DESCRIPTION
TITLE OF THE INVENTION: DOUBLE TUBE AND WELDED STRUCTURE USING THE SAME
TECHNICAL FIELD [0001]
The present invention relates to a double tube and a welded structure using the double tube. More particularly, the invention relates to a double tube excellent in weld crack resistance, which can be used as a material for high-temperature equipment with plates, metal fittings, and the like fillet-welded to the outside surface of the tube, and to a welded structure forming the high-temperature equipment manufactured by using the double tube. As one specific example of the "welded structure", there can be cited a panel (hereinafter, referred to as a "furnace wall") forming the combustion part of a power generating boiler, on which plates called fins are fillet-welded in the longitudinal direction to the outside surface of the tube.
BACKGROUND ART
[0002]
In recent years, for the power generating boiler, the new installation of "ultra super critical pressure boilers", in which the temperature and pressure of steam are raised to achieve high efficiency, has been advanced in the world. Further, the practical use of "next-generation ultra super critical pressure boilers", in which the steam temperature, being about 600°C so far, is raised to 650°C or higher, has been planned. The reason for such a trend is that energy saving, effective use of resources, and reduction in CO2 gas emission for environmental preservation have been challenges to energy problem, and have

become important industrial policies. Also, in the power generating boiler in which a fossil fuel is burnt, the reason for such a trend is that high temperature and pressure is advantageous in achieving high efficiency. [0003]
The high temperature and pressure of steam raises the temperature of tubes and pipes for transmitting steam, for example, heat-transfer tubes such as a superheater tube and a resuperheater tube, and main steam pipes during operation of such tubes and pipes. Therefore, the material used in such a harsh environment for long period of time is required to have not only high-temperature strength and high-temperature corrosion resistance but also long-term stability of metal micro-structure and excellent creep characteristics. [0004]
Accordingly, as materials for these tubes and pipes, Patent Documents 1 to 3 disclose heat resistant alloys in which the contents of Cr and Ni are increased, and moreover one kind or more of Mo and W are contained, whereby it is attempted to improve the creep rupture strength, which is a high-temperature strength. [0005]
Furthermore, to meet the exacting requirement for high-temperature strength characteristics, especially the requirement for creep rupture strength, Patent Documents 4 to 7 disclose heat resistant austenitic alloys in which, by mass percent, 28 to 38% of Cr and 35 to 60% of Ni are contained, and the precipitation of crCr phase in body-centered cubic structure consisting mainly of Cr is utilized, whereby it is attempted to further improve the creep rupture strength.
LIST OF PRIOR ART DOCUMENTS PATENT DOCUMENTS
3>

[0006]
[Patent Document l] JP60-100640A-[Patent Document 2] JP64-55352A [Patent Document 3] JP2-200756A [Patent Document 4] JP7-216511A [Patent Document 5] JP7-331390A [Patent Document 6] JP8-127848A [Patent Document 7] JP8-218140A [Patent Document 8] JP6-106237A [Patent Document 9] JP57-120002A [Patent Document 10] JP64-17806A [Patent Document 11] JP5-279801A
SUMMARY OF THE INVENTION
PROBLEMES TO BE SOLVED BY THE INVENTION
[0007]
As a material for furnace wall tube, conventionally, carbon steel or 1.25%Cr-0.5%Mo steel has been used widely. [0008]
However, due to the high temperature and pressure of steam, a furnace wall tube has also been required to have higher high-temperature strength and high-temperature corrosion resistance. [0009]
Therefore, there is a trend such that it is attempted to use 2.25 to 9%Cr heat resistant ferritic steel, in which the strength is enhanced by containing V and Nb, represented by ASME A213 Grade T91 and Grade T23, and further to use heat resistant austenitic alloys disclosed in Patent Documents 1 to 7. [0010]

As described above, the furnace wall is caused to consist of a panel by-fillet-welding fins in the longitudinal direction to the outside surface of furnace wall tube. [0011]
When fillet welding is performed, for 9%Cr heat resistant ferritic steel, preheating and/or postheating are essential from the viewpoint of preventing low-temperature weld cracks. However, preheating of the whole of long' furnace wall tube or a zone to be welded in the longitudinal direction decreases the production efficiency, and leads to an increase in cost. Further, postheating of a large-size panel that is fillet-welded also is not realistic on an industry basis from the viewpoint of cost. [0012]
For 2.25%Cr heat resistant ferritic steel, although it is said that preheating and/or postheating can be omitted, in submerged arc welding and metal active gas welding used frequently for fillet welding of furnace wall tube, low-temperature weld cracks occur in some cases. Therefore, also for the 2.25%Cr heat resistant ferritic steel, to steadily avoid the occurrence of low-temperature weld cracks, preheating and/or postheating must be performed as in the case of 9%Cr heat resistant ferritic steel, so that 2.25%Cr heat resistant ferritic steel is not realistic on an industry basis. [0013]
On the other hand, for heat resistant austenitic steel (heat resistant alloy), although excellent low-temperature weld crack resistance is provided, the thermal expansion coefficient is higher than that of heat resistant ferritic steel, so that the deformation is large. Therefore, in the case where fillet welding is performed under high restraint conditions to manufacture the panel with great dimensional accuracy, there arises a problem that hot cracking is liable to occur in a weld heat affected zone (hereinafter, referred to as a "HAZ").

Therefore, also for the heat resistant austenitic steel (heat resistant alloy), it is difficult to achieve excellent weld crack resistance during fillet welding without performing preheating or postheating. [0014]
The present invention has been made in view of the above-described situation, and accordingly an objective thereof is to provide a double tube excellent in weld crack resistance, which can be used as a material for various types of high-temperature equipment by fillet-welding plates, metal fittings, and the like (hereinafter, referred simply to as "plates" in some cases) to the outside surface of tube, and a welded structure forming the high-temperature equipment, which is manufactured by using the double tube.
MEANS FOR SOLVING THE PROBLEMS
[0015]
To solve the above-described problems, the present inventors evaluated the fillet weldability between heat resistant ferritic steel tube and plates, and the fillet weldability between heat resistant austenitic steel (heat resistant alloy) tube and plates, and conducted close examination of the occurrence behavior of weld cracks. As the result, the facts of the following items (a) and (b) were clarified. In the explanation below, for simplicity, heat resistant austenitic steel and heat resistant austenitic alloy are collectively referred simply to as "heat resistant austenitic steel" in some cases. [0016]
(a) The weld cracks during the time when a heat resistant ferritic steel tube and plates are fillet-welded to each other occur in a coarsened and hardened zone close to the fusion boundary of HAZ. Further, the occurrence of the weld cracks is remarkable in the case where fillet welding is performed by submerged arc welding, and the fracture surface shows a quasi-cleavage
t

fracture surface. From such a characteristic phenomenon, it is judged that the weld cracks are "low-temperature cracks" attributable to diffusible hydrogen. The reason why the occurrence of cracks is remarkable during the time when fillet welding is performed by applying submerged arc welding is presumed to be the increase in the amount of so-called "diffusible hydrogen" that is mixed in the weld metal and is diffused into the HAZ during welding. [0017]
(b) The weld cracks during the time when a heat resistant austenitic steel tube and plates are fillet-welded to each other occur in a coarsened crystal grain boundary close to the fusion boundary of HAZ. On the crack fracture surface, fusion traces are recognized." on the fracture surface, the concentration of P and S is recognized; and in the case where the steel contains B, the concentration of B is also recognized in addition to that of P and S. Moreover, as the wall thickness of tube is increased, the occurrence of cracks is more remarkable. From such a characteristic phenomenon, it is judged that the weld cracks are "liquation cracks" attributable to the decrease in fusing point of grain boundary caused by the grain boundary segregation of P, S and B. Further, the reason why the occurrence of cracks is more remarkable with the increase in the wall thickness of tube is presumed to be that the deformation occurring during welding becomes large, and resultantly the "restraint stress" caused by circumferential restraint increases. [0018]
From the item (a), it can be seen that, in order to suppress the low-temperature cracks occurring in the heat resistant ferritic steel tube during the time when the heat resistant ferritic steel tube and the plates are fillet-welded to each other, the measures of the following items (a-l) and (a-2) have only to be taken. [0019]
-#-3-

(a-l) To suppress the coarsening and hardening of HAZ.
(a-2) To apply a welding method in which the amount of hydrogen mixed in
during welding can be decreased as much as possible, or to promote the
discharge of hydrogen by means of preheating and/or postheating.
[0020]
However, concerning the measures of item (a-l), if the heat resistant ferritic steel tube is used as a single tube when the plates are fillet-welded to the steel tube, and welding heat input is decreased to suppress the coarsening of HAZ, the cooling rate increases and inversely the hardening is promoted. Therefore, in the case where the heat resistant ferritic steel tube is used as a single tube, it is difficult to apply the method of decreasing welding heat input to suppress the coarsening of HAZ from a practical viewpoint. [0021]
Concerning the measures of item (a-2), by the use of TIG welding, the amount of diffusible hydrogen that is mixed in the weld metal during welding can be decreased. However, for example, in the case of submerged arc welding that is used frequently for fillet welding between the furnace wall tube and the plates, it is difficult to reduce the amount of diffusible hydrogen. Also, although the hydrogen discharging effect of preheating and/or postheating is remarkable, as described before, the preheating and/or postheating are not realistic on an industry basis. [0022]
On the other hand, from the item (b), it can be seen that, in order to suppress the liquation cracks occurring in the heat resistant austenitic steel tube in the case where the heat resistant austenitic steel tube and the plates are fillet-welded to each other, the measures of the following items (b-l) and (b-2) have only to be taken. [0023]
8

(b-l) To decrease the contents of P, S and B in steel as much as possible.
(b-2) To reduce the restraint stress by means of the decrease in the wall
thickness of tube.
[0024]
However, concerning the measures of item Orl), since the treatment leads to an increase in steel production cost, more inexpensive method is desired on an industry basis. [0025]
Concerning the measures of item (b-2), from the viewpoint of assuring the strength of structure, there is a hmitation on the decrease in the wall thickness of tube. [0026]
Accordingly, to solve the above-described various problems contrary to each other, the present inventors conducted further studies. [0027]
As the result, it was clarified that the tube used for fillet welding of the plates is made of a double tube in which the inside tube is a heat resistant ferritic steel tube and the outside tube is a heat resistant austenitic steel tube, and the fusion depth of fillet weld zone is made proper, whereby the weld cracks can be prevented. [0028]
The following items (c) to (e) are new findings obtained by the present inventors. [0029]
(c) If the wall thickness of outside tube satisfies a specific condition, specifically satisfies Formula of
wall thickness (mm) of outside tube > fusion depth (mm) in fillet weld + 0.3 mm,

high-temperature strength. [0035]
Further, Patent Document 11 discloses a double tube in which a carbon steel is used for the inside tube and an austenitic Cr-Ni-Mo-Fe based alloy is used for the outside tube, whereby it is attempted to improve both of the thermal fatigue resistance and the corrosion resistance. [0036]
However, all of Patent Documents 8 to 11 do not at all describe the problems to be solved by the present invention, and as a matter of course, do not describe the measures against these problems. Therefore, even if fillet welding is performed between the double tubes disclosed in Patent Documents 8 to 11 and the plates, weld cracks cannot by any possibility be prevented. [0037]
The present invention was accomplished on the basis of the above-described findings, and the gists thereof are a double tube for welded structure and a welded structure described below. [0038]
(l) A double tube for welded structure that comprises an inside tube of a heat resistant ferritic steel having chemical composition 1 described below and an outside tube of a heat resistant austenitic steel having chemical composition 2 described below, and is used to produce a welded structure by means of forming of a fillet weld zone satisfying Formula (l) described below on the outside surface thereof, wherein the wall thicknesses (mm) of the outside tube and inside tube satisfy Formula (2) described below.
wall thickness of outside tube > fusion depth in fillet weld + 0.3 mm
... (1)
wall thickness of outside tube / (wall thickness of outside tube + wall
thickness of inside tube) < 0.4 ... (2)
vKT-W

Chemical composition V-
A chemical composition comprising, by mass percent, C- 0.01 to 0.1%, Si: 0.01 to 0.5%, Mn: 0.01 to 1%, P: 0.03% or less, S: 0.01% or less, one or more kinds of Ni and Cu: 0.01 to 1% in total, Cr: 0.5 to 3.5%, one or more kinds of Mo and W: 0.01 to 3% in total, V: 0.01 to 0.5%, Nb: 0.005 to 0.1%, Ti: 0.0005 to 0.1%, B: 0.0001 to 0.02%, Al: 0.05% or less, N: 0.0005 to 0.05%, and O: 0.01% or less, the balance being Fe and impurities. Chemical composition 2'
A chemical composition comprising, by mass percent, C: 0.1% or less, Si: 0.01 to 0.8%, Mn: 0.01 to 2%, P: 0.04% or less, S: 0.01% or less, Ni: 5 to 50%, Cr: 15 to 35%, Al: 0.05% or less, N 0.001 to 0.25%, and O: 0.01% or less, the balance being Fe and impurities. [0039]
(2) The double tube for welded structure described in item (l), wherein
the chemical composition 1 contains, by mass percent, one or more kinds of
elements selected from Ca: 0.05% or less, Mg: 0.05% or less, and REM: 0.1% or
less in lieu of a part of Fe.
[0040]
(3) The double tube for welded structure described in item (l) or (2),
wherein the chemical composition 2 contains, by mass percent, one or more
kinds of elements shown in the first group to fifth group described below in
lieu of a part of Fe.
First group: one or more kinds selected from Mo: 10% or less and W: 10% or less
Second group: one or more kinds selected from Cu: 5% or less and Co: 5% or less
Third group: one or more kinds selected from Nb: 1% or less, Ti: 1% 0r less, and V": 1% or less
|2-

Fourth group: B: 0.02% or less .
Fifth group: one or more kinds selected from Ca: 0.05% or less, Mg: 0.05% or less, and REM: 0.1% or less [0041]
(4) A welded structure using the double tube described in any one of
items (1) to (3).
[0042]
(5) The welded structure described in item (4), wherein the welded
structure is used for a furnace wall.
ADVANTAGEOUS EFFECTS OF THE INVENTION
[0043]
The double tube for welded structure of the present invention is excellent in weld crack resistance. Therefore, if the double tube of the present invention is used, a welded structure forming various types of high-temperature equipment can be manufactured by fillet-welding plates, metal fittings, and the like to the outside surface of the tube by means of ordinary submerged arc welding without performing treatment such as preheating, postheating, and cleaning of steel.
BRIEF DESCRIPTION OF THE DRAWINGS
[0044]
[Figure l] Figure 1 is a schematic view for explaining a restraint welded test
body simulating the fillet weld of furnace wall tube, which is produced in
Examples.
[Figure 2] Figure 2 is a schematic view for explaining a method for measuring
a fusion depth in fillet weld.
13

MODE FOR CARRYING OUT THE INVENTION
[0045]
The requisites for the present invention will now be described in detail. In the following description, the symbol "%" for the content of each element means "% by mass". [0046]
(A) Chemical composition 1 (chemical composition of inside tube (heat resistant ferritic steel))' C: 0.01 to 0.1%
C (carbon) is an element effective in enhancing the hardenability and steadily obtaining martensitic and/or bainitic structures. Further, C forms carbides, and contributes to the assurance of creep strength at high temperatures. In order to achieve the above-described effects, 0.01% or more of C must be contained. However, if C is contained in large amounts, the HAZ is hardened remarkably, and the lowtemperature crack susceptibility is enhanced extremely. Therefore, an upper limit is placed, and the content of C is set to 0.01 to 0.1%. The lower limit of the C content is preferably 0.015%, further preferably 0.02%. Also, the upper limit of the C content is preferably 0.09%, further preferably 0.08%. [0047]
Si: 0.01 to 0.5%
Si (silicon) has a deoxidizing function, and also is an element effective in improving the corrosion resistance and oxidation resistance at high temperatures. In order to achieve these effects, 0.01% or more of Si must be contained. However, an excessive content of Si leads to a decrease in creep ductility and toughness. Therefore, an upper limit is placed, and the content of Si is set to 0.01 to 0.5%. The lower limit of the Si content is preferably 0.05%, further preferably 0.1%. Also, the upper limit of the Si content is

preferably 0.45%, further preferably 0.4%. [0048]
Mn: 0.01 to 1%
Mn (manganese) has a deoxidizing function like Si. Manganese is an element effective in enhancing the hardenability, and in steadily obtaining martensitic and/or bainitic structures. In order to achieve these effects, 0.01% or more of Mn must be contained. However, if Mn is contained excessively, creep embrittlement and a decrease in toughness are produced. Therefore, an upper limit is placed, and the content of Mn is set to 0.01 to 1%. The lower limit of the Mn content is preferably 0.05%, further preferably 0.1%. Also, the upper limit of the Mn content is preferably 0.9%, further preferably 0.8%. [0049]
P: 0.03% or less
P (phosphorus) is an element contained as an impurity, and decreases the creep ductility together with S. Therefore, an upper limit is placed, and the content of P is set to 0.03% or less. The upper limit of the P content is preferably 0.028%, further preferably 0.025%. Although a lower limit is not especially placed on the P content, an extreme decrease in the P content leads to an increase in steel production cost. Therefore, in the case where importance is attached to cost, the lower limit of the P content is preferably 0.0005%, further preferably 0.001%. [0050]
S: 0.01% or less
S (sulfur) is an element contained as an impurity like P, and decreases the creep ductility. Therefore, an upper limit is placed, and the content of S is set to 0.01% or less. The upper limit of the S content is preferably 0.008%, further preferably 0.005%. Although a lower limit is not especially placed on

the S content, an extreme decrease in the S content leads to an increase in steel production cost. Therefore, in the case where importance is attached to cost, the lower limit of the S content is preferably 0.0001%, further preferably 0.0003%. [0051]
One or more kinds of Ni and Cu: 0.01 to 1% in total
Both of Ni (nickel) and Cu (copper) enhance the hardenability, and are elements effective in obtaining martensitic and/or bainitic structures. The above-described effects are achieved by containing 0.01% or more in total of one or more kinds of Ni and Cu. However, if more than 1% in total of one or more kinds of Ni and Cu are contained, the creep ductility decreases. Therefore, the contents of one or more kinds of Ni and Cu are set to 0.01 to 1%. The contents of one or more kinds of Ni and Cu are, in total, preferably 0.02% or more, further preferably 0.03% or more. Also, the contents of one or more kinds of Ni and Cu are, in total, preferably 0.9% or less, further preferably 0.8% or less. [0052]
Nickel and copper need not necessarily be contained compositely. If Ni is contained singly, the content of Ni has only to be 0.01 to 1%, and if Cu is contained singly, the content of Cu has only to be 0.01 to 1%. [0053]
Cr: 0.5 to 3.5%
Cr (chromium) is an element essential in assuring the oxidation resistance and high-temperature corrosion resistance in a steel for high-temperature use, and in steadily obtaining the martensitic and/or bainitic structures of matrix. In order to achieve these effects, 0.5% or more of Cr must be contained. However, an excessive content of Cr decreases the stability of carbides on account of the formation of much Cr carbides, and leads
v6

to a decrease in creep strength and toughness. Therefore, an upper limit is placed, and the content of Cr is set to 0.5 to 3.5%. The lower limit of the Cr content is preferably 0.8%, further preferably 1%. Also, the upper limit of the Cr content is preferably 3.2%, further preferably 3.0%. [0054]
One or more kinds of Mo and W: 0.01 to 3% in total
Both of Mo (molybdenum) and W (tungsten) are elements that solid-solution strengthen the matrix, and contribute to the increase in creep strength. In order to achieve these effects, 0.01% or more in total of one or more kinds of Mo and W must be contained. However, if more than 3% in total of one or more kinds of Mo and W are contained, coarse intermetallic compounds and carbides are formed, and thereby the toughness is decreased. Therefore, the contents of one or more kinds of Mo and W are set to 0.01 to 3% in total. The contents of one or more kinds of Mo and W are, in total, preferably 0.03% or more, further preferably 0.05% or more. Also, the contents of one or more kinds of Mo and W are, in total, preferably 2.8% or less, further preferably 2.5% or less. [0055]
Molybdenum and tungsten need not necessarily be contained compositely. If Mo is contained singly, the content of Mo has only to be 0.01 to 3%, and if W is contained singly, the content of W has only to be 0.01 to 3%. [0056]
V: 0.01 to 0.5%
V (vanadium) is an element that forms fine carbo-nitrides within grains, and contributes greatly to the increase in creep strength. In order to achieve this effect, 0.01% or more of V must be contained. However, if V is contained excessively, the growth rate of carbo-nitrides increases, and thereby the dispersion strengthening effect of carbo-nitrides is lost at an early stage, and

also the toughness is decreased. Therefore, an upper limit is placed, and the content of V is set to 0.01 to 0.5%. The lower limit of the V content is preferably 0.03%, further preferably 0.05%. Also, the upper limit of the V content is preferably 0.45%, further preferably 0.4%. [0057]
Nb: 0.005 to 0.1%
Nb (niobium) is an element that forms, like V, fine carbo-nitrides which are stable up to high temperatures within grains, and contributes greatly to the increase in creep strength. In order to achieve this effect, 0.005% or more of Nb must be contained. However, if Nb is contained excessively, the growth rate of carbo-nitrides increases, and thereby the dispersion strengthening effect of carbo-nitrides is lost at an early stage, and also the toughness is decreased. Therefore, an upper limit is placed, and the content of Nb is set to 0.005 to 0.1%. The lower limit of the Nb content is preferably 0.008%, further preferably 0.01%. Also, the upper limit of the Nb content is preferably 0.09%, further preferably 0.08%. [0058]
Ti: 0.0005 to 0.1%
Ti (titanium) forms fine nitrides which are stable up to high temperatures, suppresses the coarsening of crystal grains in the HAZ by means of the pinning effect, and has an effect of preventing low-temperature cracks indirectly. In order to achieve these effects, 0.0005% or more of Ti must be contained. However, if Ti is contained excessively, the nitrides become coarse, the pinning effect is lost, and also the toughness decreases. Therefore, an upper limit is placed, and the content of Ti is set to 0.0005 to 0.1%. The lower limit of the Ti content is preferably 0.0008%, further preferably 0.001%. Also, the upper limit of the Ti content is preferably 0.09%, further preferably 0.08%.
lg

[0059]
B: 0.0001 to 0.02%
B (boron) enhances the hardenability of steel, stabilizes the martensitic and/or bainitic structures, and contributes to the high-temperature strength. In order to achieve these effects, 0.0001% or more of B must be contained. However, if B is contained in large amounts, the HAZ is hardened remarkably, and the low-temperature crack susceptibility is enhanced. Therefore, an upper limit is placed, and the content of B is set to 0.0001 to 0.02%. The lower limit of the B content is preferably 0.0005%, further preferably 0.001%. Also, the upper limit of the B content is preferably 0.018%, further preferably 0.015%. [0060]
Al: 0.05% or less
Al (aluminum) has a deoxidizing effect, but if Al is contained excessively, the creep ductility and toughness decrease. Therefore, an upper limit is placed, and the content of Al is set to 0.05% or less. The upper limit of the Al content is preferably 0.045%, further preferably 0.04%. Although a lower limit is not especially placed on the Al content, if the Al content is decreased excessively, the deoxidizing effect is not achieved sufficiently and therefore the cleanliness of steel decreases, and also the production cost increases. Therefore, the lower limit of the Al content is preferably 0.0005%, further preferably 0.001%. [0061]
N: 0.0005 to 0.05%
N (nitrogen) is an element effective in combining with V, Nb or Ti to form fine nitrides and assuring the creep strength. In order to achieve this effect, 0.0005% or more of N must be contained. However, if N is contained excessively, the matrix is embrittled, and coarse nitrides are precipitated, so

that the toughness is decreased. Therefore, an upper limit is placed, and the content of N is set to 0.0005 to 0.05%. The lower limit of the N content is preferably 0.0008%, further preferably 0.001%. Also, the upper limit of the N content is preferably 0.045%, further preferably 0.04%. [0062]
O: 0.01% or less
O (oxygen) is an element existing as an impurity. If O is contained in large amounts, large amounts of oxides are formed, and thereby the workability and ductility are deteriorated. Therefore, an upper limit is placed, and the content of O is set to 0.01% or less. The upper limit of the O content is preferably 0.009%, further preferably 0.008%. A lower limit is not especially placed on the O content, an extreme decrease in the O content leads to an increase in steel production cost. Therefore, in the case where importance is attached to cost, the lower limit of the O content is preferably 0.0005%, further preferably 0.001%. [0063]
One feature of "chemical composition 1" that the inside tube (heat resistant ferritic steel) of the double tube for welded structure of the present invention has consists of the above-described elements, the balance being Fe and impurities. [0064]
The term "impurities" means elements mixed in from ore and scrap used as a raw material, the production environment, and the like when steel is produced on an industry basis. [0065]
Another feature of "chemical composition 1" that the inside tube (heat resistant ferritic steel) of the double tube for welded structure of the present invention has contains one or more kinds of elements selected from Ca, Mg and
2o

REM in lieu of a part of Fe. [0066]
In the following, explanation is given of the operational advantages of Ca, Mg and REM, which are optional elements, and the reasons why the contents of these elements are restricted. [0067]
Ca: 0.05% or less
Ca (calcium) may be contained as necessary because it improves the hot workability of steel. However, if Ca is contained excessively, Ca combines with O and decreases the cleanliness remarkably, so that the hot workability is rather impaired. Therefore, an upper limit is placed on the content of Ca, if being contained, and the content of Ca is set to 0.05% or less. The content of Ca, if being contained, is preferably 0.03% or less. [0068]
On the other hand, in order to steadily achieve the above-described effect of Ca, the content of Ca, if being contained, is preferably set to 0.0005% or more. [0069]
Mg-' 0.05% or less
Mg (magnesium) may be contained as necessary because it improves the hot workability of steel like Ca. However, if Mg is contained excessively, Mg combines with O and decreases the cleanliness remarkably, so that the hot workability is rather impaired. Therefore, an upper limit is placed on the content of Mg, if being contained, and the content of Mg is set to 0.05% or less. The content of Mg, if being contained, is preferably 0.03% or less. [0070]
On the other hand, in order to steadily achieve the above-described effect of Mg, the content of Mg, if being contained, is preferably set to 0.0005% or
v2r-

placed on the Al content,' however, if the Al content is decreased excessively, the deoxidizing effect cannot be achieved sufficiently, so that the cleanliness of steel decreases, and also the production cost rises. Therefore, the lower limit of the Al content is preferably 0.0005%, further preferably 0.001%. [0084]
N: 0.001 to 0.25%
N (nitrogen) is an element effective in stabilizing austenite phase. In order to achieve this effect, 0.001% or more of N must be contained. However, if N is contained excessively, large amounts of nitrides are precipitated, and thereby the ductility is decreased. Therefore, an upper limit is placed, and the content of N is set to 0.001 to 0.25%. The lower limit of the N content is preferably 0.002%, further preferably 0.003%. Also, the upper limit of the N content is preferably 0.24%, further preferably 0.23%. [0085]
O: 0.01% or less
O (oxygen) is an element existing as an impurity. If O is contained in large amounts, large amounts of oxides are formed, and thereby the workability and ductility are deteriorated. Therefore, an upper limit is placed, and the content of O is set to 0.01% or less. The upper limit of the O content is preferably 0.009%, further preferably 0.008%. A lower limit is not especially placed on the O content, an extreme decrease in the O content leads to an increase in steel production cost. Therefore, in the case where importance is attached to cost, the lower limit of the O content is preferably 0.0005%, further preferably 0.001%. [0086]
One feature of "chemical composition 2" that the outside tube (heat resistant austenitic steel) of the double tube for welded structure of the present invention has consists of the above-described elements, the balance
-3&-2U

being Fe and impurities. As already described, the term "impurities" means elements mixed in from ore and scrap used as a raw material, the production environment, and the like when steel is produced on an industry basis. [0087]
Another feature of "chemical composition 2" that the outside tube (heat resistant austenitic steel) of the double tube for welded structure of the present invention has contains one or more kinds of elements selected from Mo, W, Cu, Co, Nb, Ti, V, B, Ca, Mg and REM in lieu of a part of Fe. [0088]
In the following, explanation is given of the operational advantages of the above-described elements ranging from Mo to REM, which are optional elements, and the reasons why the contents of these elements are restricted, on a group basis. [0089]
First group: one or more kinds selected from Mo: 10% or less and W: 10% or less
Mo-" 10% or less
Mo (molybdenum) dissolves in matrix, and contributes greatly to the increase in creep strength at high temperatures. Molybdenum also has an effect of increasing the corrosion resistance. Therefore, Mo may be contained as necessary. However, even if the Mo content is higher than 10%, the above-described effects are saturated, and also intermetallic compounds are formed, so that the characteristics are rather decreased. Therefore, the content of Mo, if being contained, is set to 10% or less. The content of Mo, if being contained, is preferably 9% or less, further preferably 8% or less. [0090]
On the other hand, in order to steadily achieve the above-described effects of Mo, the content of Mo, if being contained, is preferably set to 0.01%
-3&-

or more, further preferably set to 0.05% or more. [0091]
W: 10% or less
W (tungsten) may be contained as necessary because it dissolves in matrix, and contributes greatly to the increase in creep strength at high temperatures like Mo. However, even if the content of W is higher than 10%, the above-described effect is saturated, and also intermetallic compounds are formed, so that the ductility is decreased. Therefore, the content of W, if being contained, is set to 10% or less. The content of W, if being contained, is preferably 9.8% or less, further preferably 9% or less. [0092]
On the other hand, in order to steadily achieve the above-described effect of W, the content of W, if being contained, is preferably set to 0.01% or more, further preferably set to 0.05% or more. [0093]
To improve the creep strength at high temperatures, Mo and W, which are elements in the first group, can be contained so that only one kind of either of these elements is contained or two kinds of these elements are contained compositely. The total content in the case where these elements are contained compositely may be 20%; however, the total content is preferably 17% or less. [0094]
Second group: one or more kinds selected from Cu: 5% or less and Co: 5% or less
Cu: 5% or less
Cu (copper) may be contained as necessary because it is an austenite forming element like Ni, and enhances the stability of austenite phase. However, if Cu is contained excessively, the hot workability decreases.

Therefore, an upper limit is placed on the content of Cu, if being contained, and the content of Cu is set to 5% or less. The content of Cu, if being contained, is preferably 4% or less, further preferably 3.5% or less. [0095]
On the other hand, in order to steadily achieve the above-described effect of Cu, the content of Cu, if being contained, is preferably set to 0.01% or more, further preferably set to 0.05% or more. . [0096]
Co: 5% or less
Co (cobalt) may be contained as necessary because it is an austenite forming element like Ni and Cu, and enhances the stability of austenite phase. However, since Co is an extremely expensive element, the excessively high content of Co leads to a significant increase in cost. Therefore, an upper limit is placed on the content of Co, if being contained, and the content of Co is set to 5% or less. The content of Co, if being contained, is preferably 4% or less, further preferably 3.5% or less. [0097]
On the other hand, in order to steadily achieve the above-described effect of Co, the content of Co, if being contained, is preferably set to 0.01% or more, further preferably set to 0.05% or more. [0098]
To enhance the stability of austenite phase, Cu and Co, which are elements in the second group, can be contained so that only one kind of either of these elements is contained or two kinds of these elements are contained compositely. The total content in the case where these elements are contained compositely may be 10%; however, the total content is preferably 7% or less. [0099]
-J28--

Third group: one or more kinds selected from Nb: 1% or less, Ti: 1% or less, and V-' 1% or less
Nb: 1% or less
Nb (niobium) may be contained as necessary because it combines with C to form fine carbides and further combines with C and N to form fine carbo-nitrides, and contributes to the increase in creep strength. However, if Nb is contained excessively, coarse carbides and carbo-nitrides are precipitated in large amounts, and thereby the creep ductility is decreased. Therefore, an upper limit is placed on the content of Nb, if being contained, and the content of Nb is set to 1% or less. The content of Nb, if being contained, is preferably 0.9% or less, further preferably 0.8% or less. [0100]
On the other hand, in order to steadily achieve the above-described effect of Nb, the content of Nb, if being contained, is preferably set to 0.01% or more, further preferably set to 0.05% or more. [0101]
Ti: 1% or less
Ti (titanium) may be contained as necessary because it forms carbo-nitrides like Nb, and contributes to the increase in creep strength. However, if Ti is contained excessively, carbo-nitrides are precipitated in large amounts, and thereby the creep ductility is decreased. Therefore, an upper limit is placed on the content of Ti, if being contained, and the content of Ti is set to 1% or less. The content of Ti, if being contained, is preferably 0.9% or less, further preferably 0.8% or less. [0102]
On the other hand, in order to steadily achieve the above-described effect of Ti, the content of Ti, if being contained, is preferably set to 0.01% or more, further preferably set to 0.05% or more.
3°

[0103]
V": 1% or less
V (vanadium) may be contained as necessary because, like Nb and Ti, V forms carbo-nitrides, and contributes to the increase in creep strength. However, if V is contained excessively, carbo-nitrides are precipitated in large amounts, and thereby the creep ductility is decreased. Therefore, an upper limit is placed on the content of V, if being contained, and the content of V is set to 1% or less. The content of V, if being contained, is preferably 0.9% or less, further preferably 0.8% or less. [0104]
On the other hand, in order to steadily achieve the above-described effect of V, the content of V, if being contained, is preferably set to 0.01% or more, further preferably set to 0.05% or more. [0105]
To improve the creep strength, Nb, Ti and V, which are elements in the third group, can be contained so that only one kind of either of these elements is contained or two or more kinds of these elements are contained compositely. The total content in the case where these elements are contained compositely may be 3%; however, the total content is preferably 2.4% or less. [0106] Fourth group: B: 0.02% or less
B (boron) may be contained as necessary because it segregates at grain boundaries and strengthens the grain boundaries, and also finely disperses grain boundary carbides, whereby improving the creep strength. However, if B is contained in large amounts, B segregates in large amounts in the high-temperature HAZ near the fusion boundary due to weld thermal cycle during welding, so that the fusing point of grain boundary is decreased, and the liquation crack susceptibility is enhanced. Therefore, an upper limit is placed
v3ff-31

on the content of B, if being contained, and the content of B is set to 0.02% or less. The content of B, if being contained, is preferably 0.018% or less, further preferably 0.015% or less. [0107]
On the other hand, in order to steadily achieve the above-described effects of B, the content of B, if being contained, is preferably set to 0.0005% or more, further preferably set to 0.001% or more. [0108]
Fifth group: one or more kinds selected from Ca: 0.05% or less, Mg: 0.05% or less, and REM: 0.1% or less
Ca: 0.05% or less
Ca (calcium) may be contained as necessary because it improves the hot workability of steel. However, if Ca is contained excessively, Ca combines with O and decreases the cleanliness remarkably, so that the hot workability is rather impaired. Therefore, an upper limit is placed on the content of Ca, if being contained, and the content of Ca is set to 0.05% or less. 'The content of Ca, if being contained, is preferably 0.03% or less. [0109]
On the other hand, in order to steadily achieve the above-de scribed effect of Ca, the content of Ca, if being contained, is preferably set to 0.0005% or more. [0110]
Mg: 0.05% or less
Mg (magnesium) may be contained as necessary because it improves the hot workability of steel like Ca. However, if Mg is contained excessively, Mg combines with O and decreases the cleanliness remarkably, so that the hot workability is rather impaired. Therefore, an upper limit is placed on the content of Mg, if being contained, and the content of Mg is set to 0.05% or less.

The content of Mg, if being contained, is preferably 0.03% or less. [0111]
On the other hand, in order to steadily achieve the above-described effect of Mg, the content of Mg, if being contained, is preferably set to 0.0005% or more. [0112]
REM: 0.1% or less
REM (rare-earth metal) may be contained as necessary because it has a strong affinity for S and improves the hot workability of steel. However, if REM is contained excessively, REM combines with O and decreases the cleanliness remarkably, so that the hot workability is rather impaired. Therefore, an upper limit is placed on the content of REM, if being contained, and the content of REM is set to 0.1% or less. The content of REM, if being contained, is preferably 0.08% or less. As described already, the "REM" 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. [0113]
On the other hand, in order to steadily achieve the above-de scribed effect of REM, the content of REM, if being contained, is preferably set to 0.0005% or more. [0114]
To improve the hot workability, Ca, Mg and REM, which are elements in the fifth group, can be contained so that only one kind of either of these elements is contained or two or more kinds of these elements are contained compositely. The total content in the case where these elements are contained compositely may be 0.2%; however, the total content is preferably 0.14% or less.
33

[0115]
(C) Relationship between wall thickness of outside tube and fusion depth in fillet weld:
When the fusion depth in fillet weld reaches the inside tube of double tube, a HAZ that has been coarsened and hardened by being exposed to a high temperature just under the fusing point is formed in the heat resistant ferritic steel forming the inside tube. Hydrogen that has been mixed in from the weld metal during welding diffuses and intrudes into the HAZ, whereby low-temperature cracks are produced in the HAZ in the inside tube. [0116]
However, if the wall thickness (mm) of the outside tube of the double tube satisfies Formula of
wall thickness of outside tube > fusion depth in fillet weld + 0.3 mm
... (1) in the relationship with the fusion depth (mm) of fillet weld zone, the weld penetration during welding stops on the outside tube side, so that the heat resistant ferritic steel of the inside tube can be prevented from being exposed to a high temperature just under the fusing point. Therefore, the coarsening and hardening of the HAZ in the inside tube are suppressed, and moreover, the diffusion of hydrogen from weld metal to the HAZ in the inside tube is also suppressed, so that low-temperature cracks can be prevented from occurring in the HAZ in the inside tube. [0117]
To steadily prevent the heat resistant ferritic steel of the inside tube from being exposed to a high temperature just under the fusing point, the wall thickness of outside tube is preferably set to "fusion depth in fillet weld + 0.5 mm" or larger. [0118]
v33--
3H

(D) Relationship between wall thickness of outside tube and "wall thickness of outside tube + wall thickness of inside tube", that is, total wall thickness of double tube:
In the case where the wall thickness of the outside tube of the double tube is large, the deformation occurring during fillet welding is large, the "restraint stress" caused by the circumferential restraint of the deformation increases, and liquation cracks occur in the heat resistant austenitic steel forming the outside tube. [0119]
However, if the wall thickness of outside tube and "the wall thickness of outside tube + the wall thickness of inside tube", that is, the total wall thickness of the double tube satisfy Formula of
wall thickness of outside tube / (wall thickness of outside tube + wall thickness of inside tube) < 0.4 ... (2),
the "restraint stress" is reduced, so that the liquation cracks in the outside tube can be prevented from occurring. [0120]
However, if the "wall thickness of outside tube / (wall thickness of outside tube + wall thickness of inside tube)" is too little, it is difficult to manufacture the double tube. Therefore, the "wall thickness of outside tube / (wall thickness of outside tube + wall thickness of inside tube)" is preferably 0.1 or more. [0121]
The double tube in accordance with the present invention is a closely-adhering double tube in which the outside tube and the inside tube are metallurgically bonded to each other, and is sometimes referred to as a "clad tube". [0122]
1$

One example of the method for manufacturing the double tube is as described below. A material that has been assembled by inserting a billet of heat resistant ferritic steel forming the inside tube into a hollow billet of heat resistant austenitic steel forming the outside tube is subjected to a so-called "hot tube-making process" such as a hot-extrusion process or a hot rolling process, whereby a double tube is produced by integrating the outside tube and the inside tube with each other. Usually, to assure the cleanliness of bonding surface, the assembling of the billets is performed in a vacuum or in an inert gas atmosphere. The double tube produced by the hot tube-making process is subjected to cold working such as rolling or drawing, and further subjected to heat treatment to complete a double tube having a required shape. Also, the double tube in accordance with the present invention may be a double tube that is lengthened by butt-welding the double tubes each manufactured by the above-described method. [0123]
The length of the fillet weld zone extending in the longitudinal direction on the outside surface of double tube may be the overall length or a part of the double tube. [0124]
Furthermore, the material of a part to be welded to the outside surface of double tube by fillet welding may be selected from carbon steel, heat resistant ferritic steel, heat resistant austenitic steel, and the like according the necessary function. [0125]
In the following, the present invention is explained more specifically by using examples. However, the present invention is not limited to the examples.
3*>

EXAMPLES [0126]
By using heat resistant ferritic steels 1 to 3 and heat resistant austenitic steels 4 to 6 each having the chemical composition given in Table 1, double tubes Tl to T7 each having an outside diameter of 63 mm, each of which consists of the inside tube and the outside tube given in Table 2, were manufactured by the hot tube-making process. [0127] [Table l]
1^

• 8 8 1 8
2 3 2 5 • « ■ S
o - § - 3
8§ 8 8
O P Q °
o 5 o 3
2 ig u io n n
_ Q O Q O © O
O o o 3 S 5 S d o o d o o
o P- IO e- ^ M
28388122 d d d d d d
B 0.003 0.004 0.003
0.001
2 —« g? eg 10 co co
5 8 8 8 8 8 8
o o d d d d
1 #388. .3
^ c$ o o d
: Fe and V
0.21 0.20 0.22
0.05
Balance Ti 0.015 0.077 0.008
0.020
—< (0 W 1.66 1.68 1.61
0.04
Tab 1 composition (n Mo 0.27
0.32
0.97 1.01

£ 3 S S S § °
Chemic£ *■■■■!■
Cu 0.03
0.02
0.01
u n io ifl ™ o w
w 8 8 8 i § 1
d d d d d d
io -< n io ^ cq
Du o o o 6 o o
c5 d Q d d d
c W ^ H IM io i* ±3 CM CN fusion depth in fillet weld + 0.3 mm
... (1)
wall thickness of outside tube / (wall thickness of outside' tube + wall
thickness of inside tube) < 0.4 ... (2)
Chemical composition V-
A chemical composition comprising, by mass percent, C: 0.01 to 0.1%, Si: 0.01 to 0.5%, Mn: 0.01 to 1%, P: 0.03% or less, S- 0.01% or less, one or more kinds of Ni and Cu-' 0.01 to 1% in total, Cr-" 0.5 to 3.5%, one or more kinds of Mo and W: 0.01 to 3% in total, V: 0.01 to 0.5%, Nb: 0.005 to 0.1%, Ti: 0.0005 to 0.1%, B: 0.0001 to 0.02%, Al: 0.05% or less, N 0.0005 to 0.05%, and O: 0.01% or less, the balance being Fe and impurities. Chemical composition 2-
A chemical composition comprising, by mass percent, C: 0.1% or less, Si: 0.01 to 0.8%, Mn-- 0.01 to 2%, P: 0.04% or less, S: 0.01% or less, Ni: 5 to 50%, Cr: 15 to 35%, Al-- 0.05% or less, N-* 0.001 to 0.25%, and O: 0.01% or less, the balance being Fe and impurities.
[Claim 2]
42.

The double tube for welded structure according to claim 1, wherein the chemical composition 1 contains, by mass percent, one or more kinds of elements selected from Ca: 0.05% or less, Mg: 0.05% or less, and REM: 0.1% or less in lieu of a part of Fe.
[Claim 3]
The double tube for welded structure according to claim 1 or 2, wherein the chemical composition 2 contains, by mass percent, one or more kinds of elements shown in the first group to fifth group described below in lieu of a part of Fe.
First group: one or more kinds selected from Mo: 10% or less and W: 10% or less
Second group: one or more kinds selected from Cu: 5% or less and Co: 5% or less
Third group: one or more kinds selected from Nb: 1% or less, Ti: 1% or less, and V: 1% or less
Fourth group: B: 0.02% or less
Fifth group: one or more kinds selected from Ca: 0.05% or less, Mg: 0.05% or less, and REM: 0.1% or less
[Claim 4]
A welded structure using the double tube according to any one of claims 1 to 3.
[Claim 5]
The welded structure according to claim 4, wherein the welded structure is used for a furnace wall.
Dated this 19th day of August, 2014.
Nippon Steel & Sumitomo Metal Corporation
(Dev Robinson) of Amarchand & Mangaldas & SureshA. Shroff & Co. Attorneys for the Applicant