EP1721023A1 - Cr-al-steel for high-temperature applications - Google Patents
Cr-al-steel for high-temperature applicationsInfo
- Publication number
- EP1721023A1 EP1721023A1 EP05711109A EP05711109A EP1721023A1 EP 1721023 A1 EP1721023 A1 EP 1721023A1 EP 05711109 A EP05711109 A EP 05711109A EP 05711109 A EP05711109 A EP 05711109A EP 1721023 A1 EP1721023 A1 EP 1721023A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloy
- applications
- ferritic steel
- alloy according
- steel alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229910000831 Steel Inorganic materials 0.000 title description 3
- 239000010959 steel Substances 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 239000011888 foil Substances 0.000 claims abstract description 6
- -1 for instance Chemical class 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 64
- 239000000956 alloy Substances 0.000 claims description 64
- 239000000463 material Substances 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 15
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910000851 Alloy steel Inorganic materials 0.000 claims 8
- 230000003647 oxidation Effects 0.000 abstract description 29
- 238000007254 oxidation reaction Methods 0.000 abstract description 29
- 230000008569 process Effects 0.000 abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 8
- 125000004122 cyclic group Chemical group 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000009853 pyrometallurgy Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002301 combined effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
-
- 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
-
- 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
-
- 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
-
- 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
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
Definitions
- the present invention relates to a product of ferritic stainless steel manufactured according to the process of this invention, which product has increased resistance to cyclic and continuous thermal load and oxidation at increased temperatures and which has improved mechanical properties at said temperatures as well as the use thereof in the form of wire, strip, foil and/or tube in high- temperature applications such as in catalytic converter applications, in heating and furnace applications.
- Fe-Cr-AI-alloys have extensive use in the temperature range above 900 °C. Thanks to the protective oxide on the surface, they resist cyclic and continuous thermal load and oxidation until the material is depleted of the oxide former, e.g., Al.
- the oxide former e.g., Al.
- the i iting-fact ⁇ rs ⁇ the service life of the entire device are the total content of Al and the mechanical strength.
- Metallic high-temperature materials in, for instance, catalytic converters or for applications for resistive heating are today normally based on thin strips or wire of ferritic Fe-Cr-AI-alloys having at least 4,5 % of Al and small amounts of reactive elements added.
- the high ductility of the metal gives a good resistance to mechanical and thermal fatigue.
- Aluminium in contents above approx. 4,5 % by weight, together with the reactive elements, imparts the material the possibility of forming a thin, protective aluminium oxide upon heating.
- the reactive elements cause that the oxide gets a considerably reduced tendency of peeling or flaking, i.e., to come loose from the metal upon cooling or mechanical deformation.
- Ferritic steel materials having low content of carbon are also embrittled by grain growth upon use in temperatures above 800 °C.
- the low content of carbon is required in order to obtain an optimal oxidation resistance of the alloy and enable plastic cold working since contents of carbon above approx. 0,02 % by weight have an embrittling effect by increasing the brittle transition temperature of the material.
- Elements that are used for solid solution hardening of high-temperature materials, such as Mo and/or W are regarded to have a considerable negative impact on the oxidation properties, and therefore the desirable content of these elements may be limited to at most 1 % such as in US 4859649 or at most 0,10 % as in EP 0667400.
- Figure 1 shows results of the oxidation testing at 1000 °C as a function of the change of mass versus time for examples D and E as well as comparative examples 1 and 3.
- Figure 2 shows results of the oxidation testing at 1100 °C as a function of the change of mass versus time for examples C, E and G as well as comparative example 1.
- a ferritic stainless steel having the following composition (in % by weight): less than 1 % of Ni, 15-25 % of Cr, 4,5-12 % of Al, 0,5-4 % of Mo, 0,01-1 ,2 % of Nb, 0-0,5 % of Ti, 0-0,5 % of Y, Sc, Zr and/or Hf, 0-0,2 % of one or more rare earth metals (REM) such as, for instance, Ce or La, 0-0,2 % of C, 0-0,2 % of N, with the balance iron and normally occurring impurities.
- REM rare earth metals
- the final product may be manufactured in the form of wire, strip, foil and/or tube.
- the final product according to the present invention is manufactured as a homogeneous material or a laminate or a material having a concentration gradient of Al, where the content of Al increases toward said surface of the product.
- the manufacture may be effected by coating a substrate material and a substrate alloy, respectively, with Al or an alloy of Al, especially by coating strips of a substrate alloy of a thickness below 1 mm with an alloy of Al.
- the mechanical properties and oxidation resistance of the alloy can be improved and optimized independently of each other.
- This process also enables a simplification of the production process when manufacture via conventional pyrometallurgy of materials having average contents of Al above the average above 4,5 % is associated with great yield losses by virtue of brittleness.
- An additional advantage of this process is that a final material may be manufactured having a gradient of Al, such that the content of Al increases toward the surface, which entails improved oxidation resistance since the for- mation of fast growing oxides such as chromium and iron oxides is prevented and the mechanical properties of the final material are improved.
- the substrate alloy may be manufactured by conventional pyrometallurgy or, for instance, powder metallurgy with the intended composition, and then the alloy is hot- and cold-rolled to final desired dimension.
- the substrate material has the following composition (in % by weight): less than 1 % of Ni, 15-27 % of Cr, 0-5 % of AI, 0,5-5 % of Mo, 0,01-2 % of Nb, 0-0,5 % of Ti, 0-0,5 % of Y, Sc, Zr and/or Hf, 0-0,2 % of one or more rare earth metals (REM) such as, for instance, Ce or La, 0-0,2 % of C, 0-0,2 % of N, with the balance iron and normally occurring impurities.
- REM rare earth metals
- the most suitable composition of the substrate material is the following (in % by weight): less than 1 % of Ni, 16-25 % of Cr, 0,5-4 % of Al, 0,7-4 % of Mo, 0,25-1 ,0 % of Nb, 0-0,5 % of Y, Sc, Zr and/or Hf, 0-0,5 % of Ti, 0-0,1 % of one or more rare earth metals (REM) such as, for instance, Ce or La, 0,02-0,2 % of C, 0-0,05 % of N, with the balance iron and normally occurring impurities.
- REM rare earth metals
- the material may be used in the as coated condition or after a diffusion- annealing.
- the most favourable compositions of the substrate material before coating are obtained if it contains 2-4 % of Al.
- This aluminium content imparts the final product an increased oxidation resistance and results in a simplified production process, i.e., the risk of production disturbances in comparison with the manufacture of a material having a aluminium content above 4 % is considerably decreased.
- the material should in total contain a content of Al that is greater than 4,5 % by weight.
- Addition of Zr and/or Hf and REM and/or Y and/or Sc provides an increased resistance to peeling and flaking of the formed oxide.
- the contents of the final product of the same elements may be supplied by adding these in the substrate alloy and/or in the alloy of Al that is used in the coating.
- the alloy according to the present invention should totally contain at least 0,1 % by weight of Ti+Nb+Zr+Hf.
- compositions of the alloy according to the invention can be manufactured by conventional metallurgy.
- a material is obtained the microstructure of which is con- trolled, the oxidation properties of which are improved, the mechanical properties of which are optimised and improved, and the maximum aluminium content of which is not limited by the embrittling effect that contents of Al above approx. 5 % by weight normally may give, both upon cold and hot working.
- the process to coat a substrate material with an alloy of Al provides a finished product the contents of which of, e.g., Mo, Nb and C can be considerably higher than in a conventionally manufactured material without the presence of these elements resulting in any noticeable deterioration of the oxidation properties.
- Coating of the substrate alloy with alloy of Al may be effected by previously known processes such as, for instance, dipping in melt, electrolytic coating, rolling together of strips of the substrate alloy and the aluminium alloy, deposi- tion of solid alloy of Al from a gas phase by so-called CVD or PVD technique.
- the coating with alloy of Al may be effected after the substrate alloy having been rolled down to desired final thickness of the product, or in larger thickness. In the latter case, a diffusion-annealing may be carried out in order to achieve a homogenization of the material, and then rolling in one or more steps is carried out in order to provide the finished product. Rolling may also be effected directly on a coated product according to the present invention having greater thickness than the desired final thickness. In this case, the rolling may be followed by annealing.
- the thickness of the coated layer of Al may be varied depending on the thickness of the substrate material, the desired aluminium content in the final product and the aluminium content in the substrate material.
- the total content of Al in the finished product has to, as has been mentioned above, always be at least 4,5 % by weight.
- the product may be used in the form of an annealed, homogeneous material or a laminate or a material having a concentration gradient of Al where the content of Al is higher at the surface than in the centre of the material.
- a lower total content and average content down to 4,0 % by weight, respectively can be allowed if the aluminium content at a distance of at most 5 ⁇ m from the surface is more than 6,0 % by weight.
- Examples of useful aluminium alloys are pure Al, Al alloyed with 0,5-25 % by weight of Si, Al alloyed with 0-2 % by weight of one or more of the elements Ce, La, Y, Zr, Hf.
- different composi- tions of the alloy of Al are more suitable than others.
- the melting point is low and that a homogeneous material or a eutectic mixture is deposited.
- the material is ductile and has similar mechanical properties as the substrate so that coating and substrate are deformed in the similar way.
- Example C and comparative example 1 were prepared in the conventional way by pyrometallurgy and hot working. From comparative example 1 , 50 ⁇ m thick strips were also prepared via hot rolling and cold rolling. Comparative example 1 is an alloy that today is used as supporting material in catalytic converters. This material has sufficient oxidation resistance for this use. However, the mechanical strength thereof is low and is regarded to be the limiting factor of the service life of the entire device.
- the very low ductility at room temperature (2 % elongation at fracture) of the alloy according to example C entails that this alloy hardly can be manufactured in the form of thin strips.
- the same alloy has, as is seen in table 1, a very good high temperature strength, thus at 700° and 900 °C the ultimate strength, for instance, is approx. 100 % higher than for comparative example 1.
- the oxidation resistance of example C and comparative example 1 at 1100 °C is shown in figure 2.
- the oxidation rate of example C is 5 % higher than of comparative example 1 , which means that the materials can be considered as equivalents as regards oxidation resistance.
- Table 1 shows compositions of examined alloys.
- Examples A and B and com- parative examples 1 and 2 were prepared in the conventional way by pyrometallurgy and hot working. Then 50 ⁇ m thick strips of all alloys were also prepared via hot rolling and cold rolling.
- the alloys according to examples A and B are all sufficiently ductile at room temperature in order to be able to be cold-rolled to very thin strips of good productivity.
- Examples D and E and comparative example 3 correspond to cold-rolled strips of alloy according to examples B and C and comparative example 2, respectively, which was coated by vaporization or sputtering with Al on both sides in such a quantity that the total content of Al corresponded to 5,5-6 % (see table 3).
- Table 3
- the obtained thickness of Al was measured by means of GDOES (glow discharge optical emission spectroscopy), a method that enables accurate measuring of compositions and thicknesses of thin surface layers.
- GDOES low discharge optical emission spectroscopy
- the analyses showed that a total content of Al of 5-6 % had been attained.
- These samples were oxidized in air at 1000 °C for up to 620 h, which is shown in figure 1.
- the alloys according to examples D and E are superior to the alloy according to comparative example 3, while the conventionally manufactured alloy of Fe-Cr-AI in comparative example 1 has a significantly better oxidation resistance than examples D and E of the alloy according to the invention.
- Examples F and G and comparative example 4 have the same composition as the alloys according to examples D and E and comparative example 3 having been annealed at 1050 °C for 10 min with the purpose of providing an equalising of the content of Al in the material.
- the ductility of the material was determined by a bending test where the smallest bending radius that the material could be bent to without fracture was determined, see table 4.
- the alloys according to the invention have a ductility being superior to comparative exam- pie 4.
- the alloy according to comparative example 4 proved to be so brittle that this alloy has to be regarded as less suitable for the use in catalytic converters.
- the alloy according to example G has an ultimate strength at 900 °C that is equally good as the conventionally manufactured material according to the invention, example C, and twice as high as the conventionally manufactured alloy of Fe-Cr-Al in comparative example 1. This means that, upon the assumption that the oxidation resistance is sufficient, this alloy can be used in a thickness that is half of the thickness of a conventional material, and thereby enable an increase in efficiency and a reduction of the material cost for the manufacture of catalytic converters.
- the alloy according to example G was oxidation tested at 1100 °C together with the alloy according to examples C and E as well as comparative example 1 , which is shown in figure 2.
- An improved oxidation resistance is obtained with the alloy according to example G, both by comparison with the same material without diffusion-annealing (example E) and with conventionally manufactured alloys.
- the comparison between example G and example C is especially interesting, since these correspond to alloys having very similar composition but different ways of production: the alloy according to example G is prepared by cold rolling to desired thickness, followed by Al coating and annealing while example C has been prepared with desired content of Al in the alloy from the beginning.
- this alloy has a better oxidation resistance than example C.
- example C has in comparison with comparative example 1 may be explained by a negative effect on the oxidation resistance by virtue of the presence of Mo and Nb in the alloy according to example C. It is known that these elements may deteriorate the oxidation resistance of an alloy. In example G, these negative effects are absent, which may be interpreted as a positive result of example G having been prepared by Al-coating. Thus, this method of manu- facture is favourable as regards the oxidation resistance of the alloy.
- the product of ferritic stainless steel manufactured according to the process of this invention has increased resistance to cyclic and continuous thermal load and oxidation at elevated temperatures and has improved mechanical properties at said temperatures, which makes it suitable for use in high-temperature applications such as in catalytic converter applications and in heating and fur- nace applications in the form of wire, strip, foil and/or tube.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Heat Treatment Of Strip Materials And Filament Materials (AREA)
- Coating With Molten Metal (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
The present invention relates to a product of ferritic stainless steel manufactured according to the process of this invention, which product has increased resistance to cyclic and continuous thermal load and oxidation at elevated temperatures and which has improved mechanical properties at said temperatures as well as use thereof in the form of wire, strip, foil and/or tube in high-temperature applications such as in catalytic converter applications, in heating and furnace applications and which has the following composition (in % by weight): less than 1 % of Ni, 15-25 % of Cr, 4,5-12 % of Al, 0,5-4 % of Mo, 0,01-1,2 % of Nb, 0-0,5 % of Ti, 0-0,5 % of Y, Sc, Zr and/or Hf, 0-0,2 % of one or more rare earth metals (REM) such as, for instance, Ce or La, 0-0,2 % of C, 0-0,2 % of N, with the balance iron and normally occurring impurities.
Description
Cr-Al-steel for high temperature applications.
The present invention relates to a product of ferritic stainless steel manufactured according to the process of this invention, which product has increased resistance to cyclic and continuous thermal load and oxidation at increased temperatures and which has improved mechanical properties at said temperatures as well as the use thereof in the form of wire, strip, foil and/or tube in high- temperature applications such as in catalytic converter applications, in heating and furnace applications.
Background
Fe-Cr-AI-alloys have extensive use in the temperature range above 900 °C. Thanks to the protective oxide on the surface, they resist cyclic and continuous thermal load and oxidation until the material is depleted of the oxide former, e.g., Al. The i iting-factϋrs^ the service life of the entire device are the total content of Al and the mechanical strength.
Description of Prior Art
Metallic high-temperature materials in, for instance, catalytic converters or for applications for resistive heating are today normally based on thin strips or wire of ferritic Fe-Cr-AI-alloys having at least 4,5 % of Al and small amounts of reactive elements added. The high ductility of the metal gives a good resistance to mechanical and thermal fatigue. Aluminium in contents above approx. 4,5 % by weight, together with the reactive elements, imparts the material the possibility of forming a thin, protective aluminium oxide upon heating. Furthermore, the reactive elements cause that the oxide gets a considerably reduced tendency of peeling or flaking, i.e., to come loose from the metal upon cooling or mechanical deformation. Conventional Fe-Cr-AI-alloys have, however, a great disadvan-
tage: they are mechanically very weak at high temperature, and tend, therefore, to be considerably deformed also at small stresses by virtue of, e.g., acceleration, changes of pressure, mechanical impacts or changes of temperature. The alloy disclosed in EP-B-290 719, which is intended for use in the manufacture of heating elements for resistive heating of furnaces etc., as well as construction parts in catalytic converters, solves the problem of decreasing the elongation of the substrate material in relation to the protective the oxide layer as a consequence of the combined effect of addition of Ti and Zr to the alloy.
Ferritic steel materials having low content of carbon are also embrittled by grain growth upon use in temperatures above 800 °C. The low content of carbon is required in order to obtain an optimal oxidation resistance of the alloy and enable plastic cold working since contents of carbon above approx. 0,02 % by weight have an embrittling effect by increasing the brittle transition temperature of the material. Elements that are used for solid solution hardening of high-temperature materials, such as Mo and/or W, are regarded to have a considerable negative impact on the oxidation properties, and therefore the desirable content of these elements may be limited to at most 1 % such as in US 4859649 or at most 0,10 % as in EP 0667400.
Summary
Therefore, it is an object of the present invention to provide an alloy of a ferritic stainless steel having elevated resistance to cyclic and continuous thermal load and oxidation at elevated temperatures.
It is an additional object of the present invention to provide a ferritic stainless steel that has improved mechanical properties for the use in applications with cyclic and continuous thermal load and oxidation at elevated temperatures such as, e.g., supporting material in converter applications, such as catalysts.
It is an additional object of the present invention to provide a ferritic stainless steel for the use in heating applications and in furnace applications.
It is an additional object of the present invention to provide a ferritic stainless steel in the form of wire, strip, foil and/or tube.
It is an additional object of the present invention to provide a process for the manufacture of a product of said alloy.
Description of the Figures
Figure 1 shows results of the oxidation testing at 1000 °C as a function of the change of mass versus time for examples D and E as well as comparative examples 1 and 3.
Figure 2 shows results of the oxidation testing at 1100 °C as a function of the change of mass versus time for examples C, E and G as well as comparative example 1.
Description of the invention
These objects are met by means of a ferritic stainless steel having the following composition (in % by weight): less than 1 % of Ni, 15-25 % of Cr, 4,5-12 % of Al, 0,5-4 % of Mo, 0,01-1 ,2 % of Nb, 0-0,5 % of Ti, 0-0,5 % of Y, Sc, Zr and/or Hf,
0-0,2 % of one or more rare earth metals (REM) such as, for instance, Ce or La, 0-0,2 % of C, 0-0,2 % of N, with the balance iron and normally occurring impurities.
The final product may be manufactured in the form of wire, strip, foil and/or tube.
The final product according to the present invention is manufactured as a homogeneous material or a laminate or a material having a concentration gradient of Al, where the content of Al increases toward said surface of the product. Thus, the manufacture may be effected by coating a substrate material and a substrate alloy, respectively, with Al or an alloy of Al, especially by coating strips of a substrate alloy of a thickness below 1 mm with an alloy of Al.
By this two-step process, the mechanical properties and oxidation resistance of the alloy can be improved and optimized independently of each other. This process also enables a simplification of the production process when manufacture via conventional pyrometallurgy of materials having average contents of Al above the average above 4,5 % is associated with great yield losses by virtue of brittleness. An additional advantage of this process is that a final material may be manufactured having a gradient of Al, such that the content of Al increases toward the surface, which entails improved oxidation resistance since the for- mation of fast growing oxides such as chromium and iron oxides is prevented and the mechanical properties of the final material are improved.
The substrate alloy may be manufactured by conventional pyrometallurgy or, for instance, powder metallurgy with the intended composition, and then the alloy is hot- and cold-rolled to final desired dimension.
In production by a coating process, before the coating the substrate material has the following composition (in % by weight): less than 1 % of Ni, 15-27 % of Cr, 0-5 % of AI, 0,5-5 % of Mo, 0,01-2 % of Nb, 0-0,5 % of Ti, 0-0,5 % of Y, Sc, Zr and/or Hf, 0-0,2 % of one or more rare earth metals (REM) such as, for instance, Ce or La, 0-0,2 % of C, 0-0,2 % of N, with the balance iron and normally occurring impurities.
The most suitable composition of the substrate material is the following (in % by weight): less than 1 % of Ni, 16-25 % of Cr, 0,5-4 % of Al, 0,7-4 % of Mo, 0,25-1 ,0 % of Nb, 0-0,5 % of Y, Sc, Zr and/or Hf, 0-0,5 % of Ti, 0-0,1 % of one or more rare earth metals (REM) such as, for instance, Ce or La, 0,02-0,2 % of C, 0-0,05 % of N, with the balance iron and normally occurring impurities.
The material may be used in the as coated condition or after a diffusion- annealing. The most favourable compositions of the substrate material before
coating are obtained if it contains 2-4 % of Al. This aluminium content imparts the final product an increased oxidation resistance and results in a simplified production process, i.e., the risk of production disturbances in comparison with the manufacture of a material having a aluminium content above 4 % is considerably decreased. After coating with alloy of Al, the material should in total contain a content of Al that is greater than 4,5 % by weight.
Mechanical stability and resistance to grain growth are provided by the presence of precipitations of carbides and/or nitrides of one or some of the elements Ti, Nb, Zr, Hf. Increased strength at high temperatures, i.e., temperatures above approx. 800 °C is also provided by the presence of Mo and/or in solid solution. In the alloy according to the present invention, Mo may entirely or partly be replaced by W with a maintained effect on the alloy.
Addition of Zr and/or Hf and REM and/or Y and/or Sc provides an increased resistance to peeling and flaking of the formed oxide. The contents of the final product of the same elements may be supplied by adding these in the substrate alloy and/or in the alloy of Al that is used in the coating. The alloy according to the present invention should totally contain at least 0,1 % by weight of Ti+Nb+Zr+Hf.
Most compositions of the alloy according to the invention can be manufactured by conventional metallurgy. However, by the two-step process according to the present invention, a material is obtained the microstructure of which is con- trolled, the oxidation properties of which are improved, the mechanical properties of which are optimised and improved, and the maximum aluminium content of which is not limited by the embrittling effect that contents of Al above approx. 5 % by weight normally may give, both upon cold and hot working. Furthermore, the process to coat a substrate material with an alloy of Al provides a finished product the contents of which of, e.g., Mo, Nb and C can be considerably higher than in a conventionally manufactured material without the presence of these elements resulting in any noticeable deterioration of the oxidation properties.
Coating of the substrate alloy with alloy of Al may be effected by previously known processes such as, for instance, dipping in melt, electrolytic coating, rolling together of strips of the substrate alloy and the aluminium alloy, deposi- tion of solid alloy of Al from a gas phase by so-called CVD or PVD technique. The coating with alloy of Al may be effected after the substrate alloy having been rolled down to desired final thickness of the product, or in larger thickness. In the latter case, a diffusion-annealing may be carried out in order to achieve a homogenization of the material, and then rolling in one or more steps is carried out in order to provide the finished product. Rolling may also be effected directly on a coated product according to the present invention having greater thickness than the desired final thickness. In this case, the rolling may be followed by annealing.
The thickness of the coated layer of Al may be varied depending on the thickness of the substrate material, the desired aluminium content in the final product and the aluminium content in the substrate material. However, the total content of Al in the finished product has to, as has been mentioned above, always be at least 4,5 % by weight. The product may be used in the form of an annealed, homogeneous material or a laminate or a material having a concentration gradient of Al where the content of Al is higher at the surface than in the centre of the material. For a material having a concentration gradient, a lower total content and average content down to 4,0 % by weight, respectively, can be allowed if the aluminium content at a distance of at most 5 μm from the surface is more than 6,0 % by weight.
Examples of useful aluminium alloys are pure Al, Al alloyed with 0,5-25 % by weight of Si, Al alloyed with 0-2 % by weight of one or more of the elements Ce, La, Y, Zr, Hf. Depending on the coating process used, different composi- tions of the alloy of Al are more suitable than others. Thus, it is, upon coating from melt, desirable that the melting point is low and that a homogeneous material or a eutectic mixture is deposited. Upon coating by rolling-on, it is required
that the material is ductile and has similar mechanical properties as the substrate so that coating and substrate are deformed in the similar way.
Example 1
Table 1 shows compositions of examined alloys. Example C and comparative example 1 were prepared in the conventional way by pyrometallurgy and hot working. From comparative example 1 , 50 μm thick strips were also prepared via hot rolling and cold rolling. Comparative example 1 is an alloy that today is used as supporting material in catalytic converters. This material has sufficient oxidation resistance for this use. However, the mechanical strength thereof is low and is regarded to be the limiting factor of the service life of the entire device.
The very low ductility at room temperature (2 % elongation at fracture) of the alloy according to example C entails that this alloy hardly can be manufactured in the form of thin strips. However, the same alloy has, as is seen in table 1, a very good high temperature strength, thus at 700° and 900 °C the ultimate strength, for instance, is approx. 100 % higher than for comparative example 1. The oxidation resistance of example C and comparative example 1 at 1100 °C is shown in figure 2. The oxidation rate of example C is 5 % higher than of comparative example 1 , which means that the materials can be considered as equivalents as regards oxidation resistance.
Example 2
Table 1 shows compositions of examined alloys. Examples A and B and com- parative examples 1 and 2 were prepared in the conventional way by pyrometallurgy and hot working. Then 50 μm thick strips of all alloys were also prepared via hot rolling and cold rolling. The alloys according to examples A and B are all
sufficiently ductile at room temperature in order to be able to be cold-rolled to very thin strips of good productivity.
Examples D and E and comparative example 3 correspond to cold-rolled strips of alloy according to examples B and C and comparative example 2, respectively, which was coated by vaporization or sputtering with Al on both sides in such a quantity that the total content of Al corresponded to 5,5-6 % (see table 3). Table 3
The obtained thickness of Al was measured by means of GDOES (glow discharge optical emission spectroscopy), a method that enables accurate measuring of compositions and thicknesses of thin surface layers. The analyses showed that a total content of Al of 5-6 % had been attained. These samples were oxidized in air at 1000 °C for up to 620 h, which is shown in figure 1. The alloys according to examples D and E are superior to the alloy according to comparative example 3, while the conventionally manufactured alloy of Fe-Cr-AI in comparative example 1 has a significantly better oxidation resistance than examples D and E of the alloy according to the invention.
Example 3
Examples F and G and comparative example 4 have the same composition as the alloys according to examples D and E and comparative example 3 having been annealed at 1050 °C for 10 min with the purpose of providing an
equalising of the content of Al in the material. The ductility of the material was determined by a bending test where the smallest bending radius that the material could be bent to without fracture was determined, see table 4.
Table 4
The smallest radius that the material was tested at was 0,38 mm. The alloys according to the invention have a ductility being superior to comparative exam- pie 4. The alloy according to comparative example 4 proved to be so brittle that this alloy has to be regarded as less suitable for the use in catalytic converters. The alloy according to example G has an ultimate strength at 900 °C that is equally good as the conventionally manufactured material according to the invention, example C, and twice as high as the conventionally manufactured alloy of Fe-Cr-Al in comparative example 1. This means that, upon the assumption that the oxidation resistance is sufficient, this alloy can be used in a thickness that is half of the thickness of a conventional material, and thereby enable an increase in efficiency and a reduction of the material cost for the manufacture of catalytic converters.
The alloy according to example G was oxidation tested at 1100 °C together with the alloy according to examples C and E as well as comparative example 1 , which is shown in figure 2. An improved oxidation resistance is obtained with the alloy according to example G, both by comparison with the same material without diffusion-annealing (example E) and with conventionally manufactured
alloys. The comparison between example G and example C is especially interesting, since these correspond to alloys having very similar composition but different ways of production: the alloy according to example G is prepared by cold rolling to desired thickness, followed by Al coating and annealing while example C has been prepared with desired content of Al in the alloy from the beginning. Apart from the improved production properties of a material that has been prepared in the way of example G, in addition this alloy has a better oxidation resistance than example C. The relatively seen lower oxidation resistance that example C has in comparison with comparative example 1 may be explained by a negative effect on the oxidation resistance by virtue of the presence of Mo and Nb in the alloy according to example C. It is known that these elements may deteriorate the oxidation resistance of an alloy. In example G, these negative effects are absent, which may be interpreted as a positive result of example G having been prepared by Al-coating. Thus, this method of manu- facture is favourable as regards the oxidation resistance of the alloy.
To sum up, it may be observed that by the combined effect of high contents of Mo and Nb, a considerable improvement in the strength is provided in compari- son with the material that is used today as well as that by using the described process, this material may be imparted the oxidation resistance required upon use at high temperatures of materials in weak dimensions and the above mentioned product forms.
The product of ferritic stainless steel manufactured according to the process of this invention has increased resistance to cyclic and continuous thermal load and oxidation at elevated temperatures and has improved mechanical properties at said temperatures, which makes it suitable for use in high-temperature applications such as in catalytic converter applications and in heating and fur- nace applications in the form of wire, strip, foil and/or tube.
CN
CM ω Q O CO I-
Claims
1. Ferritic steel alloy characterised in that it has the following composition (in % by weight): less than 1 % of Ni, 15-25 % of Cr, 4,5-12 % of Al, 0,5^ % of Mo, 0,01-1 ,2 % of Nb, 0-0,5 % of Ti, 0-0,5 % of Y, Sc, Zr and/or Hf, 0-0,2 % of one or more rare earth metals (REM) such as, for instance, Ce or La, 0-0,2 % of C, 0-0,2 % of N, with the balance iron and normally occurring impurities.
2. Ferritic steel alloy according to claim 1 characterised in that Mo entirely or partly is replaced by W.
3. Ferritic steel alloy according to claims 1 or 2 cha racterised in that it contains one or more rare earth metals (REM).
4. Ferritic steel alloy according to claim 1 characterised in that it contains at least 0,1 % in total of Ti, Nb, Zr and/or Hf.
5. Method of producing a ferritic steel alloy according to any of claims 1 to 4 characterised in coating a substrate alloy with Al or an alloy of Al, the substrate alloy having the following composition (in % by weight): less than 1 % of Ni, 15-27 % of Cr, 0-5 % of AI, 0,5-5 % of Mo, 0,01-2 % of Nb, 0-0,5 % of Ti, 0-0,5 % of Y, Sc, Zr and/or Hf, 0-0,2 % of one or more rare earth metals (REM) such as, for instance, Ce or La, 0-0,2 % of C, 0-0,2 % of N, with the balance iron and normally occurring impurities.
6. Product in the form of wire, strip, foil and/or tube for use in high-temperature applications characterised in that it is produced from a ferritic steel alloy according to any one of claims 1 to 4.
7. Use of a ferritic steel alloy according to any of claims 1 to 4 as supporting material in catalytic converter applications.
8. Use of a ferritic steel alloy according to claims 1 to 4 in heating and furnace applications.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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SE0400452A SE527742C2 (en) | 2004-02-23 | 2004-02-23 | Ferritic steel for high temperature applications, ways of making it, product and use of the steel |
PCT/SE2005/000249 WO2005080622A1 (en) | 2004-02-23 | 2005-02-21 | Cr-al-steel for high-temperature applications |
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EP1721023A1 true EP1721023A1 (en) | 2006-11-15 |
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EP05711109A Withdrawn EP1721023A1 (en) | 2004-02-23 | 2005-02-21 | Cr-al-steel for high-temperature applications |
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US (1) | US20080210348A1 (en) |
EP (1) | EP1721023A1 (en) |
JP (1) | JP2007524001A (en) |
KR (1) | KR20060127063A (en) |
CN (1) | CN1918314A (en) |
SE (1) | SE527742C2 (en) |
WO (1) | WO2005080622A1 (en) |
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EP2031080B1 (en) * | 2007-08-30 | 2012-06-27 | Alstom Technology Ltd | High temperature alloy |
WO2009045136A1 (en) * | 2007-10-05 | 2009-04-09 | Sandvik Intellectual Property Ab | The use and method of producing a dispersion strengthened steel as material in a roller for a roller hearth furnace |
DE102008018135B4 (en) * | 2008-04-10 | 2011-05-19 | Thyssenkrupp Vdm Gmbh | Iron-chromium-aluminum alloy with high durability and small changes in heat resistance |
CH699206A1 (en) * | 2008-07-25 | 2010-01-29 | Alstom Technology Ltd | High-temperature alloy. |
JP5760525B2 (en) * | 2010-03-30 | 2015-08-12 | Jfeスチール株式会社 | Stainless steel foil and catalyst carrier for exhaust gas purification apparatus using the foil |
JP5126437B1 (en) * | 2011-04-01 | 2013-01-23 | Jfeスチール株式会社 | Stainless steel foil and catalyst carrier for exhaust gas purification apparatus using the foil |
JP5561447B1 (en) * | 2012-12-17 | 2014-07-30 | Jfeスチール株式会社 | Stainless steel plate and stainless steel foil |
RU2571241C2 (en) * | 2013-12-23 | 2015-12-20 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" | Ferrite corrosion resistant steel |
CN103949863A (en) * | 2014-05-14 | 2014-07-30 | 河南飞孟金刚石工业有限公司 | Steel plate for synthesis of diamond or cubic boron nitride and making method of steel plate |
US10821706B2 (en) | 2016-05-30 | 2020-11-03 | Jfe Steel Corporation | Ferritic stainless steel sheet |
JP6237973B1 (en) * | 2016-05-30 | 2017-11-29 | Jfeスチール株式会社 | Ferritic stainless steel sheet |
CN106222577A (en) * | 2016-08-25 | 2016-12-14 | 中广核研究院有限公司 | Stainless steel alloy and preparation method thereof, the stainless steel cladding of fuel assembly |
WO2019129747A1 (en) * | 2017-12-27 | 2019-07-04 | Sandvik Intellectual Property Ab | A method for straightening of a fecral alloy tube |
JP6791458B1 (en) * | 2019-02-19 | 2020-11-25 | Jfeスチール株式会社 | Ferritic stainless steel sheet and its manufacturing method, and stainless steel sheet with Al vapor deposition layer |
WO2020255563A1 (en) * | 2019-06-19 | 2020-12-24 | Jfeスチール株式会社 | Aluminum-based plated stainless steel sheet, and method for manufacturing ferritic stainless steel sheet |
CN113621897A (en) * | 2020-05-08 | 2021-11-09 | 宝山钢铁股份有限公司 | Rare earth-containing heat-resistant alloy steel and slab continuous casting process thereof |
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CA1324456C (en) * | 1986-03-05 | 1993-11-16 | Johannes A. M. Van Broekhoven | Catalyst compositions |
DE3706415A1 (en) * | 1987-02-27 | 1988-09-08 | Thyssen Edelstahlwerke Ag | SEMI-FINISHED FERRITIC STEEL PRODUCT AND ITS USE |
JPH04354850A (en) * | 1991-05-29 | 1992-12-09 | Nisshin Steel Co Ltd | High al-containing ferritic stainless steel excellent in high temperature oxidation resistance |
JPH06389A (en) * | 1992-03-02 | 1994-01-11 | Nippon Steel Corp | Highly heat resistant metallic carrier for automobile catalyst |
JP3283286B2 (en) * | 1992-03-31 | 2002-05-20 | 新日本製鐵株式会社 | Fe-Cr-Al alloy foil for highly heat-resistant metal carrier for automobile exhaust gas purification catalyst |
JPH07233451A (en) * | 1993-12-28 | 1995-09-05 | Nisshin Steel Co Ltd | Al plated stainless steel sheet excellent in high temperature oxidation resistance |
EP0688882A4 (en) * | 1993-12-28 | 1996-03-27 | Nisshin Steel Co Ltd | Aluminum-plated stainless steel sheet with excellent high-temperature oxidation resistance |
ZA95523B (en) * | 1994-02-09 | 1995-10-02 | Allegheny Ludium Corp | Creep resistant iron-chromium-aluminum alloy substantially free of molybdenum |
JPH08155304A (en) * | 1994-12-02 | 1996-06-18 | Tanaka Kikinzoku Kogyo Kk | High temperature service combustion catalyst |
JP3210535B2 (en) * | 1994-12-20 | 2001-09-17 | 新日本製鐵株式会社 | Metal carrier for purifying exhaust gas with low heat capacity and low back pressure |
FR2760244B1 (en) * | 1997-02-28 | 1999-04-09 | Usinor | PROCESS FOR THE MANUFACTURE OF A FERRITIC STAINLESS STEEL STRAP WITH A HIGH ALUMINUM CONTENT FOR USE IN PARTICULAR FOR A MOTOR VEHICLE EXHAUST CATALYST SUPPORT |
JP3865091B2 (en) * | 1997-03-31 | 2007-01-10 | 日新製鋼株式会社 | Fe-Cr-Al ferritic stainless steel with excellent high temperature strength, high temperature oxidation resistance and diffusion bonding |
-
2004
- 2004-02-23 SE SE0400452A patent/SE527742C2/en unknown
-
2005
- 2005-02-21 JP JP2006554058A patent/JP2007524001A/en active Pending
- 2005-02-21 EP EP05711109A patent/EP1721023A1/en not_active Withdrawn
- 2005-02-21 US US10/589,945 patent/US20080210348A1/en not_active Abandoned
- 2005-02-21 WO PCT/SE2005/000249 patent/WO2005080622A1/en active Application Filing
- 2005-02-21 CN CNA2005800046979A patent/CN1918314A/en active Pending
- 2005-02-21 KR KR1020067014643A patent/KR20060127063A/en not_active Application Discontinuation
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SE0400452D0 (en) | 2004-02-23 |
CN1918314A (en) | 2007-02-21 |
WO2005080622A1 (en) | 2005-09-01 |
SE527742C2 (en) | 2006-05-30 |
KR20060127063A (en) | 2006-12-11 |
US20080210348A1 (en) | 2008-09-04 |
SE0400452L (en) | 2005-08-24 |
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