CN103946403B - Austenite is seamless refractory alloy pipe - Google Patents
Austenite is seamless refractory alloy pipe Download PDFInfo
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- CN103946403B CN103946403B CN201280056250.6A CN201280056250A CN103946403B CN 103946403 B CN103946403 B CN 103946403B CN 201280056250 A CN201280056250 A CN 201280056250A CN 103946403 B CN103946403 B CN 103946403B
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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- C—CHEMISTRY; METALLURGY
- 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
The seamless refractory alloy pipe of a kind of austenite, directly fillet welding is carried out to tube outer surface and uses, its chemical constitution is as follows: in mass %, 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%; More than a kind in Zr:0.01 ~ 0.5%, Nb:0.01 ~ 0.05% and V:0.01 ~ 0.5%; In addition more than a kind in Mo≤1%, Cu≤1%, Co≤1%, Ca≤0.05%, Mg≤0.05% and REM≤0.1% is selected from as required; And surplus is made up of Fe and impurity, average crystal particle diameter d μm of the wall thickness central part of pipe is less than 1000 μm and meets formula (d≤1500-2.5 × 10
5× B); In addition, the thickness of the oxide skin of the outside surface of pipe is less than 15 μm, the anti-thread breakage excellence of proper alignment of this austenite is seamless refractory alloy pipe, when can suppress welding, HAZ place cracks, the component of the high temperature service of hearth wall pipe that therefore can be suitable as boiler for power generation and so on.
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 boiler for power generation (hereinafter referred to as " hearth wall pipe ".) can directly carry out fillet welding to the outside surface of pipe like that and the seamless refractory alloy pipe of austenite used as the component of high temperature service.More specifically relate to having excellent high-temperature strength, there is the anti-thread breakage excellence of proper alignment among seamless compo pipe that the anti-thread breakage and Austenitic heat-resistant alloy that thermal expansivity is little of sufficient anticorrosion stress-resistant is raw material and can suppress to weld time the HAZ place seamless refractory alloy pipe of austenite that cracks.
Background technology
In recent years, about boiler for power generation, carrying out the newly-built of " the superelevation emergent pressure boiler " of the temperature that improve steam in order to high efficiency and pressure in the world.In addition, more than 650 DEG C are also planned the vapor temperature of 600 DEG C of front and back to be up to now increased to even practical to " the superelevation emergent pressure boiler of future generation " of more than 700 DEG C.This is based on energy-conservation, efficent use of resources and cuts down CO in order to protection of the environment
2what gas discharge amount became the solution task of energy problem becomes important industry policy in the lump.And be that high temperature and high-pressure trend are favourable to high efficiency because in the boiler for power generation of combustion of fossil fuels.
The high temperature of steam and high-pressure trend make the temperature during running of the heat pipe of the pipe such as superheater tube and reheater tube and so on of formation boiler and main team pipe etc. rise.Therefore, the material requirements used long-term in this harsh environment is had to the solidity to corrosion under hot strength and high temperature, especially requires the stability of metallographic structure and good creep properties.
Non-patent literature 1 with practical heat-stable material for object, the figure that to show with transverse axis be the Cr content of material, the longitudinal axis arranges out for the temperature under allowable stress 49MPa, and the temperature describing the longitudinal axis raises along with the increase of Cr content, the creep strength belonging to hot strength correspondingly improves.
In addition, non-patent literature 2 with practical heat-stable material for object, the figure that to show with transverse axis be the Ni content of material, the longitudinal axis arranges out for crack sensitivity, increase along with Ni content is shown, the crack sensitivity of the longitudinal axis diminishes, and the solidity to corrosion (anticorrosion stress-resistant is anti-thread breakage) under high temperature improves.
Patent documentation 1 ~ 3 discloses following refractory alloy, improves the content of Cr and Ni and containing more than a kind in Mo and W, attempts improving the creep-rupture strength belonging to hot strength.
In addition, in the face of requiring more and more stricter high temperature strength properties, particularly requiring creep-rupture strength, patent documentation 4 ~ 7 discloses following refractory alloy, in mass % containing the Cr of 28 ~ 38%, the Ni of 35 ~ 60%, the precipitation of the α-Cr phase of the body-centered cubic structure of effective utilization based on Cr, attempts improving creep-rupture strength further.
On the other hand, patent documentation 8 and patent documentation 9 disclose following Ni base alloy, attempt solution strengthening containing Mo and/or W, effectively utilize containing Al and Ti belong to intermetallic compound γ ' phase, specifically for Ni
3the precipitation strength of (Al, Ti), thus use under above-mentioned that harsh hot environment.
In addition, patent documentation 10 proposes following high-ni austenitic heat-resistant alloy, by adjust Al with Ti content scope, γ ' is separated out mutually and improves creep strength.
In addition, Austenitic heat-resistant alloy is generally assembled into various structure and at high temperature uses by welding.But, as non-patent literature 3 report, if Austenitic heat-resistant alloy alloying element amount increase, then there will be welding heat affected zone when welding procedure (hereinafter referred to as " HAZ ".) crack, especially adjacent with melting border HAZ place cracks this problem.
Therefore, the Austenitic heat-resistant alloy used for the component as various structure requires to prevent HAZ place from ftractureing and solder joint performance when taking into account welding.
Patent documentation 11 discloses following Austenitic heat-resistant alloy, adjusts the scope that effective B measures, prevent HAZ place from ftractureing when can guarantee processibility under high temperature and butt welding by the Fe containing specified quantitative.
In addition, patent documentation 12 discloses following Austenitic heat-resistant alloy, by the content of impurity element such as adjustment P, S and Sn, Pb etc., can prevent HAZ place from ftractureing in the long-time use procedure when butt welding and under high temperature, and creep strength is also excellent.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 60-100640 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 64-55352 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2-200756 publication
Patent documentation 4: Japanese Unexamined Patent Publication 7-216511 publication
Patent documentation 5: Japanese Unexamined Patent Publication 7-331390 publication
Patent documentation 6: Japanese Unexamined Patent Publication 8-127848 publication
Patent documentation 7: Japanese Unexamined Patent Publication 8-218140 publication
Patent documentation 8: Japanese Laid-Open Patent Publication 51-84726 publication
Patent documentation 9: Japanese Laid-Open Patent Publication 51-84727 publication
Patent documentation 10: Japanese Unexamined Patent Publication 9-157779 publication
Patent documentation 11: Japanese Unexamined Patent Publication 2011-63838 publication
Patent documentation 12: Japanese Unexamined Patent Publication 2010-150593 publication
Non-patent literature
Non-patent literature 1: increase the only light in mountain, iron and steel, Vol.80 (1994) No.8, pp.587 ~ 592 (increasing the only light in 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 (the positive Lun of little rock: metal Fu Shi Damage Injury と anti-Shi Ji 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 (Heisei 15 years, ball are kind), 948 ~ 950 pages (welding association Knitting: weld and engage Bian list the 2nd edition (Heisei 15 years, ball are 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 (one ら: IHI skill Reported, vol.49No.4 (2009), pp.185 ~ 191 are stretched in high open country)
Summary of the invention
the problem that invention will solve
As mentioned above, Austenitic heat-resistant alloy is generally assembled into various structure by welding.Further, in recent years, tend to the effective hearth wall pipe making boiler for power generation of these Austenitic heat-resistant alloy.
As the raw material of above-mentioned hearth wall pipe, in the past usual from various viewpoint considerations such as operability, employ the carbon steel or 1%Cr steel that need not implement both preheating and post-heating.
But for aforementioned " the superelevation emergent pressure boiler of future generation " that vapor temperature be increased to more than 700 DEG C, the hot strength of the carbon steel used or 1%Cr steel is insufficient in the past.Therefore, above-mentioned carbon steel and 1%Cr steel all cannot be used as the raw material of the hearth wall pipe of " superelevation emergent pressure boiler of future generation ".
On the other hand, so far the common austenite stainless steel that uses of superheater tube and reheater tube due to Ni content 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 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, and thermal linear expansion coefficient is large.Therefore, austenite stainless steel thermal change deformation when welding is large, goes wrong when making hearth wall.
It should be noted that, hearth wall is by multiple hearth wall pipe configured in parallel being formed with the panel that the fin keel (finplate) being used for this hearth wall pipe to be connected to each other or fin ray (finbar) are welded.Therefore, different from the butt welding of welding the groove face through 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, fillet welding is directly carried out (below sometimes referred to as " directly welding the outside surface of pipe " to the outside surface of pipe.) situation with compared with carrying out the situation of the butt welding of welding in groove, vpg connection becomes large at the stress concentration of reinforcement toe.Its result, the situation of directly welding the outside surface of pipe is compared with carrying out the situation of butt welding, and in welding, HAZ place becomes and easily cracks.
Therefore, the hearth wall pipe that exploitation can be suitable as " superelevation emergent pressure boiler of future generation ", the Austenitic heat-resistant alloy pipe that improves Ni content, namely the austenite seamless refractory alloy pipe developing the following Ni of improve content becomes urgent problem, described austenite is seamless refractory alloy pipe with having excellent high-temperature strength, have among seamless compo pipe that the anti-thread breakage and Austenitic heat-resistant alloy that thermal expansivity is little of sufficient anticorrosion stress-resistant is raw material, the anti-thread breakage excellence of proper alignment and can suppress welding time HAZ place crack.
Although aforementioned patent literature 1 ~ 10 discloses the improved Austenitic heat-resistant alloy of creep-rupture strength, do not study from " weldability " this viewpoint when assembling as structure, and do not consider directly to weld the outside surface of pipe completely.Therefore, how also cannot by the hearth wall pipe of the effective work " superelevation emergent pressure boiler of future generation " that is raw material with the Austenitic heat-resistant alloy proposed in above-mentioned each patent documentation.
The Austenitic heat-resistant alloy that the present inventor etc. propose in patent documentation 11 is suitable as the goods such as pipe, plate, rod and the forged article used in the heat-resistant pressure-resistant member such as boiler for power generation, chemical industry use, is especially suitable for use as massive article.In addition, the ductility that causes of high temperature process, proper alignment crack sensitivity and high-temperature aging adopting this Austenitic heat-resistant alloy can improve significantly when said products manufactures and when real machine uses reduces.
Similarly, the Austenitic heat-resistant alloy that the present inventor etc. propose in patent documentation 12 can prevent HAZ from ftractureing, and can prevent the defect because welding operation causes in welding procedure, and the creep strength in addition under high temperature is also excellent.Therefore, this austenite heat-resistance alloy can be suitable as the raw material of the high temperature service such as boiler for power generation, chemical industry equipment.
But when developing the Austenitic heat-resistant alloy proposed in above-mentioned patent documentation 11 and patent documentation 12, the present inventor etc. reckoning without directly weld the outside surface of pipe.Therefore, when the outside surface of the pipe being raw material with above-mentioned Austenitic heat-resistant alloy is directly welded, vpg connection becomes large at the stress concentration of reinforcement toe, and result is compared with carrying out the situation of butt welding, and when welding, HAZ place inevitably can become and easily crack.Therefore, during hearth wall pipe by the effective work " superelevation emergent pressure boiler of future generation " that is raw material with above-mentioned each Austenitic heat-resistant alloy, the item needing to improve is left.
The present invention makes in view of above-mentioned present situation, object is to provide following austenite seamless refractory alloy pipe, it is the Austenitic heat-resistant alloy pipe that can directly carry out fillet welding to the outside surface of pipe and use as the component of high temperature service as the hearth wall pipe of boiler for power generation, namely with having excellent high-temperature strength, there is the anti-thread breakage excellence of proper alignment among seamless compo pipe that the anti-thread breakage and Austenitic heat-resistant alloy that thermal expansivity is little of sufficient anticorrosion stress-resistant is raw material and can suppress to weld time the HAZ place seamless refractory alloy pipe of austenite that cracks.
for the scheme of dealing with problems
The present inventor etc., in order to solve foregoing problems, implement various investigation.
Its result, first confirms by the B containing appropriate amount and can give Austenitic heat-resistant alloy with sufficient hot strength.
Secondly, the present inventor etc. make the seamless tube of the various Austenitic heat-resistant alloy containing B (below sometimes referred to as " Austenitic heat-resistant alloy pipe ".), by the outside surface of this compo pipe be used as fin keel the direct fillet welding of plate, specifically with the direct fillet welding of alloy sheets of the thick 6mm with chemical constitution shown in table 2 of embodiment described later, wide 15mm, long 200mm, the crackle for HAZ place generation during welding has carried out detailed investigation.
Result has understood fully the situation of following (a) ~ (d).
When () confirms to weld a, crackle produces the content of this non-patent literature 3 at the crystal boundary of the HAZ near melting border.
B the B contained in () Austenitic heat-resistant alloy pipe measures crystal particle diameter that is more or Austenitic heat-resistant alloy pipe larger, and HAZ place more easily cracks.In addition, the toe angle of reinforcement is larger, and HAZ place more easily cracks.
The section of c crackle that () HAZ place produces confirms there is melting trace.In addition, this section there is the enrichment of B.And the crystal particle diameter of Austenitic heat-resistant alloy pipe is larger, the enrichment of B is more remarkable.
D oxide skin that the outside surface of () Austenitic heat-resistant alloy pipe generates is thicker, and the toe angle of reinforcement is larger.
According to the situation that above-mentioned (a) ~ (d) understands fully, the present inventor etc. obtain the conclusion of following (e) ~ (f).
E during () welding, the crackle of HAZ place generation is subject to the strong impact of the B being present in crystal boundary in metallurgical, the crystal particle diameter of Austenitic heat-resistant alloy pipe affects indirectly the behavior of B at grain boundaries.
F crackle that () above-mentioned HAZ place produces is subject to the strong impact at the toe angle of reinforcement in terms of mechanics.And the oxide skin that the outside surface of Austenitic heat-resistant alloy pipe generates affects toe angle indirectly.
Namely understood fully when ensure that the Austenitic heat-resistant alloy pipe of sufficient hot strength directly carries out fillet welding containing the B appropriately measured, crack for HAZ place when preventing from welding, two is effective below:
The crystal particle diameter of management Austenitic heat-resistant alloy pipe, simultaneously according to the content of crystal particle diameter adjustment B; And
The thickness of the oxide skin that the outside surface of management Austenitic heat-resistant alloy pipe exists, controls reinforcement shape.
Its reason is considered based on following (g) ~ (i).
G (), in welding procedure, makes the crystal boundary generation segregation of the HAZ of B near melting border due to Thermal Cycle.B is the element that the fusing point of crystal boundary is reduced, and thus in welding, above-mentioned B there occurs the crystal boundary melting partly of segregation, and the position of this melting is subject to welded stress and opening, generates so-called " liquation crack ".It should be noted that, when crystal particle diameter is large, the grain boundary area of per unit volume is little.Therefore, when crystal particle diameter is large, the grain boundary segregation of B becomes remarkable, and the stress that specific crystal boundary face is born becomes large, and therefore HAZ place becomes and easily cracks.
If h the toe angle of () weld seam (reinforcement) becomes large, then stress is easily concentrated to HAZ, thus becomes and more easily cracks.
When i the outside surface of () pipe being formed with thick oxide skin, except the fusing point of oxide compound is high, and when carrying out fillet welding to the outside surface of pipe and the worsened wettability of molten metal.Therefore, the toe angle of reinforcement becomes large, and the susceptibility for crackle improves.
Thus, the present inventor etc. implement research detailed further.
Its result is understood fully, when by direct with the plate (alloy sheets of the thick 6mm with chemical constitution shown in table 2 of embodiment, wide 15mm, long 200mm) being used as fin keel for the outside surface of Austenitic heat-resistant alloy pipe fillet welding, by taking the countermeasure of following (j) and (k), can prevent HAZ place from ftractureing.
J () makes the average crystal particle diameter d (μm) of the wall thickness central part of compo pipe be less than 1000 μm, and the amount of the B contained according to alloy is adjusted to the scope meeting following formula.
d≤1500-2.5×10
5×B
B in above formula represents the content (quality %) of B.
(k) in order to when improving fillet welding with the wettability of molten metal and reduce toe angle, the thickness of the oxide skin of the outside surface of compo pipe is suppressed below 15 μm.
The present invention completes based on above-mentioned opinion, and its main contents are the following shown seamless refractory alloy pipe of austenite.
(1) the seamless refractory alloy pipe of a kind of austenite, directly fillet welding is carried out to tube outer surface and uses, it is characterized in that, the chemical constitution of this austenite is seamless refractory alloy pipe is as follows: in mass %, C:0.03 ~ 0.15%, below Si:1%, below Mn:2%, below P:0.03%, below S:0.01%, Ni:35 ~ 60%, Cr:18 ~ 38%, W:3 ~ 11%, Ti:0.01 ~ 1.2%, below Al:0.5%, B:0.0001 ~ 0.01%, below N:0.02% 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,
Average crystal particle diameter d μm of the wall thickness central part of pipe is less than 1000 μm and meets following formula; In addition, the thickness of the oxide skin of the outside surface of pipe is less than 15 μm.
d≤1500-2.5×10
5×B
B in above formula represents the content of B in mass %.
(2) according to the seamless refractory alloy pipe of austenite that above-mentioned (1) is recorded, it is characterized in that, replace part Fe containing more than a kind that is selected from the element shown in following < 1 > and < 2 > in mass %.
< 1 below > Mo:1%, below Cu:1% and below Co:1%,
< 2 below > Ca:0.05%, below Mg:0.05% and below REM:0.1%.
(3) according to the seamless refractory alloy pipe of austenite that above-mentioned (1) or (2) are recorded, it is characterized in that, it is used as hearth wall pipe.
From as the material be mixed into the ore of raw material, waste material or manufacturing environment etc. when " impurity " refers to and industrially manufactures Austenitic heat-resistant alloy.
" REM " refers to the general name of total 17 kinds of 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.
the effect of invention
The anti-thread breakage excellence of proper alignment of austenite of the present invention is seamless refractory alloy pipe, when can suppress welding, HAZ place cracks.Therefore, austenite of the present invention seamless refractory alloy pipe is with having excellent high-temperature strength, the component with the high temperature service of hearth wall pipe that can be suitable as boiler for power generation and so among seamless compo pipe that the anti-thread breakage and Austenitic heat-resistant alloy that thermal expansivity is little of sufficient anticorrosion stress-resistant is raw material.
Accompanying drawing explanation
Fig. 1 carries out the figure schematically illustrated for the contained welding test body of the fillet welding making, simulate hearth wall pipe in embodiment.It should be noted that, in figure, the alloy sheets being used as fin keel is simply expressed as " fin keel ".
Fig. 2 is the figure for being described with the fillet welding of the alloy sheets being used as fin keel for test tube.It should be noted that, in figure, the alloy sheets being used as fin keel is simply expressed as " fin keel ".
Embodiment
Below each prerequisite of the present invention is described in detail.It should be noted that, in the following description, " % " expression of the content of each element means " quality % ".
(A) chemical constitution of pipe:
C：0.03～0.15％
C makes austenite stablize, and forms fine carbide at crystal boundary, and the creep strength under high temperature is improved.In order to fully obtain this effect, C content needs to be more than 0.03%.But when excessively containing C, carbide is greatly thicker and separate out in a large number, 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 set 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 for effective element the solidity to corrosion improved under high temperature and scale resistance.But, excessive containing Si when, austenitic stability reduces, thus causes toughness and creep strength to reduce.Therefore, for the content of Si arranges the upper limit, less than 1% is set to.The content of Si is preferably less than 0.8%.
In addition, content for Si need not arrange lower limit especially, but extreme minimizing cannot obtain deoxidation effect, and the cleanliness factor of alloy becomes large and cleanliness is deteriorated, and the solidity to corrosion under being also difficult to obtain 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 and Si has desoxydatoin equally.Mn also contributes to austenitic stabilization.But, when the content of Mn is excessive, cause embrittlement, the reduction of toughness and creep ductility can occur in addition.Therefore, for the content of Mn arranges the upper limit, less than 2% is set to.The content of Mn is preferably less than 1.5%.
In addition, the content for Mn also need not arrange lower limit especially, but extreme minimizing cannot obtain deoxidation effect, and make the cleanliness deterioration of alloy, 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 contains as impurity in the alloy, is the element improving liquation crack susceptibility in welding in the crystal boundary generation segregation of HAZ.Therefore, for the content of P arranges the upper limit, less than 0.03% is set to.The content of P is preferably less than 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 and P contains as impurity in the alloy equally, is the element improving 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, less than 0.01% is set to.The content of S is preferably less than 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 in order to ensure the necessary element of structure stability during long-time use.In the scope of the Cr content of aftermentioned 18 ~ 38%, in order to fully obtain the effect of above-mentioned Ni, Ni content needs to be more than 35%.But Ni is expensive element, a large amount of Ni that contains can cause cost to increase.Therefore, the upper limit is set, the content of Ni is set 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 the Ni content of above-mentioned 35 ~ 60%, in order to obtain the effect of above-mentioned Cr, Cr content needs to be more than 18%.But when the content of Cr is more than 38%, the austenitic stability degradation under high temperature, causes the reduction of creep strength.Therefore, the content of Cr is set to 18 ~ 38%.The lower limit of Cr content is preferably 20%, and in addition, the upper limit is preferably 35%.
W：3～11％
W is the element of the creep strength of solid solution in the base thus under going far towards to improve the high temperature more than 700 DEG C.In order to make this effect play fully, W content at least needs to be more than 3%.But excessive also exist effect situation that is saturated, that make creep strength reduce on the contrary containing W.In addition, W is expensive element, and thus the excessive W that contains can cause cost to increase.Therefore, the upper limit is set, the content of W is set 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 needs 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 set 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, less than 0.5% is set to.The content of Al is preferably less than 0.3%.
In addition, the content for Al need not arrange lower limit especially, but extreme minimizing fully cannot obtain deoxidation effect, makes the cleanliness deterioration of alloy on the contrary, and causes manufacturing cost to rise.Therefore, the lower limit of Al content is preferably 0.001%.The deoxidation effect obtaining Al in order to stable, guarantee that alloy has good cleanliness, the lower limit of Al content is more preferably 0.0015%.
B：0.0001～0.01％
B is by strengthening crystal boundary in crystal boundary generation segregation in use at high temperature and making grain boundary carbide fine dispersion thus improve the element needed for creep strength.In addition, B also has and clinging power is improved in crystal boundary generation segregation, contributes to improving the effect of toughness.In order to obtain these effects, B content needs to be more than 0.0001%.But, when the content of B is excessive, makes the high temperature HAZ a large amount of segregation of B near melting border due to the Thermal Cycle in welding, the fusing point of crystal boundary is reduced, promote the liquation crack susceptibility of HAZ.Therefore, the upper limit is set, the content of B is set 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, average crystal particle diameter d μm of the wall thickness central part of pipe large when, the crystal particle diameter of the HAZ near melting border becomes large, 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 is born becomes large, therefore liquation crack susceptibility promotes.
But, as aftermentioned, if make the average crystal particle diameter d (μm) of the wall thickness central part of compo pipe be less than 1000 μm and the amount (%) of the B contained according to alloy is adjusted to the scope meeting following formula, then the increase of the liquation crack susceptibility that the segregation because of B can be suppressed to cause.
d≤1500-2.5×10
5×B
B in above formula represents the content of B in mass %.
Below N:0.02%
N for make austenite stable be effective element.In the Cr content range of aforesaid 18 ~ 38%, excessive containing N time, fine nitride a large amount of in use is at high temperature separated out in crystal grain, causes the reduction of creep ductility and toughness.Therefore, for the content of N arranges the upper limit, less than 0.02% is set to.The content of N is preferably less than 0.015%.
In addition, the content for N need not arrange lower limit especially, but extreme minimizing is difficult to the effect that obtains making austenite stable, and manufacturing cost also can promote greatly.Therefore, the lower limit of N content is preferably 0.0005%.
Below O:0.008%
O (oxygen) contains as impurity in the alloy, and when its content is excessive, hot workability reduces, and causes the deterioration of toughness and ductility in addition.Therefore, for the content of O arranges the upper limit, less than 0.008% is set to.The content of O is preferably less than 0.005%.
Content for O need not 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 form fine carbide or carbonitride with C or N bonding, contribute to the raising of creep strength.Therefore, austenite of the present invention seamless refractory alloy pipe also contains the element of more than a kind 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 needs 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 set 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 needs 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 set 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 needs 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 set 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 only can contain wherein any a kind, or compound contains two or more.Total amount when compound contains these elements can be 1.5%, is preferably less than 1.2%.
The chemical constitution of a kind of austenite of the present invention seamless refractory alloy pipe is: above-mentioned each element; And surplus is made up of F and impurity.
In addition, as already described, from as the material be mixed into the ore of raw material, waste material or manufacturing environment etc. when " impurity " refers to and industrially manufactures Austenitic heat-resistant alloy.
The chemical constitution of another kind of austenite of the present invention seamless refractory alloy pipe is: replace the above-mentioned Fe of part containing the element of more than a kind that is selected from Mo, Cu, Co, Ca, Mg and REM.
Below the action effect of these arbitrary elements and the restriction reason of content are described.
Mo, Cu and Co of group < 1 > all have the effect improving creep strength.Therefore, these elements can be contained.
Below Mo:1%
Mo has the effect improving creep strength.That is, Mo has the effect that solid solution improves the creep strength under high temperature in the base.Therefore, Mo can be contained.But when excessively containing Mo, austenitic stability reduces, and causes the reduction of creep strength on the contrary.Therefore, the upper limit is arranged for the amount containing Mo sometimes, is set to less than 1%.
On the other hand, in order to the stable effect obtaining aforementioned Mo, the amount of Mo is preferably more than 0.1%.
Below Cu:1%
Cu has the effect improving creep strength.That is, Cu and Ni is austenite generting element equally, contributes to promoting phase stability and improving creep strength.Therefore, Cu can be contained.But, when excessively containing Cu, cause the reduction of hot workability.Therefore, the upper limit is arranged for the amount containing Cu sometimes, is set to less than 1%.
On the other hand, in order to the stable effect obtaining aforementioned Cu, the amount of Cu is preferably more than 0.02%.
Below Co:1%
Co has the effect improving creep strength.That is, Co and Ni and Cu is austenite generting element equally, contributes to promoting phase stability and improving creep strength.Therefore, Co can be contained.But Co is very expensive element, therefore the excessive Co that contains can cause cost significantly to increase.Therefore, the upper limit is arranged for the amount containing Co sometimes, is set to less than 1%.
On the other hand, in order to the stable effect obtaining aforementioned Co, the amount of Co is preferably more than 0.02%.
Above-mentioned Mo, Cu and Co only can contain wherein any a kind, or compound contains two or more.Total amount during these elements of compound can be 3%.
Ca, Mg and REM of group < 2 > all have the effect improving hot workability.Therefore, these elements can be contained.
Below Ca:0.05%
Ca has the effect improving hot workability.Therefore, Ca can be contained.But, when the content of Ca is excessive, with O bonding and make cleanliness significantly reduce, make hot workability deterioration on the contrary.Therefore, the upper limit is arranged for the amount containing Ca sometimes, is set to less than 0.05%.
On the other hand, in order to the stable effect obtaining aforementioned Ca, the amount of Ca is preferably more than 0.0005%.
Below Mg:0.05%
Mg and Ca has the effect improving hot workability equally.Therefore, Mg can be contained.But, when the content of Mg is excessive, with O bonding and make cleanliness significantly reduce, but make hot workability deterioration.Therefore, the upper limit is arranged for the amount containing Mg sometimes, is set to less than 0.05%.
On the other hand, in order to the stable effect obtaining aforementioned Mg, the amount of Mg is preferably more than 0.0005%.
Below REM:0.1%
REM has the effect improving hot workability.That is, the avidity of REM and S is strong, contributes to the raising of hot workability.Therefore, REM can be contained.But, when the content of REM is excessive, with O bonding and make cleanliness significantly reduce, but make hot workability deterioration.Therefore, the upper limit is arranged for the amount containing REM sometimes, is set to less than 0.1%.
On the other hand, in order to the stable effect obtaining aforementioned REM, the amount of REM is preferably more than 0.0005%.
As already described, " REM " refers to the general name of total 17 element 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, such as can with the form of mishmetal add and make the amount of REM be above-mentioned scope contain.
Above-mentioned Ca, Mg and REM only can contain wherein any a kind, or compound contains two or more.Total amount when compound contains these elements can be 0.2%.
(B) average crystal particle diameter of the wall thickness central part of pipe:
The average crystal particle diameter d μm of the wall thickness central part of pipe be necessary for less than 1000 μm and the amount of the B contained according to alloy and meet following shown in formula.
d≤1500-2.5×10
5×B
Wherein, the B in above formula represents the content of B in mass %.
First, when the average crystal particle diameter of the wall thickness central part of pipe is greater than 1000 μm, the reduction of toughness and ductility becomes remarkable.Secondly, the crystal particle diameter of the HAZ near melting border also becomes large, and in other words, the grain boundary area of per unit volume diminishes, even if the upper limit management of the B amount therefore contained by pipe is for aforesaid 0.01%, also cannot prevent the liquation crack that the segregation because of B causes.
On the other hand, the average crystal particle diameter d of the wall thickness central part of pipe is less than 1000 μm when being discontented with foot formula, the high temperature HAZ a large amount of segregation of B near melting border is made due to the Thermal Cycle in welding, the fusing point of crystal boundary is reduced, the liquation crack susceptibility of HAZ can be improved, thus cannot prevent liquation crack.
d≤1500-2.5×10
5×B
It should be noted that, although also depend on the chemical constitution of pipe, but such as carrying out solutionizing thermal treatment by keeping 0.5 ~ 5h the temperature range of 1150 ~ 1250 DEG C, the average crystal particle diameter d of the wall thickness central part of above-mentioned pipe can be made to be less than 1000 μm and to meet aforesaid " d≤1500-2.5 × 10
5× B " formula.
(C) thickness of the oxide skin of the outside surface of pipe:
It is dystectic for having the oxidation overlay film that the surface of the austenite of the present invention seamless refractory alloy pipe of the chemical constitution recorded in aforementioned (A) item is formed.And when carrying out fillet welding to the outside surface of pipe, above-mentioned oxidation overlay film can make the worsened wettability of pipe and molten metal.Therefore, when the thickness of the oxide skin of the outside surface of pipe becomes large, the toe angle of weld seam (reinforcement) becomes large, easily makes stress concentration at HAZ, becomes and easily produce liquation crack.Therefore, the thickness for the oxide skin of the outside surface of pipe arranges the upper limit, is set to less than 15 μm.The thickness of the oxide skin of the outside surface of above-mentioned pipe is preferably less than 10 μm.
Such as, by carrying out keeping the solutionizing thermal treatment of 0.5 ~ 5h the temperature range of 1150 ~ 1250 DEG C described in above-mentioned (B) item in the reducing gas such as hydrogen, thus the thickness of the oxide skin of the outside surface of pipe can be stably made to be less than 15 μm.
In addition, in an atmosphere or the solutionizing thermal treatment carried out in combustion gases described in above-mentioned (B) item and when forming oxide skin (oxide skin), by carrying out the process such as pickling, grinding, shot-peening, thus the thickness of the oxide skin of the outside surface of pipe can be stably made to be less than 15 μm.
In addition, the thickness for the oxide skin of the outside surface of pipe need not arrange lower limit especially.
Such as, carry out the process such as solutionizing thermal treatment, pickling, grinding, shot-peening in reducing gas, the thickness of the oxide skin of the outside surface of pipe can be made to be state close to 0 μm.In addition, carry out the oxide skin that mechanical grinding removes the outside surface of pipe, the thickness of this oxide skin can be made to be 0.But the thickness reducing the oxide skin of the outside surface of pipe terrifically can cause manufacturing cost surging.Therefore, the thickness of the oxide skin of the outside surface of pipe is preferably more than 0.1 μm, be more than 0.2 μm then more preferably.
Below, utilize embodiment to carry out more specific description to the present invention, but the present invention is not limited to these embodiments.
Embodiment
After adopting usual method to use vacuum induction melting stove 180kg to be had 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 being made steel billet.
Each billet hot punching rolling that the milling machine (modelmill) that uses a model will so obtain, has manufactured external diameter and has been 38mm and wall thickness is the seamless tube of 9mm.
[table 1]
Above-mentioned external diameter is 38mm and each seamless tube that wall thickness is 9mm to cut into 200mm long, carry out making temperature 1150 ~ 1280 DEG C range, make the hold-time at this temperature in the solutionizing thermal treatment of the range of 0.5 ~ 5h, made different various for test tubes of the average crystal particle diameter d of wall thickness central part.
Then, the obtained outside surface for test tube is ground, makes oxide layer thicknesses that various change occur.
Each for test tube for what outside surface has been ground after above-mentioned solutionizing thermal treatment, measure the oxide layer thicknesses of the average crystal particle diameter d of wall thickness central part and the outside surface of pipe respectively as follows.
The average crystal particle diameter d (μm) of wall thickness central part obtains as follows: with the central part for test tube of 200mm length for benchmark, the mode being transverse section with detected face before and after it cuts out 5 test films, and be circumferentially cut to 4, then mirror ultrafinish is carried out, with the observation by light microscope carrying out wall thickness central part after chloroazotic acid corrosion.
That is, for each test film after cut-out, under multiplying power 100 times, carry out a visual field 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 every for above-mentioned test film a slice, obtain average crystal particle diameter d (μm) by its 1.128 times.
The oxide layer thicknesses of the outside surface of pipe is obtained as follows: for each for test tube, by 20 test films mirror ultrafinish again used for the average crystal particle diameter d (μm) measuring above-mentioned wall thickness central part, under the state keeping grinding, carry out observation by light microscope.
That is, supply test tube about each, the every a slice for 20 test films is observed under multiplying power 400 times, measures 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 layer thicknesses of the outside surface of pipe.
In addition, use aforementioned after solutionizing thermal treatment, ground outside surface each for test tube and the alloy sheets being used as fin keel cutting into the long thick 6mm of 200mm, wide 15mm with chemical constitution shown in table 2, the contained welding test body simulating the fillet welding of hearth wall pipe shown in construction drawing 1.
It should be noted that, each fillet welding for test tube and above-mentioned alloy sheets is implemented 4 positions as illustrated in fig. 2.Specifically, use commercially available welding rod (AWS standard A 5.14ERNiCrCoMo-1) and ceramics flux (bondflux), implement union-melt weld with heat input 12kJ/cm.
[table 2]
For obtained each contained welding test body, the mode being transverse section with detected face respectively from 4 fillet welding positions cuts out each 5 test films, then carries out mirror ultrafinish.
Then, with chloroazotic acid corrosion, opticmicroscope is used to carry out microexamination (microscopicexamination), for each meter 20 place weld part of contained welding test body, investigation supplies the HAZ place of test tube with or without liquation crack, obtains liquation crack production rate.
It should be noted that, liquation crack production rate defines with " (section number/20 cracked) × 100 (%) ", by liquation crack production rate be only 0 (zero) test body be judged to be " qualified ", other are judged to be " defective ".
Table 3 shows above-mentioned each test-results.Wherein, the B amount that contains in the raw alloy for test tube is described in table 3 in the lump and by " EQU=1500-2.5 × 10
5× B " value of EQU obtained.
[table 3]
According to table 3, employ the seamless tube meeting condition given to this invention for test tube symbol A1, A6, A7, B1 ~ B3, C1 ~ C3, D1, E1 and F1 when, liquation crack production rate is 0, namely confirms that in all sections, HAZ place does not produce liquation crack.Therefore, when the known seamless tube meeting 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 proper alignment anti-thread breakage.
On the other hand, although be for raw material with the alloy A ~ F of chemical constitution in scope given to this invention, but when the thickness of the oxide skin of the average crystal particle diameter of wall thickness central part of pipe or the outside surface of pipe exceedes the confession test tube symbol of the upper limit given to this invention, HAZ place produces liquation crack, cannot be used for the hearth wall pipe outside surface of pipe directly being carried out to fillet welding.
When for test tube symbol A2, A3, D2, E2 and F2, although the average crystal particle diameter d of the wall thickness central part of pipe is lower than 1000 μm, do not meet the following formula of the amount defined of the B contained according to alloy, therefore HAZ place produces liquation crack.And liquation crack production rate becomes large along with above-mentioned average crystal particle diameter d and raises.
d≤1500-2.5×10
5×B
When for test tube symbol C4, the average crystal particle diameter d of the wall thickness central part of pipe is more than 1000 μm, and therefore HAZ place produces liquation crack.
When for test tube symbol A4 and A5, the thickness of the oxide skin of the outside surface of pipe is more than 15 μm, 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 anti-thread breakage excellence of proper alignment of austenite of the present invention is seamless refractory alloy pipe, when can suppress welding, HAZ place cracks.Therefore, austenite of the present invention seamless refractory alloy pipe is with having excellent high-temperature strength, the component with the also high temperature service of hearth wall pipe that can be suitable as boiler for power generation and so among seamless compo pipe that the anti-thread breakage and Austenitic heat-resistant alloy that thermal expansivity is little of sufficient anticorrosion stress-resistant is raw material.
Claims (3)
1. the seamless refractory alloy pipe of austenite, directly fillet welding is carried out to the outside surface of pipe and uses, it is characterized in that, the chemical constitution of this austenite is seamless refractory alloy pipe is as follows: in mass %, C:0.03 ~ 0.15%, below Si:1%, below Mn:2%, below P:0.03%, below S:0.01%, Ni:35 ~ 60%, Cr:18 ~ 38%, W:3 ~ 11%, Ti:0.01 ~ 1.2%, below Al:0.5%, B:0.0001 ~ 0.005%, below N:0.02% 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,
Average crystal particle diameter d μm of the wall thickness central part of pipe is less than 1000 μm and meets following formula; In addition, the thickness of the oxide skin of the outside surface of pipe is less than 15 μm,
d≤1500-2.5×10
5×B
B in above formula represents the content of B in mass %.
2. the seamless refractory alloy pipe of austenite according to claim 1, it is characterized in that, part Fe is replaced in mass % containing more than a kind that is selected from the element shown in following < 1 > and < 2 >
< 1 below > Mo:1%, below Cu:1% and below Co:1%,
< 2 below > 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 used as hearth wall pipe.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011249875A JP5212533B2 (en) | 2011-11-15 | 2011-11-15 | Seamless austenitic heat-resistant alloy tube |
| JP2011-249875 | 2011-11-15 | ||
| 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 |
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| CN103946403A CN103946403A (en) | 2014-07-23 |
| CN103946403B true CN103946403B (en) | 2016-02-17 |
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| EP (1) | EP2781612B1 (en) |
| JP (1) | JP5212533B2 (en) |
| KR (1) | KR101632520B1 (en) |
| CN (1) | CN103946403B (en) |
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2012
- 2012-11-07 PL PL12850463T patent/PL2781612T3/en unknown
- 2012-11-07 WO PCT/JP2012/078788 patent/WO2013073423A1/en active Application Filing
- 2012-11-07 EP EP12850463.6A patent/EP2781612B1/en active Active
- 2012-11-07 CN CN201280056250.6A patent/CN103946403B/en active Active
- 2012-11-07 KR KR1020147015980A patent/KR101632520B1/en active IP Right Grant
- 2012-11-07 IN IN3492DEN2014 patent/IN2014DN03492A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1068035A (en) * | 1996-08-29 | 1998-03-10 | Sumitomo Metal Ind Ltd | Nickel-chromium alloy excellent in intergranular stress corrosion cracking resistance, and its production |
| EP1338663A1 (en) * | 2000-11-16 | 2003-08-27 | Sumitomo Metal Industries, Ltd. | Ni-base heat-resistant alloy and weld joint using the same |
| JP2004035911A (en) * | 2002-06-28 | 2004-02-05 | Japan Science & Technology Corp | Method of producing high temperature oxidation resistant, heat-resistant alloy member on which rhenium-containing alloy film is covered |
| CN1814840A (en) * | 2006-02-17 | 2006-08-09 | 刘相法 | P-si intermediate alloy and preparing method |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2781612A1 (en) | 2014-09-24 |
| EP2781612B1 (en) | 2018-06-06 |
| IN2014DN03492A (en) | 2015-06-26 |
| JP5212533B2 (en) | 2013-06-19 |
| KR20140091061A (en) | 2014-07-18 |
| CN103946403A (en) | 2014-07-23 |
| WO2013073423A1 (en) | 2013-05-23 |
| EP2781612A4 (en) | 2016-03-02 |
| JP2013104109A (en) | 2013-05-30 |
| PL2781612T3 (en) | 2018-11-30 |
| KR101632520B1 (en) | 2016-06-21 |
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