CN1946864A - Steel product for cargo oil tank - Google Patents
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- CN1946864A CN1946864A CN 200580012361 CN200580012361A CN1946864A CN 1946864 A CN1946864 A CN 1946864A CN 200580012361 CN200580012361 CN 200580012361 CN 200580012361 A CN200580012361 A CN 200580012361A CN 1946864 A CN1946864 A CN 1946864A
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Abstract
A steel product for a cargo oil tank which has a chemical composition containing C: 0.01 to 0.2 %, Si: 0.01 to 1 %, Mn: 0.05 to 2 %, P: 0.05 % or less, S: 0.01 % or less, Ni: 0.01 to 1 %, Cu: 0.05 to 2 %, W: 0.01 to 1 %, Cr: 0.1 % or less, Al: 0.1 % or less, N: 0.001 to 0.01 %, and O (oxygen):0.0001 to 0.005 %. Preferably, alpha and beta, both being shown in the following, are 0.75 or less and 0.8 or less, respectively, and Ceq* represented by the formula (1) is 0.38 or less. alpha = (1-0.691xCu)x(1-0.221xNi)x(1-0.142xW) beta = (1-0.444xCu)x(1-0.156xNi)x(1-0.630xW) Ceq* = C + Mn/6 + Ni/15 + Cu/15 + W/10 + Cr/5 + Mo/5 ----(1) The above steel product for a cargo oil tank is excellent in the resistance to the corrosion over the whole of the surface or at a part of the surface under a circumstance of the corrosion by a crude oil and sea water, and also is excellent in the toughness of both of the mother material and a welded zone.
Description
Technical field
The present invention relates to the crude oil tank corrosion-resistant steel, relating in particular to the crude oil tank that is provided with in oil carrier is steel product for cargo oil tank.
Background technology
Nearest crude oil tanker need possess double hull (double hull).
Fig. 1 represent the double hull structure oil carrier, be the local section mode chart of double hull oil carrier.In the double hull oil carrier, the inboard of oil cargo tank 10 when not loading crude oil, is mounted with seawater owing to be positioned at the ballast tank 12 in the outside of oil cargo tank 10, so be under the corrosive environment of seawater owing to crude oil is under the corrosive environment when loading crude oil.
That is, the inwall 14 of oil cargo tank is under the corrosive environment of crude oil, and outer wall 16 is under the corrosive environment of seawater.
Therefore, at first, under the corrosive situation in considering the oil cargo tank that causes because of crude oil, its forms of corrosion roughly is divided into dual mode.A kind of is that another kind is the local corrosion that causes in base plate 20 in the general corrosion of the gas phase portion generation of top plate portion 18.Especially contain hydrogen sulfide (H at loading
2During S) crude oil, because the H that contains in the crude oil
2The part of S is transferred in the gas phase, so the ceiling portion of oil cargo tank becomes extremely harsh corrosive environment.
In corrosive environment as described above, report has following example: cause general corrosion at the cabin backboard face that becomes oil cargo tank ceiling portion, corrosion speed is the example of the above very large general corrosion of 0.3mm/.In addition, also there is following situation: produce pitting attack at the oil cargo tank base plate, reach the big pitting attack advance rate of several mm/.
According to such situation, though being implemented application, the material of oil cargo tank carries out in a part, the cost of the application at initial stage and approximately per 10 years application again is very big.In addition, on flat dunnage, even under the situation of having implemented application, also existence produces the situation of pitting attack because of the shortcoming portion of filming.Therefore, present situation is to have considered the thickness of slab design of corrosion allowance, deals with general corrosion and local corrosion.In addition, on base plate, implement termly to check, repair by built-up welding for the part that the pitting attack degree of depth is big, but the problem that produces is that maintenance cost is too high.
And if corrosion allowance is set, then can produce following shortcoming: the thickness increase of invar material makes the manufacturing cost of cargo tank rise crude oil loading amount minimizing etc.Therefore, urgent hope is developed the reduction that can realize corrosion allowance and can be suppressed cost steel product for cargo oil tank that rise, excellent corrosion resistance.
In addition, owing to welding in order to constitute cargo tank in the shipbuilding stage, so only be that good corrosion resistance does not have much effects yet, the material of hope is the material of the intensity of weld part, toughness, weldability etc.
As the oil cargo tank steel, for example proposing respectively has: the spy opens the steel of the necessary composition of the disclosed Cu of comprising and Mg in the 2000-17381 communique; In addition, the spy opens the steel of the necessary composition of the disclosed Cr of comprising and Al in the 2001-107180 communique.But, in the disclosed steel of these communiques, do not consider fully to contain H at crude oil
2H under the situation of S
2Therefore the influence that S brings corrosion, exists the oil cargo tank of actual oil carrier can't obtain the situation of sufficient erosion resistance.
The spy opens the 2003-82435 communique and is conceived to the interior forms of corrosion of oil cargo tank, discloses the technology of the steel of the equal excellence of performance aspect general corrosion and local corrosion two.But, in the method, although can improve erosion resistance really,, but do not consider for the toughness of welded-joint.Owing in actual oil carrier, certainly exist welding joint, so the problem that exists the toughness of this part to descend.
On the other hand, such as has been described, the outer wall 16 of oil cargo tank 10 is in the corrosion under the briny environment of the corrosive environment that is different from above such crude oil.
Also must consider two kinds of forms of corrosions in this case.This is because be in briny environment, and promptly the ceiling portion 22 in the ballast tank 12 is in and does wet seawater spittle environment repeatedly, and part in addition is in seawater dipping environment.
Even under this corrosive environment of sea water, the corrosive environment of top plate portion and side plate, base plate is also different.Top plate portion is in the spittle dipping of the seawater that is loaded, and the wet environment (below, be called seawater spittle environment) repeatedly of doing of bearing that day and night temperature causes.Such seawater spittle environment is generally considered to be very harsh corrosive environment.On the other hand, side plate and base plate are in the environment that flooded by seawater all the time (below, be called seawater dipping environment), and this corrosive environment is also harsher.
Owing to be in such corrosive environment, so the outside wall surface of oil cargo tank has been implemented corrosion protection based on application.But it is aging As time goes on to film, and especially corrodes easily in thickness thin edge, bight.Though steel itself also have erosion resistance, the erosion resistance deficiency of these steel, therefore frequency of maintenance such as application increases again, safeguards that needed expense enlarges markedly.
The material of the oil cargo tank that uses in the oil carrier of double hull structure requires respectively crude oil corrosive environment and corrosive environment of sea water are had the erosion resistance of height gradually like this.
Summary of the invention
The objective of the invention is to, a kind of steel product for cargo oil tank is provided, it has excellently in general corrosion and local corrosive resistivity under two kinds of environment of crude oil corrosive environment and corrosive environment of sea water simultaneously, and the toughness of mother metal, weld part is also excellent.
Present inventors are in order to develop such steel, the corrosive environment of the oil carrier that simulation is actual and testing.
That is, rare gas element and H have been carried out containing
2Corrosion test under the dried wet environment repeatedly of S.This is to be used for reproducing to be mounted with containing H
2The corrosive environment that the cabin backboard face of the oil carrier of the reality of the crude oil of S is seen.
This experiment is by the experimental installation shown in Fig. 2 (a) and (b), the experiment that the steel with the composition shown in the table 1 is carried out.In Fig. 2, (a) be the reproduction experiment of gas phase portion, (b) be the reproduction experiment of base plate.In addition, the concrete operations etc. for experiment describe in an embodiment.
Its result about the erosion resistance of gas phase portion and base plate, obtains following opinion.
(1) in the reproduction of the gas phase portion experiment, observed the effect that the element of Cu, Ni, W, Mo, P, Cr, Al brings erosion resistance, but the effect of Cu is best, makes erosion resistance decline owing to add Cr, Al.
(2) for the erosion resistance of improving base plate, it is the most resultful adding Cu, P.
Therefore, these helped the element of erosion resistance carry out various combinations, carried out a series of experiment.These result of experiment obtain following opinion.
(3) by with W and Cu with Ni is compound contains, further improve anti-general corrosion and anti-pitting attack.
(4) if except Cu and Ni, add more than one of Mo, Ti, Zr, Sb, Sn, Ca, Mg, Nb, V, B, then further improve anti-general corrosion and anti-pitting attack.
(5) if except Cu and Ni, further add more than one of Mo, Ti, Zr, Sb, Sn, Ca, Mg, Nb, V, B, then the application life-span is longer than in the past.
(6) by the amount of restriction Cr and Al, that can suppress that sour water causes does general corrosion under the wet environment repeatedly.
Then, similarly, implemented to be equivalent to the seawater spittle environment of the corrosive environment that the crude oil tank outer wall exposes and the corrosion experiment under the seawater dipping environment, its result obtains following opinion.
(7) under seawater spittle environment, the interpolation of Cu, Ni is resultful, and then by adding W, Mo, erosion resistance further improves.
(8) under seawater dipping environment, the interpolation of Cu is resultful, and then by compound interpolation Ni, W, Mo, erosion resistance further improves.
(9) as described above, by further interpolation Ti, Zr, Sb, Sn, Ca, Mg, Nb, V, B, improved the erosion resistance under seawater spittle environment, the seawater dipping environment.
(10) by using above-mentioned steel, the application life-span is longer than in the past.
At this, purport of the present invention is the steel product for cargo oil tank shown in following (1)～(4).
(1) in quality %, contain that C:0.01～0.2%, Si:0.01～1%, Mn:0.05～2%, P:0.05% are following, S:0.01% is following, Ni:0.01～1%, Cu:0.05～2%, W:0.01～1%, Cr:0.1% is following, Al:0.1% is following, N:0.001～0.01%, O (oxygen): 0.0001～0.005%, the steel product for cargo oil tank that constitutes by surplus Fe and impurity.
(2) a kind of steel product for cargo oil tank is the steel that contain above-mentioned (1) described composition, it is characterized in that, below Biao Shi α is below 0.75, and β is below 0.8, and the Ceq* shown in the formula (1) is below 0.38,
α＝(1-0.691×Cu)×(1-0.221×Ni)×(1-0.142×W)
β＝(1-0.444×Cu)×(1-0.156×Ni)×(1-0.630×W)
Ceq*＝C+Mn/6+Ni/15+Cu/15+W/10+Cr/5+Mo/5
……(1)。
(3) according to above-mentioned (1) or (2) described steel product for cargo oil tank, be the steel that contain above-mentioned (1) described composition, it is characterized in that following formula a is below 0.85, b is below 0.9,
a＝(1-0.26×Cu)×(1-0.18×Ni)×(1-0.42×W)
b＝(1-0.18×Cu)×(1-0.18×Ni)×(1-0.27×W)。
(4) according to the described steel product for cargo oil tank in above-mentioned (1)～(3), it is characterized in that, in quality %, also contain (i) Mo:0.05～1%, Ti:0.005～0.1%, Zr:0.005～0.2%, Sb:0.01～0.2%, Sn:0.01～0.2%, (ii) Ca:0.0003～0.01%, Mg:0.0003～0.01%, (iii) one or more of Nb:0.005～0.1%, V:0.005～0.1%, B:0.0003～0.01%.
(5) according to each described steel product for cargo oil tank in above-mentioned (1)～(4), it is for having implemented anti-corrosive treatment to single face at least.
(6) a kind of crude oil tanker, it has the cargo tank that adopts each described steel in above-mentioned (1)～(5) and constitute.
According to steel of the present invention, can improve the erosion resistance under the corrosive environment of oil cargo tank, and can reduce maintenance cost significantly.
Description of drawings
Fig. 1 is the profile schema diagram of double hull oil carrier;
Fig. 2 (a) is the schematic illustration figure of experimental installation of the reproduction test of expression gas phase portion, and Fig. 2 (b) is the schematic illustration figure of experimental installation of the reproduction test of expression base plate.
Embodiment
Below, be elaborated for each prerequisite of the present invention.In addition, " % " of the amount of each element expression is meant " quality % ".
(A) chemical constitution of steel
C:C is the element that is used to guarantee as necessity of the intensity of material, and amount is more than 0.01%.But, if amount surpass 0.2% weldability descend.In addition, along with the increase of C amount, under the dried wet environment repeatedly that sour water causes, become negative electrode, along with the growing amount that promotes the corrosive cementite increases and the weldability deterioration.Therefore, be limited to 0.2% on.
Si:Si is the element of necessity of deoxidation, contains more than 0.01% in order to obtain sufficient deoxidation effect.But,, then damage the toughness of mother metal and welded-joint if amount surpasses 1%.Therefore, the amount of Si is 0.01～1%.The scope of preferred amount is 0.01～0.8%, and preferred scope is 0.01～0.5%.
Mn:Mn is low-cost and has the element of the effect of the intensity that improves steel that in order to obtain this effect, amount is more than 0.05%.But if amount surpasses 2%, then weldability worsens, and joint toughness also worsens.Therefore, the amount of Mn is 0.05～2%.The scope of preferred amount is 0.05～1.8%, and preferred scope is 0.05～1.5%.
P:P is the impurity element that contains in the steel, can reduce weldability.Especially, if its amount surpasses 0.05%, then weldability significantly descends.Therefore, the amount of P is below 0.05%.In addition, though P descends weldability, but then, P has the effect that improves interior anti-general corrosion of crude oil tank and anti-pitting attack and then the raising erosion resistance under seawater spittle environment, seawater dipping environment, so, can contain more than 0.01% in order to improve these erosion resistances.The preferred upper limit of the amount of P is 0.04%, and the preferred upper limit is 0.03%.
S:S is the impurity element that contains in the steel, if its amount surpasses 0.01%, then produces MnS in a large number in steel, and MnS becomes the corrosive starting point and produces general corrosion and pitting attack.Therefore, the amount of S is below 0.01%.The preferred upper limit of S amount is 0.008%, and the preferred upper limit is 0.005%.In addition, the S amount is low more good more.
Ni:Ni improves not contain H
2The element of doing the anti-general corrosion under the wet environment repeatedly of S.Ni has the sulfide protective membrane that forms non-corrosibility under moistening hydrogen-sulfide environmental and improves the effect of anti-general corrosion and improve the effect of anti-pitting attack.And then, also have the effect that improves the erosion resistance under seawater spittle environment, the seawater dipping environment.These effects are to obtain by the Ni that contains more than 0.01%.If especially contain more than 0.05%, then can access significant more effect.But, even the Ni amount surpasses 1%, because of described effect is saturated, so only can increase cost.Therefore, the amount of Ni is 0.01～1%.The scope of preferred amount is 0.05～1%, and preferred scope is 0.1～1%.
Cu:Cu improves not contain H
2The element of doing the anti-general corrosion under the wet environment repeatedly of S is that 0.05% effect when above is remarkable at amount, is that 0.1% effect when above is more remarkable at amount.
In addition; Cu also has following effect: the anti-general corrosion under the dried wet environment repeatedly that raising sour water causes; and exist under the situation of hydrogen sulfide; significantly improve anti-general corrosion and anti-pitting attack by the sulfide protective membrane that forms insoluble; and then, also have the effect that the inhibition point corrosion produces under the situation that has S.In addition, also has the effect that improves the erosion resistance under seawater spittle environment, the seawater dipping environment.In order to obtain these effects, the amount of Cu is made as more than 0.05%, if amount is more than 0.1%, then can access more practical effect.
But in either case, if the Cu amount surpasses 2%, then its effect is saturated, on the other hand weldability is brought detrimentally affect, so be limited to 2% on it.
W:W improves not contain H
2The element of doing the anti-general corrosion under the wet environment repeatedly of S.W also has the sulfide protective membrane of formation non-corrosibility under moistening hydrogen-sulfide environmental and improves the effect of anti-general corrosion and improve the effect of anti-pitting attack.And then W also has the acid proof effect of raising.In addition, also has the effect that improves the erosion resistance under seawater spittle environment, the seawater dipping environment.
W with Cu, Ni the coexistence situation under, compare with the effect of independent interpolation, erosion resistance further improves, and together is important element with Cu, Ni in the present invention.
In order to obtain these effects, the amount of W is preferred more than 0.01%.But if the W amount surpasses 1%, the saturated cost of then described effect increases, and related weldability worsens, so its amount is preferably in below 1%.
Cr:Cr is the element that improves the erosion resistance under the seawater dipping environment, contains H but obviously reduce
2S do wet environment repeatedly, be sour water cause do anti-general corrosion under the wet environment repeatedly.Especially, if its amount surpasses 0.1%, then the anti-general corrosion under above-mentioned environment significantly descends.Therefore, on be limited to below 0.1%, preferably below 0.05%.In other words, be limited in below 0.1% as impurity.
Al:Al is the deoxidation effective elements to steel, but in the present invention, owing to contain the Si of the amount of having narrated, so can be by the Si deoxidation.Therefore, because not special necessity is carried out deoxidation treatment with Al, so can not add Al.On the other hand, if add Al energetically, then not only general corrosion significantly worsens, and descends owing to thickization of nitride causes flexible.Therefore, the upper limit of its amount is preferably below 0.1%.In other words, be limited in below 0.1% as impurity.
N:N has following effect: become ammonia and dissolve, the pH that suppresses base plate pitting attack portion descends, and improves anti-pitting attack thus.
This effect is obtaining more than 0.001% by its amount, if but surpass 0.01%, then the toughness of welded-joint worsens, so the N amount is 0.001～0.01%.Be preferably 0.001～0.006%, more preferably 0.001～0.005%.
O:O (oxygen) has following effect: become the oxide compound of ferrite product nucleus and make and organize miniaturization, improve the toughness of welded-joint.But,, then form oxide based nonmetallic impurity (CaO, MgO, the Al of the starting point that becomes pitting attack easily if amount is excessive
2O
3Deng), erosion resistance is descended, and the toughness of mother metal is descended, so the O amount is 0.0001～0.005%.
At this, in suitable way of the present invention, stipulate that following formula α is below 0.75, β is below 0.8.α, β are respectively the anti-general corrosion under the expression crude oil corrosive environment and the index of anti-pitting attack, are the empirical formulas of trying to achieve by experiment.
α＝(1-0.691×Cu)×(1-0.221×Ni)×(1-0.142×W)
β＝(1-0.444×Cu)×(1-0.156×Ni)×(1-0.630×W)
In addition, steel product for cargo oil tank of the present invention owing to normally be assembled into cargo tank by welding procedure, wishes to satisfy the weldability of regulation.Therefore, in the present invention, the carbon equivalent Ceq that the steel of preferred following formula (1) expression is formed
*Below 0.38.
Ceq*＝C+Mn/6+Ni/15+Cu/15+W/10+Cr/5+Mo/5
……(1)
And then, in suitable way of the present invention, stipulating following formula a below 0.85, b is below 0.9.A, b are respectively the indexs of the erosion resistance under expression seawater spittle environment, the seawater dipping environment, are the empirical formulas of trying to achieve by experiment.
a＝(1-0.26×Cu)×(1-0.18×Ni)×(1-0.42×W)
b＝(1-0.18×Cu)×(1-0.18×Ni)×(1-0.27×W)
In the present invention, in order further to improve resistivity, can cooperate that Mo, Ti, Zr, Sb, Sn, Ca, Mg, Nb, V, B's is at least a for general corrosion.
Mo:Mo improves not contain H
2The element of doing the anti-general corrosion under the wet environment repeatedly of S.Mo also has the sulfide protective membrane of formation non-corrosibility under moistening hydrogen-sulfide environmental and improves the effect of anti-general corrosion and improve the effect of anti-pitting attack.And then Mo also has the acid proof effect of raising.In addition, Mo also has the effect that improves the erosion resistance under seawater spittle environment, two kinds of environment of seawater dipping environment.Even the amount of these effect impurity levels also can access, but in order to obtain significant more effect, the amount of preferred Mo is more than 0.05%.More preferably more than 0.06%.But if the amount of Mo surpasses 1%, then not only effect is saturated but also impair weldability, and cost also can increase.Therefore, under the situation of adding Mo, its amount is preferably in below 1%.In addition, the lower value of the Mo amount during interpolation more preferably 0.1%, further preferably 0.3%.
Ti:Ti has following effect: by forming the generation that TiS suppresses to become the MnS of corrosive starting point, improve anti-general corrosion and anti-pitting attack.And then, under seawater spittle environment, seawater dipping environment, also have the corrosive effect at inhibition initial stage.Ti also has the effect of the intensity that improves steel.In addition, Ti also has the flexible effect that improves steel.Even the amount of these effect impurity levels also can access, but in order to obtain significant more effect, the amount of preferred Ti is more than 0.005%.But,, only can increase cost because of described effect is saturated even the amount of Ti surpasses 0.1%.Therefore, under the situation of adding Ti, its amount is preferably in below 0.1%.In addition, the lower value of the amount of the Ti during interpolation more preferably 0.01%, further preferably 0.05%.
Zr: it has following effect: preferentially form sulfide, suppress generation, the anti-general corrosion of improvement of MnS.In addition, it is the element that is difficult to form nitride that Zr compares with Ti, and all also have the feature that forms sulfide more efficiently.Even the amount of this effect impurity levels also can access, but in order to obtain significant more effect, preferably its amount is more than 0.005%.But,, then can cause toughness to descend if the amount of Zr surpasses 0.2%.Therefore, under the situation of adding Zr, its amount is preferably in below 0.2%.
Sb:Sb has following effect: improve the anti-general corrosion of doing under the wet environment repeatedly, and improve acid resistance.And then also have:, improve the effect of anti-pitting attack by the erosion resistance under the low environment of the pH value of raising pitting attack portion.In addition, also have in the effect that when the pH value reduces, improves erosion resistance under the seawater spittle environment.Even the amount of these effect impurity levels also can access, but in order to obtain significant more effect, the amount of preferred Sb is more than 0.01%.But even the amount of Sb surpasses 0.2%, described effect also can be saturated.Therefore, under the situation of adding Sb, its amount is preferably in below 0.2%.In addition, the lower value of the amount of the Sb during interpolation preferably 0.05%.
Sn:Sn and Sb are same, have following effect: improve the anti-general corrosion of doing under the wet environment repeatedly, and improve acid resistance.And then also have:, improve the effect of anti-pitting attack by the erosion resistance under the low environment of the pH value of raising pitting attack portion.In addition, also have in the effect that when the pH value reduces, improves erosion resistance under the seawater spittle environment.Even the amount of these effect impurity levels also can access, but in order to obtain significant more effect, the amount of preferred Sn is more than 0.01%.But even the amount of Sn surpasses 0.2%, described effect also can be saturated.Therefore, under the situation of adding Sn, its amount is preferably in below 0.2%.In addition, the lower value of the amount of the Sn during interpolation preferably 0.05%.
In addition, in the present invention,, can cooperate that Ca, Mg's is at least a in order to improve erosion resistance.
Ca:Ca has following effect: water-soluble and become alkali when corrosion reaction, improve erosion resistance by the pH value decline that suppresses the steel interface.The gas phase portion in the crude oil tank and the pitting attack portion of base plate are the environment of low pH value, and performance improves the effect of the erosion resistance under such environment.In addition, even under seawater spittle environment, owing to be the muriatic environment that has high density, so pH value descends and promotes and corrodes during corrosion reaction, so under such environment, also can bring into play effect.Can access these effects by amount more than 0.0003%, if but surpass 0.01% then effect can be saturated, so the amount of Ca is 0.0003～0.01%.Preferred range is 0.0003～0.006%, more preferably 0.0003～0.005%.
Mg:Mg is also same with Ca, and the pH value at the steel interface when having by the inhibition corrosion reaction descends and improves the effect of erosion resistance.Can access these effects by amount more than 0.0003%, if but surpass 0.01% then effect can be saturated, so the amount of Mg is 0.0003～0.01%.Preferred range is 0.0003～0.006%, more preferably 0.0003～0.005%.
In addition, in the present invention,, can cooperate that Nb, V and B's is at least a in order further to improve the intensity of steel.
Nb:Nb is the element with effect of the intensity that improves steel.This effect can obtain more than 0.005% by amount, if but surpass 0.1%, then toughness can worsen, so amount is 0.005～0.1%.Preferred range is 0.005～0.06%, more preferably 0.005～0.05%.
V:V is also same with Nb, is the element with effect of the intensity that improves steel.This effect can obtain more than 0.005% by amount, if but surpass 0.1%, then toughness and weldability can worsen, so amount is 0.005～0.1%.Preferred range is 0.005～0.06%, more preferably 0.005～0.05%.
B:B is also same with Nb, V, is the element with effect of the intensity that improves steel.This effect can obtain more than 0.0003% by amount, if but surpass 0.01%, then toughness can worsen, so amount is 0.0003～0.01%.Preferred range is 0.0003～0.006%, more preferably 0.0003～0.005%.
In order to make steel of the present invention, for example can be for suppressing the amount of S than the lowland and having implemented the bloom slab that RH, DH, the induction stirring etc. in system steel stage are handled, in Heating temperature be about 1100 ℃～1200 ℃, every rolling draft once is more than 3%, final rolling temperature is to carry out hot rolling under the condition about 700～900 ℃, after rolling the finishing, naturally cooling in atmosphere is perhaps from Ar
3The above temperature of point is interior with 5 ℃ of speed of cooling/cool off more than the s to about at least 570 ℃ temperature province, and naturally cooling is made in atmosphere afterwards.In addition, said temperature all is the temperature of the surface portion of steel.
Steel of the present invention, typical example are sheet material, but also comprise rod, pipe, shape material.Directly use also can show good anti-corrosion, reduce corrosion allowance, but under the situation of the anti-corrosive treatment of its surface having been carried out cover by the protection against corrosion tunicle that is made of organic resin or metal, the weather resistance of protection against corrosion tunicle improves, and erosion resistance further improves.
At this, as constitute the protection against corrosion tunicle by organic resin, can enumerate: the resin coating of ethene butyral system, epoxy system, polyurethane series, phthalic acid system etc., as the protection against corrosion tunicle that constitutes by metal, can enumerate: the plating tunicle of Zn or Al etc. or sprayed.
In addition, improve the reason of the weather resistance of protection against corrosion tunicle and think:, can suppress the expansion of the protection against corrosion tunicle that the substrate Corrosion Of Steel from protection against corrosion tunicle defective part causes or peel off as the corrosive result of obvious inhibition as the steel of the present invention of substrate.
Can adopt usual method to carry out covering the anti-corrosive treatment of steel surface by above-mentioned protection against corrosion tunicle.In addition, there is no need and must implement the protection against corrosion tunicle to whole of steel, can be only to the single face of the part of the steel that are exposed to the face corrosive environment under, for example following of the situation of steel plate to the such anti-corrosive treatment of single face enforcement.
Embodiment 1
Utilize the vacuum melting stove, melting has 28 kinds of steel of the chemical constitution shown in the table 1, makes after the bloom of 50kg, carries out heat forged with usual method, and having made thickness is the briquet of 120mm.
Then, the thickness that will obtain by above-mentioned forging is the briquet of 120mm, carries out hot rolling in heating under 1150 ℃ after 2 hours, and having formed thickness is the steel plate of 20mm.In addition, creating conditions of the steel plate of above-mentioned 20mm is following " manufacturing process 1 " or " manufacturing process 2 ".
" manufacturing process 1 ": be with thickness be 120mm briquet 1150 ℃ down heating carry out hot rolling after 2 hours, under 750 ℃, be processed into thickness 20mm, in atmosphere, naturally cool to the manufacture method of room temperature afterwards.
" manufacturing process 2 ": be to be that the briquet of 120mm is 1150 ℃ of down heating after 2 hours with thickness, carry out hot rolling, under 850 ℃, be processed into thickness 20mm,, in atmosphere, naturally cool to the manufacture method of room temperature afterwards afterwards in water-cooled in 800 ℃ to 500 ℃ temperature province.
From the thickness that produces like this is on each steel plate of 20mm, and taking off width is that 25mm, length are that 50mm, thickness are the test film of 4mm, offers the corrosion test of the cabin backboard face environment of having simulated actual oil carrier.Be called corrosion test 1.In addition, this corrosion test has supposed that crude oil contains H
2Cargo tank gas phase portion under the situation of S.
Promptly, shown in Fig. 2 (a), prepare the Glass Containers 30 that the 0.1 quality %NaCl aqueous solution 31 enters into bottom 1/3 part, on the other hand, the open upper end of the lid 34 airtight above-mentioned Glass Containerss of the vinylformic acid system by the test film 32 that takes off has been installed below (the top board test of Fig. 2 (a)).Lid 34 has gas supply port 36, and this gas supply port 36 possesses gas inlet 36a, outlet 36b, then, the Glass Containers after airtight 30 is arranged in the thermostatic bath 38, applies 50 ℃ * 20 hours → 25 ℃ * 4 hours temperature cycle in four months.At this moment, the gas phase portion 40 in Glass Containers, simulation is during ballast and full load, from described gas supply port, alternately is blown into following two kinds of gas A and gas B with the interval in two weeks.
Gas A: in volume %, 5%O2-13%CO
2-0.02%SO
2-residue N
2
Gas B: in volume %, 5%O2-13%CO
2-0.02%SO
2-0.25%H
2S-remains N
2
After four months corrosion test, according to the minimizing quality of each test film, having obtained with " mm/ " is the corrosion speed (general corrosion speed) of unit.Table 2 is that above-mentioned each test-results is represented together as the creating conditions of steel plate of corrosion test 1 and thickness 20mm.
Embodiment 2
This test is to adopt the test film identical with embodiment 1, has supposed the test of base plate of the steel product for cargo oil tank of actual oil carrier.
That is, shown in Fig. 2 (b), prepare to be equipped with the Glass Containers 30 of 40 ℃ of artificial seawaters 42, corrosion test sheet 44 be impregnated in (the base plate test of Fig. 2 (b)) in the artificial seawater.Then, the Glass Containers after airtight 30 is arranged in the thermostatic bath 38, has implemented 28 days dip test.Be blown into above-mentioned gas B from the gas inlet 36a of gas supply port 36.Be called corrosion test 2.In addition, among the figure, the member identical with Fig. 2 (a) represented with same-sign.
The mensuration of the pitting attack degree of depth is on the corrosion test sheet after the test, and with the degree of depth of the pitting attack generating unit in the above-mentioned part 46 of circle, promptly smearing mud with the part that does not produce pitting attack partly is that benchmark utilizes milscale to implement.At this, adopt value in pitting attack generating unit degree of depth maximum as the pitting attack degree of depth.
After having carried out 28 days corrosion test, according to the pitting attack degree of depth of each test film, having obtained with " mm/ " is the pitting attack speed of unit.Table 2 is represented above-mentioned each test-results together as the creating conditions of steel plate of corrosion test 2 and thickness 20mm.
Embodiment 3
Preparing two thicknesss of slab that obtain by described manufacture method 1,2 is the rolling stock of 20mm, by the three electrode FCB methods of heat input 120kJ/cm, implements plate and connects welding, has made welding joint.In the welding joint after making, respectively take off No. 4 charpy impact test sheets of three JIS regulations from the central part of thickness of slab, implemented charpy impact test with under 0 ℃ of the temperature for various steel.In addition, otch (notch) position becomes the heat affected zone apart from joint portion 1mm.To be shown in the table 2 together at three mean values of the absorption energy (J) in the summer coomb's test Coomb and the result of described corrosion test 1,2.
In addition, represent in the table 1 that it is α, β and the Ceq that will become the index of weldability that the index of erosion resistance is arranged
*Represent with chemical ingredients.
From the result of the corrosion test shown in the table 21,2 and welding joint test also as can be seen, among Comparative examples A, S, U～X, the AA, owing to suitably do not add alloying element, so α has surpassed 0.75, perhaps β has surpassed 0.8, erosion resistance deficiency in corrosion test 1 or 2.In addition, comparative example T does not contain Ni, W, erosion resistance deficiency in corrosion test 1,2.In addition, comparative example S, W, Z are owing to Cr, Mo, Ni are superfluous respectively, so Ceq
*Height cracks during welding etc., can not take off the charpy impact test sheet.In comparative example X, AA, joint toughness descends, and considers under the situation that is applicable to actual cargo tank its weldability, welding joint characteristic deficiency.In addition, among the Comparative examples A B, α is below 0.75, and β is below 0.8, and Ceq
*Below 0.38, but because the Ni amount surpasses 1%, so the cost height is little for the corrosion countermeasure superiority of the increase of existing application or corrosion allowance.
On the other hand, example of the present invention all shows good anti-corrosion in corrosion test 1,2, and does not have the problem of weldability, joint characteristic.
The foregoing description 1～3rd with the relevant test of corrosion test under the former oil environment, is narrated the corrosion test of briny environment below.
Embodiment 4
This is a corrosion test of having simulated seawater spittle environment.
From 28 kinds of steel shown in the table 1, from each steel plate of the thickness 20mm that obtains by described manufacture method 1 or 2, taking off width is that 60mm, length are that 100mm, thickness are the test film of 3mm, at Okinawa Prefecture Miyako Jima (bank off sea is apart from 5m) towards the south, from horizontal tilt under 30 ° the state, implemented the weather exposure test in 1 year.
This environment is the environment that the spittle of seawater directly puts on test film, is the test that is equivalent under the corrosive environment of seawater spittle environment of ballast tank top plate portion.
Test film after test is removed corrosion product, by removing the weight difference of test front and back with surface-area, obtains average thickness of slab reduction, and being converted into " mm/ " is the corrosion speed of unit.
Table 2 is represented above-mentioned each test-results together as the creating conditions of steel plate of corrosion test 3 and thickness 20mm.
Embodiment 5
Carried out the corrosion test under seawater dipping environment in this example.That is, use and test film that embodiment 4 is same, in the nature seawater that draw up in Wakayama Ken Hainan city, flood half a year from seawater.
This environment is the corrosive environment that is equivalent to the seawater dipping environment of the side plate back side of crude oil tank and the base plate back side, ballast tank side.
Test film after test is removed dirt settling and corrosion product, by removing the weight difference of test front and back with surface-area, obtains average thickness of slab reduction, and being converted into " mm/ " is the corrosion speed of unit.
Table 2 is represented above-mentioned each test-results together as the creating conditions of steel plate of corrosion test 4 and thickness 20mm.In addition, be that the chemical ingredients of a, b and table 1 makes up and represents with the index of erosion resistance.
From the result of the corrosion test shown in the table 23,4 as can be seen, in Comparative examples A, S～U, W, Y, AA, owing to suitably do not add alloying element, so a has surpassed 0.85, perhaps b has surpassed 0.9, erosion resistance deficiency in corrosion test 3 or 4.For other comparative example, be difficult in corrosion test 3,4, can to guarantee fully erosion resistance to a certain degree, in addition, the erosion resistance deficiency of above-mentioned corrosion test 1,2.On the other hand, in example of the present invention, in corrosion test 1,2, all show good anti-corrosion, and erosion resistance is also good in corrosion test 3,4, and weldability, joint characteristic are also no problem.
[table 1]
| Steel grade | C | Si | Mn | P | S | Al | N | O | Cu | Ni | W | Cr | Mo | Ti | Zr | Sb | Sn | Ca | Mg | Nb | V | B | α | β | a | b | Ceq * | |
| A | 0.15 | 0.25 | 1.1 | 0.02 | 0.002 | 1 | 1 | 1 | 0.33 | Comparative example | ||||||||||||||||||
| B | 0.08 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.5 | 0.25 | 0.3 | 0.01 | 0.592 | 0.606 | 0.726 | 0.8 | 0.35 | Example | ||||||||||
| C | 0.09 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.5 | 0.25 | 0.3 | 0.01 | 0.15 | 0.592 | 0.606 | 0.726 | 0.8 | 0.36 | Example | |||||||||
| D | 0.09 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.5 | 0.25 | 0.3 | 0.01 | 0.01 | 0.592 | 0.606 | 0.726 | 0.8 | 0.36 | Example | |||||||||
| E | 0.08 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.5 | 0.25 | 0.3 | 0.01 | 0.01 | 0.592 | 0.606 | 0.726 | 0.8 | 0.35 | Example | |||||||||
| F | 0.06 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.5 | 0.25 | 0.3 | 0.01 | 0.2 | 0.592 | 0.606 | 0.726 | 0.8 | 0.37 | Example | |||||||||
| G | 0.09 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.5 | 0.25 | 0.3 | 0.01 | 0.1 | 0.592 | 0.606 | 0.726 | 0.8 | 0.36 | Example | |||||||||
| H | 0.1 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.3 | 0.1 | 0.2 | 0.01 | 0.753 | 0.746 | 0.829 | 0.88 | 0.33 | Example | ||||||||||
| I | 0.07 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.7 | 0.3 | 0.4 | 0.01 | 0.455 | 0.491 | 0.644 | 0.74 | 0.36 | Example | ||||||||||
| J | 0.06 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.55 | 0.22 | 0.25 | 0.01 | 0.004 | 0.569 | 0.615 | 0.737 | 0.81 | 0.32 | Example | |||||||||
| K | 0.08 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.55 | 0.22 | 0.25 | 0.01 | 0.005 | 0.569 | 0.615 | 0.737 | 0.81 | 0.34 | Example | |||||||||
| L | 0.06 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.55 | 0.22 | 0.21 | 0.01 | 0.01 | 0.572 | 0.633 | 0.75 | 0.82 | 0.32 | Example | |||||||||
| M | 0.06 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.55 | 0.21 | 0.21 | 0.01 | 0.02 | 0.574 | 0.634 | 0.752 | 0.82 | 0.32 | Example | |||||||||
| N | 0.06 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.54 | 0.22 | 0.21 | 0.01 | 0.001 | 0.579 | 0.637 | 0.753 | 0.82 | 0.32 | Example | |||||||||
| O | 0.06 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.55 | 0.22 | 0.21 | 0.01 | 0.01 | 0.02 | 0.001 | 0.572 | 0.633 | 0.75 | 0.82 | 0.32 | Example | |||||||
| P | 0.06 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.55 | 0.22 | 0.21 | 0.01 | 0.1 | 0.005 | 0.572 | 0.633 | 0.75 | 0.82 | 0.32 | Example | ||||||||
| Q | 0.06 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.55 | 0.22 | 0.21 | 0.01 | 0.005 | 0.02 | 0.572 | 0.633 | 0.75 | 0.82 | 0.32 | Example | ||||||||
| R | 0.06 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.55 | 0.22 | 0.21 | 0.01 | 0.15 | 0.01 | 0.001 | 0.572 | 0.633 | 0.75 | 0.82 | 0.32 | Example | |||||||
| S | 0.04 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 1 | 1 | 1 | 1 | 1 | 0.42 | Comparative example | |||||||||||||
| T | 0.15 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.5 | 0.655 | 0.778 | 0.87 | 0.91 | 0.37 | Comparative example | |||||||||||||
| U | 0.15 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.5 | 0.89 | 0.922 | 0.91 | 0.91 | 0.37 | Comparative example | |||||||||||||
| V | 0.08 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 1 | 0.779 | 0.844 | 0.82 | 0.82 | 0.33 | Comparative example | |||||||||||||
| W | 0.04 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 1 | 1 | 1 | 1 | 1 | 0.42 | Comparative example | |||||||||||||
| X | 0.09 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 1 | 0.858 | 0.37 | 0.58 | 0.73 | 0.37 | Comparative example | |||||||||||||
| Y | 0.08 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.4 | 0.2 | 0.3 | 0.692 | 0.797 | 0.864 | 0.89 | 0.36 | Comparative example | |||||||||||
| Z | 0.04 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.3 | 2 | 0.5 | 0.3 | 0.442 | 0.596 | 0.59 | 0.61 | 0.54 | Comparative example | ||||||||||
| AA | 0.15 | 0.25 | 1.1 | 0.3 | 0.002 | 0.02 | 0.003 | 0.0008 | 1 | 1 | 1 | 1 | 0.33 | Comparative example | ||||||||||||||
| AB | 0.09 | 0.25 | 1.1 | 0.02 | 0.002 | 0.02 | 0.003 | 0.0008 | 0.2 | 1.2 | 0.1 | 0.62 | 0.69 | 0.712 | 0.74 | 0.38 | Comparative example |
[table 2]
| Create conditions | Corrosion test 1 | Corrosion test 2 | Joint toughness | Corrosion test 3 | Corrosion test 4 | ||
| A | 1 | 0.28 | 11.7 | 121 | 0.81 | 0.22 | Comparative example |
| B | 1 | 0.12 | 4.9 | 102 | 0.35 | 0.07 | Example |
| C | 1 | 0.09 | 4.1 | 80 | 0.29 | 0.07 | Example |
| D | 2 | 0.10 | 3.9 | 101 | 0.31 | 0.06 | Example |
| E | 1 | 0.10 | 4.0 | 100 | 0.32 | 0.06 | Example |
| F | 2 | 0.09 | 4.1 | 85 | 0.28 | 0.07 | Example |
| G | 1 | 0.08 | 3.7 | 83 | 0.24 | 0.07 | Example |
| H | 2 | 0.13 | 5.2 | 111 | 0.3 | 0.08 | Example |
| I | 1 | 0.06 | 3.1 | 92 | 0.24 | 0.05 | Example |
| J | 1 | 0.07 | 3.9 | 135 | 0.31 | 0.07 | Example |
| K | 2 | 0.07 | 3.8 | 108 | 0.31 | 0.07 | Example |
| L | 1 | 0.08 | 4.2 | 140 | 0.34 | 0.08 | Example |
| M | 1 | 0.08 | 4.1 | 133 | 0.32 | 0.08 | Example |
| N | 1 | 0.08 | 4.2 | 134 | 0.34 | 0.09 | Example |
| O | 1 | 0.08 | 4.2 | 140 | 0.34 | 0.08 | Example |
| P | 1 | 0.07 | 3.8 | 115 | 0.29 | 0.08 | Example |
| Q | 2 | 0.08 | 4.3 | 126 | 0.34 | 0.08 | Example |
| R | 1 | 0.07 | 3.9 | 102 | 0.31 | 0.08 | Example |
| S | 1 | 0.54 | 8.7 | - | 0.8 | 0.1 | Comparative example |
| T | 2 | 0.20 | 9.1 | 105 | 0.7 | 0.18 | Comparative example |
| U | 1 | 0.23 | 10.1 | 120 | 0.73 | 0.18 | Comparative example |
| V | 1 | 0.19 | 9.1 | 122 | 0.33 | 0.11 | Comparative example |
| W | 1 | 0.21 | 9.2 | - | 0.54 | 0.2 | Comparative example |
| X | 1 | 0.24 | 9.2 | 31 | 0.25 | 0.08 | Comparative example |
| Y | 2 | 0.18 | 8.6 | 93 | 0.74 | 0.11 | Comparative example |
| Z | 1 | 0.08 | 4.2 | - | 0.28 | 0.05 | Comparative example |
| AA | 2 | 0.21 | 7.2 | 23 | 0.53 | 0.18 | Comparative example |
| AB | 2 | 0.13 | 5.1 | 106 | 0.32 | 0.06 | Comparative example |
Claims (6)
1. steel product for cargo oil tank, wherein,
In quality %, contain that C:0.01～0.2%, Si:0.01～1%, Mn:0.05～2%, P:0.05% are following, S:0.01% is following, Ni:0.01～1%, Cu:0.05～2%, W:0.01～1%, Cr:0.1% is following, Al:0.1% is following, N:0.001～0.01%, O:0.0001～0.005%, and constitute by surplus Fe and impurity.
2. steel product for cargo oil tank according to claim 1, wherein,
Following formula α is below 0.75, and β is below 0.8, and the Ceq* shown in the formula (1) is below 0.38,
α＝(1-0.691×Cu)×(1-0.221×Ni)×(1-0.142×W)
β＝(1-0.444×Cu)×(1-0.156×Ni)×(1-0.630×W)
Ceq*＝C+Mn/6+Ni/15+Cu/15+W/10+Cr/5+Mo/5
……(1)。
3. steel product for cargo oil tank according to claim 1 and 2, wherein,
Following formula a is below 0.85, and b is below 0.9,
a＝(1-0.26×Cu)×(1-0.18×Ni)×(1-0.42×W)
b＝(1-0.18×Cu)×(1-0.18×Ni)×(1-0.27×W)。
4. according to each described steel product for cargo oil tank in the claim 1～3, wherein,
In quality %, also contain one or more the element of selecting at least one group from following group (i)～(iii),
(i) one or more of Mo:0.05～1%, Ti:0.005～0.1%, Zr:0.005～0.2%, Sb:0.01～0.2%, Sn:0.01～0.2%
(ii) one or both of Ca:0.0003～0.01%, Mg:0.0003～0.01%
(iii) one or more of Nb:0.005～0.1%, V:0.005～0.1%, B:0.0003～0.01%.
5. according to each described steel product for cargo oil tank in the claim 1～4, wherein,
On the face of at least a portion, has the protection against corrosion tunicle.
6. crude oil tanker, wherein,
Has the cargo tank that adopts each described steel in the claim 1～5 and constitute.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP119128/2004 | 2004-04-14 | ||
| JP2004119128 | 2004-04-14 | ||
| JP305666/2004 | 2004-10-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298645B (en) * | 2007-05-02 | 2011-03-30 | 株式会社神户制钢所 | Steel plate having superior pitting corrosion resistance and manufacturing method thereof |
| CN102605255A (en) * | 2012-01-19 | 2012-07-25 | 武汉钢铁(集团)公司 | 400Mpa grade corrosion resistant reinforcing steel bar |
| CN102618786A (en) * | 2011-01-25 | 2012-08-01 | 株式会社神户制钢所 | Ship steel with excellent corrosion resistance |
| CN102686760A (en) * | 2010-07-09 | 2012-09-19 | 住友金属工业株式会社 | Corrosion-resistant steel material for cargo oil tank |
| TWI391499B (en) * | 2007-07-27 | 2013-04-01 | Jfe Steel Corp | Hot-rolled shape steel for ships and process for manufacturing the same |
| CN103484776A (en) * | 2012-06-12 | 2014-01-01 | 株式会社神户制钢所 | Corrosion-resistant steel material for ship |
| TWI460285B (en) * | 2007-09-25 | 2014-11-11 | Jfe Steel Corp | Hot-rolled shapes for crude oil tank and process for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101298645B (en) * | 2007-05-02 | 2011-03-30 | 株式会社神户制钢所 | Steel plate having superior pitting corrosion resistance and manufacturing method thereof |
| TWI391499B (en) * | 2007-07-27 | 2013-04-01 | Jfe Steel Corp | Hot-rolled shape steel for ships and process for manufacturing the same |
| TWI460285B (en) * | 2007-09-25 | 2014-11-11 | Jfe Steel Corp | Hot-rolled shapes for crude oil tank and process for manufacturing the same |
| CN102686760A (en) * | 2010-07-09 | 2012-09-19 | 住友金属工业株式会社 | Corrosion-resistant steel material for cargo oil tank |
| CN102618786A (en) * | 2011-01-25 | 2012-08-01 | 株式会社神户制钢所 | Ship steel with excellent corrosion resistance |
| CN102605255A (en) * | 2012-01-19 | 2012-07-25 | 武汉钢铁(集团)公司 | 400Mpa grade corrosion resistant reinforcing steel bar |
| CN103484776A (en) * | 2012-06-12 | 2014-01-01 | 株式会社神户制钢所 | Corrosion-resistant steel material for ship |
| CN103484776B (en) * | 2012-06-12 | 2015-10-21 | 株式会社神户制钢所 | Corrosion-resistant steel material for ship and vessel |
| CN104911498A (en) * | 2015-06-26 | 2015-09-16 | 武汉钢铁(集团)公司 | Atmospheric-corrosion-resistant steel bar and production method thereof |
| CN107118598A (en) * | 2017-06-06 | 2017-09-01 | 界首市七曜新能源有限公司 | Gas cooler external coating, gas cooler and preparation method thereof |
| CN107177801A (en) * | 2017-06-06 | 2017-09-19 | 界首市七曜新能源有限公司 | High pressure resistant easy heat-conducting gas cooler and preparation method thereof |
| CN111655887A (en) * | 2018-01-26 | 2020-09-11 | 日本制铁株式会社 | Steel for anchor chain and anchor chain |
| CN114107800A (en) * | 2021-09-14 | 2022-03-01 | 鞍钢股份有限公司 | Longitudinal variable-thickness steel plate for upper deck of crude oil cargo oil tank and production method |
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