CN1524130A - Ferritic stainless steel for member of exhaust gas flow passage - Google Patents
Ferritic stainless steel for member of exhaust gas flow passage Download PDFInfo
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- CN1524130A CN1524130A CNA02813138XA CN02813138A CN1524130A CN 1524130 A CN1524130 A CN 1524130A CN A02813138X A CNA02813138X A CN A02813138XA CN 02813138 A CN02813138 A CN 02813138A CN 1524130 A CN1524130 A CN 1524130A
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 42
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000010935 stainless steel Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 description 45
- 239000010959 steel Substances 0.000 description 45
- 238000012360 testing method Methods 0.000 description 17
- 239000011651 chromium Substances 0.000 description 16
- 229910000851 Alloy steel Inorganic materials 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 230000035882 stress Effects 0.000 description 12
- 238000000137 annealing Methods 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 239000002912 waste gas Substances 0.000 description 6
- 230000002939 deleterious effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000010960 cold rolled steel Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910000967 As alloy Inorganic materials 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004881 precipitation hardening Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910006291 Si—Nb Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Classifications
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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
-
- 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
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
-
- 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
- C22C38/18—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
-
- 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
-
- 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
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
-
- 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
-
- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Abstract
A ferritic stainless steel for use in a member of an exhaust gas flow passage, which has a chemical composition, in mass %: C: 0.03 % or less, Si: 1.0 % or less, Mn: 1.5 % or less, Ni: 0.6 % or less, Cr: 10 to 20 %, Nb: 0.50 % or less, Cu: 0.8 to 2.0 %, Al: 0.03 % or less, V: 0.03 to 0.20 %, N: 0.03 % or less, provided that Nb>=8(C+N) is satisfied, and balance: Fe and inevitable impurities. Ti and B may be optionally contained in amounts of 0.05 to 0.30 and 0.0005 to 0.02 mass %, respectively. The ferritic stainless steel exhibits a thermal resistance comparable to that of a ferritic stainless steel containing Nb and Mo added thereto, and also is excellent in formability, the toughness at a low temperature and weldability.
Description
Technical field
The present invention relates to the ferritic stainless steel of a kind of thermotolerance, low-temperature flexibility and excellent weldability, it can be used as the pipe element of discharging waste gas, for example exhaust pipeline, anterior pipeline, central duct and the catalytic converter shell in the oil engine such as automobile.
Background technology
The automobile pipe element of discharging waste gas is directly exposed to when driving a car in the high-temperature atmosphere that contains waste gas, and stands by re-lighting and brake and the thermal stresses that vibration caused when driving.When start up the car the winter of cold district, mechanical stress is applied at low temperatures the pipe element.Thereby, must have wearing quality in severe environment as the material of pipe element.
Because pipe element is by with steel plate or sealing of tube or be shaped as shape of product and make, for this purpose steel must have good thermotolerance, weldability and formability.Do not ftracture when forming steel plate or pipe in secondary processing and make the pipe element anti-at low temperatures mechanical stress that becomes, toughness, especially low-temperature flexibility also are key propertys.
Ferritic stainless steel is compared with austenitic stainless steel, because little, thermal fatigue resistance of its thermal expansivity and rust-proofing skin peel force, through being often used as the material of these pipe elements.Low price also is an advantage of ferritic stainless steel.
In order to improve the hot strength of the ferritic stainless steel that is lower than austenitic stainless steel in essence, various innovative approachs have been proposed so far.For example, JP3-274245A discloses Nb steel alloy and Nb, Si steel alloy as new SUS430J1 stainless steel, and JP5-125491A discloses Nb, Mo steel alloy.Especially Nb, Mo steel alloy owing to its excellent high-temperature intensity and thermal fatigue resistance, can be used as the parts or the member that are exposed in the abominable high-temperature atmosphere.Yet bad formability and inferior low-temperature flexibility are the shortcomings of Nb, Mo steel alloy.Although it is announced some reports, still not enough to the improvement of this purpose to improving formability and low-temperature flexibility.Consuming expensive at high proportion Mo also is a shortcoming of Nb, Mo steel alloy.
In addition, needn't make hot strength (for example, thermal fatigue resistance) and high temperature oxidation resistance (being measured as the ultimate temperature of improper oxidation) simultaneously with high level to some parts or member.Have complex configuration, but parts that do not contact with high-temp waste gas or member occasion, hot strength is more important than high temperature oxidation resistance, and formability and low-temperature flexibility also are important factors, so that stainless steel plate or pipe are shaped as complex configuration.Yet, Nb, Mo steel alloy must be used for emphatically thermotolerance and not consider this parts or the member that bad formability, inferior low-temperature flexibility and valency are high.
Summary of the invention
The present invention aims to provide a kind of ferritic stainless steel that is used as the pipe element of discharging waste gas.An object of the present invention is in order to make the ferritic stainless steel that does not contain expensive Mo also have the thermotolerance that is similar to Nb, Mo steel alloy except that good formability, low-temperature flexibility and weldability.
The present invention proposes a kind of ferritic stainless steel, this stainless C of consisting of is up to 0.03 quality %, Si and is up to 1.0 quality %, Mn and is up to that V, N that Cu, Al that Cr, Nb that 1.5 quality %, Ni be up to 0.6 quality %, 10～20 quality % be up to 0.50 quality %, 0.8～2.0 quality % be up to 0.03 quality %, 0.03～0.20 quality % are up to 0.03 quality % and surplus is iron except that unavoidable impurities, and the Nb that satisfies condition 〉=8 (C+N).
This ferritic stainless steel does not contain Mo as alloy element, but the Ti that randomly contains 0.05～0.30 quality % with the B of further improvement formability and/or 0.0005～0.02 quality % with further improvement secondary formability.
Description of drawings
Fig. 1 is the graphic representation of ferritic stainless steel 0.2% yielding stress effect when representing Cu to elevated temperature.
Embodiment
Such as SUH409L, these stainless steels of SUS430J1I and SUS429 have been used as the good material of thermotolerance in the atmosphere, and pipe element is exposed in this atmosphere.Heating is up to 800～900 ℃ some parts or member, requires to be significantly higher than the hot strength of conventional steel.This parts or member have complicated profile usually, so that it is made by formability and the good stainless steel of low-temperature flexibility, this performance is that the Mo steel alloy is not available.In addition, owing to the thermal stresses that repeats to be applied on the complex configuration, these parts or member may be owing to thermal fatigue is destroyed.
The inventor has studied and has examined the effect of different-alloy element to this parts or component performance, and found, by V and two kinds of elements of Cu being added to the Nb of par, in the Mo steel alloy, ferritic stainless steel all is improved aspect 900 ℃ hot strength, formability and the low-temperature flexibility being lower than.
By measuring 0.2% yielding stress, some Nb alloy ferritic stainless steels that contain small proportion V and different ratios Cu have been checked 700 ℃ and 800 ℃ of following elevated temperature tension tests.Test-results proves that by adding the Cu of small proportion V and control ratio, hot strength improves significantly to the level that is similar to Nb, Mo steel alloy.
Fig. 1 shows the ferritic stainless steel test-results with the 17Cr-0.4Nb-0.1V essentially consist that adds Cu in varing proportions.Fig. 1 also shows the intensity as the SUS444 steel of Nb, Mo steel alloy Comparative Examples with 18Cr-2Mo-0.4Nb essentially consist.
Pointed as Fig. 1,0.2% yield value of stress under 700 ℃ and 800 ℃ increases significantly rising with Cu content.Cu be 0.8 quality % or when higher 0.2% yield value of stress be similar to or be better than containing the SUS444 steel of 2 quality %Mo of having an appointment.The inventor is confirmed by another test-results that 0.2% yield value of stress under 900 ℃ is not brought up to the level of SUS444 by increasing V and Cu content, contains the Nb ferritic stainless steel but be higher than.In a word, it is effective to the hot strength that improvement is lower than 900 ℃ of hot-zones to add V and two kinds of elements of Cu, and is being higher than not remarkable trouble under 900 ℃ of temperature.
Improve hot strength in the Nb steel alloy and might make description below by V and two kinds of elements of Cu are added to: when the stainless metallographic structure of observation the present invention after short or long for some time of heating, detect the Particle Distribution of Nb and Cu compound.The particle that this observations means V compound preferential precipitation when the heating beginning is so that Nb and Cu remain on dissolved state and make Nb and the Cu compound precipitates at last to the effective particulate of precipitation hardening.Can not flock together when uniform distribution becomes the long-term heating of being deposited in of particulate in the steel matrix when the heating beginning, so that precipitation hardening keeps effectively long-time.
Make free C and N change into the V of carbonitride by having, for the ratio of the dissolving Nb that improves hot strength also remains on than the higher value of no V steel that contains Nb with same ratio.The hot strength that has guaranteed to be reached for by the consumption of saving Nb this purpose necessity is compared in the increase of dissolving Nb with no V steel, the result has improved formability and low-temperature flexibility.
The carbonitride of Nb and V increases in the annealing substrate of ferritic stainless steel of the present invention.The increase of carbonitride has suppressed the welded heat affecting zone crystal growth and has become coarse grain, thereby improves toughness.By increasing carbonitride, also suppressed formation to the deleterious chromium carbide of intergranular corrosion resistance.
By following explanation, each self-applying of ferritic stainless steel interalloy element of the present invention will become apparent.
C is up to 0.03 quality % N and is up to 0.03 quality %
C and N are considered to hot strength, creep strength effective elements for example, but excessive C and N reduce oxidation-resistance, formability, low-temperature flexibility and weldability unfriendly.Contain in the alloy system that is useful on the V that C and N is fixed as carbonitride and Nb of the present invention, must add V and Nb with ratio corresponding to C and N concentration.Thereby for fear of V and the Nb that increase causes material price to rise, C and N content separately are controlled in 0.03 quality % or still less (be preferably 0.015 quality % or still less).
Si is up to 1.0 quality %
Si is a kind of to the high-temperature oxidation resistance effective elements, but is not so effective to being lower than 900 ℃ hot strength.Excessive Si makes the ferrite stainless hardening of steel, causes reducing formability and low-temperature flexibility.On this meaning, Si content is decided to be 1.0 quality % or still less (is preferably 0.1～0.5 quality %).
Mn is up to 1.5 quality %
Mn is a kind of improvement high-temperature oxidation resistance of ferritic stainless steel, the especially alloy element of rust-proofing skin peel force performance, but excessive Mn reduces formability and weldability.Because Mn is a kind of austenite stabilizer element, be added into the formation that causes in the steel that contains less ratio Cr thermal fatigue strength and the deleterious martensitic phase of formability with Mn is excessive.Thereby Mn content is decided to be 1.5 quality % or still less (be preferably 0.5 quality % or still less).
Ni is up to 0.6 quality %
Ni is a kind of austenite stabilizer element.Excessive N i is added in the steel that contains less ratio Cr, identical with Mn, accelerated formation to thermal fatigue strength and the deleterious martensitic phase of formability.Excessive N i also makes the steel cost rise.Thereby Ni content is decided to be 0.6 quality % or still less (be preferably 0.5 quality % or still less).
Cr is 10～20 quality %
Cr is the oxidation-resistance of stablizing the fundamental element of ferritic phase and improve high temperature when using to key property.Oxidation-resistance becomes better when Cr content increases, but excessive Cr causes stainless embrittlement, causes improving hardness and reduces formability.On this meaning, Cr content is set in 10～20 quality % scopes.Preferably, the temperature during according to use, Cr is controlled in suitable value.For example, the Cr of 16～19 quality % is favourable to not being higher than 950 ℃ of oxidation-resistances under the temperature, and the Cr of 12～16 quality % is favourable to not being higher than 900 ℃ of oxidation-resistances under the temperature.
The Nb of 8 (C+N)～0.50 quality %
Nb is fixed into carbonitride with C and N, and the hot strength when also improving in being dissolved in steel matrix state.Yet excessive N b is unfavorable to formability, low-temperature flexibility and antagonism welding heat fragility.It is necessary to fixation of C and N that Nb is not less than 8 (C+N), but in order to keep suitable formability, low-temperature flexibility and tension stress type hot crackability, the upper limit of Nb is decided to be 0.5 quality %.Preferably, Nb content is controlled in by 8 (C+N)+0.10 to 0.45 quality % scope.
0.8 the Cu of～2.0 quality %
Cu is a most important element in the alloy system of the present invention.In the temperature range that the inventor has studied and examined, most of Cu is dissolved in the annealed steel matrix and when thermal treatment and precipitates.Cu precipitation demonstrates strengthening effect identical with Mo when the heating beginning, but this strengthening effect is passed gradually in time and died down.In order to obtain being suitable for the Cu that Fig. 1 indicates the hot strength needs at least 0.8 quality % of purpose.Yet when Cu content increased, formability, low-temperature flexibility and weldability reduced.Be controlled at 2.0 quality % by the upper limit and suppressed the detrimental action of Cu formability, low-temperature flexibility and weldability with Cu content.Preferably, Cu content is set in 1.0～1.7 quality % scopes.
Al is up to 0.03 quality %
Al adds as deoxidant element in process for making.But excessive Al reduces the outward appearance of stainless steel plate and also formability, low-temperature flexibility and weldability is played deleterious effect.On this meaning, preferably, Al content is controlled at minimum possibility level, so its upper limit is decided to be 0.03 quality %.
0.03 the V of～0.20 quality %
Add the hot strength of V improvement ferritic stainless steel when Nb and Cu coexistence is arranged.It is also effective to the toughness of formability, low-temperature flexibility, intergranular corrosion resistance and welded heat affecting zone to add V with Nb.Be 0.03 quality % or shown these effects when higher at V, but it is quite unfavorable to formability and low-temperature flexibility to be higher than the excessive V of 0.20 quality %.On this meaning, V content is set in 0.03～0.20 quality % scope (being preferably 0.04～0.15 quality %).
0.05 the Ti of～0.30 quality %
Ti is a kind of optional elements that improves blue gram Ford (Lankford) value (r) and improvement ferritic stainless steel formability, and is 0.05 quality % or has shown its effect when higher at Ti.Yet excessive Ti promotes the generation of the deleterious TiN of stainless steel outward appearance and also reduces formability and low-temperature flexibility.About this point, even when adding Ti for the improvement formability, Ti will remain on minimum possibility ratio.Thereby the upper limit of Ti content is decided to be 0.30 quality % (being preferably 0.20 quality %).
0.0005 the B of～0.02 quality %
B is another optional elements of rimose when improving stainless steel secondary formability and suppressing multistage shaping.Be 0.0005 quality % or shown effect when higher at B, but excessive B causes the reduction of productivity and weldability formability.On this meaning, B content is set in 0.0005～0.02 quality % scope (being preferably 0.001～0.01 quality %).
The Mo of 0～0.10 quality %
Alloy system of the present invention is to suppose not add under the expensive situation of Mo as a kind of alloy element to design, but Mo might be involved as a kind of impurity when steel-making.Because it is harmful to formability, low-temperature flexibility and weldability to contain the Mo of higher proportion, it should be controlled in less than 0.10 quality %.
To the element beyond above-mentioned without any restriction, but common impurities, as P, S and O, preferably be controlled in minimum may level.Consider hot workability, oxidation-resistance etc., the upper limit of P, S, O is preferably and is decided to be 0.04 quality %, 0.03 quality % and 0.02 quality % respectively.For thermotolerance can be added at least a element among W, Zr, Y and the REM (rare earth metal), or be at least a element among hot workability interpolation Ca, Mg and the Co.
In order to obtain good thermotolerance when the hot-roll annealing state, as long as Cu is dissolved in the steel matrix in advance, just there is no particular limitation to working condition.Can not be hot-rolled down to the occasion of pre-determined thickness at ferritic stainless steel, by repeating cold rollingly to give identical stable on heating steel plate with the hot-rolled steel sheet of annealing with the annealing preparation.Make Cu be dispersed into particulate by any stage, further improved hot strength in preparation technology.After making annealing hot rolling or cold-rolled steel sheet be shaped as or be welded into certain profile (comprise and produce steel pipe), still keep such premium properties.
To make other characteristics of the present invention apparent by following embodiment.
Melting has the various ferritic stainless steels of chemical constitution shown in table 1 or the table 2 and is cast as the 30kg ingot in vacuum oven.With this ingot forging, hot rolling, annealing, be cold-rolled to 2.0mm or 1.2mm thickness, and final annealing.Table 1 shows composition of the present invention, and table 2 shows the contrast composition.
In table 2, the o.11 steel is corresponding to SUS430J11, and No. 15 steel is corresponding to SUH409L, and No. 16 steel is corresponding to the 14Cr-Si-Nb steel, and No. 17 steel is corresponding to SUS444.So far, any in these steel has been used as the exhaust pipeline material.
The chemical constitution of table 1 ferritic stainless steel of the present invention
| Number | Alloy element (quality %) | |||||||||||||
| ??C | ??Si | ??Mn | ??Ni | ??Cr | ??Nb | ??Ti | ??Mo | ??Cu | ??Al | ??B | ??V | ??N | ??[Nb] | |
| ??1 | ??0.015 | ??0.31 | ??0.15 | ??0.10 | ??17.09 | ??0.35 | ??- | ??0.01 | ??0.85 | ??0.01 | ??- | ??0.10 | ??0.009 | ??0.16 |
| ??2 | ??0.010 | ??0.28 | ??0.17 | ??0.11 | ??17.13 | ??0.36 | ??- | ??0.01 | ??1.50 | ??0.01 | ??- | ??0.11 | ??0.008 | ??0.22 |
| ??3 | ??0.008 | ??0.32 | ??0.05 | ??0.10 | ??17.02 | ??0.33 | ??- | ??0.01 | ??1.93 | ??0.01 | ??- | ??0.10 | ??0.010 | ??0.19 |
| ??4 | ??0.012 | ??0.33 | ??0.22 | ??0.09 | ??10.71 | ??0.35 | ??- | ??- | ??1.42 | ??0.01 | ??- | ??0.12 | ??0.011 | ??0.17 |
| ??5 | ??0.011 | ??0.39 | ??0.50 | ??0.09 | ??14.01 | ??0.38 | ??- | ??- | ??1.45 | ??0.01 | ??30 | ??0.12 | ??0.006 | ??0.24 |
| ??6 | ??0.007 | ??0.21 | ??0.16 | ??0.21 | ??19.52 | ??0.33 | ??- | ??- | ??1.51 | ??0.01 | ??20 | ??0.11 | ??0.008 | ??0.21 |
| ??7 | ??0.007 | ??0.81 | ??0.18 | ??0.12 | ??12.03 | ??0.31 | ??0.15 | ??0.04 | ??1.50 | ??0.03 | ??10 | ??0.06 | ??0.006 | ??0.21 |
| ??8 | ??0.011 | ??0.30 | ??1.21 | ??0.10 | ??17.44 | ??0.36 | ??0.20 | ??0.03 | ??1.53 | ??0.03 | ??50 | ??0.03 | ??0.009 | ??0.20 |
| ??9 | ??0.011 | ??0.36 | ??0.12 | ??0.11 | ??17.42 | ??0.21 | ??0.11 | ??0.09 | ??1.51 | ??0.02 | ??150 | ??0.04 | ??0.007 | ??0.07 |
| ??10 | ??0.028 | ??0.33 | ??0.31 | ??0.11 | ??17.40 | ??0.45 | ??0.07 | ??0.02 | ??1.48 | ??0.01 | ??20 | ??0.04 | ??0.021 | ??0.06 |
B content is by the ppm unit representation.
[Nb] is with Nb-8[C+N] calculate.
Mark (-) is meant the value that is lower than detection limit.
The chemical constitution of table 2 contrast ferritic stainless steel
| Number | Alloy element (quality %) | |||||||||||||
| ??C | ??Si | ??Mn | ??Ni | ??Cr | ??Nb | ??Ti | ??Mo | ??Cu | ??Al | ??B | ??V | ??N | ??[Nb] | |
| ?11 | ??0.008 | ??0.30 | ??0.28 | ??0.14 | ??17.00 | ??0.37 | ??- | ??0.02 | ? 0.60 | ??0.03 | ??- | ? - | ??0.011 | ??0.22 |
| ?12 | ??0.010 | ??0.36 | ??0.28 | ??0.17 | ??16.99 | ??0.38 | ??- | ??0.01 | ? 4.08 | ??0.01 | ??- | ??0.04 | ??0.012 | ??0.20 |
| ?13 | ??0.008 | ? 1.38 | ??0.26 | ??0.17 | ??17.06 | ??0.41 | ??0.01 | ??0.01 | ??1.48 | ??- | ??- | ? - | ??0.013 | ??0.24 |
| ?14 | ??0.009 | ??0.35 | ??0.32 | ??0.31 | ??17.24 | ? 0.74 | ??- | ??0.01 | ??2.48 | ??0.02 | ??- | ? 0.01 | ??0.013 | ??0.56 |
| ?15 | ??0.020 | ??0.42 | ??0.39 | ??0.10 | ??12.16 | ? 0.01 | ? 0.23 | ? 0.02 | ? - | ??0.02 | ??- | ? - | ??0.014 | ? -0.26 |
| ?16 | ??0.011 | ? 1.10 | ??0.98 | ??0.10 | ??14.75 | ??0.50 | ??- | ? 0.01 | ? 0.03 | ??- | ??- | ? - | ??0.012 | ??0.31 |
| ?17 | ??0.012 | ??0.40 | ??0.70 | ??0.22 | ??18.28 | ??0.50 | ??- | ? 1.94 | ? 0.24 | ??0.01 | ??20 | ??0.04 | ??0.011 | ??0.32 |
| ?18 | ??0.011 | ??0.82 | ??0.25 | ??0.11 | ??17.42 | ??0.45 | ??0.01 | ??0.02 | ??1.69 | ? 0.34 | ? 20 | ? 0.01 | ??0.021 | ??0.19 |
| ?19 | ??0.012 | ??0.31 | ??0.29 | ??0.11 | ??19.55 | ??0.20 | ??0.01 | ??- | ??0.82 | ??- | ??- | ? 0.02 | ??0.008 | ??0.04 |
B content is by the ppm unit representation.
[Nb] is with Nb-8[C+N] calculate.
Mark (-) is meant the value that is lower than detection limit.
Mark underscore numeral is outside the present invention's regulation.
By elevated temperature tension test, high-temperature oxidation test, room temperature tensile test and charpy impact test have been checked the various annealing cold-rolled steel sheets of thickness 2.0mm.The various annealing cold-rolled steel sheets of thickness 1.2mm have been detected by the tension type hot cracking test.
In elevated temperature tension test, under JIS G0567 defined terms in 800 ℃ of tension test pieces, so that measure its 0.2% yielding stress.
In high-temperature oxidation test, under JIS Z2281 defined terms in 850 ℃, 900 ℃, 950 ℃ and 1100 ℃ of each temperature heat test pieces 200 hours.Detect by an unaided eye the heating test block to detect the appearance of improper oxidation (being the growth of block thick-oxide on the steel plate thickness direction).Be heated by observations determination test piece and do not have the ultimate temperature of improper oxidation.
In the room temperature tensile test, the cold-rolled steel sheet of respectively annealing of thickness 2.0mm is shaped as test block 13B and under JIS Z2241 defined terms, stretches to measure its post-rift unit elongation.
In charpy impact test, under JIS Z2242 defined terms, be that small size (sub-sized) test block of 20mm imposes impact to thickness, to detect ductility-brittle transition temperature in each temperature of-75 ℃ ,-50 ℃ ,-25 ℃, 0 ℃ and 25 ℃.
In the tension type hot cracking test, the two ends of the test block of length 40mm and width 20mm are clamped and carried out tig welding under the conditions that test block is applied tensile stress along its longitudinal direction, begin the minimum strain of rimose so that detect test block.By estimate stretching resistance type hot tearing performance with the detected ultimate strain of this mode.
Test-results is shown in table 3
Show by table 3, the present invention the 1st to No. 10 steel any, have 0.2% yielding stress at 800 ℃, apparently higher than Nb, No. 16 steel of Si alloy be similar to or be better than Nb, No. 17 steel of Mo alloy.The unit elongation value of room temperature tensile test, the ultimate strain value of the ductility of charpy impact test-brittle transition temperature value and tension type hot cracking test also are similar to or are better than Nb, No. 17 steel of Mo alloy.These results have proved, do not need Mo just to reach the purpose performance as alloy element.When the result of the 4th, 5 and No. 12 steel is compared to each other, be appreciated that when reducing Cr content, the ultimate temperature that undesired oxidation occurs becomes lower.Because Cr is to the effect of undesired oxidation, Cr content will be set at suitable value according to the temperature that steel member or parts are exposed.
Do not have the 11st, 15,16 and No. 19 steel of contrast of V and Cu, except that 800 ℃ of hot strengths are bad, have formability, low-temperature flexibility and weldability the purpose desired level.Contain No. 12 steel of contrast of excessive Cu, hot strength is good, but formability and weldability are lower than No. 17 steel Nb, Mo steel alloy, so that is difficult to be shaped as or be welded into shape of product.
Contain specialized range Cu of the present invention, but excessive No. 13 steel of contrast and No. 14 steel of contrast that contains excessive Nb of Si, hot strength is good, but formability, low-temperature flexibility and weldability are lower than the 1st to No. 10 steel of the present invention.
No. 18 steel of contrast that contains less V and excessive Al have thermotolerance and formability that the 1st to No. 10 steel is identical with the present invention, but low-temperature flexibility is bad, causes occurring when producing or use trouble.It is bad owing to lacking the V hot strength to contrast No. 9 steel.
No. 17 steel of contrast that contains Mo has the 1st to No. 10 identical performance of steel with the present invention, but its low-temperature flexibility is lower.The cost of No. 17 steel must be higher than the 1st to No. 10 steel of the present invention owing to consume about 2 quality %Mo.
The evaluation of table 3 test-results
| Number | 0.2% yielding stress (N/mm in the time of 800 ℃ 2) | The ultimate temperature of improper oxidation (℃) | Unit elongation after the forging (%) | Transition temperature (℃) | Ultimate strain | |
| ??1 | ????35 ????45 ????47 ????43 ????44 ????44 ????45 ????43 ????36 ????35 | ??1000 ??1000 ??1000 ??850 ??900 ??1000 ??950 ??1000 ??1000 ??1000 | ??34 ??32 ??31 ??34 ??33 ??32 ??32 ??34 ??35 ??32 | ????-50 ????-50 ????-50 ????-50 ????-50 ????-50 ????-50 ????-50 ????-50 ????-50 | ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ | The embodiment of the invention |
| ??2 | ||||||
| ??3 | ||||||
| ??4 | ||||||
| ??5 | ||||||
| ??6 | ||||||
| ??7 | ||||||
| ??8 | ||||||
| ??9 | ||||||
| ??10 | ||||||
| ??11 | ??? 24????50 ????45 ? ????47 ? ??? 18??? 25????35 ????40 ? ??? 30 | ??1000 ??950 ??1100 ? ??1000 ? ??850 ??950 ??1000 ??1000 ? ??1000 | ??34 ? 29? 28? ??30 ? ??37 ??35 ??32 ??31 ? ??32 | ????-50 ????-25 ??? 0? ??? 0? ????-75 ????-50 ????-25 ???? 0? ????-25 | ○ × ×? ×? ○ ○ ○ ○ ? ○ | Comparative Examples |
| ??12 | ||||||
| ??13 | ||||||
| ??14 | ||||||
| ??15 | ||||||
| ??16 | ||||||
| ??17 | ||||||
| ??18 | ||||||
| ??19 |
3% or the bigger limit have strain to be evaluated as mark zero, and less than 3% be evaluated as mark *.
The underscore reference numerals does not meet the purpose performance.
According to the invention described above, by specific Alloying Design, especially control the content of V and Cu, and do not need expensive Mo, make ferritic stainless steel not reduce thermotolerance being improved aspect formability, low-temperature flexibility and the weldability.This stainless steel that proposes recently can be used as member or the parts or the pipe element of motor car engine, for example shell of the gas exhaust duct of discharging waste gas, anterior pipeline, central duct, catalytic converter.
Claims (4)
1. ferritic stainless steel of pipe element as the discharging automobile exhaust gas, the described stainless C of consisting of is up to 0.03 quality %, Si and is up to 1.0 quality %, Mn and is up to that V, N that Cu, Al that Cr, Nb that 1.5 quality %, Ni be up to 0.6 quality %, 10～20 quality % be up to 0.50 quality %, 0.8～2.0 quality % be up to 0.03 quality %, 0.03～0.20 quality % are up to 0.03 quality % and surplus is iron except that unavoidable impurities, and the Nb that satisfies condition 〉=8 (C+N).
2. ferritic stainless steel as claimed in claim 1, wherein the Mo of the inevitable impurity of conduct is controlled in the scope less than 0.10 quality %.
3. ferritic stainless steel as claimed in claim 1 or 2, described stainless steel also contain the Ti of 0.05～3.0 quality % in addition.
4. as each described ferritic stainless steel in the claim 1 to 3, described stainless steel also contains the B of 0.0005～0.02 quality % in addition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP204444/2001 | 2001-07-05 | ||
| JP2001204444 | 2001-07-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1524130A true CN1524130A (en) | 2004-08-25 |
| CN1225566C CN1225566C (en) | 2005-11-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB02813138XA Expired - Lifetime CN1225566C (en) | 2001-07-05 | 2002-07-04 | Ferritic stainless steel for member of exhaust gas flow passage |
Country Status (8)
| Country | Link |
|---|---|
| US (4) | US20040170518A1 (en) |
| EP (1) | EP1413640B1 (en) |
| JP (2) | JP4197492B2 (en) |
| KR (1) | KR20040007764A (en) |
| CN (1) | CN1225566C (en) |
| DE (1) | DE60204323T2 (en) |
| ES (1) | ES2240764T3 (en) |
| WO (1) | WO2003004714A1 (en) |
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2002
- 2002-07-04 DE DE60204323T patent/DE60204323T2/en not_active Expired - Lifetime
- 2002-07-04 ES ES02743819T patent/ES2240764T3/en not_active Expired - Lifetime
- 2002-07-04 JP JP2003510470A patent/JP4197492B2/en not_active Expired - Lifetime
- 2002-07-04 WO PCT/JP2002/006768 patent/WO2003004714A1/en active IP Right Grant
- 2002-07-04 KR KR10-2004-7000076A patent/KR20040007764A/en not_active Application Discontinuation
- 2002-07-04 EP EP02743819A patent/EP1413640B1/en not_active Expired - Lifetime
- 2002-07-04 US US10/482,718 patent/US20040170518A1/en not_active Abandoned
- 2002-07-04 CN CNB02813138XA patent/CN1225566C/en not_active Expired - Lifetime
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- 2008-11-06 US US12/233,122 patent/US20090053093A1/en not_active Abandoned
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2010
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| CN105537875B (en) * | 2016-01-18 | 2018-03-09 | 山西太钢不锈钢股份有限公司 | A kind of manufacture method of ferritic stainless steel welded tube |
| CN106319373A (en) * | 2016-08-16 | 2017-01-11 | 盐城市科瑞达科技咨询服务有限公司 | Micro spherical ferritic stainless steel powder and preparation method thereof |
| CN108531824A (en) * | 2016-08-16 | 2018-09-14 | 刘可 | A kind of application of minute spherical ferritic stainless steel powder |
| CN109790605A (en) * | 2016-09-28 | 2019-05-21 | 株式会社Posco | The ferritic stainless steel adsorbed with reduced carbon slag and its manufacturing method for exhaust system heat exchanger |
| CN109790605B (en) * | 2016-09-28 | 2021-10-29 | 株式会社Posco | Ferritic stainless steel with reduced carbon slag adsorption for exhaust system heat exchangers and method of making same |
| CN114364820A (en) * | 2019-08-05 | 2022-04-15 | 株式会社Posco | Ferritic stainless steel with improved high temperature creep resistance and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040170518A1 (en) | 2004-09-02 |
| JP5138504B2 (en) | 2013-02-06 |
| EP1413640A4 (en) | 2004-12-15 |
| KR20040007764A (en) | 2004-01-24 |
| US20090053093A1 (en) | 2009-02-26 |
| DE60204323D1 (en) | 2005-06-30 |
| EP1413640B1 (en) | 2005-05-25 |
| EP1413640A1 (en) | 2004-04-28 |
| DE60204323T2 (en) | 2006-01-26 |
| JPWO2003004714A1 (en) | 2004-10-28 |
| CN1225566C (en) | 2005-11-02 |
| JP2008297631A (en) | 2008-12-11 |
| US20110176954A1 (en) | 2011-07-21 |
| ES2240764T3 (en) | 2005-10-16 |
| JP4197492B2 (en) | 2008-12-17 |
| US20100119404A1 (en) | 2010-05-13 |
| WO2003004714A1 (en) | 2003-01-16 |
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