CN103946403A - Seamless austenite heat-resistant alloy tube - Google Patents
Seamless austenite heat-resistant alloy tube Download PDFInfo
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- CN103946403A CN103946403A CN201280056250.6A CN201280056250A CN103946403A CN 103946403 A CN103946403 A CN 103946403A CN 201280056250 A CN201280056250 A CN 201280056250A CN 103946403 A CN103946403 A CN 103946403A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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Abstract
A seamless austenite heat-resistant alloy tube of the present invention is made with a chemical composition comprising, in terms of mass percent, C: 0.03-0.15%, Si <= 1%, Mn <= 2%, P <= 0.03%, S <= 0.01%, Ni: 35-60%, Cr: 18-38%, W: 3-11%, Ti: 0.01-1.2%, Al <= 0.5%, B: 0.0001-0.01%, N <= 0.02%, and O <= 0.008%; at least one chosen from Zr: 0.01-0.5%, Nb: 0.01-0.05%, and V: 0.01-0.5%; and, if necessary, at least one chosen from Mo <= 1%, Cu <= 1%, Co <= 1%, Ca <= 0.05%, Mg <= 0.05%, and REM <= 0.1%; with the remainder consisting of Fe and impurities. The average crystal grain diameter (d[mu]m) at the central section of the thickness of the tube is 1000 [mu]m or less and fulfills the expression (d <= 1500 - 2.5 105 B). The thickness of an oxide layer on the outer surface of the tube is 15 [mu]m or less, and the outer surface of the tube is directly fillet welded. The alloy tube of the present invention has outstanding resistance to weld cracking and can suppress the appearance of cracks in the heat-affected zone during welding, and therefore can favorably be used as a member for high-temperature devices such as furnace wall pipes for boilers for electricity generation.
Description
Technical field
The present invention relates to the seamless refractory alloy pipe of austenite.Be specifically related to the pipe of the hearth wall as formed generating boiler (hereinafter referred to as " hearth wall pipe ".) can directly carry out fillet welding and the seamless refractory alloy pipe of austenite that uses as the member of high temperature service to the outside surface of pipe like that.More specifically relate to taking having excellent high-temperature strength, there is sufficient anticorrosion stress-resistant crackle and the little austenite heat-resistant alloy of thermal expansivity resistance to welding crack among the seamless compo pipe of raw material is excellent HAZ place cracks can suppress to weld time the seamless refractory alloy pipe of austenite.
Background technology
In recent years, about generating boiler, carrying out in the world and improving the newly-built of the temperature of steam and " the superelevation emergent pressure boiler " of pressure for high efficiency.In addition, also planning by the vapor temperature of 600 DEG C of front and back be up to now increased to 650 DEG C above even practical to more than 700 DEG C " superelevation emergent pressure boiler of future generation ".This is based on energy-conservation, efficent use of resources and cuts down CO for protection of the environment
2gas output become energy problem solution task become in the lump important industry policy.And be that high temperature and high-pressure trend are favourable to high efficiency because use in boiler in the generating of combustion of fossil fuels.
The temperature rise when high temperature of steam and high-pressure trend make to form the running of heat pipe and main team pipe etc. of the such as superheater tube of pipe of boiler and reheater tube and so on.Therefore, there are solidity to corrosion, especially requirement under hot strength and high temperature to have the stability of metallographic structure and good creep properties for the long-term material requirements using in this harsh environment.
Non-patent literature 1 is taking practical heat-stable material as object, the Cr content taking transverse axis as material, the figure that the temperature of the longitudinal axis under allowable stress 49MPa arranges out are shown, and the temperature of having described the longitudinal axis raises along with the increase of Cr content, the creep strength that belongs to hot strength correspondingly improves.
In addition, non-patent literature 2 is taking practical heat-stable material as object, the Ni content taking transverse axis as material, the figure that the longitudinal axis arranges out as crack sensitivity are shown, increase along with Ni content is shown, the crack sensitivity of the longitudinal axis diminishes, and the solidity to corrosion (anticorrosion stress-resistant crackle) under high temperature improves.
Patent documentation 1～3 discloses following refractory alloy, improve the content of Cr and Ni and contain Mo and W in more than a kind, attempt improving the creep-rupture strength that belongs to hot strength.
In addition, in the face of requiring more and more stricter hot strength characteristic, particularly requirement to have creep-rupture strength, patent documentation 4～7 discloses following refractory alloy, contain 28～38% Cr, 35～60% Ni in quality %, effectively separating out of α-Cr phase of the body-centered cubic structure of utilization taking Cr as main body, attempts further improving creep-rupture strength.
On the other hand, patent documentation 8 and patent documentation 9 disclose following Ni base alloy, contain Mo and/or W and attempt solution strengthening, contain Al and Ti and effectively utilize belong to the γ ' phase of intermetallic compound, be particularly Ni
3the precipitation strength of (Al, Ti), thus under above-mentioned that harsh hot environment, use.
In addition, patent documentation 10 has proposed following high-ni austenitic heat-resistant alloy, by adjust Al and Ti content scope, γ ' is separated out mutually improved creep strength.
In addition, austenite heat-resistant alloy is generally assembled into various structures and at high temperature uses by welding.But, as non-patent literature 3 is reported, if the alloying element amount of austenite heat-resistant alloy increases, in the time of welding procedure, there will be welding heat affected zone (hereinafter referred to as " HAZ ".) crack, especially crack this problem with the HAZ place of melting border adjacency.
Therefore the austenite heat-resistant alloy, using for the member as various structures requires to prevent that HAZ place from ftractureing and solder joint performance while taking into account welding.
Patent documentation 11 discloses following austenite heat-resistant alloy, and the Fe by containing specified quantitative also adjusts the scope of effective B amount, can guarantee processibility under high temperature and butt welding time, prevents that HAZ place from ftractureing.
In addition, patent documentation 12 discloses following austenite heat-resistant alloy, by adjusting the content of the impurity elements such as P, S and Sn, Pb, can in the long-time use procedure in the time of butt welding and under high temperature, prevent HAZ place cracking, and creep strength is also excellent.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 60-100640 communique
Patent documentation 2: Japanese kokai publication sho 64-55352 communique
Patent documentation 3: Japanese kokai publication hei 2-200756 communique
Patent documentation 4: Japanese kokai publication hei 7-216511 communique
Patent documentation 5: Japanese kokai publication hei 7-331390 communique
Patent documentation 6: Japanese kokai publication hei 8-127848 communique
Patent documentation 7: Japanese kokai publication hei 8-218140 communique
Patent documentation 8: Japanese kokai publication sho 51-84726 communique
Patent documentation 9: Japanese kokai publication sho 51-84727 communique
Patent documentation 10: Japanese kokai publication hei 9-157779 communique
Patent documentation 11: TOHKEMY 2011-63838 communique
Patent documentation 12: TOHKEMY 2010-150593 communique
Non-patent literature
Non-patent literature 1: increase the only light in mountain, iron and steel, Vol.80 (1994) No.8, pp.587～592 (the only light in increasing mountain: iron と Steel, Vol.80 (1994) No.8, pp.587～592)
Non-patent literature 2: the positive human relations of little rock, corrosion of metal damage and anticorrosion technique (nineteen eighty-three, agne-shofu company), 452～453 pages (positive Lun of little rock: the anti-Shi Ji of metal Fu Shi Damage Injury と Intraoperative (nineteen eighty-three, (strain) ア グ ネ Cheng Wind society), 452～453 ペ ー ジ)
Non-patent literature 3: Institute of Welding compiles, welded joint handbook the 2nd edition (put down into 15 years, ball kind), 948～950 pages (welding the Knitting of association: weld and engage Bian list the 2nd edition (put down into 15 years, ball kind), 948～950 ペ ー ジ)
Non-patent literature 4: first-class is stretched in high open country, IHI skill report, vol.49No.4 (2009), pp.185～191 (ら is stretched in high open country: IHI skill Reported, vol.49No.4 (2009), pp.185～191)
Summary of the invention
the problem that invention will solve
As mentioned above, austenite heat-resistant alloy is generally assembled into various structures by welding.And in recent years, trend is the hearth wall pipe with boiler by the effective do generating of these austenite heat-resistant alloys.
As the raw material of above-mentioned hearth wall pipe, conventionally consider from the various viewpoints such as operability in the past, use and needn't implement the two carbon steel or 1%Cr steel of preheating and post-heating.
But, for aforementioned, vapor temperature being increased to 700 DEG C of above " superelevation emergent pressure boilers of future generation ", the carbon steel in the past using or the hot strength of 1%Cr steel are inadequate.Therefore, above-mentioned carbon steel and 1%Cr steel all cannot be as the raw materials of the hearth wall pipe of " superelevation emergent pressure boiler of future generation ".
On the other hand, the common austenite stainless steel that superheater tube and reheater tube use is so far because Ni content is few, thus hearth wall and so in the environment of internal flow high-temperature water, produce stress corrosion cracking.Therefore, for common austenite stainless steel, can not be used as the raw material of the hearth wall pipe of " superelevation emergent pressure boiler of future generation ".
And austenite stainless steel is as shown in an example in non-patent literature 4, thermal linear expansion coefficient is large.Therefore, austenite stainless steel thermal change deformation in the time of welding is large, in the time making hearth wall, goes wrong.
It should be noted that, hearth wall is by forming by multiple hearth wall pipe configured in parallel and with the panel for this hearth wall pipe fin keel connected to one another (fin plate) or fin ray (fin bar) are welded.Therefore, from different to the butt welding of welding through the groove face of mechanical workout, need to the outside surface of the pipe under manufacture state directly and fin keel or fin ray carry out fillet welding.
As mentioned above, the outside surface of pipe is directly carried out to fillet welding (below sometimes referred to as " outside surface to pipe directly welds ".) situation with compared with the situation of the butt welding of welding in groove, on vpg connection, become large at the stress concentration of reinforcement toe.Its result, the situation that the outside surface of pipe is directly welded is compared with carrying out the situation of butt welding, and in welding, HAZ place becomes easily and cracks.
Therefore, exploitation can be suitable as austenite heat-resistant compo pipe hearth wall pipe, that improved Ni content of " superelevation emergent pressure boiler of future generation ", develop the following seamless refractory alloy pipe of austenite that has improved Ni content and become urgent problem, described austenite is seamless refractory alloy pipe taking having excellent high-temperature strength, there is sufficient anticorrosion stress-resistant crackle and the little austenite heat-resistant alloy of thermal expansivity among the seamless compo pipe of raw material, resistance to welding crack excellent and can suppress to weld time HAZ place crack.
Although aforementioned patent document 1～10 discloses the improved austenite heat-resistant alloy of creep-rupture strength, " weldability " this viewpoint when assembling as structure is not studied, and does not consider the outside surface of pipe directly to weld completely.Therefore, how also cannot be by the austenite heat-resistant alloy to propose in above-mentioned each patent documentation the hearth wall pipe as the effective work " superelevation emergent pressure boiler of future generation " of raw material.
The austenite heat-resistant alloy that the inventor etc. propose in patent documentation 11 is suitable as generating boiler, chemical industry and the goods such as the pipe, plate, rod and the forged article that use in heat-resistant pressure-resistant member such as uses, and is especially suitable for use as massive article.In addition, the ductility that high temperature process, resistance to welding crack sensibility and the high-temperature aging while adopting this austenite heat-resistant alloy can improve significantly said products manufacture and when real machine uses causes reduces.
Similarly, the austenite heat-resistant alloy that the inventor etc. propose in patent documentation 12 can prevent HAZ cracking, and can in welding procedure, prevent the defect causing because of welding operation, and the creep strength under high temperature is also excellent in addition.Therefore, this austenite heat-resistance alloy can be suitable as the raw material of the high temperature services such as generating boiler, chemical industry equipment.
But when the austenite heat-resistant alloy that proposes in exploitation above-mentioned patent documentation 11 and patent documentation 12, the inventor etc. reckoning without directly weld the outside surface of pipe.Therefore, to taking above-mentioned austenite heat-resistant alloy in the situation that the outside surface of the pipe of raw material directly welds, on vpg connection, become large at the stress concentration of reinforcement toe, result is compared with carrying out the situation of butt welding, and in the time of welding, HAZ place can inevitably become easily and crack.Therefore,, during by the hearth wall pipe of the effective work taking above-mentioned each austenite heat-resistant alloy as raw material " superelevation emergent pressure boiler of future generation ", stay and need the item improved.
The present invention makes in view of above-mentioned present situation, object is to provide following austenite seamless refractory alloy pipe, it is if generating is with can directly carrying out fillet welding and the austenite heat-resistant compo pipe that uses as the member of high temperature service to the outside surface of pipe the hearth wall pipe of boiler, at HAZ place cracks taking having excellent high-temperature strength, when having sufficient anticorrosion stress-resistant crackle and a little austenite heat-resistant alloy of thermal expansivity resistance to welding crack excellence can suppressing to weld among the seamless compo pipe of raw material the seamless refractory alloy pipe of austenite.
for the scheme of dealing with problems
The inventor etc., in order to solve foregoing problems, have implemented various investigation.
Its result, has first confirmed the B by containing appropriate amount and can give austenite heat-resistant alloy with sufficient hot strength.
Secondly, the seamless tube of the various austenite heat-resistant alloys that the making such as the inventor contain B is (below sometimes referred to as " austenite heat-resistant compo pipe ".), by the outside surface of this compo pipe be used as the direct fillet welding of plate of fin keel, specifically with the thick 6mm with chemical constitution shown in table 2 of embodiment described later, the direct fillet welding of alloy sheets of wide 15mm, long 200mm, for when welding, the crackle of HAZ place generation has carried out detailed investigation.
Result has been understood fully the situation of following (a)～(d).
(a) while having confirmed welding, crackle produces the content of this non-patent literature 3 at the crystal boundary of the HAZ near melting border.
(b) the B amount crystal particle diameters more or austenite heat-resistant compo pipe that contain in austenite heat-resistant compo pipe are larger, and HAZ place more easily cracks.In addition, the toe angle of reinforcement is larger, and HAZ place more easily cracks.
(c) section of the crackle that HAZ place produces confirms to have melting trace.In addition, on this section, there is the enrichment of B.And the crystal particle diameter of austenite heat-resistant compo pipe is larger, the enrichment of B is more remarkable.
(d) oxide skin generating on the outside surface of austenite heat-resistant compo pipe is thicker, and the toe angle of reinforcement is larger.
According to the situation of above-mentioned (a)～(d) understand fully, the inventor etc. have obtained the conclusion of following (e)～(f).
(e) crackle of when welding HAZ place generation is subject to the strong effect of the B that is present in crystal boundary aspect metallurgical, and the crystal particle diameter of austenite heat-resistant compo pipe is affecting indirectly the behavior of B at grain boundaries.
(f) crackle that above-mentioned HAZ place produces is subject to the strong effect at the toe angle of reinforcement in terms of mechanics.And the oxide skin generating on the outside surface of austenite heat-resistant compo pipe affects toe angle indirectly.
Understood fully the B to containing appropriate amount and guaranteed that the austenite heat-resistant compo pipe of sufficient hot strength directly carries out in the situation of fillet welding, HAZ place cracks when preventing from welding, below two be effective:
The crystal particle diameter of management austenite heat-resistant compo pipe, simultaneously according to the content of crystal particle diameter adjustment B; And
The thickness of the oxide skin existing on the outside surface of management austenite heat-resistant compo pipe, controls reinforcement shape.
Its reason is considered based on following (g)～(i).
(g) in welding procedure, because Thermal Cycle makes the crystal boundary generation segregation of the HAZ of B melting border near.B is the element that makes the melting point depression of crystal boundary, thereby the crystal boundary melting partly of segregation has occurred above-mentioned B in welding, this melting position be subject to welding heat stress and opening generates so-called " liquation crack ".It should be noted that, in the large situation of crystal particle diameter, the grain boundary area of per unit volume is little.Therefore, in the large situation of crystal particle diameter, the grain boundary segregation of B becomes significantly, and the stress that specific crystal boundary face bears becomes large, and therefore HAZ place becomes easily and cracks.
(h) if the toe angle of weld seam (reinforcement) becomes large, stress is easily concentrated to HAZ, thereby becomes more easily and crack.
(i) on the outside surface of pipe, be formed with in the situation of thick oxide skin, except the fusing point of oxide compound high, and in the time that the outside surface of pipe is carried out to fillet welding and the wettability variation of molten metal.Therefore, it is large that the toe angle of reinforcement becomes, and improves for the susceptibility of crackle.
Thereby the inventor etc. have implemented further detailed research.
Its result is understood fully, by in the situation of the outside surface of austenite heat-resistant compo pipe and the direct fillet welding of the plate (the thick 6mm with chemical constitution shown in table 2 of embodiment, the alloy sheets of wide 15mm, long 200mm) of being used as fin keel, following by taking (j) and countermeasure (k), can prevent HAZ place cracking.
(j) (μ is m) below 1000 μ m, and the amount of the B containing according to alloy is adjusted to the scope that meets following formula to make the average crystalline particle diameter d of the wall thickness central part of compo pipe.
d≤1500-2.5×10
5×B
B in above formula represents the content (quality %) of B.
(k) reducing with the wettability of molten metal when improving fillet welding, is suppressed at the thickness of the oxide skin of the outside surface of compo pipe below 15 μ m toe angle.
The present invention completes based on above-mentioned opinion, and its main contents are the seamless refractory alloy pipe of austenite shown in following.
(1) the seamless refractory alloy pipe of a kind of austenite, tube outer surface is directly carried out fillet welding and used, it is characterized in that, the chemical constitution of this austenite is seamless refractory alloy pipe is as follows: in quality %, C:0.03～0.15%, Si:1% is following, Mn:2% is following, P:0.03% is following, S:0.01% is following, Ni:35～60%, Cr:18～38%, W:3～11%, Ti:0.01～1.2%, Al:0.5% are following, B:0.0001～0.01%, N:0.02% are following and below O:0.008%; And in Zr:0.01～0.5%, Nb:0.01～0.5% and V:0.01～0.5% more than a kind; And surplus is made up of Fe and impurity,
The average crystalline particle diameter d μ m of the wall thickness central part of pipe is below 1000 μ m and meets following formula; In addition, the thickness of the oxide skin of the outside surface of pipe is below 15 μ m.
d≤1500-2.5×10
5×B
B in above formula represents the content in the B of quality %.
(2) the seamless refractory alloy pipe of austenite of recording according to above-mentioned (1), it is characterized in that, contain to be selected from quality % and more than a kind replace part Fe in the element shown in following < 1 > and < 2 >.
Below < 1 > Mo:1%, below Cu:1% and below Co:1%,
Below < 2 > Ca:0.05%, below Mg:0.05% and below REM:0.1%.
(3) the seamless refractory alloy pipe of austenite of recording according to above-mentioned (1) or (2), is characterized in that, it is as hearth wall pipe.
" impurity " refers to the material of sneaking into from the ore as raw material, waste material or manufacturing environment etc. in the time of industrial manufacture austenite heat-resistant alloy.
" REM " refers to the general name of 17 kinds of elements of total of Sc, Y and lanthanon, and the content of REM refers to the total content of the one kind or two or more element in REM.
the effect of invention
The resistance to welding crack excellence of austenite of the present invention is seamless refractory alloy pipe, can suppress to weld time, HAZ place cracks.Therefore, the seamless refractory alloy pipe of austenite of the present invention taking having excellent high-temperature strength, there is sufficient anticorrosion stress-resistant crackle and the little austenite heat-resistant alloy of thermal expansivity and can be suitable as the member of the high temperature service of hearth wall pipe of generating boiler and so among the seamless compo pipe of raw material.
Brief description of the drawings
The figure that Fig. 1 schematically illustrates for the contained welding test body of fillet welding of having made, having simulated hearth wall pipe in embodiment.It should be noted that, in figure, the alloy sheets of being used as fin keel is simply expressed as to " fin keel ".
Fig. 2 is for the figure describing for test tube and the fillet welding of alloy sheets of being used as fin keel.It should be noted that, in figure, the alloy sheets of being used as fin keel is simply expressed as to " fin keel ".
Embodiment
Be described in detail for each prerequisite of the present invention below.It should be noted that, in the following description, " % " of the content of each element represents to mean " quality % ".
(A) chemical constitution of pipe:
C：0.03～0.15％
C makes austenite stable, and forms fine carbide at crystal boundary, and the creep strength under high temperature is improved.In order fully to obtain this effect, C content need to be more than 0.03%.But, excessively containing in the situation of C, carbide chap is separated out greatly and in a large number, and therefore the ductility of crystal boundary reduces, and the reduction of toughness and creep strength can occur in addition.Therefore, the upper limit is set, the content of C is made as to 0.03～0.15%.The lower limit of C content is preferably 0.04%, and in addition, the upper limit is preferably 0.12%.
Below Si:1%
Si has desoxydatoin, and is effective element for improving solidity to corrosion under high temperature and scale resistance.But in the excessive situation that contains Si, austenitic stability reduces, thereby cause toughness and creep strength to reduce.Therefore,, for the content of Si arranges the upper limit, be made as below 1%.The content of Si is preferably below 0.8%.
In addition, content for Si needn't arrange lower limit especially, but extreme minimizing cannot obtain deoxidation effect, and the cleanliness factor of alloy becomes large and cleanliness is deteriorated, and be also difficult to obtain solidity to corrosion under high temperature and the raising effect of scale resistance, manufacturing cost also promotes greatly.Therefore, the lower limit of Si content is preferably 0.02%.
Below Mn:2%
Mn is same with Si has desoxydatoin.Mn also contributes to austenitic stabilization.But, when the content of Mn is excessive, cause embrittlement, can there is in addition the reduction of toughness and creep ductility.Therefore,, for the content of Mn arranges the upper limit, be made as below 2%.The content of Mn is preferably below 1.5%.
In addition, for the content of Mn, lower limit also needn't be set especially, but extreme minimizing cannot obtain deoxidation effect, makes the cleanliness of alloy deteriorated, and be difficult to obtain stabilization of austenite effect, manufacturing cost also promotes greatly.Therefore, the lower limit of Mn content is preferably 0.02%.
Below P:0.03%
P is contained in alloy as impurity, is the element that improves liquation crack susceptibility in welding in the crystal boundary generation segregation of HAZ.Therefore,, for the content of P arranges the upper limit, be made as below 0.03%.The content of P is preferably below 0.02%.
In addition, it is preferred that the content of P reduces as much as possible, but minimizing extremely can cause the increase of manufacturing cost.Therefore, the lower limit of P content is preferably 0.0005%.
Below S:0.01%
S is same with P to be contained in alloy as impurity, is the element that improves liquation crack susceptibility in welding in the crystal boundary generation segregation of HAZ.In addition, S still causes dysgenic element to the toughness after long-time use.Therefore,, for the content of S arranges the upper limit, be made as below 0.01%.The content of S is preferably below 0.005%.
In addition, it is preferred that the content of S reduces as much as possible, but minimizing extremely can cause the increase of manufacturing cost.Therefore, the lower limit of S content is preferably 0.0001%.
Ni：35～60％
Ni is effective element for obtaining austenite, is the necessary element of structure stability during in order to ensure long-time use.In the scope of the Cr content of aftermentioned 18～38%, in order fully to obtain the effect of above-mentioned Ni, Ni content need to be more than 35%.But Ni is expensive element, contains in a large number Ni and can cause cost to increase.Therefore, the upper limit is set, the content of Ni is made as to 35～60%.The lower limit of Ni content is preferably 38%, and in addition, the upper limit is preferably 55%.
Cr：18～38％
Cr is in order to ensure the scale resistance under high temperature and the necessary element of solidity to corrosion.In the scope of above-mentioned 35～60% Ni content, in order to obtain the effect of above-mentioned Cr, Cr content need to be more than 18%.But when the content of Cr exceedes 38%, the austenitic stability degradation under high temperature, causes the reduction of creep strength.Therefore, the content of Cr is made as to 18～38%.The lower limit of Cr content is preferably 20%, and in addition, the upper limit is preferably 35%.
W：3～11％
Thereby W is solid-solubilized in the element that goes far towards to improve the creep strength under the high temperature that exceedes 700 DEG C in matrix.For this effect is brought into play fully, it is more than 3% that W content at least needs.But also there is effect situation saturated, that on the contrary creep strength is reduced in the excessive W of containing.In addition, W is expensive element, thereby the excessive W of containing can cause cost to increase.Therefore, the upper limit is set, the content of W is made as to 3～11%.The lower limit of W content is preferably 5%, and in addition, the upper limit is preferably 10%.
Ti：0.01～1.2％
Ti separates out in crystal grain with fine carbonitride form, is conducive to the creep strength under high temperature.In order to obtain this effect, Ti content need to be more than 0.01%.But, when the content of Ti is excessive, separate out in a large number with carbonitride form, cause the reduction of creep ductility and toughness.Therefore, the upper limit is set, the content of Ti is made as to 0.01～1.2%.The lower limit of Ti content is preferably 0.05%, and in addition, the upper limit is preferably 1.0%.
Below Al:0.5%
Al is the element with desoxydatoin.But when the content of Al is excessive, the cleanliness of alloy is significantly deteriorated, hot workability and ductility reduce.Therefore,, for the content of Al arranges the upper limit, be made as below 0.5%.The content of Al is preferably below 0.3%.
In addition, for the content of Al, lower limit needn't be set especially, but extreme minimizing cannot fully obtain deoxidation effect, make on the contrary the cleanliness of alloy deteriorated, and cause manufacturing cost to rise.Therefore, the lower limit of Al content is preferably 0.001%.For the stable deoxidation effect that obtains Al, guarantee that alloy has good cleanliness, the lower limit of Al content more preferably 0.0015%.
B：0.0001～0.01％
Thereby B is by strengthening crystal boundary and make the fine dispersion of grain boundary carbide improve the required element of creep strength in crystal boundary generation segregation in use at high temperature.In addition, B also has in crystal boundary generation segregation the effect that makes clinging power raising, contributes to improve toughness.In order to obtain these effects, B content need to be more than 0.0001%.But, when the content of B is excessive, because the Thermal Cycle in welding makes near the high temperature HAZ a large amount of segregations of B melting border, make the melting point depression of crystal boundary, promote the liquation crack susceptibility of HAZ.Therefore, the upper limit is set, the content of B is made as to 0.0001～0.01%.The lower limit of B content is preferably 0.0005%, and in addition, the upper limit is preferably 0.005%.
It should be noted that, in the large situation of the average crystalline particle diameter d μ m of the wall thickness central part of pipe, it is large that the crystal particle diameter of HAZ melting border near becomes, in other words, the grain boundary area of per unit volume diminishes, encourage the grain boundary segregation of B, and the stress that specific crystal boundary face bears becomes large, therefore liquation crack susceptibility lifting.
But, as described later, if (μ is m) that 1000 μ m amount (%) following and the B that contains according to alloy is adjusted to the scope that meets following formula, can suppress the increase of the liquation crack susceptibility causing because of the segregation of B to make the average crystalline particle diameter d of the wall thickness central part of compo pipe.
d≤1500-2.5×10
5×B
B in above formula represents the content in the B of quality %.
Below N:0.02%
N is effective element for austenite is stablized.In aforesaid 18～38% Cr content range, excessive while containing N, fine nitride a large amount of in use are at high temperature separated out in crystal grain, cause the reduction of creep ductility and toughness.Therefore,, for the content of N arranges the upper limit, be made as below 0.02%.The content of N is preferably below 0.015%.
In addition, for the content of N, lower limit needn't be set especially, but extreme minimizing is difficult to obtain the effect that makes austenite stable, manufacturing cost also can promote greatly.Therefore, the lower limit of N content is preferably 0.0005%.
Below O:0.008%
O (oxygen) is contained in alloy as impurity, and when its content is excessive, hot workability reduces, and causes in addition the deteriorated of toughness and ductility.Therefore,, for the content of O arranges the upper limit, be made as below 0.008%.The content of O is preferably below 0.005%.
Content for O needn't arrange lower limit especially, but extreme minimizing can cause the rising of manufacturing cost.Therefore, the lower limit of O content is preferably 0.0005%.
Below, Zr, Nb and V, all with C or N bonding and form fine carbide or carbonitride, contribute to the raising of creep strength.Therefore, the seamless refractory alloy pipe of austenite of the present invention also contains a kind of above element in Zr:0.01～0.5%, Nb:0.01～0.5% and V:0.01～0.5% except above-mentioned element from C to O.
Zr：0.01～0.5％
Zr and C or N bonding and form fine carbide or carbonitride, contribute to the raising of creep strength.In order to obtain this effect, Zr content need to be more than 0.01%.But, when the content of Zr is excessive, separate out in a large number with carbide or carbonitride form, cause the reduction of creep ductility.Therefore, the upper limit is set, the content of Zr is made as to 0.01～0.5%.The lower limit of Zr content is preferably 0.015%, and in addition, the upper limit is preferably 0.4%.
Nb：0.01～0.5％
Nb and C or N bonding and form fine carbide or carbonitride, contribute to the raising of creep strength.In order to obtain this effect, Nb content need to be more than 0.01%.But, when the content of Nb is excessive, separate out in a large number with carbide or carbonitride form, cause the reduction of creep ductility.Therefore, the upper limit is set, the content of Nb is made as to 0.01～0.5%.The lower limit of Nb content is preferably 0.015%, and in addition, the upper limit is preferably 0.4%.
V：0.01～0.5％
V and C or N bonding and form fine carbide or carbonitride, contribute to the raising of creep strength.In order to obtain this effect, V content need to be more than 0.01%.But, when the content of V is excessive, separate out in a large number with carbide or carbonitride form, cause the reduction of creep ductility.Therefore, the upper limit is set, the content of V is made as to 0.01～0.5%.The lower limit of V content is preferably 0.015%, and in addition, the upper limit is preferably 0.4%.
Above-mentioned Zr, Nb and V can only contain wherein any a kind, or compoundly contain two or more.Compound total amount while containing these elements can be 1.5%, is preferably below 1.2%.
The chemical constitution of the seamless refractory alloy pipe of a kind of austenite of the present invention is: above-mentioned each element; And surplus is made up of F and impurity.
In addition, as already described, " impurity " refers to the material of sneaking into from the ore as raw material, waste material or manufacturing environment etc. in the time of industrial manufacture austenite heat-resistant alloy.
The chemical constitution of the seamless refractory alloy pipe of another kind of austenite of the present invention is: contain the a kind of above element being selected from Mo, Cu, Co, Ca, Mg and REM and replace the above-mentioned Fe of part.
Describe for the action effect of these arbitrary elements and the restriction reason of content below.
Mo, Cu and the Co of group < 1 > all have the effect that improves creep strength.Therefore, can contain these elements.
Below Mo:1%
Mo has the effect that improves creep strength., Mo has the effect that is solid-solubilized in matrix and improves the creep strength under high temperature.Therefore, can contain Mo.But, excessively containing in the situation of Mo, austenitic stability reduces, and causes on the contrary the reduction of creep strength.Therefore, for the amount of the Mo containing sometimes, the upper limit is set, is made as below 1%.
On the other hand, for the stable effect that obtains aforementioned Mo, the amount of Mo is preferably more than 0.1%.
Below Cu:1%
Cu has the effect that improves creep strength.That is, Cu is same with Ni is austenite generting element, contributes to promote phase stability and improves creep strength.Therefore, can contain Cu.But, excessively contain in the situation of Cu, cause the reduction of hot workability.Therefore, for the amount of the Cu containing sometimes, the upper limit is set, is made as below 1%.
On the other hand, for the stable effect that obtains aforementioned Cu, the amount of Cu is preferably more than 0.02%.
Below Co:1%
Co has the effect that improves creep strength.That is, Co is same with Ni and Cu is austenite generting element, contributes to promote phase stability and improves creep strength.Therefore, can contain Co.But Co is very expensive element, therefore the excessive Co of containing can cause cost significantly to increase.Therefore, for the amount of the Co containing sometimes, the upper limit is set, is made as below 1%.
On the other hand, for the stable effect that obtains aforementioned Co, the amount of Co is preferably more than 0.02%.
Above-mentioned Mo, Cu and Co can only contain wherein any a kind, or compoundly contain two or more.Total amount when compound these elements can be 3%.
Ca, Mg and the REM of group < 2 > all have the effect that improves hot workability.Therefore, can contain these elements.
Below Ca:0.05%
Ca has the effect that improves hot workability.Therefore, can contain Ca.But, when the content of Ca is excessive, with O bonding, cleanliness is significantly reduced, make on the contrary hot workability deteriorated.Therefore, for the amount of the Ca containing sometimes, the upper limit is set, is made as below 0.05%.
On the other hand, for the stable effect that obtains aforementioned Ca, the amount of Ca is preferably more than 0.0005%.
Below Mg:0.05%
Mg is same with Ca has the effect that improves hot workability.Therefore, can contain Mg.But, when the content of Mg is excessive, with O bonding, cleanliness is significantly reduced, but make hot workability deteriorated.Therefore, for the amount of the Mg containing sometimes, the upper limit is set, is made as below 0.05%.
On the other hand, for the stable effect that obtains aforementioned Mg, the amount of Mg is preferably more than 0.0005%.
Below REM:0.1%
REM has the effect that improves hot workability.That is, the avidity of REM and S is strong, contributes to the raising of hot workability.Therefore, can contain REM.But, when the content of REM is excessive, with O bonding, cleanliness is significantly reduced, but make hot workability deteriorated.Therefore, for the amount of the REM containing sometimes, the upper limit is set, is made as below 0.1%.
On the other hand, for the stable effect that obtains aforementioned REM, the amount of REM is preferably more than 0.0005%.
As already described, " REM " refers to the general name of total 17 elements of Sc, Y and lanthanon, and the content of REM refers to the total content of the one kind or two or more element in REM.
It should be noted that, about REM, be generally contained in mishmetal.Therefore, for example can taking the form of mishmetal add and the amount that make REM as above-mentioned scope contain.
Above-mentioned Ca, Mg and REM can only contain wherein any a kind, or compoundly contain two or more.Compound total amount while containing these elements can be 0.2%.
(B) the average crystalline particle diameter of the wall thickness central part of pipe:
The average crystalline particle diameter d μ m of the wall thickness central part of pipe is necessary for 1000 μ m the amount following and B that contains according to alloy and meets the formula shown in following.
d≤1500-2.5×10
5×B
Wherein, the B in above formula represents the content in the B of quality %.
First, the average crystalline particle diameter of the wall thickness central part of pipe is greater than in the situation of 1000 μ m, and it is remarkable that the reduction of toughness and ductility becomes.Secondly, the crystal particle diameter of HAZ melting border near also becomes greatly, and in other words, the grain boundary area of per unit volume diminishes, even if the upper limit management of the B therefore pipe being contained amount is aforesaid 0.01%, also cannot prevent the liquation crack causing because of the segregation of B.
On the other hand, the average crystalline particle diameter d of the wall thickness central part of pipe is in the following situation of being discontented with foot formula of 1000 μ m, because the Thermal Cycle in welding makes near the high temperature HAZ a large amount of segregations of B melting border, make the melting point depression of crystal boundary, the liquation crack susceptibility of HAZ can be improved, thereby liquation crack cannot be prevented.
d≤1500-2.5×10
5×B
It should be noted that, although also depend on the chemical constitution of pipe, but for example keep 0.5～5h to carry out solutionizing thermal treatment by the temperature range at 1150～1250 DEG C, the average crystalline particle diameter d that can make the wall thickness central part of above-mentioned pipe is below 1000 μ m and meets aforesaid " d≤1500-2.5 × 10
5× B " formula.
(C) thickness of the oxide skin of the outside surface of pipe:
It is dystectic having the oxidation overlay film forming on the surface of the seamless refractory alloy pipe of austenite of the present invention of the chemical constitution of record in aforementioned (A) item.And in the time that the outside surface of pipe is carried out to fillet welding, above-mentioned oxidation overlay film can make the wettability variation of pipe and molten metal.Therefore,, when the thickness of the oxide skin of the outside surface of pipe becomes large, it is large that the toe angle of weld seam (reinforcement) becomes, and easily makes stress concentration at HAZ, becomes easy generation liquation crack.Therefore, for the thickness of the oxide skin of the outside surface of pipe, the upper limit is set, is made as below 15 μ m.The thickness of the oxide skin of the outside surface of above-mentioned pipe is preferably below 10 μ m.
For example, by carry out above-mentioned (B) described solutionizing thermal treatment that keeps 0.5～5h the temperature range of 1150～1250 DEG C in the reducing gas such as hydrogen, be below 15 μ m thereby can stably make the thickness of the oxide skin of the outside surface of pipe.
In addition, in atmosphere or in combustion gases, carry out above-mentioned (B) described solutionizing thermal treatment and form oxide skin (oxide skin), by carrying out the processing such as pickling, grinding, shot-peening, be below 15 μ m thereby can stably make the thickness of the oxide skin of the outside surface of pipe.
In addition, for the thickness of the oxide skin of the outside surface of pipe, lower limit needn't be set especially.
For example, carry out the processing such as solutionizing thermal treatment in reducing gas, pickling, grinding, shot-peening, the thickness that can make the oxide skin of the outside surface of pipe is the state that approaches 0 μ m.In addition, carry out mechanical grinding and remove the oxide skin of the outside surface of pipe, the thickness that can make this oxide skin is 0.But the thickness that reduces terrifically the oxide skin of the outside surface of pipe can cause manufacturing cost surging.Therefore, more than the thickness of the oxide skin of the outside surface of pipe is preferably 0.1 μ m, be 0.2 μ m above more preferably.
Below, utilize embodiment to carry out more specific description to the present invention, but the present invention is not limited to these embodiment.
Embodiment
Adopt usual method to use vacuum induction melting stove that 180kg is had after the various alloy meltings of chemical constitution shown in table 1, carry out ingot casting and make steel ingot, then this steel ingot heat forged is made to steel billet.
Use a model milling machine (model mill) by the each billet hot punching rolling so obtaining, and having manufactured external diameter is the seamless tube that 38mm and wall thickness are 9mm.
[table 1]
Be that each seamless tube that 38mm and wall thickness are 9mm cuts into 200mm length by above-mentioned external diameter, make temperature the range of 1150～1280 DEG C, make the solutionizing thermal treatment in the range of 0.5～5h of hold-time at this temperature, made different various for test tubes of the average crystalline particle diameter d of wall thickness central part.
Then, the obtained outside surface for test tube is ground, make oxide skin thickness that various variations occur.
Each for test tube for what outside surface has been ground after above-mentioned solutionizing thermal treatment, measure as follows respectively the oxide skin thickness of the average crystalline particle diameter d of wall thickness central part and the outside surface of pipe.
(μ m) obtains the average crystalline particle diameter d of wall thickness central part as follows: the central part for test tube of growing taking 200mm is as benchmark, from cutting out 5 test films to be detected face as the mode in transverse section before and after it, and be cut to 4 along circumferential direction, then carry out mirror ultrafinish, with the observation by light microscope that carries out wall thickness central part after chloroazotic acid corrosion.
That is, for the each test film after cutting off, under 100 times of multiplying powers, carry out a visual field and observe, adopt the process of chopping to measure the average crystal grain slice length of 20 every a slices of test film.By the further arithmetical mean of average crystal grain slice length of the every a slice of above-mentioned test film, (μ m) to obtain average crystalline particle diameter d by its 1.128 times.
The oxide skin thickness of the outside surface of pipe is obtained as follows: for each test tube that supplies, by the average crystalline particle diameter d that measures above-mentioned wall thickness central part, (m) 20 test films mirror ultrafinish again used of μ is carried out observation by light microscope under the state that keeps grinding.
That is,, observe under 400 times of multiplying powers for every a slices of 20 test films for test tube about each, measure the thickness of the oxide compound of the outside surface of pipe.Then, by the value arithmetical mean of the thickness of the oxide compound of 20 test films, as the oxide skin thickness of the outside surface of pipe.
In addition, use aforementioned ground outside surface after solutionizing thermal treatment each for test tube and there is the alloy sheets of being used as fin keel that cuts into long thick 6mm, wide 15mm of 200mm of chemical constitution shown in table 2, the simulation shown in construction drawing 1 the contained welding test body of fillet welding of hearth wall pipe.
It should be noted that, respectively implement 4 positions as illustrated in fig. 2 for the fillet welding of test tube and above-mentioned alloy sheets.Particularly, use commercially available welding rod (AWS standard A 5.14ER NiCrCoMo-1) and ceramics flux (bond flux), implement union-melt weld with heat input 12kJ/cm.
[table 2]
For obtained each contained welding test body, from 4 fillet welding positions respectively taking be detected face as the mode in transverse section cuts out each 5 test films, then carry out mirror ultrafinish.
Then, with chloroazotic acid corrosion, use opticmicroscope to carry out microexamination (microscopic examination), for each meter 20 place's weld parts of restraining welding test body, investigation has or not liquation crack for the HAZ place of test tube, obtains liquation crack production rate.
It should be noted that, liquation crack production rate defines with " (section number/20 that crack) × 100 (%) ", be only that 0 (zero) test body is judged to be " qualified " by liquation crack production rate, other are judged to be " defective ".
Table 3 shows above-mentioned each test-results.Wherein, in table 3, recorded in the lump for the B amount containing in the raw alloy of test tube and by " EQU=1500-2.5 × 10
5× B " value of the EQU that obtains.
[table 3]
According to table 3, use in the situation for test tube symbol A1, A6, A7, B1～B3, C1～C3, D1, E1 and F1 of the seamless tube that meets condition given to this invention, liquation crack production rate is 0, confirms that in all sections, HAZ place does not produce liquation crack.Therefore when, the known seamless tube that meets condition given to this invention directly carries out fillet welding to the outside surface of pipe and uses as hearth wall pipe, also there is sufficient resistance to welding crack.
On the other hand, although be that the alloy A～F in scope given to this invention is raw material taking chemical constitution, but the thickness of the oxide skin of the average crystalline particle diameter of the wall thickness central part of pipe or the outside surface of pipe exceedes in the situation for test tube symbol of the upper limit given to this invention, HAZ place produces liquation crack, cannot be used for the outside surface of pipe directly to carry out the hearth wall pipe of fillet welding.
In situation for test tube symbol A2, A3, D2, E2 and F2, although the average crystalline particle diameter d of the wall thickness central part of pipe, lower than 1000 μ m, does not meet the following formula of the amount defined of the B containing according to alloy, therefore HAZ place produces liquation crack.And liquation crack production rate is along with above-mentioned average crystalline particle diameter d becomes large and raises.
d≤1500-2.5×10
5×B
In situation for test tube symbol C4, the average crystalline particle diameter d of the wall thickness central part of pipe exceedes 1000 μ m, and therefore HAZ place produces liquation crack.
In situation for test tube symbol A4 and A5, the thickness of the oxide skin of the outside surface of pipe exceedes 15 μ m, and therefore HAZ place produces liquation crack.And the thickness of the oxide skin of the outside surface of above-mentioned pipe is larger, liquation crack production rate is higher.
utilizability in industry
The resistance to welding crack excellence of austenite of the present invention is seamless refractory alloy pipe, can suppress to weld time, HAZ place cracks.Therefore, the seamless refractory alloy pipe of austenite of the present invention taking having excellent high-temperature strength, there is sufficient anticorrosion stress-resistant crackle and the little austenite heat-resistant alloy of thermal expansivity and also can be suitable as the member of the high temperature service of hearth wall pipe of generating boiler and so among the seamless compo pipe of raw material.
Claims (3)
1. the seamless refractory alloy pipe of austenite, the outside surface of pipe is directly carried out fillet welding and used, it is characterized in that, the chemical constitution of this austenite is seamless refractory alloy pipe is as follows: in quality %, C:0.03～0.15%, Si:1% is following, Mn:2% is following, P:0.03% is following, S:0.01% is following, Ni:35～60%, Cr:18～38%, W:3～11%, Ti:0.01～1.2%, Al:0.5% are following, B:0.0001～0.01%, N:0.02% are following and below O:0.008%; And in Zr:0.01～0.5%, Nb:0.01～0.5% and V:0.01～0.5% more than a kind; And surplus is made up of Fe and impurity,
The average crystalline particle diameter d μ m of the wall thickness central part of pipe is below 1000 μ m and meets following formula; In addition, the thickness of the oxide skin of the outside surface of pipe is below 15 μ m,
d≤1500-2.5×10
5×B
B in above formula represents the content in the B of quality %.
2. the seamless refractory alloy pipe of austenite according to claim 1, it is characterized in that, contain to be selected from quality % and more than a kind replace part Fe in the element shown in following < 1 > and < 2 >
Below < 1 > Mo:1%, below Cu:1% and below Co:1%,
Below < 2 > Ca:0.05%, below Mg:0.05% and below REM:0.1%.
3. the seamless refractory alloy pipe of austenite according to claim 1 and 2, is characterized in that, it is as hearth wall pipe.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-249875 | 2011-11-15 | ||
| JP2011249875A JP5212533B2 (en) | 2011-11-15 | 2011-11-15 | Seamless austenitic heat-resistant alloy tube |
| PCT/JP2012/078788 WO2013073423A1 (en) | 2011-11-15 | 2012-11-07 | Seamless austenite heat-resistant alloy tube |
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| Publication Number | Publication Date |
|---|---|
| CN103946403A true CN103946403A (en) | 2014-07-23 |
| CN103946403B CN103946403B (en) | 2016-02-17 |
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| CN201280056250.6A Active CN103946403B (en) | 2011-11-15 | 2012-11-07 | Austenite is seamless refractory alloy pipe |
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| Country | Link |
|---|---|
| EP (1) | EP2781612B1 (en) |
| JP (1) | JP5212533B2 (en) |
| KR (1) | KR101632520B1 (en) |
| CN (1) | CN103946403B (en) |
| IN (1) | IN2014DN03492A (en) |
| PL (1) | PL2781612T3 (en) |
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| EP2287349B1 (en) * | 2008-06-16 | 2019-03-27 | Nippon Steel & Sumitomo Metal Corporation | Austenitic heat-resistant alloy, heat-resistant pressure member comprising the alloy, and method for manufacturing the same member |
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- 2012-11-07 EP EP12850463.6A patent/EP2781612B1/en active Active
- 2012-11-07 KR KR1020147015980A patent/KR101632520B1/en active IP Right Grant
- 2012-11-07 CN CN201280056250.6A patent/CN103946403B/en active Active
- 2012-11-07 WO PCT/JP2012/078788 patent/WO2013073423A1/en active Application Filing
- 2012-11-07 IN IN3492DEN2014 patent/IN2014DN03492A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104073739A (en) * | 2014-07-25 | 2014-10-01 | 太原钢铁(集团)有限公司 | Heatproof stainless steel seamless steel pipe and manufacture method of stainless steel and seamless steel pipe |
| CN105483492A (en) * | 2015-12-08 | 2016-04-13 | 江苏华冶科技有限公司 | High-temperature-resisting alloy material for radiant tube and casting process of high-temperature-resisting alloy material |
| CN107868885A (en) * | 2016-09-26 | 2018-04-03 | 宝钢特钢有限公司 | A kind of abros and its slab production method |
| CN111601913A (en) * | 2018-01-10 | 2020-08-28 | 日本制铁株式会社 | Austenitic heat-resistant alloy and method for producing same |
| CN111601913B (en) * | 2018-01-10 | 2022-03-04 | 日本制铁株式会社 | Austenitic heat-resistant alloy and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2781612A4 (en) | 2016-03-02 |
| IN2014DN03492A (en) | 2015-06-26 |
| JP2013104109A (en) | 2013-05-30 |
| CN103946403B (en) | 2016-02-17 |
| EP2781612B1 (en) | 2018-06-06 |
| PL2781612T3 (en) | 2018-11-30 |
| KR20140091061A (en) | 2014-07-18 |
| WO2013073423A1 (en) | 2013-05-23 |
| KR101632520B1 (en) | 2016-06-21 |
| EP2781612A1 (en) | 2014-09-24 |
| JP5212533B2 (en) | 2013-06-19 |
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