CN102892913B - Welded joint having excellent corrosion resistance, and crude oil tank - Google Patents

Welded joint having excellent corrosion resistance, and crude oil tank Download PDF

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Publication number
CN102892913B
CN102892913B CN201180024222.1A CN201180024222A CN102892913B CN 102892913 B CN102892913 B CN 102892913B CN 201180024222 A CN201180024222 A CN 201180024222A CN 102892913 B CN102892913 B CN 102892913B
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quality
steel
welding
corrosion
welding joint
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CN102892913A (en
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钓之郎
小森务
角博幸
大井健次
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JFE Steel Corp
JFE Engineering Corp
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NKK Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3053—Fe as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3053—Fe as the principal constituent
    • B23K35/3073—Fe as the principal constituent with Mn as next major constituent
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Butt Welding And Welding Of Specific Article (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Arc Welding In General (AREA)

Abstract

Disclosed are: a welded joint which exhibits excellent localized corrosion resistance in a crude oil tank; and a crude oil tank equipped with the welded joint. Specifically disclosed is a crude oil tank equipped with a welded joint, wherein the welded joint is produced by welding steel materials to each other, wherein each of the steel materials comprises (in mass%) 0.03 to 0.16% of C, 0.05 to 1.50% of Si, 0.1 to 2.0% of Mn, 0.025% or less of P, 0.010% or less of S, 0.005 to 0.10% of Al, 0.008% or less of N, more than 0.1% and not more than 0.5% of Cr, 0.03 to 0.4% of Cu, at least one element selected from W (0.01 to 1.0%), Mo (0.01 to 0.5%), Sn (0.001 to 0.2%) and Sb (0.001 to 0.4%), a welded metal produced by the welding contains Cu in an amount of 0.05 to 0.5 mass% and Mo and W in the total amount of 0.03 to 1.0 mass%, and wherein the difference between the corrosion potential of each of the steel materials and the corrosion potential of the welded metal is 60 mV or less.

Description

The welding joint of excellent corrosion resistance and petroleum tank
Technical field
The oil groove (oil tank) of the crude oil carrier (crude oil tanker) that the present invention relates to weld steel and form, for delivery of or the tank of storage crude oil (crude oil) (following, be generically and collectively referred to as " petroleum tank (crude oil tank) "), in particular to having alleviated the welding joint (weld joint) of the local corrosion (local corrosion) (spot corrosion (pitting corrosion)) in above-mentioned petroleum tank and having there is the petroleum tank of this welding joint.Should illustrate, the steel that use in petroleum tank of the present invention comprise Plate Steel (thick steel plate), steel sheet (thin steel sheet) and shaped steel (shaped steel).
Background technology
In the past; think the effect of corrosion inhibition (corrosion suppression action) by crude oil itself of the steel that use in the base plate (bottom plate) of the petroleum tank of oil carrier etc., in the effect of corrosion inhibition of the protective coating from crude oil (protective coating) (oil reservoir (oil coating)) of petroleum tank internal surface formation, thereby can not produce corrosion.But, by nearest research, find out and in the steel of tank bottom, produce bowl type (bowl-shaped) local corrosion (spot corrosion).As the reason that this local corrosion occurs, can enumerate following several etc.:
(1) take the existence that salt high density ground that sodium-chlor (sodium chloride) is representative dissolves the agglutinating water (brine, salt solution) forming,
(2) because the oil reservoir due to excessively cleaning departs from,
(3) high density of the sulfide containing in crude oil (sulfide),
(4) dissolve in dew and enclosed the O for the explosion-proof rare gas element of petroleum tank (inert gases) 2, CO 2, SO 2deng high density.
In fact, when the harbour of real ship checks, analyze and be trapped in the result of the water in petroleum tank, chloride ion and the sulfate ion of high density detected.
Yet the effective means that prevents whole corrosion as described above and local corrosion is steel surface to be implemented to recoat cover (heavy coating), and steel are cut off from corrosive environment (corrosion environment).But with regard to the coating operation of petroleum tank, the area of its coating is huge, in addition, deteriorated owing to filming, cause just need to again applying 1 time for approximately 10 years, so produce huge expense in checking, applying.And then the impaired part of filming of covering through recoat is noted on the contrary can corrosion promoting under the corrosive environment of petroleum tank.
For etching problem as described above, proposed somely improve the erosion resistance of steel itself and improve the technology of the erosion resistance of petroleum tank under corrosive environment.Following technology is for example disclosed in patent documentation 1: will be in quality %, contain that C:0.001～0.2%, Si:0.01～2.5%, Mn:0.1～2%, P:0.03% are following, S:0.02% is following, Cu:0.01～1.5%, Al:0.001～0.3%, N:0.001～0.01%, and then contain a kind or 2 kinds in Mo:0.01～0.5% and W:0.01～1%, surplus by Fe and the steel that inevitably impurity forms be welded to one another and while forming welding joint, the mode that meets following 3 formulas with the content of the Cu in welding metal, Mo, W forms welding joint.
The Cu content (quality %) >=0.153 of Cu content (quality the %)/steel of 3 >=welding metal >=(Mo content+W content (quality %) of welding metal)/(Mo content+W content (quality %) of steel) >=0.15
-0.3≤(the Cu content (quality %) of Cu content (quality the %)-steel of welding metal)≤0.5
In addition, following technology is disclosed in patent documentation 2: will be in quality %, contain C:0.001～0.2%, Si:0.01～2.5%, Mn:0.1～2%, below P:0.03%, below S:0.02%, Cu:0.01～1.5%, Al:0.001～0.3%, N:0.001～0.01%, and then contain a kind or 2 kinds in Mo:0.01～0.5% and W:0.01～1%, surplus by Fe and the steel that inevitably impurity forms be welded to one another and while forming crude oil tank, with the Cu in welding metal, Mo, the mode that the content of W meets 2 following formulas forms welding joint.
The Cu content (quality %) >=0.153 of Cu content (quality the %)/steel of 3 >=welding metal >=(Mo content+W content (quality %) of welding metal)/(Mo content+W content (quality %) of steel) >=0.15
Patent documentation
Patent documentation 1: TOHKEMY 2005-021981 communique
Patent documentation 2: TOHKEMY 2005-023421 communique
Summary of the invention
Yet, in the technology that patent documentation 1 and patent documentation 2 are recorded, be difficult to the local corrosion producing in oil carrier base plate and welding joint (spot corrosion) to be suppressed at below 4mm between 2.5 years.In other words, in the Investigation On Corrosion of real ship in recent years, the pH that has found out the solution of the spot corrosion inside that results from oil carrier base plate and weld part is (research of the new shape corrosion movement of reference 242 research department meeting crude oil carrier is with reference to putting down into 13 Japan shipbuilding research department of annual report book/Corporation proceedings) below 1.0.Conventionally, well-known is that Corrosion Of Steel speed in Acidic Liquid is controlled by hydrogen reduction reaction, and when pH reduces, corrosion speed increases by leaps and bounds.Therefore, as recording in the embodiment of above-mentioned patent documentation 1 and patent documentation 2 in the dip test under pH2.0, fully do not reflect the corrosive environment of real ship.
In addition, with regard to the steel of the prior aries such as above-mentioned patent documentation 1 and patent documentation 2, as the element that improves erosion resistance, must add Cu, but Cu be added on hot rolling time cause surface crack, so exist infringement to manufacture the problem of stability.
Therefore, the object of the present invention is to provide a kind of excellent steel of manufacturing (manufacturability) that do not cause the problems such as crackle during by hot rolling to weld to form, the welding joint of the resistance to local corrosion excellence in oil carrier oil groove portion and there is the petroleum tank of this welding joint.
The inventor etc. have carried out further investigation repeatedly in order to solve above-mentioned problem.It found that, while forming petroleum tank by the steel that composition composition control to the optimum range of steel improved to erosion resistance in welding, the content of the Cu containing in the welding metal of welding joint, Mo and W is controlled to optimum range, can significantly alleviate the local corrosion producing in the welding joint of petroleum tank, thereby complete the present invention.
, the present invention is a kind of welding joint of excellent corrosion resistance, it is characterized in that, steel to be welded to one another and the welding joint of the petroleum tank that forms, described steel contain C:0.03～0.16 quality %, Si:0.05～1.50 quality %, Mn:0.1～2.0 quality %, below P:0.025 quality %, below S:0.010 quality %, Al:0.005～0.10 quality %, below N:0.008 quality %, Cr: surpass 0.1 quality % and be below 0.5 quality %, Cu:0.03～0.4 quality %, and, contain and be selected from W:0.01～1.0 quality %, Mo:0.01～0.5 quality %, one kind or two or more in Sn:0.001～0.2 quality % and Sb:0.001～0.4 quality %, and then, the X value of take by following (1) formula definition is as below 0.5, the Z value being defined by following (2) formula is that the mode below 0.15 contains mentioned component, surplus consists of Fe and inevitable impurity, the welding metal of welding joint contains Cu:0.05～0.5 quality % and (Mo+W): 0.03～1.0 quality %, the difference of the corrosion potential of steel and the corrosion potential of welding metal is below 60mV.At this, the above-mentioned symbol of element in various represents the content (quality %) of its element;
X value=(1-0.8 * Cu 0.5) * { 1-(0.8 * W+0.4 * Mo) 0.3} * { 1-(Sn+0.4 * Sb) 0.3} * { 1-(0.05 * Cr+0.03 * Ni+0.03 * Co) 0.3} * { 1+2 * (S/0.01+P/0.025) } ... (1)
Z value=(1+10 * Sn) * (Cu-0.7 * Ni) ... (2)
The steel that use in welding joint of the present invention, is characterized in that, on the basis forming, further contain the composition that is selected from least 1 group in following A～D group at mentioned component.
A group: be selected from a kind or 2 kinds in Ni:0.005～0.4 quality % and Co:0.01～0.4 quality %
B group: be selected from one kind or two or more in Nb:0.001～0.1 quality %, Ti:0.001～0.1 quality %, Zr:0.001～0.1 quality % and V:0.002～0.2 quality %
C group: be selected from one kind or two or more in Ca:0.0002～0.01 quality %, REM:0.0002～0.015 quality % and Y:0.0001～0.1 quality %
D group: B:0.0002～0.003 quality %
In addition, the present invention is a kind of petroleum tank, it is characterized in that, has above-mentioned welding joint.
According to the present invention, the local corrosion that can produce in the whole position that comprises welding joint is suppressed at oil groove, the conveying of the crude oil carrier that welds steel and form or stores the petroleum tanks such as tank of crude oil, so industrially play particularly preferred effect.
Accompanying drawing explanation
Fig. 1 is the explanatory view of the testing apparatus of use during the local corrosion (spot corrosion) of explanation embodiment is tested.
Embodiment
First, the one-tenth of the steel that use in petroleum tank of the present invention is grouped into and is described.
C:0.03～0.16 quality %
C is the element that improves the intensity of steel, in the present invention, and in order to ensure desirable intensity, more than adding 0.03 quality %.On the other hand, the interpolation over 0.16 quality % can make the toughness (toughness) of weldability (weldability) and welding heat affected zone (welded heat affected zone) reduce.Thus, C is made as to the scope of 0.03～0.16 quality %.The scope of 0.06～0.16 quality % more preferably.
Si:0.05～1.50 quality %
Si is the element adding as de-acidying agent, but is also to improving the effective element of intensity of steel.Therefore, in the present invention, in order to ensure desirable intensity, add Si more than 0.05 quality %.But the interpolation that surpasses 1.50 quality % can make the toughness drop of steel.Thus, Si is made as to the scope of 0.05～1.50 quality %.The scope of 0.15～0.50 quality % more preferably.
Mn:0.1～2.0 quality %
Mn is the element that improves the intensity of steel, in the present invention, and in order to obtain desirable intensity, more than adding 0.1 quality %.On the other hand, the interpolation over 2.0 quality % can make the toughness of steel and weldability reduce.Thus, Mn is made as to the scope of 0.1～2.0 quality %.Should illustrate, from maintaining high strength and inhibition, make the viewpoint of formation of the inclusion of erosion resistance variation, preferably the scope of 0.5～1.6 quality %, the more preferably scope of 0.7～1.4 quality %.
Below P:0.025 quality %
P makes the harmful element of the toughness drop of steel in grain boundary segregation, preferably reduce as much as possible.Particularly, if added, surpass 0.025 quality %, toughness significantly reduces.In addition, if P adds, surpass 0.025 quality %, also can bring bad impact to the erosion resistance in tank oil groove.Thus, P is made as below 0.025 quality %.Be preferably below 0.015 quality %.
Below S:0.010 quality %
S can form the MnS as non-metallic inclusion (non-metal inclusion), becomes the starting point of local corrosion, is the harmful element that resistance to local corrosion is reduced, and preferably reduces as much as possible.Particularly, the interpolation over 0.010 quality % can cause resistance to local corrosion to reduce significantly.Thus, the upper limit of S is made as to 0.010 quality %.Be preferably below 0.005 quality %.
Al:0.005～0.10 quality %
Al is the element adding as de-acidying agent, in the present invention, and more than adding 0.005 quality %.But if add to surpass 0.10 quality %, the toughness drop of steel, so be made as 0.10 quality % by the upper limit of Al.Be preferably the scope of 0.01～0.05 quality %.The scope of 0.02～0.04 quality % more preferably.
Below N:0.008 quality %
N is the harmful element that makes toughness drop, preferably reduces as much as possible.Particularly, if add, surpass 0.008 quality %, toughness significantly reduces, so the upper limit is made as to 0.008 quality %.Be preferably below 0.006 quality %, more preferably below 0.004 quality %.
Cr: surpass 0.1 quality % and be below 0.5 quality %
Cr is accompanied by the carrying out of corrosion and moves in rusty scale, by blocking-up Cl -to rusty scale, invade and inhibition Cl -concentrated to rusty scale and ferritic interface.In addition, while being coated with the priming paint (primer) that contains Zn, can form Cr, Zn composite oxides centered by Fe, make the long-time survival of Zn in surface of steel plate, so can improve by leaps and bounds erosion resistance.Above-mentioned effect is remarkable especially with the part contacting from the separated liquid that contains high density salinity of crude oil oil content the base plate as oil carrier oil groove, by the steel to the above-mentioned part that contains Cr, implement the prime treatment that contains Zn, thereby with the steel comparison that does not contain Cr, can especially improve erosion resistance.With regard to the effect of above-mentioned Cr, if add 0.1 quality % with next insufficient, on the other hand, the interpolation that surpasses 0.5 quality % can make the toughness variation of weld part.Therefore, Cr is made as and surpasses 0.1 quality % and be the scope below 0.5 quality %.More preferably the scope of 0.11～0.3 quality %.The further preferred scope of 0.12～0.2 quality %.
Cu:0.03～0.4 quality %
Cu is the element that improves the intensity of steel, and is present in the corrosion of invar and in the rust that generates, has the effect that improves erosion resistance.These effects cannot obtain fully when adding lower than 0.03 quality %, on the other hand, surpass 0.4 quality % if add, except improve the effect of erosion resistance saturated, also can when hot-work, cause the problems such as surface crack.Therefore,, from the stable viewpoint of manufacturing steel of the present invention, need to add Cu with the scope of 0.03～0.4 quality %.In addition, the effect that Cu adds is accompanied by the increase of addition and saturated, so from cost-benefit viewpoint, the preferred scope of 0.008～0.15 quality %.More preferably the scope of 0.01～0.14 quality %.
With regard to steel of the present invention, except mentioned component, also need to contain a kind of being selected from W, Mo, Sn and Sb or two or more with following ranges.
W:0.01～1.0 quality %
W, except having the effect that suppresses the spot corrosion in oil carrier oil groove portion base plate, also has the effect of whole the corrosion that suppresses oil carrier upperdeck portion.During the W of above-mentioned effect more than adding 0.01 quality %, show.But if surpass 1.0 quality %, this effect is saturated.Therefore, with the scope of 0.01～1.0 quality %, add W.Be preferably 0.01～0.5 quality %, more preferably the scope of 0.02～0.3 quality %.
Should illustrate, W has the reasons are as follows of effect of raising erosion resistance as described above: in the rust generating being accompanied by steel plate corrosion, generate WO 4 2-, because of this WO 4 2-existence, can suppress chloride ion (chloride ion) and invade surface of steel plate, and then the position declining at pH such as the anode portion (anode) of surface of steel plate, generates FeWO 4, because of this FeWO 4existence, also can suppress chloride ion to the intrusion of surface of steel plate.In addition, think by by WO 4 2-the restraining effect that the absorption of steel surface is caused (inhibitory action), also can suppress the corrosion of steel.
Mo:0.01～0.5 quality %
Mo not only has the effect that suppresses the spot corrosion in oil carrier oil groove portion base plate, also has and improves resistance to whole corrodibility of oil carrier upperdeck back part, the effect of the erosion resistance after the coating in the corrosive environment that salt water retting and high-humidity repeatedly occur as ballast box (ballast tank).The effect of above-mentioned Mo shows when above adding 0.01 quality %, if but surpass 0.5 quality %, its effect is saturated.Thus, Mo is made as to the scope of 0.01～0.5 quality %.Be preferably 0.02～0.5 quality %, more preferably the scope of 0.03～0.4 quality %.
Should illustrate, the reason that Mo has the effect of raising erosion resistance as described above is thought as follows: identical with W, in the rust generating being accompanied by steel plate corrosion, generate MoO 4 2-, think due to this MoO 4 2-existence, can suppress chloride ion to the intrusion of surface of steel plate.
Sn:0.001～0.2 quality %, Sb:0.001～0.4 quality %
Sn and Sb, except having the effect that suppresses the spot corrosion in oil carrier oil groove portion base plate, also have the effect of whole the corrosion that suppresses oil carrier upperdeck portion.Above-mentioned effect more than adding Sn:0.001 quality %, Sb:0.001 quality % shows when above.On the other hand, even if add Sn: surpass 0.2 quality % and Sb: surpass 0.4 quality %, its effect is also saturated.And then, the surface crack when adding in a large number Sn and can encourage the hot-work causing because of Cu.Thus, preferably with above-mentioned scope, add Sn and Sb respectively.
In addition, with regard to steel of the present invention, except as above-mentioned composition that must be essential, also preferably with following ranges, contain a kind or 2 kinds that is selected from Ni and Co.
Ni:0.005～0.4 quality %, Co:0.01～0.4 quality %
Ni and Co have to be made the rust particle miniaturization generating and significantly improves the erosion resistance under naked state and yellow zinc chromate primer paint (zinc primer) has been implemented to the effect of the erosion resistance under the state of epoxies coating (epoxy coating).Therefore,, in the situation that needs further improve erosion resistance, preferably auxiliarily add these elements.Above-mentioned effect more than adding Ni:0.005 quality %, Co:0.01 quality % shows when above.On the other hand, even if add Ni: surpass 0.4 quality %, Co: surpass 0.4 quality %, its effect is also saturated.The effect of surface crack when in addition, Ni has the hot-work producing in the steel that suppresses to contain Cu, Sn.Thus, preferably with above-mentioned scope, add Ni and Co respectively.
In addition, with regard to steel of the present invention, containing on the basis of above-mentioned essential composition and selectivity added ingredients (Ni, Co) with above-mentioned optimum range, the mode that further need to meet below 0.5 with the X value by the definition of following (1) formula contains these compositions.
X value=(1-0.8 * Cu 0.5) * { 1-(0.8 * W+0.4 * Mo) 0.3} * { 1-(Sn+0.4 * Sb) 0.3} * { 1-(0.05 * Cr+0.03 * Ni+0.03 * Co) 0.3} * { 1+2 * (S/0.01+P/0.025) } ... (1)
At this, the symbol of element in above-mentioned formula represents the content (quality %) of its element, and the element not containing is with 0(zero) calculate.
Above-mentioned (1) formula is to evaluate the formula of each composition on the impact of oil carrier oil groove internal corrosion, the coefficient table of the composition that erosion resistance is improved is shown negative, will the coefficient table of the composition of erosion resistance variation is just shown in addition.Therefore, the steel that the value of X is less, erosion resistance is more excellent.The inventor etc. have found out the relation between the value of above-mentioned X and the erosion resistance of the steel under the corrosive environment in oil carrier oil groove, found that if X is below 0.5, the excellent corrosion resistance under the corrosive environment in oil carrier oil groove, if but X surpasses 0.5, above-mentioned erosion resistance variation.Therefore,, for steel of the present invention, while determining the content of P, S, Cr, Cu, W, Mo, Sn, Sb, Ni and Co, the mode that need to become below 0.5 with above-mentioned X value is carried out Composition Design.
In addition, with regard to steel of the present invention, on the basis of containing mentioned component at the optimum range with above-mentioned, also need to take and contain Cu, Sn and Ni by the Z value of following (2) formula definition as the mode below 0.15.
Z value=(1+10 * Sn) * (Cu-0.7 * Ni) ... (2)
At this, the symbol of element in above-mentioned formula represents the content (quality %) of its element, and the element not containing is with 0(zero) calculate.It is the reasons are as follows: Cu is the element of the surface crack while causing hot-work, and in addition, Sn is the element encouraging by the crackle due to above-mentioned Cu.On the other hand, Ni is to preventing by the effective element of harm due to above-mentioned element, but in order to show the above-mentioned effect of Ni, and mode that need to above-mentioned to meet (2) formula is added Ni.
In addition, with regard to steel of the present invention, for the object that improves the intensity of steel, on the basis of mentioned component, can also add and be selected from one kind or two or more in Nb, Ti, V and Zr with following ranges.
Nb:0.001～0.1 quality %, Ti:0.001～0.1 quality %, Zr:0.001～0.1 quality % and V:0.002～0.2 quality %
Nb, Ti, Zr and V are all the elements that improve steel strength, can intensity as required carry out suitably selecting to add.In order to obtain above-mentioned effect, more than preferably Nb, Ti, Zr all add 0.001 quality %, more than V adds 0.002 quality %.But, if all adding, Nb, Ti, Zr surpass 0.1 quality %, and V adds and surpasses 0.2 quality %, and toughness drop, so preferably add Nb, Ti, Zr, V with above-mentioned scope respectively.
And then, with regard to steel of the present invention, in order to improve intensity or to improve toughness, on the basis of mentioned component, can also add and be selected from one kind or two or more in Ca, REM and Y with following ranges.
Ca:0.0002～0.01 quality %, REM:0.0002～0.015 quality % and Y:0.0001～0.1 quality %
Ca, REM and Y all improve and produce effect the toughness of welding heat affected zone, can add as required.Above-mentioned effect can by adding, Ca:0.0002 quality % be above, REM:0.0002 quality % is above, Y:0.0001 quality % with on obtain, if add to surpass the mode of Ca:0.01 quality %, REM:0.015 quality %, Y:0.1 quality %, can cause on the contrary the reduction of toughness, so preferably add Ca, REM, Y with above-mentioned scope respectively.
And then, with regard to steel of the present invention, on the basis of mentioned component, can also contain B with following ranges.
B:0.0002～0.003 quality %
B is the element that improves steel strength, can add as required.In order to obtain above-mentioned effect, more than preferably adding 0.0002 quality %.But, if add, surpass 0.003 quality %, toughness drop.Thus, preferably with the scope of 0.0002～0.003 quality %, add B.
Should illustrate, the optimum selection of steels using in petroleum tank of the present invention is manufactured in accordance with the following methods.
, optimum selection of steels of the present invention is manufactured as follows: use converter (steel converter) or electric furnace (electric furnace), the known refining procedures (refinery process) such as vacuum outgas (vacuum degassing equipment), by being adjusted to, being applicable to the steel that one-tenth of the present invention is grouped into and carrying out melting, utilize Continuous casting process (continuous casting process) or ingot casting-split rolling method method to make steel billet (plate slab (steel slab)), then, this material is reheated, then carry out hot rolling (hot rolling), make Plate Steel, the steel such as steel sheet and shaped steel.
Preferably by the temperature that temperature is made as 900～1200 ℃ that reheats before above-mentioned hot rolling.Heating temperature is during lower than 900 ℃, and resistance to deformation is large, is difficult to carry out hot rolling.On the other hand, if Heating temperature surpasses 1200 ℃, austenite grain (austenite grain) coarsening, cause toughness drop, in addition, by the oxidization burning loss (scale loss) due to oxidation, also become significantly, yield rate (yield ratio) reduces.Preferred Heating temperature is 1000～1150 ℃.
In addition, while being rolled into the steel of desirable shape, size in hot rolling, preferably finish rolling end temp is made as more than 750 ℃.During lower than 750 ℃, it is large that the resistance to deformation of steel becomes, and rolling load increases, and is difficult to be rolled, or produces till rolled stock reaches the waiting time of the rolling temperature of regulation, so rolling efficiency reduces.
Steel after hot rolling are cooling can be air cooling (air cooling), accelerate any means in cooling (accelerated cooling), in the time of need to obtaining more high strength, preferably accelerates cooling.Should illustrate, accelerate when cooling, preferably speed of cooling is made as to 2～80 ℃/sec, by cooling, stop the scope that temperature is made as 650～300 ℃.Speed of cooling, lower than 2 ℃/sec, cooling when stopping temperature and surpassing 650 ℃, is accelerated cooling effect little, cannot realize sufficient high strength.On the other hand, speed of cooling surpasses 80 ℃/sec, cooling while stopping temperature lower than 300 ℃, the toughness drop of the steel that obtain, or the shape of steel produces distortion.
The welding joint of the petroleum tank next, forming welding steel of the present invention describes.
For the welding joint of the petroleum tank forming with regard to the steel plate that is adjusted into above-mentioned suitable composition and manufactures is welded to one another, need to contain Cu, Mo and the W in welding metal with following ranges.
Cu:0.05～0.5 quality %, (Mo+W): 0.03～1.0 quality %
The discoveries such as the inventor, the impact of the erosion resistance of the alloying constituent Welded Joints in welding metal is subject to the impact institute left and right of the total content of Cu and Mo and W, the in the situation that of compound interpolation Cu and Mo and/or W, due to the synergistic effect of these elements, the erosion resistance of welding joint is significantly improved.But the Cu in the welding metal of welding joint during lower than 0.03 quality %, cannot expect above-mentioned synergistic effect lower than the total amount of the Mo in 0.05 quality % or welding metal and W, the erosion resistance of welding joint reduces.On the other hand, when the total amount that the Cu in welding metal surpasses 0.5 quality % or the Mo in welding metal and W surpasses 1.0 quality %, the erosion resistance of comparing welding metal with mother metal (steel) portion especially improves, so the corrosion occurring can concentrate on mother metal portion.In addition, also exist the low-temperature flexibility of welding joint to reduce such harm.Therefore, in the present invention, the total content of the Cu content in welding metal and Mo and W is limited in respectively to above-mentioned scope.Should illustrate, the content of Mo and W is not as long as its total amount, in above-mentioned scope, also can contain the either party in Mo and W.
Should illustrate, the content of the Cu in above-mentioned welding metal, Mo and W is controlled to above-mentioned scope, preferably according to the one-tenth of steel (mother metal), be grouped into and welding conditions, suitably select the welding material (welding wire (weld wire)) using in welding.Be for example following method: make and there is the welding wire that the target of the Cu in welding metal, Mo and W is formed to the composition of trying to achieve by the thinning ratio of mother metal (dilution ratio) conversion, use it to weld.
In addition, the welding process of using in welding as petroleum tank of the present invention, can be used as FAB welding, FCB welding, the RF of one side single track submerged arc welding method (one-side submerged arc welding) to weld such high heat input welding (high-heat input welding), co3 gas arc welding meets (CO 2welding (CO 2arc welding)) such low_input_power welding (small-heat input welding) etc., but from the chemical composition composition control of welding metal is considered in the viewpoint of optimum range, need to be the welding process of using welding wire.
Should illustrate, at this, FAB welding refers in the registered trademark relevant to the welding process of Kobe Steel Ltd., and the liner material by formations such as cellotape, solid fluxs is directly layered on to the steel plate back side, welds the method that forms root run by single track.In addition, FCB welding refers in the registered trademark relevant to the welding process of Kobe Steel Ltd., scatters liner solder flux on copper coin, by being pressed in the steel plate back side, welds the method that forms root run by single track.In addition, RF method refers in the registered trademark relevant to the welding process of Kobe Steel Ltd., the jig frame that under liner solder flux containing welding heat curable resin, overlapping basic solder flux forms is layered on to the steel plate back side, press the solder flux in press box, by single track, weld the method that forms root run.
In addition, with regard to the welding joint of petroleum tank of the present invention, in order to obtain good erosion resistance, need to make the difference of the corrosion potential in the independent corrosion test solution of corrosion potential (corrosion potential) in the independent corrosion test solution of steel (mother metal) (corrosion test liquid solution) and welding metal is below 60mV.The corrosion potential of steel is than the corrosion potential of welding metal when surpassing 60mV, and the corrosion of generation can concentrate on welding metal, and on the contrary, the corrosion potential of welding metal is than the corrosion potential of steel when surpassing 60mV, and the corrosion of generation can concentrate on steel.Therefore, the difference of the corrosion potential of the corrosion potential of the steel in corrosion test solution and welding metal is limited to below 60mV.
At this, above-mentioned corrosion potential is that each test film that the mother metal portion of the position from thickness of slab 1/4 and welding metal portion are cut out is immersed in the testing liquid of regulation, uses Ag/AgCl standard electrode (standard reference electrode) to measure from dipping and starts the corrosion potential 10 minutes and the value that obtains.Should illustrate, the testing liquid using in the mensuration of above-mentioned corrosion potential is preferably simulated the solution of corrosive environment of the oil carrier base plate of real ship, for example, in the situation that simulation is from the salt solution that is trapped in the crude oil of oil carrier base plate, by Cl, be the more than 2.0 quality % aqueous solution while being modeled to the corrosive fluid of the spot corrosion inside occurring in oil carrier base plate, preferably use the acidic aqueous solution below pH2.0.Should illustrate, above-mentioned acidic aqueous solution can contain Cl.
Embodiment
With vacuum melting furnace, to thering is the steel of the heterogeneity composition of No.1～36 shown in table 1-1 and table 1-2, carry out melting and make steel ingot, or carry out melting with converter, continuous casting, make plate slab, these are reheated after 1150 ℃, making finish rolling end temp is the hot rolling of 800 ℃, makes the Plate Steel of thickness of slab 25mm.
For the Plate Steel of No.1～36 that obtain thus, utilize magnetic-particle test investigation whether to have the crackle of surface of steel plate, by what crackle do not detected, be judged to be zero, by detect being judged to be of crackle *.
Then, each steel plate of above-mentioned No.1～36 is welded and makes welding joint according to the welding process of recording in table 2 each other.Should illustrate, for the heat input of each welding process, FCB is welded as 146kJ/cm, and FAB is welded as 180kJ/cm, CO 2be welded as 1.5kJ/cm.Groove is all double V-groove.At this, the composition control of the Cu in the welding metal of each welding joint, Mo and W carries out as follows: make and have the target composition of Cu, Mo and W according to mother metal thinning ratio (CO 2weld that 47% left and right is welded in 11% left and right, FAB, FCB welds 67% left and right) conversion and the welding wire of the composition of trying to achieve is used it to weld.Should illustrate, in FCB welding, use solder flux (PF-I55E/ Kobe Steel Ltd. system) and liner solder flux (PF-I50R/ Kobe Steel Ltd. system), in FAB welding, use solder flux (PF-I52E/ Kobe Steel Ltd. system), weighting agent (RR-2/ Kobe Steel Ltd. system) and liner material (FA-B1/ Kobe Steel Ltd. system).
Should illustrate, FCB welding refers to and on copper coin, scatters liner solder flux as mentioned above, by being pressed in the steel plate back side, welds the method that forms root run by single track.In addition, FAB welding refers to the liner material consisting of cellotape, solid flux etc. is directly layered on to the steel plate back side, welds the method that forms root run by single track.
Then, for above-mentioned welding joint, Cu, the Mo in use atomic absorption analysis method (atomic absorption spectrometry) mensuration welding metal and the content of W.
And then, use Ag/AgCl standard electrode and potentiostat (potentiostatically), NaCl(pH0.85 to 10 quality %) the independent corrosion potential of the mother metal in corrosion test liquid and the independent corrosion potential of welding metal of welding joint are measured, and try to achieve its potential difference (difference in potential).
And, in order to evaluate the erosion resistance of welding joint to the spot corrosion in the base plate of oil carrier oil groove portion, carried out by local corrosion (spot corrosion) test that will put below simulated oil bottomplate environment.First, position from the thickness of slab 1/4 of the Plate Steel welding joint of above-mentioned No.1～36, so that the width of welding metal and test film walks abreast and is positioned at central mode, cut out the rectangle small pieces of width 25mm * length 60mm * thickness 4mm, with the sand paper (emery paper) of 600 granularities, its whole face is ground.
Then, preparation by the NaCl of 10 quality % for the aqueous solution concentrated hydrochloric acid (concentrated hydrochloric acid) be modulated into the testing liquid that Cl ionic concn 10 quality %, pH0.85 form, in the hole of opening in the 3mm on test film top φ, through line (thread), hung, each test film is all carried out flooding the corrosion test of 168 hours in the testing liquid of 2L.Should illustrate, 30 ℃ are heated, remained on to testing liquid in advance, every testing liquid more renewing for 24 hours.
The device using in above-mentioned corrosion test is shown in to Fig. 1.This corrosion testing apparatus is the doublet type device of corrosion test groove 2, thermostatic bath 3, in corrosion test groove (corrosion test bath) 2, adds above-mentioned testing liquid 4, and test film 1 is hung and be impregnated in wherein by line 5.The temperature of experimental liquid 4 is that the temperature that joins the water 6 of thermostatic bath (constanttemperature bath) 3 by adjustment keeps.
After above-mentioned corrosion test, remove after the rust that is created on test film surface, quality measurement, converts the of poor quality of test front and back according to whole surface-area, obtain the thickness of slab reduction (corrosion speed on two sides) in 1 year.By corrosion speed, be consequently that 1.0mm/ is following and at mother metal portion and weld part, take Visual Confirmation there is no the average evaluation of local corrosion be resistance to local corrosion good (zero), corrosion speed surpassed to 1.0mm/ or the either party in mother metal portion, weld part and take Visual Confirmation to have the average evaluation of local corrosion be resistance to local corrosion poor (*).
The poor measurement result of the result of above-mentioned magnetic-particle test (magnetic-particle testing), the analytical results of welding metal, corrosion potential and the result of corrosion resistance test are shown in Table 2 in the lump with become to be grouped into X value and the Z value of trying to achieve by each steel plate.From this table 2, mother metal and welding metal meet the condition that becomes to be grouped into, meets X value and Z value of the present invention and then corrosion potential poorly meets No.1～4,6 of condition of the present invention, 7 and 10～29 Plate Steel does not have the generation of crackle when rolling, and the corrosion resistance test of having simulated oil carrier base plate environment all demonstrates good erosion resistance, on the other hand, the No.5,8 of discontented foot condition of the present invention, 9 and 30～36 Plate Steel crack, and/or do not obtain good erosion resistance when rolling.
Nomenclature
1: test film
2: corrosion test groove
3: thermostatic bath
4: experimental liquid
5: line
6: water
Table 1-1
Table 1-2
Table 2
[table 2]

Claims (10)

1. a welding joint, is steel to be welded to one another and the welding joint of the petroleum tank that forms, and described steel contain:
C:0.03～0.16 quality %,
Si:0.05～1.50 quality %,
Mn:0.1～2.0 quality %,
Below P:0.025 quality %,
Below S:0.010 quality %,
Al:0.005～0.10 quality %,
Below N:0.008 quality %,
Cr: surpass 0.1 quality % and be below 0.5 quality %,
Cu:0.03～0.4 quality %,
And, contain and be selected from one kind or two or more in W:0.01～1.0 quality %, Mo:0.01～0.5 quality %, Sn:0.001～0.2 quality % and Sb:0.001～0.4 quality %,
And then, take the X value that defines as below 0.5, contain described composition by the Z value of following (2) formula definition as the mode below 0.15 in following (1) formula,
Surplus consists of Fe and inevitable impurity;
The welding metal of described welding joint contains Cu:0.05～0.5 quality % and (Mo+W): 0.03～1.0 quality %, and the difference of the corrosion potential of steel and the corrosion potential of welding metal is below 60mV;
X value=(1-0.8 * Cu 0.5) * { 1-(0.8 * W+0.4 * Mo) 0.3} * { 1-(Sn+0.4 * Sb) 0.3} * { 1-(0.05 * Cr+0.03 * Ni+0.03 * Co) 0.3} * { 1+2 * (S/0.01+P/0.025) } ... (1)
Z value=(1+10 * Sn) * (Cu-0.7 * Ni) ... (2)
Wherein, the symbol of element in above-mentioned formula represents the content (quality %) of its element.
2. welding joint according to claim 1, wherein, on the basis that described steel are grouped at described one-tenth, further contains a kind or 2 kinds that is selected from Ni:0.005～0.4 quality % and Co:0.01～0.4 quality %.
3. welding joint according to claim 1 and 2, wherein, on the basis that described steel are grouped at described one-tenth, further contain and be selected from one kind or two or more in Nb:0.001～0.1 quality %, Ti:0.001～0.1 quality %, Zr:0.001～0.1 quality % and V:0.002～0.2 quality %.
4. welding joint according to claim 1 and 2, wherein, on the basis that described steel are grouped at described one-tenth, further contain and be selected from one kind or two or more in Ca:0.0002～0.01 quality %, REM:0.0002～0.015 quality % and Y:0.0001～0.1 quality %.
5. welding joint according to claim 3, wherein, on the basis that described steel are grouped at described one-tenth, further contain and be selected from one kind or two or more in Ca:0.0002～0.01 quality %, REM:0.0002～0.015 quality % and Y:0.0001～0.1 quality %.
6. welding joint according to claim 1 and 2, wherein, on the basis that described steel are grouped at described one-tenth, further contains B:0.0002～0.003 quality %.
7. welding joint according to claim 3, wherein, on the basis that described steel are grouped at described one-tenth, further contains B:0.0002～0.003 quality %.
8. welding joint according to claim 4, wherein, on the basis that described steel are grouped at described one-tenth, further contains B:0.0002～0.003 quality %.
9. welding joint according to claim 5, wherein, on the basis that described steel are grouped at described one-tenth, further contains B:0.0002～0.003 quality %.
10. a petroleum tank, has the welding joint described in any one in claim 1～9.
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