EP2781612B1 - Seamless austenite heat-resistant alloy tube - Google Patents

Seamless austenite heat-resistant alloy tube Download PDF

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Publication number
EP2781612B1
EP2781612B1 EP12850463.6A EP12850463A EP2781612B1 EP 2781612 B1 EP2781612 B1 EP 2781612B1 EP 12850463 A EP12850463 A EP 12850463A EP 2781612 B1 EP2781612 B1 EP 2781612B1
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Prior art keywords
tube
less
content
resistant alloy
contained
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German (de)
English (en)
French (fr)
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EP2781612A1 (en
EP2781612A4 (en
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Kana Joutoku
Atsuro Iseda
Hirokazu Okada
Hiroyuki Hirata
Mitsuru Yoshizawa
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Nippon Steel Corp
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Nippon Steel and Sumitomo Metal Corp
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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
    • 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%
    • 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%
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a seamless austenitic heat-resistant alloy tube. More particularly, it relates to a seamless austenitic heat-resistant alloy tube that can be used as a high-temperature equipment member, such as a tube constituting a furnace wall of power generation boiler (hereinafter, referred to as a "water wall tubeโ€), by allowing direct fillet-welding of the outer surface of the tube.
  • a high-temperature equipment member such as a tube constituting a furnace wall of power generation boiler (hereinafter, referred to as a "water wall tube"
  • the higher temperature and higher pressure of steam raise the temperature at the time when a tube constituting a boiler, for example, a heat-transfer tube such as a superheater tube and a resuperheater tube and a main steam tube is in operation. Therefore, the material that is used in such a severe environment for a long period of time is required to have a high temperature strength and corrosion resistance at high temperatures, above all, long-term stability of metal micro-structure and high creep properties.
  • Non Patent Document 1 Fujimitu Masuyama: Journal of The Iron and Steel Institute of Japan, Vol.80 (1994) No.8, pp.587-592 ) shows a graph in which the abscissas represent the Cr content of material and the ordinates represent the temperature at an allowable stress of 49 MPa for a practicable heat-resistant material, and describes that, with the increase in Cr content, the temperature on the ordinates, and therefore, the creep strength as a high temperature strength increases.
  • Non Patent Document 2 Masamichi Koiwa: Metal Corrosion Damage and Anticorrosion Technique (1983, Agune Syoufuusha Corp.), pp.452-453 ) shows a graph in which the abscissas represent the Ni content of material and the ordinates represent the crack susceptibility for a practicable heat-resistant material, and describes that, with the increase in Ni content, the crack susceptibility on the ordinates decreases, and the corrosion resistance (stress corrosion cracking resistance) at high temperatures increases.
  • Patent Documents 1 to 3 JP60-100640A , JP64-55352A and JP2-200756A ) disclose heat-resistant alloys in which by increasing the contents of Cr and Ni, and moreover, by containing one or more kinds of Mo and W, an attempt is made to improve creep rupture strength as a high temperature strength.
  • Patent Documents 4 to 7 JP7-216511A , JP7-331390A , JP8-127848A and JP8-218140A ) disclose heat-resistant alloys in which 28 to 38% of Cr and 35 to 60% of Ni are contained, and by utilizing the precipitation of โ‡ -Cr phase of body-centered cubic structure consisting mainly of Cr, an attempt is made to further improve creep rupture strength.
  • Patent Documents 8 and 9 JP51-84726A and JP51-84727A disclose Ni-based alloys in which by containing Mo and/or W, solid-solution strengthening is attempted, and also by utilizing the precipitation strengthening of โ‡ ' phase, which is an intermetallic compound containing Al and Ti, specifically Ni 3 (Al, Ti), the use in the severe high-temperature environment is made possible.
  • Patent Document 10 JP9-157779A proposes a high-Ni austenitic heat-resistant alloy in which by controlling the content ranges of Al and Ti and by precipitating โ‡ ' phase, the creep strength is improved.
  • the austenitic heat-resistant alloys are assembled into various structures by welding, and the structures are used at high temperatures.
  • Non Patent Document 3 Edited by Japan Welding Society: Welding and Joining Handbook 2nd edition (2003, Maruzen), pp.948-950
  • HAZ welding heat affected zone
  • the austenitic heat-resistant alloy used as a member of various structures is required to achieve both of prevention of cracks in the HAZ at the welding time and provision of weld joint performance.
  • Patent Document 11 JP2011-63838A discloses an austenitic heat-resistant alloy in which by containing a specific amount of Fe and by controlling the effective B amount range, the assurance of workability at high temperatures and the prevention of cracks in the HAZ at the butt welding time are made possible.
  • Patent Document 12 JP2010-150593A discloses an austenitic heat-resistant alloy in which by controlling the contents of impurity elements such as Sn and Pb in addition to P and S, cracks in the HAZ can be prevented when butt welding is performed and when a welded structure is used for a long period of time, and moreover, the alloy is also excellent in creep strength.
  • the austenitic heat-resistant alloys are generally assembled into various structures by welding.
  • a carbon steel or a 1%Cr steel which need not be subjected to both of preheating and postheating, has generally been used.
  • the ordinary austenitic stainless steel which has been used so far as a superheater tube or a resuperheater tube, is subjected to stress corrosion cracking in the environment in which high-temperature water flows therein, such as a furnace wall, because of low content of Ni. Therefore, the ordinary austenitic stainless steel as well cannot be used as a starting material for the water wall tube of the "next-generation ultra-supercritical pressure boilers"
  • the austenitic stainless steel has a high linear thermal expansion coefficient as shown in one example in Non Patent Document 4 ( Shinichi Takano et al.: IHI Technical Review, vol.49 No.4 (2009), pp.185-191 ). Therefore, for the austenitic stainless steel, the heat deformation becomes large when welding is performed, and there arises a problem when the furnace wall is manufactured.
  • the furnace wall is formed by a panel in which a plurality of water wall tubes are arranged in parallel, and are welded to fin plates or fin bars for connecting the water wall tubes to each other. Therefore, unlike the butt welding in which machined groove faces are welded, it is necessary to fillet-weld the outer surface of the as-produced tube directly to the fin plates or the fin bars.
  • the outer surface of the tube is directly fillet-welded (hereinafter, sometimes referred simply to as "the outer surface of the tube is directly welded") as described above, as compared with the case of butt welding in which welding is performed in the groove, in terms of shape, the stress concentration in an excess weld metal toe portion increases. As a result, in the case where the outer surface of the tube is directly welded, as compared with the case of butt welding, cracks are liable to be generated in the HAZ during welding.
  • an immediate challenge is the development of an austenitic heat-resistant alloy tube having an increased Ni content that can be used suitably as the water wall tube of the "next-generation ultra-supercritical pressure boilers ", that is, the development of a seamless austenitic heat-resistant alloy tube having an increased Ni content that is excellent in weld crack resistance and capable of restraining the generation of cracks in a HAZ at the time of welding among seamless alloy tubes that are excellent in high temperature strength, have sufficient stress corrosion cracking resistance, and are produced using an austenitic heat-resistant alloy having a low thermal expansion coefficient as a starting material.
  • Patent Documents 1 to 10 disclose austenitic heat-resistant alloys having an improved creep rupture strength.
  • studies are not conducted from the viewpoint of "weldability" at the time when a structure is assembled, and moreover, to weld the outer surface of tube directly is not considered at all. Therefore, the tubes produced by using the austenitic heat-resistant alloys proposed in these Patent Documents as starting materials cannot at all be used as the water wall tubes of the "next-generation ultra-supercritical pressure boilers ".
  • the austenitic heat-resistant alloy proposed in the Patent Document 11 by the present inventors is suitable for being used as a product, such as a tube, plate, bar, and forgings, that is used as a heat-resistant pressure-resistant part for power generation boilers, chemical industry, or the like, especially as a large-sized product.
  • a product such as a tube, plate, bar, and forgings
  • the high-temperature workability, the resistance to weld crack susceptibility, and further the decrease in ductility caused by high-temperature aging at the time when the product is produced and at the time when actual equipment is used can be improved remarkably.
  • the austenitic heat-resistant alloy proposed in the Patent Document 12 by the present inventors cracks in the HAZ can be prevented, and a defect attributable to welding workability, which is formed during the welding work, can also be prevented. Further, this austenitic heat-resistant alloy is excellent in creep strength at high temperatures. Therefore, this austenitic heat-resistant alloy can be suitably used as a starting material for high-temperature equipment for power generation boilers, chemical industry plants, or the like.
  • the present invention has been made in view of the above-described present situation, and accordingly an objective thereof is to provide a seamless austenitic heat-resistant alloy tube that can be used as a high-temperature equipment member, such as a water wall tube of power generation boiler, by allowing direct fillet-welding of the outer surface of tube, that is, a seamless austenitic heat-resistant alloy tube excellent in weld crack resistance and capable of restraining the generation of cracks in a HAZ at the time of welding among seamless alloy tubes that are excellent in high temperature strength, have sufficient stress corrosion cracking resistance, and are produced using an austenitic heat-resistant alloy having a low thermal expansion coefficient as a starting material.
  • the present inventors prepared seamless tubes of various austenitic heat resistant alloys containing B (hereinafter, sometimes referred simply to as โ€œaustenitic heat-resistant alloy tubesโ€), fillet-welded the outer surfaces of these alloy tubes directly to a plate compared to a fin plate, specifically, an alloy plate of 6 mm thick, 15 mm wide, and 200 mm long having the chemical composition given in Table 2 of Examples, described later, and conducted detailed examination of the cracks formed in the HAZ when welding is performed.
  • austenitic heat-resistant alloy tubes various austenitic heat resistant alloys containing B
  • the present invention was completed on the basis of the above-described findings, and the gist thereof is seamless austenitic heat-resistant alloy tubes described below.
  • impurities mean impurity elements mixed from ore and scrap used as a raw material or a production environment when the austenitic heat-resistant alloy is produced on an industry basis.
  • the "REMโ€ is the general term of a total of seventeen elements consisting of Sc, Y, and lanthanoids, and the REM content means the total content of one kind or two or more kinds of elements of the REM.
  • the seamless austenitic heat-resistant alloy tube of the present invention is excellent in weld crack resistance and capable of restraining the generation of cracks in a HAZ at the time of welding. Therefore, among seamless alloy tubes that are excellent in high temperature strength, have sufficient stress corrosion cracking resistance, and are produced using an austenitic heat-resistant alloy having a low thermal expansion coefficient as a starting material, the seamless austenitic heat-resistant alloy tube of the present invention can be used suitably as a high-temperature equipment member such as a water wall tube of power generation boiler.
  • C carbon stabilizes austenite, forms fine carbides at the grain boundary, and improves the creep strength at high temperatures.
  • 0.03% or more of C must be contained.
  • the carbides become coarse, and precipitate in large amounts, so that the ductility of grain boundary is decreased, and further, the toughness and creep strength are also decreased. Therefore, the upper limit is placed, and the C content is set to 0.03 to 0.15%.
  • the preferable lower limit of C content is 0.04%, and the preferable upper limit thereof is 0.12%.
  • Si silicon is an element that has a deoxidizing function, and is effective in improving the corrosion resistance and oxidation resistance at high temperatures. However, if Si is contained excessively, the stability of austenite decreases, and therefore the toughness and creep strength are decreased. Therefore, the upper limit is placed, and the Si content is set to 1% or less. The Si content is preferably 0.8% or less.
  • the lower limit of Si content need not be placed especially. However, if the Si content decreases extremely, the deoxidizing effect is not achieved sufficiently, the index of cleanliness of alloy is increased and the cleanliness is deteriorated, and also the advantageous effect of improving the corrosion resistance and oxidation resistance at high temperatures becomes less liable to be achieved. Also, the production cost increases greatly. Therefore, the preferable lower limit of Si content is 0.02%.
  • Mn manganese
  • Mn has a deoxidizing function like silicon. Manganese also contributes to the stabilization of austenite. However, if Mn is contained excessively, embrittlement occurs, and further, the toughness and creep ductility decrease. Therefore, the upper limit is placed, and the Mn content is set to 2% or less. The Mn content is preferably 1.5% or less.
  • the lower limit of Mn content also need not be placed especially. However, if the Mn content decreases extremely, the deoxidizing effect is not achieved sufficiently, the cleanliness of alloy is deteriorated, and also the austenite stabilizing effect becomes less liable to be achieved. Also, the production cost increases greatly. Therefore, the preferable lower limit of Mn content is 0.02%.
  • P phosphorus
  • the alloy is an impurity, and is an element that segregates at the grain boundary of HAZ during welding and enhances the liquation cracking susceptibility. Therefore, the upper limit is placed, and the P content is set to 0.03% or less. The P content is preferably 0.02% or less.
  • the P content is preferably decreased as far as possible. However, the extreme decrease leads to the increase in production cost. Therefore, the preferable lower limit of P content is 0.0005%.
  • S sulfur
  • S is, like P, contained in the alloy as an impurity, and is an element that segregates at the grain boundary of HAZ during welding and enhances the liquation cracking susceptibility. Further, S is an element that exerts an adverse influence on the toughness after long-term use. Therefore, the upper limit is placed, and the S content is set to 0.01% or less. The S content is preferably 0.005% or less.
  • the S content is preferably decreased as far as possible. However, the extreme decrease leads to the increase in production cost. Therefore, the preferable lower limit of S content is 0.0001%.
  • Ni nickel is an element effective in obtaining austenite, and also, is an element essential in assuring the structural stability at the time of long-term use.
  • Ni is an expensive element, so that the containing of much Ni leads to the increase in cost. Therefore, the upper limit is placed, and the Ni content is set to 35 to 60%.
  • the preferable lower limit of Ni content is 38%, and the preferable upper limit thereof is 55%.
  • Cr chromium
  • Cr is an element essential in assuring the oxidation resistance and corrosion resistance at high temperatures.
  • 18% or more of Cr must be contained.
  • the Cr content is set to 18 to 38%.
  • the preferable lower limit of Cr content is 20%, and the preferable upper limit thereof is 35%.
  • W tungsten
  • W tungsten
  • 3% or more of W must be contained.
  • W is an expensive element, so that the containing of much W leads to the increase in cost. Therefore, the upper limit is placed, and the W content is set to 3 to 11%.
  • the preferable lower limit of W content is 5%, and the preferable upper limit thereof is 10%.
  • Ti titanium precipitates in grains as fine carbo-nitrides, and contributes to the creep strength at high temperatures. In order to achieve this effect, 0.01% or more of Ti must be contained. However, if Ti is contained excessively, Ti precipitates in large amounts as carbo-nitrides, and decreases the creep ductility and toughness. Therefore, the upper limit is placed, and the Ti content is set to 0.01 to 1.2%. The preferable lower limit of Ti content is 0.05%, and the preferable upper limit thereof is 1.0%.
  • Al is an element having a deoxidizing function. However, if Al is contained excessively, the cleanliness of alloy is remarkably deteriorated, and the hot workability and ductility are decreased. Therefore, the upper limit is placed, and the Al content is set to 0.5% or less. The Al content is preferably 0.3% or less.
  • the lower limit of Al content need not be placed especially. However, if the Al content decreases extremely, the deoxidizing effect is not achieved sufficiently, the cleanliness of alloy is inversely deteriorated, and the production cost is increased. Therefore, the preferable lower limit of Al content is 0.001%. In order to stably achieve the deoxidizing effect of Al and to assure the high cleanliness of alloy, the lower limit of Al content is further preferably set to 0.0015%.
  • B boron
  • B is an element necessary to strengthen the grain boundary by segregating at the grain boundary during the use at high temperatures and to improve the creep strength by finely dispersing the grain boundary carbides.
  • B has effects of improving the sticking force by segregating at the grain boundary and of contributing to the improvement in toughness.
  • 0.0001% or more of B must be contained.
  • B is contained excessively, B is segregated in large amounts in the high-temperature HAZ near the fusion boundary, so that the fusing point of grain boundary is lowered, and the liquation cracking susceptibility of HAZ is enhanced. Therefore, the upper limit is placed, and the B content is set to 0.0001 to 0.005%.
  • the preferable lower limit of B content is 0.0005%.
  • the grain diameter of HAZ near the fusion boundary increases, in other words, the grain boundary area per unit volume decreases, so that the grain-boundary segregation of B is promoted, and the stress applied to a specific grain boundary face increases. Therefore, the liquation cracking susceptibility is enhanced.
  • the average grain diameter d ( โ‡ m) at the center of the wall thickness of the alloy tube is regulated so as to be 1000 โ‡ m or smaller, and to be in the range satisfying the following formula according to the amount (%) of B contained in the alloy, the increase in liquation cracking susceptibility caused by the segregation of B can be restrained.
  • d 1500 โ‡ 2.5 โ‡ 10 5 โ‡ B
  • letter B represents the content by mass percent of B.
  • N nitrogen
  • Cr Cr
  • the N content is set to 0.02% or less.
  • the N content is preferably 0.015% or less.
  • the lower limit of N content need not be placed especially. However, if the N content decreases extremely, the effect of stabilizing austenite is less liable to be achieved, and the production cost also increases greatly. Therefore, the preferable lower limit of N content is 0.0005%.
  • O oxygen
  • the alloy is contained in the alloy as an impurity. If O is contained excessively, the hot workability is decreased, and further, the toughness and ductility are deteriorated. Therefore, the upper limit is placed, and the O content is set to 0.008% or less. The O content is preferably 0.005% or less.
  • the lower limit of O content need not be placed especially. However, if the O content decreases extremely, the production cost increases. Therefore, the preferable lower limit of O content is 0.0005%.
  • the seamless austenitic heat-resistant alloy tube of the present invention is caused to contain, in addition to the above-described elements ranging from C to O, one or more kinds of elements of Zr: 0.01 to 0.5%, Nb: 0.01 to 0.5%, and V: 0.01 to 0.5%.
  • Zr zirconium combines with C or N to form fine carbides or carbo-nitrides, and contributes to the improvement in creep strength. In order to achieve this effect, 0.01% or more of Zr must be contained. However, if Zr is contained excessively, it precipitates in large amounts as carbides or carbo-nitrides, and therefore the creep ductility is decreased. Therefore, the upper limit is placed, and the Zr content is set to 0.01 to 0.5%. The preferable lower limit of Zr content is 0.015%, and the preferable upper limit thereof is 0.4%.
  • Nb niobium
  • C or N combines with C or N to form fine carbides or carbo-nitrides, and contributes to the improvement in creep strength.
  • 0.01% or more of Nb must be contained.
  • the upper limit is placed, and the Nb content is set to 0.01 to 0.5%.
  • the preferable lower limit of Nb content is 0.015%, and the preferable upper limit thereof is 0.4%.
  • V vanadium
  • 0.01% or more of V must be contained.
  • the upper limit is placed, and the V content is set to 0.01 to 0.5%.
  • the preferable lower limit of V content is 0.015%, and the preferable upper limit thereof is 0.4%.
  • Zr, Nb and V Only any one kind of Zr, Nb and V can be contained, or two or more kinds of these elements can be contained compositely.
  • the total amount in the case where these elements are contained compositely may be 1.5%; however, the total amount is preferably 1.2% or less.
  • One of the seamless austenitic heat-resistant alloy tubes of the present invention is an alloy tube having the chemical composition consisting of the above-described elements, the balance being Fe and impurities.
  • the "impuritiesโ€ mean impurity elements mixed from ore and scrap used as a raw material or a production environment when the austenitic heat-resistant alloy is produced on an industry basis.
  • Another of the seamless austenitic heat-resistant alloy tubes of the present invention is an alloy tube having the chemical composition containing, in lieu of a part of Fe, one or more elements selected from Mo, Cu, Co, Ca, Mg and REM.
  • Any of Mo, Cu and Co belonging to the โ‡ 1> group has a function of improving the creep strength. Therefore, these elements may be contained.
  • Mo mobdenum
  • Mo has a function of improving the creep strength. That is, Mo dissolves in matrix and has a function of improving the creep strength at high temperatures. Therefore, Mo may be contained. However, if Mo is contained excessively, the stability of austenite is decreased, and the creep strength is rather decreased. Therefore, the upper limit of the amount of Mo, if contained, is placed, and the Mo content is set to 1% or less.
  • the Mo content is preferably 0.1% or more.
  • Cu copper
  • Cu has a function of improving the creep strength. That is, Cu is, like Ni, an austenite forming element, and therefore enhances the phase stability and contributes to the improvement in creep strength. Therefore, Cu may be contained. However, if Cu is contained excessively, the hot workability is decreased. Therefore, the upper limit of the amount of Cu, if contained, is placed, and the Cu content is set to 1% or less.
  • the Cu content is preferably 0.02% or more.
  • Co has a function of improving the creep strength. That is, Co is, like Ni and Cu, an austenite forming element, and therefore enhances the phase stability and contributes to the improvement in creep strength. Therefore, Co may be contained. However, Co is a very expensive element, so that the excessive containing of Co leads to a significant increase in cost. Therefore, the upper limit of the amount of Co, if contained, is placed, and the Co content is set to 1% or less.
  • the Co content is preferably 0.02% or more.
  • Any of Ca, Mg and REM belonging to the โ‡ 2> group has a function of improving the hot workability. Therefore, these elements may be contained.
  • Ca (calcium) has a function of improving the hot workability. Therefore, Ca may be contained. However, if Ca is contained excessively, it combines with O, and remarkably decreases the cleanliness, so that the hot workability is rather deteriorated. Therefore, the upper limit of the amount of Ca, if contained, is placed, and the Ca content is set to 0.05% or less.
  • the Ca content is preferably 0.0005% or more.
  • Mg manganesium
  • Mg has, like Ca, a function of improving the hot workability. Therefore, Mg may be contained. However, if Mg is contained excessively, it combines with O, and remarkably decreases the cleanliness, so that the hot workability is rather deteriorated. Therefore, the upper limit of the amount of Mg, if contained, is placed, and the Mg content is set to 0.05% or less.
  • the Mg content is preferably 0.0005% or more.
  • REM rare-earth metal
  • REM has a function of improving the hot workability. That is, REM has a strong affinity for S, and contributes to the improvement in hot workability. Therefore, REM may be contained. However, if REM is contained excessively, it combines with O, and remarkably decreases the cleanliness, so that the hot workability is rather deteriorated. Therefore, the upper limit of the amount of REM, if contained, is placed, and the REM content is set to 0.1% or less.
  • the REM content is preferably 0.0005% or more.
  • the "REMโ€ is the general term of a total of seventeen elements consisting of Sc, Y, and lanthanoids, and the REM content means the total content of one kind or two or more kinds of elements of the REM.
  • the REM is generally contained in a Mischmetal. Therefore, REM may be contained by being added in a form of Mischmetal so that the REM content is in the above-described range.
  • Only any one kind of Ca, Mg and REM can be contained, or two or more kinds of these elements can be contained compositely.
  • the total amount in the case where these elements are contained compositely may be 0.2%.
  • the average grain diameter d โ‡ m at the center of the wall thickness of the tube must be 1000 โ‡ m or smaller and must satisfy the formula expressed by d โ‡ 1500 โ‡ 2.5 โ‡ 10 5 โ‡ B according to the amount of B contained in the alloy.
  • letter B represents the content (mass%) of B.
  • the toughness and ductility are decreased remarkably. Further, the grain diameter of HAZ near the fusion boundary also increases, in other words, the grain boundary area per unit volume decreases. Therefore, even if the upper limit of amount of B contained in the tube is controlled to 0.005%, the liquation cracking caused by the segregation of B cannot be prevented.
  • the average grain diameter d at the center of the wall thickness of the tube is 1000 โ‡ m or smaller, in the case where the average grain diameter d does not satisfy the formula of d โ‡ 1500 โ‡ 2.5 โ‡ 10 5 โ‡ B, B is segregated in large amounts in the high-temperature HAZ near the fusion boundary, so that the fusing point of grain boundary is lowered, and the liquation cracking susceptibility of HAZ is enhanced. Therefore, the liquation cracking cannot be prevented.
  • the average grain diameter d at the center of the wall thickness of the tube can be made such as to be 1000 โ‡ m or smaller and to satisfy the formula of "d โ‡ 1500 - 2.5 โ‡ 10 5 โ‡ B".
  • the oxide film formed on the surface of the seamless austenitic heat-resistant alloy tube of the present invention having the chemical composition described in the above item (A), has a high fusing point. Moreover, this oxide film deteriorates the wettability with molten metal when the outer surface of tube is fillet-welded. Therefore, if the thickness of oxide layer on the outer surface of tube increases, the toe angle of weld bead (excess weld metal) becomes large, so that stresses are easily concentrated on the HAZ, and liquation cracking is liable to occur. Therefore, the upper limit of the thickness of oxide layer on the outer surface of tube is placed, and the thickness is set to 15 โ‡ m or smaller. The thickness of oxide layer on the outer surface of tube is preferably 10 โ‡ m or smaller.
  • the thickness of oxide layer on the outer surface of tube can be made 15 โ‡ m or smaller stably.
  • the thickness of oxide layer on the outer surface of tube can be made 15 โ‡ m or smaller stably by performing treatment such as pickling, grinding, or shot blasting.
  • the lower limit of the thickness of oxide layer on the outer surface of tube need not be placed especially.
  • the thickness of oxide layer on the outer surface of tube may be made in a state close to 0 โ‡ m by performing the solid solution heat treatment in a reducing gas or by performing treatment such as pickling, grinding, or shot blasting.
  • the thickness of oxide layer may be made zero by performing mechanical grinding to remove the oxide layer on the outer surface of tube.
  • the thickness of oxide layer on the outer surface of tube is preferably 0.1 โ‡ m or larger, further preferably 0.2 โ‡ m or larger.
  • the seamless tube having an outside diameter of 38 mm and a wall thickness of 9 mm was cut to a length of 200 mm, and the cut seamless tube was subjected to solid solution heat treatment, in which the temperature was set at 1150 to 1280ยฐC, and the holding time at those temperatures was changed in the range of 0.5 to 5 hours.
  • the average grain diameter d at the center of the wall thickness of the tube and the thickness of oxide layer on the outer surface of tube were measured by the methods as described below.
  • the average grain diameter d ( โ‡ m) at the center of the wall thickness of the tube was determined as described below.
  • Five test specimens were cut out of the front and rear portions with the central portion of the 200 mm-long test specimen tube being the reference so that the surface to be measured is the transverse surface.
  • Each of the test specimens was cut into four pieces in the circumferential direction, the surface to be measured was mirror-polished and etched with aqua regia, and the wall thickness central portion was observed under an optical microscope.
  • the thickness of oxide layer on the outer surface of tube was determined as described below.
  • the twenty test specimens that had been used to measure the average grain diameter d ( โ‡ m) at the center of the wall thickness of the tube as described above were mirror-polished again, and in the polished state, were observed under an optical microscope.
  • each of the twenty test specimens was observed at โ‡ 400 magnification to measure the thickness of oxide on the outer surface of tube.
  • the values of thicknesses of oxide on the twenty test specimens were arithmetically averaged to determine the thickness of oxide layer on the outer surface of tube.
  • each test specimen tube the outer surface of which had been polished after the solid solution heat treatment and alloy plates compared to fin plates that had the chemical composition given in Table 2, and had been cut to a 200-mm length, each having a thickness of 6 mm and a width of 15 mm, a restraint weld test body simulating the fillet-welding of a water wall tube, which is shown in Figure 1 , was prepared.
  • each of the test specimen tubes and the alloy plates were fillet-welded at four places. More specifically, by using a commercially available welding wire (AWS Standard A5.14 ER NiCrCoMo-1) and bonded flux, submerged arc welding was performed at a heat input of 12 kJ/cm. TABLE 2 Chemical Composition (mass %) Balance: Fe and Impuritles C Si Mn P S Ni Cr W Ti Al B N 0 Nb Mo 0.09 0.29 0.92 0.010 0.0003 44.6 22.8 6.87 0.09 0.03 0.0013 0,008 0.006 0.18 0.13
  • test specimens were etched with aqua regia, and were examined under an optical microscope.
  • the presence or absence of liquation cracking in the HAZ of test specimen tube was examined, and the liquation cracking incidence rate was determined.
  • the liquation cracking incidence rate was defined as "(number of cracking occurrence sections / 20) โ‡ 100(%)", and only the test bodies in which the liquation cracking incidence rate was zero were judged to be โ€œacceptableโ€, and the other test bodies were judged to be "unacceptableโ€.
  • Table 3 reveals that, for test specimen tube signs A1, A6, A7, B1 to B3, C1 to C3, D1, E1 and F1, in which a seamless tube satisfying the claimed conditions, the liquation cracking incidence rate was zero, that is, in all sections, the occurrence of liquation cracking in the HAZ was not recognized. Therefore, it is apparent that the seamless tube satisfying the claimed conditions had sufficient weld crack resistance even in the case of being used by allowing direct fillet-welding of the outer surface of tube as in the case of a water wall tube.
  • the seamless austenitic heat-resistant alloy tube of the present invention is excellent in weld crack resistance and capable of restraining the generation of cracks in a HAZ at the time of welding. Therefore, among seamless alloy tubes that are excellent in high temperature strength, have sufficient stress corrosion cracking resistance, and are produced using an austenitic heat-resistant alloy having a low thermal expansion coefficient as a starting material, the seamless austenitic heat-resistant alloy tube of the present invention can be used suitably as a high-temperature equipment member such as a water wall tube of power generation boiler.

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EP12850463.6A 2011-11-15 2012-11-07 Seamless austenite heat-resistant alloy tube Active EP2781612B1 (en)

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KR101280114B1 (ko) * 2008-06-16 2013-06-28 ์‹ ๋‹›ํ…Œ์ธ ์Šค๋ฏธํ‚จ ์นด๋ถ€์‹œํ‚ค์นด์ด์ƒค ์˜ค์Šคํ…Œ๋‚˜์ดํŠธ๊ณ„ ๋‚ด์—ด ํ•ฉ๊ธˆ ๋ฐ ์ด ํ•ฉ๊ธˆ์œผ๋กœ ์ด๋ฃจ์–ด์ง€๋Š” ๋‚ด์—ด ๋‚ด์•• ๋ถ€์žฌ์™€ ๊ทธ ์ œ์กฐ ๋ฐฉ๋ฒ•
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KR20140091061A (ko) 2014-07-18
JP5212533B2 (ja) 2013-06-19
IN2014DN03492A (zh) 2015-06-26
EP2781612A1 (en) 2014-09-24
CN103946403A (zh) 2014-07-23
CN103946403B (zh) 2016-02-17
EP2781612A4 (en) 2016-03-02
WO2013073423A1 (ja) 2013-05-23
JP2013104109A (ja) 2013-05-30
PL2781612T3 (pl) 2018-11-30
KR101632520B1 (ko) 2016-06-21

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