preferably it is 0.03% or more. If it is contained in a large amount, coarse Cr carbide precipitates at the grain boundaries during heat treatment, and the oxidation resistance at high temperature is lowered, so the content is made 0.10% or less. Preferably it is 0.08% or less.
- Si 0.2% or more and 2.0% or less Si is one of the most important elements in the steel sheet of the present invention.
- Si is an element that forms a high Si amount film composed of SiO 2 on the surface of the steel sheet and makes diffusion bonding difficult. Therefore, Si is contained by 0.2% or more. Preferably, it is 0.31% or more, more preferably 0.5% or more. If contained in a large amount, the toughness is reduced and the manufacturability of the plate is deteriorated, so the content is made 2.0% or less. Preferably it is 1.8% or less, More preferably, it is 1.20%.
- Mn 1.5% or less Mn is an element that contributes to preventing brittle fracture during hot working and strengthening steel. However, if contained in a large amount, the corrosion resistance deteriorates, so the content is made 1.5% or less. Preferably it is 1.35% or less, More preferably, it is 1.2% or less.
- the lower limit includes 0%, but unavoidably about 0.001% is mixed from the iron raw material and usually remains in the steel sheet. Therefore, 0.001% is a practical lower limit. In order to surely obtain the above effect, 0.21% or more is preferable, and 0.5% or more is more preferable.
- Mo 1.0% or less Mo is an element contributing to the improvement of corrosion resistance. However, even if contained in a large amount, the cost is significantly increased, so the content is made 1.0% or less. Preferably, it is 0.80% or less, more preferably 0.7% or less.
- the lower limit includes 0%, but it is unavoidably mixed from the iron raw material and about 0.001% and remains in the steel sheet. Therefore, 0.001% is a practical lower limit. In order to surely obtain the above effect, 0.02% or more is preferable, and 0.5% or more is more preferable.
- Cr 15.0% or more and 22.0% or less
- Cr is a basic element of stainless steel, and is an element that forms a metal oxide layer Cr 2 O 3 on the surface of the steel sheet and enhances corrosion resistance. Therefore, Cr is contained 15.0% or more. Preferably it is 16.1% or more, more preferably 17.0% or more. However, Cr is also a strong ferrite stabilizing element, and if it is contained in a large amount, ⁇ ferrite that inhibits the hot workability of the material is generated, so its content is made 22.0% or less. Preferably it is 21.0%, More preferably, it is 20.0% or less.
- Ni 4.5% or more and 10.0% or less
- Ni is an austenite-generating element and is an element necessary for stabilizing the austenite phase at room temperature.
- Ni is also an element effective for improving high-temperature strength. Therefore, Ni is contained 4.5% or more. Preferably it is 4.9% or more, more preferably 5.0% or more.
- the Ni content is 10.0% or less. Preferably it is 9.5% or less, More preferably, it is 8.0% or less.
- Cu 1.0% or less
- Cu is an austenite-forming element and is an element capable of adjusting the stability of the austenite phase. However, if it is contained in a large amount, it segregates at the grain boundary during the production process, remarkably hinders hot workability and makes production difficult. Preferably it is 0.8% or less, More preferably, it is 0.70% or less.
- the lower limit includes 0%, but it is unavoidably mixed from the iron raw material and about 0.001% and remains in the steel sheet. Therefore, 0.001% is a practical lower limit. In order to surely obtain the above effect, 0.02% or more is preferable, and 0.5% or more is more preferable.
- Nb 0.30% or less
- Nb is an element that forms fine carbides or nitrides, contributes to high strength, and suppresses softening due to recrystallization at high temperatures. However, even if contained in a large amount, the cost is increased, so the content is made 0.30% or less. Preferably it is 0.20% or less, More preferably, it is 0.079% or less.
- the lower limit includes 0%, but it is unavoidably mixed from the iron raw material and about 0.001% and remains in the steel sheet. Therefore, 0.001% is a practical lower limit. In order to surely obtain the above effect, 0.01% or more is preferable.
- N 0.01% or more and 0.15% or less
- N is a solid solution strengthening element, and is an element contributing to the improvement of high temperature strength. Therefore, N is contained by 0.01% or more. Preferably it is 0.03% or more, More preferably, it is 0.04% or more. On the other hand, if it is contained in a large amount, a large number of coarse nitrides that become the starting point of fracture are produced in the production process of the steel sheet, hot workability is deteriorated, and production may be difficult. The following. Preferably it is 0.13% or less, More preferably, it is 0.12% or less.
- the balance is Fe and inevitable impurities.
- the austenitic stainless steel sheet of the present invention has a film formed on at least a part of the surface, and after reducing Fe in the film, the maximum Si content in the range from the surface layer to 10 nm is 10%.
- the Si-enriched layer having the maximum Fe content of 8.5% or less is provided.
- the film is an oxide film mainly composed of an oxide.
- Si in the film in the present invention exists mainly as Si oxide (SiO 2 ). Si oxide exists stably at high temperature compared with Cr oxide which is a general film composition of stainless steel.
- the Si content on the outermost surface of the coating is set to 10.0% or more. Preferably it is 12.5% or more, More preferably, it is 14.0% or more.
- the upper limit is not particularly defined, but is 30.0% on the practical steel plate.
- Maximum Fe content in the range from the surface layer to 10 nm 8.5% or less Since Fe is present in a large amount in the base material of austenitic stainless steel, it can be present in the vicinity of the bonding interface as Fe oxide. However, Fe oxide disappears more easily in the diffusion bonding process than SiO 2 and Cr 2 O 3 . For this reason, when a large amount of Fe is present in the vicinity of the bonding interface, even if SiO 2 in the surface film is concentrated, it is difficult to suppress the diffusion of Fe, and the effect of suppressing the bonding is insufficient. It becomes. Therefore, the maximum Fe content in the range from the surface layer to 10 nm is set to 8.5% or less.
- Si-enriched layer thickness 5 nm or more
- the thickness of the Si concentrated layer is set to 5 nm or more. Preferably it is 8 nm or more.
- FIG. 3 shows the definition of the maximum Si amount (% by mass) and the Si concentrated layer thickness (nm) based on the relationship between the distance from the surface (nm) and the Si amount (% by mass).
- the thickness of the Si concentrated layer is a thickness until the Si amount becomes 1/2 of the maximum Si amount (1/2 Si amount in the figure).
- the Si amount on the outermost surface of the film is 10% or more as a surface state in which diffusion bonding is difficult.
- finish annealing of austenitic stainless steel is performed in a mixed atmosphere of H 2 and N 2 in order to maintain surface gloss, and the temperature is about 1100 to 1150 ° C.
- the coating may be partially broken or divided, and a new Cr oxide coating may be generated on the new surface, thereby reducing the amount of Si in the coating.
- the finish annealing is preferably carried out by maintaining at 750 to 1000 ° C. in a mixed atmosphere of H 2 and N 2 . This is because a predetermined Si-enriched layer is formed on the surface layer of the film (see FIG. 1).
- a preferable lower limit of the treatment temperature is 800 ° C, and a preferable upper limit is 950 ° C.
- the in-furnace time is not particularly defined as long as the steel plate can be soaked at the above processing temperature, but if the time is too short, Si concentration in the film may be insufficient, so the in-furnace time is 10 seconds or more is desirable.
- the dew point of the mixed atmosphere of H 2 and N 2 is high, the film formed during the heat treatment becomes a film mainly composed of Cr oxide, so the dew point is preferably ⁇ 45 ° C. or lower. Preferably, it is ⁇ 60 ° C. or lower. On the other hand, in order to obtain an excessively low dew point, a large cost is required. Therefore, in practice, the dew point is set to ⁇ 70 ° C. or higher. Preferably, it is ⁇ 65 ° C. or higher.
- the mixing ratio of H 2 and N 2 is not particularly limited, but the mixing ratio is preferably 1/19 or more in order to obtain an atmosphere exhibiting sufficient reducing properties.
- increasing the proportion of expensive hydrogen gas has a problem in economy, so it is preferable to set it to 1/2 or less.
- an electrolytic cleaning process is performed in which the steel sheet after heat treatment is subjected to electrolytic treatment in a predetermined liquid to remove the film generated by the heat treatment.
- the film-modified electrolytic treatment has a part in common with the conventional electrolytic cleaning treatment in that the electrolytic treatment is performed in a predetermined solution.
- the film-modified electrolytic treatment is performed after reducing Fe in the film and then in the film. This is greatly different in that it is performed to enrich Si.
- the steel sheet is preferably passed through a nitric acid aqueous solution having a liquid temperature of 30 to 50 ° C. and a concentration of about 5 to 10% while applying a voltage so that the steel sheet becomes positive. If the liquid temperature or concentration is too low, a sufficient reforming effect cannot be obtained, and if the liquid temperature or concentration is too high, the surface roughness of the steel sheet may be increased or the electrolytic cell may be damaged.
- This electrolytic treatment is preferably performed so that the current density is 100 mA / cm 2 or more with respect to the plate area.
- Si is concentrated after reducing Fe in the film on the surface of the steel sheet (see FIG. 2).
- it is 150 mA / cm 2 or more.
- Si in the electrolysis process, Fe, Cr, etc. are eluted and removed from the surface by oxidation reaction, but Si present as SiO 2 is not oxidized any more and remains on the surface. It is to do.
- Si does not concentrate on the steel sheet surface, and particularly when the current density is about 20 mA / cm 2, which is the current density during general electrolytic cleaning treatment, the amount of Si is reduced. (See FIG. 2).
- the current density is preferably 300 mA / cm 2 or less (see FIG. 2). Preferably it is 250 mA / cm 2 or less.
- the concentration of Si is small, so the energization time should be 10 seconds or more. Preferably it is 15 seconds or more.
- the upper limit of the energization time is not particularly defined, but is practically about 60 seconds.
- a voltage may be applied by using a steel plate as a positive electrode or a negative electrode, or a voltage may be applied by alternately repeating positive and negative, but the time for energization using the steel plate as a positive electrode is more than twice the time for energization as a negative electrode. To do. Also in this case, the time for energizing the steel plate as positive is set to 10 seconds or more.
- the conditions in the examples are one example of conditions used for confirming the feasibility and effects of the present invention, and the present invention is based on this one example of conditions. It is not limited.
- the present invention can adopt various conditions as long as the object of the present invention is achieved without departing from the gist of the present invention.
- Table 1 shows the chemical composition of the test steel.
- the maximum Si amount is the Si amount (% by mass) at which the Si amount is maximum
- the maximum Fe amount is the Fe amount (% by mass) at which the Fe amount is maximum
- the Si concentrated layer thickness is the outermost surface To a position where the Si amount is a half of the maximum Si amount.
- the steel plate was processed into two ⁇ 8 mm disk-shaped test pieces. Two test pieces were overlapped, and a load of 20 MPa was applied in a vacuum chamber at 750 ° C., followed by pressurization for 30 seconds.
- Steel plates 1 to 7 (invention examples) shown in Table 2 are steel plates that satisfy the provisions of the present invention and are difficult to be diffusion bonded.
- the steel plates 8 to 13 of the comparative examples are steel plates that are easy to be diffusion bonded.
- the steel sheet 8 has a very low maximum Si content in the film. This is due to the low temperature of the film modification heat treatment.
- the steel sheet 9 is a steel sheet that has a high dew point at the time of film reforming heat treatment and is easy to be diffusion bonded because it is a film mainly composed of Cr oxide.
- the steel plate 10 is SUS304, which was prototyped under relatively general manufacturing conditions. Although the heat treatment temperature and the current density during the electrolytic treatment have general conditions, the maximum amount of Si in the film is low and the Si concentrated layer depth is also small, so that the steel plate 10 is a steel plate that is easily joined. Since the maximum amount of Si is extremely low, the steel plate 11 is a steel plate that does not concentrate Si on the surface of the steel plate even by a film reforming heat treatment under appropriate conditions and is easily diffusion bonded.
- the steel plate 12 is also a steel plate that is easy to be diffusion bonded because the maximum amount of Si in the film is low and the Si concentrated layer depth is also small. This is because the film modification heat treatment and the film modification electrolytic treatment are not performed.
- the steel plate 13 is a steel plate that is easily diffusion-bonded because the maximum amount of Si in the film is in the range defined by the present invention, but the maximum Fe amount is excessive. This is because the energization time as a negative electrode is long.
- the maximum Si amount in the Si concentrated layer is 10% by mass or more, the Si concentrated layer thickness is 5 nm or more, and the maximum Fe amount in the Si concentrated layer is 8.5% or less.
- the ratio of the grain boundary straddling the bonding interface is rapidly reduced, and the effect of suppressing diffusion bonding is exhibited.
- “ ⁇ ” in the figure is the point of Comparative Example 13.
- the maximum amount of Si in the film is in the range specified by the present invention, but the maximum Fe amount is excessive, so that the ratio of grain boundaries straddling the bonding interface was high.
- the present invention it is possible to provide industrially stable austenitic stainless steel that is difficult to be diffusion bonded even at high temperatures. Therefore, the present invention has high applicability in the stainless steel manufacturing / utilizing industry.
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Abstract
Description
前記オーステナイト系ステンレス鋼板の化学組成が、質量%で、
C:0.01%以上0.10%以下、
Si:0.2%以上2.0%以下、
Mn:1.5%以下、
Mo:1.0%以下、
Cr:15.0%以上22.0%以下、
Ni:4.5%以上10.0%以下、
Cu:1.0%以下、
Nb:0.30%以下、
N:0.01%以上0.15%以下、
残部がFe及び不可避不純物であり、
前記皮膜が、その表層から10nmまでの範囲の最大Si量が10.0%以上で、かつ最大Fe量が8.5%以下であるSi濃化層を備え、
前記Si濃化層の厚さが5nm以上である、拡散接合し難いオーステナイト系ステンレス鋼板。 (1) An austenitic stainless steel sheet having a film formed on at least a part of its surface,
The chemical composition of the austenitic stainless steel sheet is mass%,
C: 0.01% or more and 0.10% or less,
Si: 0.2% or more and 2.0% or less,
Mn: 1.5% or less,
Mo: 1.0% or less,
Cr: 15.0% to 22.0%,
Ni: 4.5% or more and 10.0% or less,
Cu: 1.0% or less,
Nb: 0.30% or less,
N: 0.01% or more and 0.15% or less,
The balance is Fe and inevitable impurities,
The film includes a Si-concentrated layer having a maximum Si amount in a range from the surface layer to 10 nm of 10.0% or more and a maximum Fe amount of 8.5% or less,
An austenitic stainless steel sheet in which the thickness of the Si-concentrated layer is 5 nm or more and is difficult to be diffusion bonded.
本発明鋼板の化学組成は、オーステナイト系ステンレス鋼板を得るのに必要な化学組成に、高温強度などの耐熱性、更に、高Si皮膜を得るのに必要な化学組成を加えて規定されている。具体的には、以下の通りである。ただし、%は、質量%を意味する。 1. Chemical composition of austenitic stainless steel sheet The chemical composition of the steel sheet of the present invention is the chemical composition necessary for obtaining an austenitic stainless steel sheet, heat resistance such as high-temperature strength, and chemical composition necessary for obtaining a high Si film. In addition, it is stipulated. Specifically, it is as follows. However,% means the mass%.
Cは、固溶強化や析出強化によって高温での高強度化に寄与する元素である。従って、Cは0.01%以上含有させる。好ましくは0.03%以上である。多量に含有すると、熱処理時に粗大なCr炭化物が結晶粒界に析出し、高温での耐酸化性が低下するので、その含有量は0.10%以下とする。好ましくは0.08%以下である。 C: 0.01% or more and 0.10% or less C is an element that contributes to high strength at high temperatures by solid solution strengthening or precipitation strengthening. Therefore, C is contained in an amount of 0.01% or more. Preferably it is 0.03% or more. If it is contained in a large amount, coarse Cr carbide precipitates at the grain boundaries during heat treatment, and the oxidation resistance at high temperature is lowered, so the content is made 0.10% or less. Preferably it is 0.08% or less.
Siは、本発明鋼板において最も重要な元素の一つである。Siは、鋼板表面にSiO2から構成されるSi量の高い皮膜を形成し、拡散接合をし難くする作用をなす元素である。従って、Siは0.2%以上含有させる。好ましくは、0.31%以上であり、より好ましくは、0.5%以上である。多量に含有すると、靭性が低下し、板の製造性が劣化するので、その含有量は2.0%以下とする。好ましくは1.8%以下であり、より好ましくは1.20%である。 Si: 0.2% or more and 2.0% or less Si is one of the most important elements in the steel sheet of the present invention. Si is an element that forms a high Si amount film composed of SiO 2 on the surface of the steel sheet and makes diffusion bonding difficult. Therefore, Si is contained by 0.2% or more. Preferably, it is 0.31% or more, more preferably 0.5% or more. If contained in a large amount, the toughness is reduced and the manufacturability of the plate is deteriorated, so the content is made 2.0% or less. Preferably it is 1.8% or less, More preferably, it is 1.20%.
Mnは、熱間加工時の脆性破壊防止と鋼の強化に寄与する元素である。しかし、多量に含有すると、耐食性が劣化するので、その含有量は1.5%以下とする。好ましくは1.35%以下であり、より好ましくは1.2%以下である。下限は0%を含むが、鉄原料から不可避的に0.001%程度混入し、通常は鋼板中に残留する。よって、0.001%が実質的な下限である。上記の効果を確実に得るためには、0.21%以上が好ましく、0.5%以上がより好ましい。 Mn: 1.5% or less Mn is an element that contributes to preventing brittle fracture during hot working and strengthening steel. However, if contained in a large amount, the corrosion resistance deteriorates, so the content is made 1.5% or less. Preferably it is 1.35% or less, More preferably, it is 1.2% or less. The lower limit includes 0%, but unavoidably about 0.001% is mixed from the iron raw material and usually remains in the steel sheet. Therefore, 0.001% is a practical lower limit. In order to surely obtain the above effect, 0.21% or more is preferable, and 0.5% or more is more preferable.
Moは、耐食性の向上に寄与する元素である。しかし、多量に含有させても、コストの大幅な上昇を招くので、その含有量は1.0%以下とする。好ましくは、0.80%以下、より好ましくは0.7%以下である。下限は0%を含むが、鉄原料から不可避的に0.001%程度混入し、鋼板中に残留する。よって、0.001%が実質的な下限である。上記の効果を確実に得るためには、0.02%以上が好ましく、0.5%以上がより好ましい。 Mo: 1.0% or less Mo is an element contributing to the improvement of corrosion resistance. However, even if contained in a large amount, the cost is significantly increased, so the content is made 1.0% or less. Preferably, it is 0.80% or less, more preferably 0.7% or less. The lower limit includes 0%, but it is unavoidably mixed from the iron raw material and about 0.001% and remains in the steel sheet. Therefore, 0.001% is a practical lower limit. In order to surely obtain the above effect, 0.02% or more is preferable, and 0.5% or more is more preferable.
Crは、ステンレス鋼の基本元素であり、鋼板表面に金属酸化物層Cr2O3を形成し、耐食性を高める作用をなす元素である。よって、Crは15.0%以上含有させる。好ましくは16.1%以上であり、より好ましくは17.0%以上である。しかし、Crは、強力なフェライト安定化元素でもあり、多量に含有すると、素材の熱間加工性を阻害するδフェライトが生成するので、その含有量は22.0%以下とする。好ましくは21.0%であり、より好ましくは20.0%以下である。 Cr: 15.0% or more and 22.0% or less Cr is a basic element of stainless steel, and is an element that forms a metal oxide layer Cr 2 O 3 on the surface of the steel sheet and enhances corrosion resistance. Therefore, Cr is contained 15.0% or more. Preferably it is 16.1% or more, more preferably 17.0% or more. However, Cr is also a strong ferrite stabilizing element, and if it is contained in a large amount, δ ferrite that inhibits the hot workability of the material is generated, so its content is made 22.0% or less. Preferably it is 21.0%, More preferably, it is 20.0% or less.
Niは、オーステナイト生成元素であり、室温でオーステナイト相を安定化するのに必要な元素である。また、Niは、高温強度の向上にも有効な元素でもある。よって、Niは4.5%以上含有させる。好ましくは4.9%以上であり、より好ましくは5.0%以上である。しかし、多量に含有すると、冷間圧延時の加工誘起マルテンサイト変態が抑制される。さらに、Niは高価な元素であり、多量の添加は、コストの大幅な上昇を招く。それ故、Ni含有量は10.0%以下とする。好ましくは9.5%以下であり、より好ましくは8.0%以下である。 Ni: 4.5% or more and 10.0% or less Ni is an austenite-generating element and is an element necessary for stabilizing the austenite phase at room temperature. Ni is also an element effective for improving high-temperature strength. Therefore, Ni is contained 4.5% or more. Preferably it is 4.9% or more, more preferably 5.0% or more. However, if contained in a large amount, the processing-induced martensitic transformation during cold rolling is suppressed. Furthermore, Ni is an expensive element, and a large amount of addition causes a significant increase in cost. Therefore, the Ni content is 10.0% or less. Preferably it is 9.5% or less, More preferably, it is 8.0% or less.
Cuは、オーステナイト生成元素であり、オーステナイト相の安定度を調整することが可能な元素である。しかし、多量に含有すると、製造過程で粒界に偏析し、熱間加工性を顕著に阻害し、製造が困難になる場合があるので、1.0%以下とする。好ましくは0.8%以下であり、より好ましくは0.70%以下である。下限は0%を含むが、鉄原料から不可避的に0.001%程度混入し、鋼板中に残留する。よって、0.001%が実質的な下限である。上記の効果を確実に得るためには、0.02%以上が好ましく、0.5%以上がより好ましい。 Cu: 1.0% or less Cu is an austenite-forming element and is an element capable of adjusting the stability of the austenite phase. However, if it is contained in a large amount, it segregates at the grain boundary during the production process, remarkably hinders hot workability and makes production difficult. Preferably it is 0.8% or less, More preferably, it is 0.70% or less. The lower limit includes 0%, but it is unavoidably mixed from the iron raw material and about 0.001% and remains in the steel sheet. Therefore, 0.001% is a practical lower limit. In order to surely obtain the above effect, 0.02% or more is preferable, and 0.5% or more is more preferable.
Nbは、微細な炭化物又は窒化物を形成して、高強度化に寄与し、高温での再結晶による軟化を抑制する作用をなす元素である。しかし、多量に含有させても、コストの上昇を招くので、0.30%以下とする。好ましくは0.20%以下であり、より好ましくは0.079%以下である。下限は0%を含むが、鉄原料から不可避的に0.001%程度混入し、鋼板中に残留する。よって、0.001%が実質的な下限である。上記効果を確実に得るためには、0.01%以上が好ましい。 Nb: 0.30% or less Nb is an element that forms fine carbides or nitrides, contributes to high strength, and suppresses softening due to recrystallization at high temperatures. However, even if contained in a large amount, the cost is increased, so the content is made 0.30% or less. Preferably it is 0.20% or less, More preferably, it is 0.079% or less. The lower limit includes 0%, but it is unavoidably mixed from the iron raw material and about 0.001% and remains in the steel sheet. Therefore, 0.001% is a practical lower limit. In order to surely obtain the above effect, 0.01% or more is preferable.
Nは、Cと同様に固溶強化元素であり、高温強度の向上に寄与する元素である。よって、Nは0.01%以上含有させる。好ましくは0.03%以上であり、より好ましくは0.04%以上である。一方、多量に含有すると、鋼板の製造過程で、破壊の起点となる粗大な窒化物が多数生成して、熱間加工性が劣化し、製造が困難となる場合があるので、0.15%以下とする。好ましくは0.13%以下であり、より好ましくは0.12%以下である。 N: 0.01% or more and 0.15% or less N, like C, is a solid solution strengthening element, and is an element contributing to the improvement of high temperature strength. Therefore, N is contained by 0.01% or more. Preferably it is 0.03% or more, More preferably, it is 0.04% or more. On the other hand, if it is contained in a large amount, a large number of coarse nitrides that become the starting point of fracture are produced in the production process of the steel sheet, hot workability is deteriorated, and production may be difficult. The following. Preferably it is 0.13% or less, More preferably, it is 0.12% or less.
本発明のオーステナイト系ステンレス鋼板は、表面の少なくとも一部に皮膜が形成されており、皮膜中のFeを低減した上で、その表層から10nmまでの範囲の最大Si量が10%以上で、かつ最大Fe量が8.5%以下であるSi濃化層を備える。皮膜は、主として酸化物で構成される、酸化皮膜である。 2. Si Concentrated Layer The austenitic stainless steel sheet of the present invention has a film formed on at least a part of the surface, and after reducing Fe in the film, the maximum Si content in the range from the surface layer to 10 nm is 10%. The Si-enriched layer having the maximum Fe content of 8.5% or less is provided. The film is an oxide film mainly composed of an oxide.
高温での拡散接合を抑制するためには、拡散を抑制する鋼板表面の皮膜を高温でも維持することが有効である。本発明における皮膜中のSiは、主としてSi酸化物(SiO2)として存在する。Si酸化物は、ステンレス鋼の一般的な皮膜組成であるCr酸化物と比較して、高温で安定して存在する。 Maximum amount of Si in the range from the surface layer to 10 nm: 10.0% or more In order to suppress diffusion bonding at high temperatures, it is effective to maintain a coating on the surface of the steel sheet that suppresses diffusion even at high temperatures. Si in the film in the present invention exists mainly as Si oxide (SiO 2 ). Si oxide exists stably at high temperature compared with Cr oxide which is a general film composition of stainless steel.
Feは、オーステナイト系ステンレス鋼の母材に多量に存在するため、Fe酸化物として接合界面近傍に存在し得る。しかし、Fe酸化物は、SiO2およびCr2O3に比べて拡散接合工程において容易に消失する。このため、接合界面近傍にFeが多量に存在する場合は、表面皮膜中のSiO2を濃化させたとしても、Feの拡散を抑制することが困難であり、接合を抑制する効果は不十分となる。よって、表層から10nmまでの範囲の最大Fe量を8.5%以下とする。 Maximum Fe content in the range from the surface layer to 10 nm: 8.5% or less Since Fe is present in a large amount in the base material of austenitic stainless steel, it can be present in the vicinity of the bonding interface as Fe oxide. However, Fe oxide disappears more easily in the diffusion bonding process than SiO 2 and Cr 2 O 3 . For this reason, when a large amount of Fe is present in the vicinity of the bonding interface, even if SiO 2 in the surface film is concentrated, it is difficult to suppress the diffusion of Fe, and the effect of suppressing the bonding is insufficient. It becomes. Therefore, the maximum Fe content in the range from the surface layer to 10 nm is set to 8.5% or less.
前述のとおり、皮膜中のSi量が多いと拡散接合が抑制されるが、Si濃化層が薄いと、長時間、高温に曝された際、皮膜が、徐々に金属と酸素ガスに分解され、ステンレス鋼部品同士が接合してしまう。それ故、Si濃化層の厚さを5nm以上とする。好ましくは8nm以上である。 Si-enriched layer thickness: 5 nm or more As described above, diffusion bonding is suppressed when the amount of Si in the film is large. However, when the Si-enriched layer is thin, the film is exposed to high temperatures for a long time. It is gradually decomposed into metal and oxygen gas, and the stainless steel parts are joined together. Therefore, the thickness of the Si concentrated layer is set to 5 nm or more. Preferably it is 8 nm or more.
次に、本発明のオーステナイト系ステンレス鋼板を製造するのに適した方法について説明する。溶製、熱間圧延などは、従来と同様の方法で行ってもよい。以下、最終仕上げ処理としての皮膜改質熱処理と皮膜改質電解処理の条件を示すが、これら処理以外の処理には特段の条件はない。 3. Manufacturing Method Next, a method suitable for manufacturing the austenitic stainless steel sheet of the present invention will be described. Melting, hot rolling and the like may be performed by the same method as in the past. In the following, conditions for the film modification heat treatment and the film modification electrolytic treatment as the final finishing treatment are shown, but there are no special conditions for treatments other than these treatments.
前述の通り、拡散接合し難い表面状態として、皮膜最表面(表層から10nmの範囲)のSi量を10%以上とすることが重要である。一般に、オーステナイト系ステンレス鋼の仕上げ焼鈍は、表面の光沢を維持するため、H2とN2の混合雰囲気で実施され、その温度は、1100~1150℃程度である。 3-1. Film Modification Heat Treatment As described above, it is important that the Si amount on the outermost surface of the film (in the range of 10 nm from the surface layer) is 10% or more as a surface state in which diffusion bonding is difficult. In general, finish annealing of austenitic stainless steel is performed in a mixed atmosphere of H 2 and N 2 in order to maintain surface gloss, and the temperature is about 1100 to 1150 ° C.
通常、熱処理後の鋼板を所定の液中で電解処理を行うことにより、熱処理で生成した皮膜を除去する、電解洗浄処理が行われている。皮膜改質電解処理は、所定の液中で電解処理を行う点で従来の電解洗浄処理と共通する部分があるが、皮膜改質電解処理は、皮膜中のFeを低減した上で皮膜中のSiを濃化するために実施するものである点で大きく異なる。具体的には、液温が30~50℃で、濃度が5~10%程度の硝酸水溶液中で、鋼板が正になるように電圧を印加しながら、鋼板を通板させるのがよい。液温または濃度が低すぎると、十分な改質効果が得られず、液温や濃度が高すぎると、鋼板の表面粗さを増加させたり、電解槽を痛めたりする可能性がある。 3-2. Film Modification Electrolytic Treatment Usually, an electrolytic cleaning process is performed in which the steel sheet after heat treatment is subjected to electrolytic treatment in a predetermined liquid to remove the film generated by the heat treatment. The film-modified electrolytic treatment has a part in common with the conventional electrolytic cleaning treatment in that the electrolytic treatment is performed in a predetermined solution. However, the film-modified electrolytic treatment is performed after reducing Fe in the film and then in the film. This is greatly different in that it is performed to enrich Si. Specifically, the steel sheet is preferably passed through a nitric acid aqueous solution having a liquid temperature of 30 to 50 ° C. and a concentration of about 5 to 10% while applying a voltage so that the steel sheet becomes positive. If the liquid temperature or concentration is too low, a sufficient reforming effect cannot be obtained, and if the liquid temperature or concentration is too high, the surface roughness of the steel sheet may be increased or the electrolytic cell may be damaged.
表1に、供試材の鋼の化学組成を表1に示す。 (Example 1)
Table 1 shows the chemical composition of the test steel.
鋼板表面に形成された皮膜を、Arイオンでスパッタリングしながら、GD-OESを用いて、皮膜の最表面から100nm程度以下の深さまでのSi量およびFe量を測定した(図3、参照)。最大Si量は、Si量が最大となるSi量(質量%)であり、最大Fe量は、Fe量が最大となるFe量(質量%)であり、Si濃化層厚さは、最表面から、Si量が最大Si量の1/2のSi量となる位置までの厚さである。 Maximum Si amount, maximum Fe amount, and Si concentrated layer thickness While sputtering the film formed on the steel sheet surface with Ar ions, GD-OES is used to form Si up to a depth of about 100 nm or less from the outermost surface of the film. The amount and the amount of Fe were measured (see FIG. 3). The maximum Si amount is the Si amount (% by mass) at which the Si amount is maximum, the maximum Fe amount is the Fe amount (% by mass) at which the Fe amount is maximum, and the Si concentrated layer thickness is the outermost surface To a position where the Si amount is a half of the maximum Si amount.
鋼板から、FIB加工により表面酸化物を含むように切り出し、TEM―EDSを用いて、表面酸化物の結晶構造と組成分析を行い、表面酸化物の主要構成物質を同定した。 Identification of the main constituents of surface oxides Cut out from steel plates to include the surface oxides by FIB processing, and use TEM-EDS to analyze the crystal structure and composition of the surface oxides. Was identified.
鋼板を2枚のφ8mmの円盤状試験片に加工した。2枚の試験片を重ね、750℃の真空チャンバー内で、荷重を20MPa負荷して、30秒間加圧した。 Bondability The steel plate was processed into two φ8 mm disk-shaped test pieces. Two test pieces were overlapped, and a load of 20 MPa was applied in a vacuum chamber at 750 ° C., followed by pressurization for 30 seconds.
As described above, according to the present invention, it is possible to provide industrially stable austenitic stainless steel that is difficult to be diffusion bonded even at high temperatures. Therefore, the present invention has high applicability in the stainless steel manufacturing / utilizing industry.
Claims (1)
- 表面の少なくとも一部に皮膜が形成されたオーステナイト系ステンレス鋼板であって、
前記オーステナイト系ステンレス鋼板の化学組成が、質量%で、
C:0.01%以上0.10%以下、
Si:0.2%以上2.0%以下、
Mn:1.5%以下、
Mo:1.0%以下、
Cr:15.0%以上22.0%以下、
Ni:4.5%以上10.0%以下、
Cu:1.0%以下、
Nb:0.30%以下、
N:0.01%以上0.15%以下、
残部がFe及び不可避不純物であり、
前記皮膜が、その表層から10nmまでの範囲の最大Si量が10.0%以上で、かつ最大Fe量が8.5%以下であるSi濃化層を備え、
前記Si濃化層の厚さが5nm以上である、拡散接合し難いオーステナイト系ステンレス鋼板。
An austenitic stainless steel sheet having a film formed on at least a part of the surface,
The chemical composition of the austenitic stainless steel sheet is mass%,
C: 0.01% or more and 0.10% or less,
Si: 0.2% or more and 2.0% or less,
Mn: 1.5% or less,
Mo: 1.0% or less,
Cr: 15.0% to 22.0%,
Ni: 4.5% or more and 10.0% or less,
Cu: 1.0% or less,
Nb: 0.30% or less,
N: 0.01% or more and 0.15% or less,
The balance is Fe and inevitable impurities,
The film includes a Si-concentrated layer having a maximum Si amount in a range from the surface layer to 10 nm of 10.0% or more and a maximum Fe amount of 8.5% or less,
An austenitic stainless steel sheet in which the thickness of the Si-concentrated layer is 5 nm or more and is difficult to be diffusion bonded.
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- 2015-09-10 JP JP2016547507A patent/JP6376218B2/en active Active
- 2015-09-10 CN CN201580048499.6A patent/CN106687622B/en active Active
- 2015-09-10 WO PCT/JP2015/075766 patent/WO2016039429A1/en active Application Filing
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018094620A (en) * | 2016-12-16 | 2018-06-21 | 日新製鋼株式会社 | Stainless steel material for diffusion joining jig |
JP7033847B2 (en) | 2016-12-16 | 2022-03-11 | 日鉄ステンレス株式会社 | Release member |
WO2019176073A1 (en) * | 2018-03-15 | 2019-09-19 | 日新製鋼株式会社 | Stainless steel material for use in diffusion bonding jigs |
KR20190109225A (en) * | 2018-03-15 | 2019-09-25 | 닛테츠 닛신 세이코 가부시키가이샤 | Stainless Steel for Diffusion Bonding Jig |
EP3567127A4 (en) * | 2018-03-15 | 2019-11-13 | Nisshin Steel Co., Ltd. | STAINLESS STEEL MATERIAL FOR USE IN BROADCAST WELDING TEMPLATES |
US10695874B2 (en) | 2018-03-15 | 2020-06-30 | Nisshin Steel Co., Ltd. | Stainless steel material for diffusion bonding jig |
KR102220875B1 (en) | 2018-03-15 | 2021-02-25 | 닛테츠 닛신 세이코 가부시키가이샤 | Release member composed of stainless steel for diffusion bonding jig with excellent deformation suppression and releasability |
JP2020037123A (en) * | 2018-09-05 | 2020-03-12 | 日本製鉄株式会社 | Diffusion bonded article and manufacturing method thereof |
JP7274837B2 (en) | 2018-09-05 | 2023-05-17 | 日鉄ステンレス株式会社 | Diffusion bonded product and its manufacturing method |
Also Published As
Publication number | Publication date |
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KR101939510B1 (en) | 2019-01-16 |
CN106687622A (en) | 2017-05-17 |
KR20170044756A (en) | 2017-04-25 |
JPWO2016039429A1 (en) | 2017-07-06 |
CN106687622B (en) | 2019-05-03 |
JP6376218B2 (en) | 2018-08-22 |
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