WO2013114833A1 - フェライト系ステンレス箔 - Google Patents
フェライト系ステンレス箔 Download PDFInfo
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- WO2013114833A1 WO2013114833A1 PCT/JP2013/000355 JP2013000355W WO2013114833A1 WO 2013114833 A1 WO2013114833 A1 WO 2013114833A1 JP 2013000355 W JP2013000355 W JP 2013000355W WO 2013114833 A1 WO2013114833 A1 WO 2013114833A1
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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
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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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
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
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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
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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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
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium 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
- 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
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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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
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2807—Metal other than sintered metal
- F01N3/281—Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0268—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment between cold rolling steps
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/02—Metallic plates or honeycombs, e.g. superposed or rolled-up corrugated or otherwise deformed sheet metal
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2530/00—Selection of materials for tubes, chambers or housings
- F01N2530/02—Corrosion resistive metals
- F01N2530/04—Steel alloys, e.g. stainless steel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12431—Foil or filament smaller than 6 mils
Definitions
- the present invention relates to a ferritic stainless steel foil excellent in shape change resistance, film peel resistance and manufacturability.
- a metal honeycomb can obtain a large aperture ratio (aperture ratio) as compared with a ceramic honeycomb carrier, is excellent in thermal shock resistance and vibration resistance, and is used in an increasing proportion.
- the shape of the carrier when mounted on a large vehicle such as a truck, the shape of the carrier also becomes large, and therefore, metal honeycombs having a high degree of freedom in shape are often used.
- the metal honeycomb is formed, for example, by alternately stacking flat stainless steel foil (flat foil) and corrugated stainless steel foil (corrugated foil) to form a honeycomb structure, and further A catalyst material (catalytic material) is applied to the surface of the stainless steel foil and used for an exhaust gas purification device.
- An example of a metal honeycomb is shown in FIG. 1, which is prepared by winding a stack of flat foils 1 and wave foils 2 into a roll and fixing the outer periphery thereof with an external cylinder 3 It is a honeycomb 4.
- stainless steel for metal honeycombs a high Al-containing ferritic stainless steel foil represented by 20 mass% Cr-5 mass% Al or 18 mass% Cr-3 mass% Al is mainly used.
- the temperature of the exhaust gas purifier may increase due to a catalytic reaction in addition to the exhaust gas temperature, and may reach a high temperature of 1000 ° C. or more. Therefore, a high Al-containing ferritic stainless steel foil which is extremely excellent in oxidation resistance at high temperature is applied to the catalyst carrier.
- the catalyst carrier is required to have a shape which does not change even when exposed to repeated high temperatures, not to peel off an oxide film during cooling, and to be excellent in adhesion to a washcoat.
- a high Al content ferritic stainless steel foil is widely used because of its excellent properties.
- the exhaust gas temperature of a diesel vehicle is not as high as that of a gasoline vehicle, and in most cases, the ultimate temperature is about 800 ° C.
- the maximum reached temperature of the exhaust gas is further lowered. Therefore, when the stainless steel foil of 20 mass% Cr-5 mass% Al or 18 mass% Cr-3 mass% Al described above is applied to a low exhaust gas temperature vehicle such as a diesel vehicle, the oxidation resistance is excessive. It was almost always the case.
- these high Al-containing ferritic stainless steel foils are excellent in oxidation resistance, their productivity is poor and their production cost is high.
- Patent Document 1 diffusion bondability (diffusion) at the time of molding of a carrier by limiting the Al content to the impurity level to 0.8 mass% and forming a Cr oxide film without forming an Al oxide film at a high temperature
- a stainless steel foil metal honeycomb with improved bondability is disclosed.
- Patent Document 2 limits the Al content to the impurity level to 0.8% by mass, and contains Mo in the range of 0.3 to 3% by mass to prevent oxidation resistance, diffusion bonding resistance and sulfuric acid resistance.
- a stainless steel foil metal honeycomb with improved corrosion is disclosed.
- Patent Document 3 the workability is reduced by reducing the Al content to 1.5 to less than 2.5% by mass based on an 18% by mass Cr-3% by mass Al steel and further limiting the grain size. Discloses a stainless steel which is compatible with the above.
- Patent Document 3 when used as a foil, when Al is depleted during high temperature oxidation and Cr film starts to be formed, it is also generated due to the difference in the thermal expansion coefficient of the film, since the yield strength of the metal is not sufficient. The resulting stress causes a shape change. As described above, in the stainless steel foil in which Al is reduced to improve the manufacturability, the shape change at high temperature and the oxide film exfoliation caused by the difference of the oxide film have become major problems.
- the present inventors diligently studied to solve the above-mentioned problems, and it was found that when the exhaust gas temperature is lower than that of a gasoline car, even if it is a low Al-containing steel, the required oxidation resistance is satisfied. We have found a way to improve shape change resistance and film peel resistance.
- Nb 0.01 to 1.0%
- Mo 0.01 to 3.0%
- W one or more of 0.01 to 3.0% by mass%
- In total 0.01 to 3.0%.
- the stainless steel foil obtained by the present invention is a catalyst carrier for exhaust gas purification devices of so-called off-road diesel vehicles such as agricultural machines such as tractors and combines, construction machinery such as bulldozers and shovels, etc. Preferred. Furthermore, they may be used as catalyst carriers for diesel cars, gasoline cars and motorcycles and outer casings of these catalyst carriers, members for exhaust piping of mufflers for cars and motorcycles, members for exhaust pipes of heating appliances and combustion appliances, etc. Although it is good, it is not particularly limited to these applications.
- the inventors of the present invention conducted a detailed study on the shape change resistance, the film peel resistance and the manufacturability at high temperature of a ferritic stainless steel foil which does not form Al 2 O 3 oxide (oxide) on the surface.
- the present invention has been made by the following findings.
- stainless steel foil mainly points out the stainless steel whose plate
- Precipitation strengthening by addition of Cu is effective for improvement of high temperature strength.
- a solid solution strengthening element such as Nb, Mo or W
- Cu lowers the oxidation resistance at high temperatures. Therefore, the present inventors have found that by simultaneously containing an appropriate amount of Al that does not affect the manufacturability, it is possible to secure necessary oxidation resistance even when a strengthening element is added. It reached.
- Component Composition The component composition of the present invention will be described below. In addition, all% in component composition is made into the mass%.
- the C content is 0.05% or less, preferably 0.02% or less. More preferably, it is 0.01% or less. However, it is preferable to reduce the C content as much as possible.
- Si 2.0% or less Si is an element improving the oxidation resistance. However, if the content is more than 2.0%, the toughness is lowered and the processability is lowered to make production difficult. Therefore, the Si content is 2.0% or less, preferably 1.0% or less. More preferably, it is 0.5% or less. However, in order to further improve the oxidation resistance, it is preferable to contain 0.05% or more, more preferably 0.1% or more.
- Mn 1.0% or less
- the Mn content is 1.0% or less, preferably 0.5% or less.
- Mn has the effect of fixing S in steel, it is preferably contained 0.01% or more, more preferably 0.05% or more.
- the S content is 0.005% or less, preferably 0.003% or less. More preferably, it is 0.001% or less, but it is more preferable to reduce as much as possible.
- the P content is 0.05% or less, preferably 0.03% or less, but it is more preferable to reduce as much as possible.
- Cr 11.0 to 25.0% Cr is an essential element for securing the oxidation resistance and strength at high temperature, and therefore it is added at 11.0% or more. However, if the Cr content exceeds 25.0%, the processability is reduced and the excellent manufacturability which is the object of the present invention can not be achieved. Therefore, the Cr content is in the range of 11.0 to 25.0%. Preferably, it is in the range of 13.0 to 20.0%. In consideration of the balance between the production cost and the oxidation resistance, it is more preferably in the range of 15.0 to 18.0%.
- Ni 0.05 to 0.30% Since Ni has the effect of improving the brazability at the time of catalyst carrier molding, its content is made 0.05% or more. However, when the content of Ni, which is an austenite-stabilizing element, exceeds 0.30%, when Cr begins to be oxidized, austenite is formed and the thermal expansion coefficient of the foil (thermal expansion coefficient) ), Causing defects such as foil pinching and breakage (cell breakage). Therefore, the Ni content is in the range of 0.05 to 0.30%. Preferably, it is in the range of 0.08 to 0.20%.
- Al 0.01 to 1.5% Since Al is an element that improves the oxidation resistance of ferritic stainless steel at high temperature, it is added by 0.01% or more. However, if it is added in excess of 1.5%, the toughness of the slab or hot-rolled sheet is reduced and the productivity is reduced. Therefore, it is in the range of 0.01 to 1.5%. It is preferably 0.05 to 1.0%, more preferably 0.1 to 1.0%. In consideration of the balance between manufacturability and oxidation resistance, it is more preferably in the range of 0.2 to 0.8%.
- Cu 0.01 to 2.0%
- Cu is also an element effective in improving the corrosion resistance and the salt corrosion resistance.
- the Cu content is in the range of 0.01 to 2.0%. In view of shape change resistance and low cost, it is preferably in the range of 0.05 to 1.5%. In the case where high temperature strength is required, the range of 0.2 to 1.5% is more preferable.
- the N content is 0.10% or less.
- the N content is 0.05% or less. More preferably, it is 0.01% or less.
- the basic component composition of the present invention is as described above, and can further contain one or more of Nb, Mo, and W as a selection element in consideration of strength at high temperatures and processability.
- Nb 0.01 to 1.0%
- Mo 0.01 to 3.0%
- W 0.01 to 3.0% or one or more in total: 0.01 to 3 .0%
- Nb increases the strength of the foil at high temperatures, and improves the shape change resistance and the film peeling resistance. The effect is obtained by containing Nb 0.01% or more.
- the amount is preferably in the range of 0.01 to 1.0%. More preferably, it is in the range of 0.1 to 0.7%. Furthermore, in consideration of the balance between strength at high temperature and manufacturability, the range of 0.3 to 0.6% is more preferable.
- Mo and W can both be contained as selective elements because they increase the strength at high temperature and the life of the catalyst support becomes good. In addition, these elements stabilize the oxide film and improve the salt corrosion resistance. Such effects are all obtained at a content of 0.01% or more. On the other hand, if it exceeds 3.0%, the production becomes difficult due to a decrease in processability. Therefore, when Mo and W are contained, the amounts thereof should be in the range of 0.01 to 3.0%, respectively. preferable. More preferably, it is in the range of 1.5 to 2.5%.
- the total amount thereof is preferably in the range of 0.01 to 3.0%. If it is less than 0.01%, the desired effect can not be obtained, and if it exceeds 3.0%, the processability is greatly reduced. More preferably, it is in the range of 1.5 to 2.5%.
- REM can be contained for the purpose of improvement of an oxide film.
- REM 0.01 to 0.20% REM is Sc, Y and lanthanoid elements (elements with atomic numbers 57 to 71 such as La, Ce, Pr, Nd, Sm), and the content is the total amount of these elements.
- REM improves the adhesion of the oxide film and has a very remarkable effect on improving the peeling resistance of the film. Such an effect is obtained with an REM content of 0.01% or more.
- the REM content exceeds 0.20%, these elements are concentrated and precipitated in the grain boundaries, and are melted at high temperature heating to cause surface defects of the hot-rolled sheet. Therefore, when REM is contained, its amount is preferably in the range of 0.01 to 0.20%. More preferably, it is in the range of 0.03 to 0.10%.
- one or more of Ti, Zr, Hf, Ca and Mg can be contained.
- Ti 0.01 to 1.0%
- Ti is an element that fixes C and N in steel to improve workability and corrosion resistance, and the effect is obtained with a Ti content of 0.01% or more.
- Ti is an element susceptible to oxidation, and if its content exceeds 1.0%, a large amount of Ti oxide is mixed in the film, and the brazing property is significantly reduced, and the oxidation resistance at high temperature Also falls. Therefore, when Ti is contained, its amount is preferably in the range of 0.01 to 1.0%. More preferably, it is in the range of 0.05 to 0.20%.
- Zr 0.01 to 0.20%
- Zr combines with C and N in steel to improve creep characteristics.
- the toughness is improved, the processability is improved to facilitate the production of the foil.
- the oxide film is concentrated at grain boundaries in the oxide film to improve the oxidation resistance at high temperatures and the strength at high temperatures, in particular, the shape change resistance.
- Such an effect is obtained when the Zr content is 0.01% or more, but when the Zr content exceeds 0.20%, an intermetallic compound is formed with Fe or the like to reduce the oxidation resistance. Therefore, when Zr is contained, its amount is preferably in the range of 0.01 to 0.20%. More preferably, it is in the range of 0.01 to 0.05%.
- Hf 0.01 to 0.20% Hf improves the adhesion between the Al 2 O 3 film and the base iron, and further suppresses the decrease in solid solution Al (solute Al), so it has the effect of improving the oxidation resistance at high temperatures.
- the Hf content is preferably 0.01% or more.
- the Hf content is preferably in the range of 0.01 to 0.20%, and more preferably in the range of 0.02 to 0.10%.
- Ca 0.0010 to 0.0300%
- Ca has the function of improving the adhesion of the Al 2 O 3 film. In order to acquire such an effect, it is preferable to make Ca content into 0.0010% or more. On the other hand, when the Ca content exceeds 0.0300%, the toughness is lowered and the oxidation resistance at high temperature is also lowered. Therefore, the Ca content is preferably in the range of 0.0010% to 0.0300%, and more preferably in the range of 0.0020% to 0.0100%.
- Mg 0.0015 to 0.0300% Mg, like Ca, works to improve the adhesion of the Al 2 O 3 film. In order to acquire such an effect, it is preferable to make Mg content into 0.0015% or more. On the other hand, when the Mg content exceeds 0.0300%, the toughness is lowered and the oxidation resistance at high temperature is also lowered. Therefore, the Mg content is preferably in the range of 0.0015% to 0.0300%, and more preferably in the range of 0.0020% to 0.0100%.
- Normal stainless steel manufacturing equipment can be used for manufacture of the said ferritic stainless steel foil.
- a steel containing the above-mentioned composition is melted by a converter or an electric furnace, etc., and after secondary refining by VOD (Vacuum oxygen decarburization) or AOD (Argon oxygen decarburization), the ingot-slab rolling method or continuous rolling
- VOD Vauum oxygen decarburization
- AOD Argon oxygen decarburization
- the steel slab is made by casting method.
- the cast slabs are loaded into a heating furnace and heated to 1150 ° C. to 1250 ° C. before being subjected to the hot rolling process.
- the surface scale of the hot-rolled steel strip thus obtained is removed by shot blasting, pickling, mechanical polishing or the like, and cold rolling and annealing are repeated several times to obtain a stainless steel foil having a foil thickness of 100 ⁇ m or less.
- the thickness of the foil should be about 50 to 100 ⁇ m when it is required to be particularly resistant to vibration and durability when it is used as a catalyst carrier for exhaust gas purification devices, and in particular a high cell density and low back pressure are required. In the case where it is used, it is preferable to set it to about 25 to 50 ⁇ m.
- a steel of the chemical composition shown in Table 1 melted by vacuum melting is heated to 1200 ° C. and hot-rolled at a temperature range of 900 to 1200 ° C. to form a hot-rolled steel plate having a thickness of 3 mm.
- a strip-like test piece 25 mm wide and 300 mm long was cut out and subjected to a repeated bending test.
- bending is repeated several times with a bending radius of 25 mm, and it is sufficient if it is not broken even after 10 or more bendings.
- steel No. Steel Nos. 1 to 16 did not break even when processed 10 times or more and had good workability. However, steel No. 1 having an Al content exceeding the range of the present invention. Since No. 17 was broken by bending three times, it was judged that the workability of the hot-rolled sheet was insufficient, and was excluded from the subsequent examination.
- steel No. The hot rolled steel sheets of 1 to 16 were annealed at 1000 ° C. for 1 minute in the atmosphere, pickled and cold rolled to obtain cold rolled steel sheets of 1.0 mm thickness. These cold-rolled steel sheets are annealed at 950 to 1050 ° C. for 1 minute in the atmosphere, then pickled, repeated cold rolling and annealing with a cluster mill several times, width 100 mm, foil thickness A foil of 40 ⁇ m was obtained.
- the cold-rolled steel sheet and foil thus obtained were evaluated for strength (rupture stress) at high temperature, shape change resistance, film peeling resistance and oxidation resistance at high temperature by the following method. .
- the measurement results of the 0.2% proof stress are as follows: x less than 15 MPa is x (defective), 15 (good) is 15 MPa or more and less than 35 MPa is ⁇ (good), ⁇ (superior) is 35 MPa or more. I satisfied the purpose.
- the measurement results are as follows: x (poor) over 3%, ⁇ (good) over 1% and 3% or less, ⁇ (good) or ⁇ (good) if peeling is hardly observed at 1% or less If it is excellent, the object of the present invention is satisfied.
- Steel No. which is an invention example. It can be seen that 1 to 9 and 13 to 15 have high strength at high temperatures, high resistance to shape change, and are also excellent in film peel resistance and oxidation resistance at high temperatures. Furthermore, since these steels are excellent in toughness, it has been possible to produce them efficiently using ordinary stainless steel production equipment. On the other hand, steel No. 1 which is a comparative example. 10 to 12 and 16 are inferior in at least one of the strength at high temperature, the shape change resistance, the film peeling resistance and the oxidation resistance, and are unsuitable for use as a catalyst carrier.
- a stainless steel foil suitable for a catalyst carrier for an exhaust gas purification device which is used at a relatively low temperature of about 800 ° C. or lower at which the maximum exhaust gas temperature is reached, is efficiently produced using ordinary stainless steel production equipment. It is possible to be industrially very effective.
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Abstract
Description
以下に、本発明の成分組成について説明する。なお、成分組成における%は、全て質量%とする。
C含有量が0.05%を超えると、高温での強度が低下し、耐酸化性も低下する。また、靭性の低下による製造性の低下も招く。よって、C含有量は0.05%以下、好ましくは0.02%以下とする。さらに好ましくは0.01%以下である。但し、C含有量は極力低減することが好ましい。
Siは耐酸化性を改善する元素であるが、含有量が2.0%を超えると、靭性が低下するとともに、加工性の低下により製造が困難になる。よって、Si含有量は2.0%以下、好ましくは1.0%以下とする。さらに好ましくは0.5%以下とする。但し、耐酸化性をより向上させる場合には、0.05%以上含有させるのが好ましく、より好ましくは0.1%以上含有させる。
Mn含有量が1.0%を超えると、高温での耐酸化性が低下する。よって、Mn含有量は1.0%以下、好ましくは0.5%以下とする。但し、Mnは鋼中のSを固定する効果があるため、0.01%以上含有させるのが好ましく、より好ましくは0.05%以上含有させる。
S含有量が0.005%を超えると、触媒担体における皮膜の密着性や高温での耐酸化性が低下する。よって、S含有量は0.005%以下、好ましくは0.003%以下とする。より好ましくは0.001%以下であるが、極力低減することがより好ましい。
P含有量が0.05%を超えると、触媒担体における酸化皮膜の密着性や高温での耐酸化性が低下する。よって、P含有量は0.05%以下、好ましくは0.03%以下とするが、極力低減することがより好ましい。
Crは高温での耐酸化性および強度を確保する上で必要不可欠な元素であるので、11.0%以上添加する。しかし、Cr含有量が25.0%を超えると、加工性が低下し、本発明の目的である優れた製造性を達成できなくなる。よって、Cr含有量は11.0~25.0%の範囲とする。好ましくは13.0~20.0%の範囲である。製造コストと耐酸化性のバランスを考慮すると、より好ましくは15.0~18.0%の範囲である。
Niは触媒担体成形時のロウ付け性(brazability)を向上する効果があるため、その含有量は0.05%以上とする。しかし、オーステナイト安定化元素(austenite-stabilizing element)であるNiの含有量が0.30%を超える場合は、Crが酸化され始めた際、オーステナイトが生成して箔の熱膨張係数(thermal expansion coefficient)を増加させ、箔の括れや破断(セル切れ)などの不具合が発生する。よって、Ni含有量は0.05~0.30%の範囲とする。好ましくは0.08~0.20%の範囲である。
Alはフェライト系ステンレス鋼の高温での耐酸化性を改善する元素であるので、0.01%以上添加する。しかし、1.5%を超えて添加すると、スラブや熱延板の靭性が低下し製造性が低下する。したがって、0.01~1.5%の範囲とする。好ましくは0.05~1.0%であり、より好ましくは0.1~1.0%の範囲である。製造性と耐酸化性とのバランスを考慮すると、より好ましくは0.2~0.8%の範囲である。
Cuを添加すると、微細な析出物が生じて箔自身の強度が上昇し、酸化皮膜と地鉄の間に熱膨張差が生じた際のクリープ変形を抑制する効果があるので、0.01%以上添加する。さらに、Cuは、耐食性向上および耐塩害腐食性(salt corrosion resistance)の改善に効果的な元素でもある。しかし、Cu含有量が2.0%を超えると、耐酸化性が低下するうえ、加工が困難となり、コスト増大を招く。よって、Cu含有量は0.01~2.0%の範囲とする。耐形状変化性および低コストを考慮すると、好ましくは0.05~1.5%の範囲である。さらに高温強度が必要な場合は0.2~1.5%の範囲とするのがより好ましい。
N含有量が0.10%を超えると、靱性が低下するとともに、加工性の低下により製造が困難となる。よって、N含有量は0.10%以下とする。好ましくは0.05%以下である。さらに好ましくは0.01%以下である。
Nbは箔の高温での強度を上昇させ、耐形状変化性および耐皮膜剥離性を良好にする。その効果は、Nbを0.01%以上含有することにより得られる。一方、1.0%を超えて含有すると、加工性が低下し製造を困難にするため、Nbを含有する場合は、その量は0.01~1.0%の範囲とすることが好ましい。より好ましくは0.1~0.7%の範囲である。さらに、高温での強度と製造性のバランスを考慮すると0.3~0.6%の範囲とするのがさらに好ましい。
REMとは、Sc、Yおよびランタノイド系元素(La、Ce、Pr、Nd、Smなど原子番号57~71までの元素)であり、含有量はこれらの元素の総量である。一般に、REMは酸化皮膜の密着性を改善し、皮膜の耐剥離性向上に極めて顕著な効果を有する。このような効果は0.01%以上のREM含有量で得られる。一方、REM含有量が0.20%を超えると、これらの元素が結晶粒界に濃化して析出し、高温加熱時に溶融して熱延板の表面欠陥の要因となる。よって、REMを含有する場合は、その量は0.01~0.20%の範囲とすることが好ましい。より好ましくは0.03~0.10%の範囲とする。
Tiは鋼中のC、Nを固定し加工性および耐食性を向上させる元素であり、その効果は0.01%以上のTi含有で得られる。しかし、Tiは酸化されやすい元素であり、その含有量が1.0%を超えると、Ti酸化物が皮膜中に多量に混入し、ロウ付け性が著しく低下するとともに、高温での耐酸化性も低下する。よって、Tiを含有する場合は、その量は0.01~1.0%の範囲とすることが好ましい。より好ましくは0.05~0.20%の範囲とする。
Zrは鋼中のC、Nと結合し、クリープ特性を改善する。また、靭性が向上するとともに、加工性が向上して箔の製造を容易にする。さらに、酸化皮膜中において粒界に濃化して高温での耐酸化性や、高温での強度、特に耐形状変化性を向上させる。このような効果は、0.01%以上のZr含有で得られるが、Zr含有量が0.20%を超えると、Feなどと金属間化合物をつくり、耐酸化性を低下させる。よって、Zrを含有する場合は、その量は0.01~0.20%の範囲とすることが好ましい。より好ましくは0.01~0.05%の範囲とする。
HfはAl2O3皮膜と地鉄の密着性を良好にし、さらに固溶Al(solute Al)の減少を抑制するため、高温での耐酸化性を向上させる効果がある。このような効果を得るには、Hf含有量は0.01%以上含有することが好ましい。一方、Hf含有量が0.20%を超えると、高温酸化を促進して耐酸化性を低下させてしまう。したがって、Hf含有量は0.01~0.20%の範囲とすることが好ましく、0.02~0.10%の範囲とすることがより好ましい。
Caは、Al2O3皮膜の密着性を向上する働きがある。このような効果を得るには、Ca含有量は0.0010%以上とすることが好ましい。一方、Ca含有量が0.0300%を超えると、靭性が低下し、高温での耐酸化性も低下する。よって、Ca含有量は0.0010~0.0300%の範囲とすることが好ましく、0.0020~0.0100%の範囲とすることがより好ましい。
Mgは、Caと同様に、Al2O3皮膜の密着性を向上する働きがある。このような効果を得るには、Mg含有量は0.0015%以上とすることが好ましい。一方、Mg含有量が0.0300%を超えると、靭性が低下し、高温での耐酸化性も低下する。よって、Mg含有量は0.0015~0.0300%の範囲とすることが好ましく、0.0020~0.0100%の範囲とすることがより好ましい。
当該フェライト系ステンレス箔の製造には、通常のステンレス鋼製造設備を用いることができる。前述の成分組成を含有する鋼を、転炉や電気炉などで溶製し、VOD(Vacuum oxygen decarburization)やAOD(Argon oxygen decarburization)で二次精錬した後、造塊-分塊圧延法や連続鋳造法で鋼スラブとする。鋳造後のスラブを加熱炉(heating furnace)に装入し、1150℃~1250℃に加熱した後に熱間圧延工程に供する。こうして得られた熱延鋼帯について、ショットブラスト、酸洗、機械研磨などで表面スケールを除去し、冷間圧延と焼鈍を複数回繰り返し行なうことで箔厚100μm以下のステンレス箔を得る。箔の厚みは、排ガス浄化装置用触媒担体とした際に、特に耐振動特性や耐久性が必要である場合は50~100μm程度とし、特に高いセル密度(cell density)や低背圧が必要とされる場合は25~50μm程度とすることが好ましい。
まず、板厚1mmの冷延鋼板に、波板(corrugated sheet)と平板(flat sheet)の接点を拡散接合あるいはロウ付け接合する際の熱処理をシミュレートして、1200℃×30分の熱処理を4×10-5 Torr(5.3×10-3 Pa)以下の真空中で行った。次に、熱処理後の冷延鋼板より図2に示す試験片を切り出し、800℃にて高温引張試験を実施して0.2%耐力を測定した。このとき、引張速度は、最初0.2mm/min、耐力を超えた後は、5mm/minとした。0.2%耐力の測定結果は、15MPa未満を×(不良)、15MPa以上35MPa未満を○(良)、35MPa以上を◎(優)とし、○(良)あるいは◎(優)を本発明の目的を満足するとした。
まず、箔厚40μmの箔に、拡散接合あるいはロウ付け接合時の熱処理に相当する1200℃×30分の熱処理を4×10-5 Torr(5.3×10-3 Pa)以下の真空中で行った。次に、熱処理後の箔より100mm幅×50mm長さの試験片を長さ方向に直径5mmの円筒状に丸め、端部をスポット溶接により留めたものを、各箔からそれぞれ3個作製し、大気雰囲気炉中で1150℃×400時間加熱して、3個の平均の寸法変化量(加熱前の円筒長さに対する加熱後の円筒長さの増分の割合)を測定した。平均の寸法変化量の測定結果は、5%超えを×(不良)、3%超え5%以下を○(良)、3%以下を◎(優)とし、○(良)あるいは◎(優)を本発明の目的を満足するとした。
まず、箔厚40μmの箔に、拡散接合あるいはロウ付け接合時の熱処理に相当する1200℃×30分の熱処理を4×10-5 Torr(5.3×10-3 Pa)以下の真空中で行った。次に、熱処理後の箔より20mm幅×30mm長さの試験片を3個採取し、大気雰囲気炉中で[800℃×20min保持→200℃以下まで冷却]を1サイクルとして、300サイクル繰返した。試験終了後の試験片を目視で観察し、検査実施部の面積に対するスケール剥離部の面積の割合を求めた(剥離面積/検査実施面積×100)。測定結果が、3%超えを×(不良)、1%超え3%以下を○(良)、1%以下でほぼ剥離が見られないものを◎(優)とし、○(良)あるいは◎(優)であれば本発明の目的を満足するとした。
まず、箔厚40μmの箔に、拡散接合あるいはロウ付け接合時の熱処理に相当する1200℃×30分の熱処理を4×10-5 Torr(5.3×10-3 Pa)以下の真空中で行った。次に、熱処理後の箔より20mm幅×30mm長さの試験片を3個採取し、大気雰囲気炉中で800℃×400時間加熱して、3個の平均の酸化増量(加熱前後重量変化を初期の表面積で除した量)を測定した。このとき、酸化増量には、加熱後に試験片から剥離したスケールも回収し、加えた。平均の酸化増量の測定結果は、10g/m2超えを×(不良)、5g/m2超え10g/m2以下を○(良)、5g/m2以下を◎(優)とし、○(良)あるいは◎(優)を本発明の目的を満足するとした。
2 波箔
3 外筒
4 メタルハニカム
Claims (5)
- 質量%で、C:0.05%以下、Si:2.0%以下、Mn:1.0%以下、S:0.005%以下、P:0.05%以下、Cr:11.0~25.0%、Ni:0.05~0.30%、Al:0.01~1.5%、Cu:0.01~2.0%、N:0.10%以下を含有し、残部がFeおよび不可避的不純物から成ることを特徴とするフェライト系ステンレス箔。
- さらに、質量%で、Nb:0.01~1.0%、Mo:0.01~3.0%、W:0.01~3.0%のうちの1種または2種以上を合計で:0.01~3.0%含有することを特徴とする請求項1に記載のフェライト系ステンレス箔。
- さらに、質量%で、REMを0.01~0.20%含有することを特徴とする請求項1または2に記載のフェライト系ステンレス箔。
- さらに、質量%で、Ti:0.01~1.0%、Zr:0.01~0.20%、Hf:0.01~0.20%、Ca:0.0010~0.0300%およびMg:0.0015~0.0300%のうちの1種または2種以上を含有することを特徴とする請求項1乃至3の何れかに記載のフェライト系ステンレス箔。
- 箔厚が100μm以下であることを特徴とする請求項1乃至4の何れかに記載のフェライト系ステンレス箔。
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- 2013-01-24 MX MX2014009125A patent/MX346735B/es active IP Right Grant
- 2013-01-24 ES ES13743347.0T patent/ES2651071T3/es active Active
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- 2013-01-24 CA CA2860746A patent/CA2860746C/en not_active Expired - Fee Related
- 2013-01-24 JP JP2013556251A patent/JP5522330B2/ja active Active
- 2013-01-24 CN CN201380007345.3A patent/CN104093872B/zh active Active
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- 2013-01-24 EP EP13743347.0A patent/EP2811044B1/en active Active
- 2013-01-24 WO PCT/JP2013/000355 patent/WO2013114833A1/ja active Application Filing
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Cited By (11)
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WO2015015728A1 (ja) * | 2013-07-30 | 2015-02-05 | Jfeスチール株式会社 | フェライト系ステンレス箔 |
US10151020B2 (en) | 2013-07-30 | 2018-12-11 | Jfe Steel Corporation | Ferritic stainless steel foil |
EP3109334A4 (en) * | 2014-02-17 | 2017-11-15 | Nippon Steel & Sumikin Materials Co., Ltd. | Stainless steel foil and method for manufacturing same |
WO2019189174A1 (ja) * | 2018-03-27 | 2019-10-03 | 日鉄ステンレス株式会社 | フェライト系ステンレス鋼およびその製造方法、フェライト系ステンレス鋼板およびその製造方法、ならびに燃料電池用部材 |
JP2019173075A (ja) * | 2018-03-27 | 2019-10-10 | 日鉄ステンレス株式会社 | フェライト系ステンレス鋼板およびその製造方法、ならびに燃料電池用部材 |
JP2019173074A (ja) * | 2018-03-27 | 2019-10-10 | 日鉄ステンレス株式会社 | フェライト系ステンレス鋼板およびその製造方法、ならびに燃料電池用部材 |
JP2019173072A (ja) * | 2018-03-27 | 2019-10-10 | 日鉄ステンレス株式会社 | フェライト系ステンレス鋼およびその製造方法、ならびに燃料電池用部材 |
US11667986B2 (en) | 2018-03-27 | 2023-06-06 | Nippon Steel Stainless Steel Corporation | Ferritic stainless steel and method for manufacturing same, ferritic stainless steel sheet and method for manufacturing same, and fuel cell member |
WO2021177063A1 (ja) * | 2020-03-02 | 2021-09-10 | Jfeスチール株式会社 | 固体酸化物型燃料電池用フェライト系ステンレス鋼 |
JPWO2021177063A1 (ja) * | 2020-03-02 | 2021-09-10 | ||
JP7151892B2 (ja) | 2020-03-02 | 2022-10-12 | Jfeスチール株式会社 | 固体酸化物型燃料電池用フェライト系ステンレス鋼 |
Also Published As
Publication number | Publication date |
---|---|
JP5522330B2 (ja) | 2014-06-18 |
KR20140117476A (ko) | 2014-10-07 |
MX2014009125A (es) | 2014-08-27 |
MX346735B (es) | 2017-03-30 |
EP2811044A4 (en) | 2015-04-08 |
TWI467033B (zh) | 2015-01-01 |
CA2860746A1 (en) | 2013-08-08 |
EP2811044B1 (en) | 2017-10-04 |
US9920409B2 (en) | 2018-03-20 |
EP2811044A1 (en) | 2014-12-10 |
JPWO2013114833A1 (ja) | 2015-05-11 |
CA2860746C (en) | 2017-12-19 |
CN104093872A (zh) | 2014-10-08 |
TW201335388A (zh) | 2013-09-01 |
US20150010771A1 (en) | 2015-01-08 |
CN104093872B (zh) | 2017-07-21 |
ES2651071T3 (es) | 2018-01-24 |
RU2578308C1 (ru) | 2016-03-27 |
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