CN102686760A - Corrosion-resistant steel material for cargo oil tank - Google Patents
Corrosion-resistant steel material for cargo oil tank Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- 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
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- 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
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- 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
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
Abstract
Disclosed is a corrosion-resistant steel material for a cargo oil tank, which has excellent resistance to general corrosion and local corrosion and is characterized by containing, in mass%, 0.01-0.2% of C, 0.01-1.0% of Si, 0.05-2.0% of Mn, 0.002-0.1% of P, 0.01% or less of S, 0.01-2.0% of Cu, 0.01-1.0% of Ni, more than 0% but less than 0.01% of W and 0.1% or less of Al, with the balance made up of Fe and impurities. The corrosion-resistant steel material for a cargo oil tank may additionally contain one or more elements selected from among Cr, Mo, Ti, Zr, Sb, Sn, Nb, V, B, Ca, Mg and REM. The surface of the corrosion-resistant steel material for a cargo oil tank may be coated with a sulfide layer or an anti-corrosion coating film.
Description
Technical field
The present invention relates to the steel that a kind of oil cargo tank that is used for the crude oil tank of oil tanker is used.
Background technology
The etch state of the oil cargo tank of oil tanker roughly is divided into two kinds.A kind of is that another kind is the local corrosion that causes in base plate in the general corrosion of the gas phase portion generation of top plate portion.Particularly contain hydrogen sulfide (H at loading
2During S) crude oil, because the H that is contained in the crude oil
2The part of S is transferred in the gas phase, so corrosive environment is extremely harsh.
Also have report to claim, in the corrosive environment of above-mentioned that kind, be prone to cause general corrosion in the cabin backboard face that becomes oil cargo tank ceiling portion, corrosion speed is very big, has reached more than the 0.3mm/.In addition, also have following situation: in the easy origination point corrosion of the base plate of oil cargo tank, the pitting attack tempo is up to number mm/.
In view of such situation, the internal surface of the steel of oil cargo tank is implemented application, though being the part, this enforcements application carries out, the cost that the cost of initial stage application reaches about per 10 years application again is bigger.In addition, on flat dunnage, even under the situation of having implemented application, the defective part origination point corrosion that also can film certainly sometimes.Therefore, practical situation are to have considered the thickness of slab design of corrosion allowance, as the countermeasure of reply general corrosion, local corrosion.For example carry out estimating the corrosion allowance thickness of slab design such, that considered corrosion allowance of 2mm for the use in 20 years.And, on base plate, implement inspection termly, utilize built-up welding to repair for the bigger part of the pitting attack degree of depth, but therefore can produce huge maintenance cost, and become problem.
And, if considered the thickness of slab design of corrosion allowance,, also can produce the crude oil loading amount and reduce and the such shortcoming of the corresponding amount of the thickness of slab of having considered corrosion allowance then because the thickness of steel correspondingly increases, and not only the manufacturing cost of cargo tank rises.Thereby urgent expectation is developed and a kind ofly can be sought to reduce corrosion allowance and can prevent cost steel product for cargo oil tank that rise, excellent corrosion resistance.
In addition, in the shipbuilding stage, weld in order to construct cargo tank, thereby have welded-joint, therefore, the intensity, toughness, weldableness etc. of expecting the good and welded-joint of erosion resistance not only are excellent material also.
Use steel as oil cargo tank, for example in patent documentation 1, proposed to contain the steel of Cu and Mg, in addition, in patent documentation 2, proposed the steel that conduct must composition contains Cr and Al as essential composition.But, do not consider fully to contain H at crude oil
2H under the situation of S
2Therefore the influence that S brings corrosion, might can't obtain sufficient erosion resistance in being equipped on the oil cargo tank of real ship.H in the environment of crude oil tank base plate particularly
2The influence of S is very big, therefore, must guarantee have H
2Erosion resistance in the environment of S.
In addition, disclosed in the patent documentation 3, contain the steel that Cu and Ni form as essential composition and improved interior anti-general corrosion property and the anti-pitting attack property of oil cargo tank.
But,,, therefore have the such problem of melting cost rising of steel owing to the alloying constituent that contains the such costliness of Cu and Ni though these steel have improved erosion resistance really.Particularly the price of these elements is surging in recent years, even the content of alloying constituent is lower, the cost of alloying constituent is also higher, and makes that comparing cost with the coating process of common iron can increase significantly.
And; In patent documentation 4, disclose a kind of conduct and must contain Cu:0.05%～2%, Ni:0.01%～1%, W:0.01%～1%, N:0.001%～0.01% and O (oxygen) by composition: 0.0001%～0.005% steel, and improve anti-general corrosion property and the anti-local corrosion property in the oil cargo tank.
But,, therefore leave the such problem of melting cost rising of steel because these steel contain the alloying constituent of the such costliness of Cu and Ni.
Patent documentation 1: TOHKEMY 2000-17381 communique
Patent documentation 2: TOHKEMY 2001-107180 communique
Patent documentation 3: TOHKEMY 2003-82435 communique
Patent documentation 4: TOHKEMY 2005-325439 communique
Summary of the invention
The present invention promptly accomplishes in view of above-mentioned present situation, and its purpose is to provide a kind of resistivity for general corrosion, local corrosion oil cargo tank good and that cost-performance is higher to use the erosion resistance steel.
The inventor simulates the corrosive environment of crude oil in the real ship in order to reach above-mentioned problem, tests for the general corrosion that produces in the gas phase portion of top plate portion with in the local corrosion that base plate causes.That is,, containing rare gas element and H to gas phase portion
2S does in the wet environment repeatedly, has carried out containing H having loaded
2The reproduction test of the corrosion product layer that the cabin backboard face of the real ship of the crude oil of S is seen.And, to base plate, carried out simulation and in high concentration chloride solution, tested from oil coating defective part origination point corrosive.
This experiment be utilize Fig. 1 and testing apparatus shown in Figure 2 to after among the embodiment that states steel that use, that have various chemical constitutions carry out.In addition, Fig. 1 is the reproduction testing apparatus of gas phase portion, and Fig. 2 is the reproduction testing apparatus of base plate.
Its result about the erosion resistance of gas phase portion and base plate, obtains the opinion shown in following (a)～(c).
(a) in the reproduction of gas phase portion test, can be clear and definite in promptly about the test of the general corrosion that produces at the cargo tank top plate portion: no matter whether contain alloying element, corrosion speed does not all rely on the time basically.Thereby in gaseous environment, the anticorrosion ability of corrosion product is less, need contain the erosion resistance that alloying element seeks to improve mother metal self through making it.
Under the general corrosion environment, making its way that contains Cu, Ni, W element is effectively, and through contain these elements compoundly, this effect can further increase.Particularly, suppress the anode dissolution reaction of steel, thereby improve the erosion resistance of mother metal self through contain Cu and W compoundly.
(b) in the reproduction of base plate test, can be clear and definite in promptly about the test of the local corrosion that causes in base plate: the pitting attack speed at corrosion initial stage does not have the difference of steel grade basically, but along with effluxion, according to the difference of steel grade, pitting attack speed can descend.Thereby in the base plate environment, the anticorrosion ability of corrosion product is dominated.That is,, just can seek to improve erosion resistance as long as can on steel surface, form the corrosion product that delays to corrode development at the corrosion initial stage.
Under situation about steel being positioned under the local corrosion environment, can form the iron rust (layer of β-FeOOH) at steel surface usually.But, if contain Cu, Ni, W, then at first form sulfurized layer at steel surface, form the iron rust layer afterwards.Because this sulfurized layer can significantly suppress the anode dissolution reaction, therefore helps to improve erosion resistance.The layer that particularly contains the sulfide of W or also contain the sulfide of Mo can show cation selective, has by sulfurized layer and suppresses Cl
-The effect that ion sees through, therefore, formation contain W sulfide or also contain Mo sulfide the layer situation under, can help to improve erosion resistance especially.
(c) this shows; Under the general corrosion environment and under any environment under the local corrosive environment; Making it contain Cu, Ni and W all is outbalance, in order under two kinds of environment, all to obtain higher erosion resistance, need make Cu, Ni and W be respectively suitable content.
The present invention promptly is based on above-mentioned opinion and accomplishes, and the main contents of its invention are that the oil cargo tank shown in following (1)～(7) uses the erosion resistance steel.
(1) a kind of corrosion resistant steel for cargo oil tanks material; It is characterized in that; By quality % contain C:0.01%～0.2%, Si:0.01%～1.0%, Mn:0.05%～2.0%, P:0.002%～0.1%, below the S:0.01%, Cu:0.01%～2.0%, Ni:0.01%～1.0%, W: greater than 0% and less than 0.01%, below the Al:0.1%, surplus is made up of Fe and impurity.
(2) according to the corrosion resistant steel for cargo oil tanks material of above-mentioned (1); It is characterized in that, by quality % contain below a kind of or two or more parts that substitute Fe in the following element: the Cr:5.0%, below the Mo:1.0%, below the Ti:0.2%, below the Zr:0.2%, below the Sb:0.3% and below the Sn:0.3%.
(3) according to the corrosion resistant steel for cargo oil tanks material of above-mentioned (1) or (2); It is characterized in that, by quality % contain below a kind of or two or more parts that substitute Fe in the following element: the Nb:0.1%, below the V:0.2% and below the B:0.01%.
(4) according to any corrosion resistant steel for cargo oil tanks material in above-mentioned (1)～(3); It is characterized in that, by below a kind of or two or more parts that substitute Fe in the following element of quality %: the Ca:0.01%, below the Mg:0.01% and below the REM:0.01%.
According to corrosion resistant steel for cargo oil tanks material any in above-mentioned (1)～(4), it is characterized in that (5) sulfide that has Cu, Ni and W from the teeth outwards perhaps also has the layer of the sulfide of Mo.
According to corrosion resistant steel for cargo oil tanks material any in above-mentioned (1)～(4), it is characterized in that (6) surface is covered by the protection against corrosion tunicle.
(7) according to corrosion resistant steel for cargo oil tanks material any in above-mentioned (1)～(4), it is characterized in that, utilize the protection against corrosion tunicle across by the sulfide of Cu, Ni and W or the middle layer covering surfaces that also constitutes by the sulfide of Mo.
Adopt the present invention, can provide a kind of and use the erosion resistance steel for the good oil cargo tank of the resistivity of general corrosion, local corrosion.
Description of drawings
Fig. 1 representes the reproduction testing apparatus of gas phase portion.
Fig. 2 representes the reproduction testing apparatus of base plate.
Fig. 3 representes the acid dipping testing apparatus.
Embodiment
Below, specify the present invention.In addition, " % " expression " quality % " of the content of each element.
(A) chemical constitution
C：0.01％～0.2％
C is in order to ensure as the necessary element of the intensity of material, and needing its content is more than 0.01%.But if its content surpasses 0.2%, then weldableness descends.In addition, along with the increase of the content of C, in sour environment, become negative electrode and promote the growing amount of corrosive cementite to increase, with this, weldableness worsens.Therefore, its upper limit is made as 0.2%.Be limited to 0.15% on preferred, be limited to 0.04% under preferred.
Si：0.01％～1.0％
Si is the necessary element of deoxidation, in order to obtain sufficient deoxidation effect, need contain the Si more than 0.01%.But,, then damage the toughness of mother metal and welded-joint if its content surpasses 1%.Therefore, making the content of Si is 0.01%～1.0%.Be limited to 0.8% on preferred, be limited to 0.5% on preferred.Be limited to 0.04% under preferred, be limited to 0.10% under preferred.
Mn：0.05％～2.0％
Mn has the element of effect that improves the intensity of steel with low cost, and in order to obtain this effect, needing its content is more than 0.05%.But if its content surpasses 2.0%, then weldableness variation, and joint toughness is variation also.Therefore, making the content of Mn is 0.05%～2.0%.Be limited to 1.8% on preferred, be limited to 1.6% on preferred.Be limited to 0.3% under preferred, be limited to 0.5% under preferred.
P：0.002％～0.1％
P has the effect that improves anti-general corrosion property and anti-pitting attack property.In addition, the content of P is many more usually, and acid resistance is poor more, but in containing the steel of Cu, can improve acid resistance through containing P.Can bring into play the acid proof effect in the steel that above-mentioned such anti-general corrosion property of raising and the acid proof effect in the anti-pitting attack property and raising contain Cu through containing P more than 0.002%.But if its content surpasses 0.1%, then weldableness significantly descends.Therefore, making the content of P is 0.002%～0.1%.Be limited to 0.08% on preferred, be limited to 0.06% on preferred.Be limited to 0.003% under preferred, be limited to 0.004% under preferred.
Below the S:0.01%
S is present in the steel as impurity inevitably.But, if its content surpasses 0.01%, then in steel, generating MnS in a large number, MnS can become the corrosive starting point and general corrosion and pitting attack take place.Therefore, making the content of S is below 0.01%.Be limited to 0.008% on preferred, be limited to 0.005% on preferred.In addition, the content of S is low more good more.
Cu：0.01％～2.0％
Cu is not only the element that improves anti-general corrosion property, but also is that (under the local corrosion environment) together forms the element that sulfurized layer improves anti-pitting attack property with S under the base plate environment in oil cargo tank.Cu through containing more than 0.01% can bring into play above-mentioned effect, even but the content of Cu surpasses 2.0%, and not only above-mentioned effect can be saturated, and the crackle when preventing hot rolling and the content of the Ni that contains also increases, and therefore can cause cost to increase.Therefore, making the content of C u is 0.01%～2.0%.Be limited to 1.8% on preferred, be limited to 1.5% on preferred.Be limited to 0.05% under preferred, be limited to 0.10% under preferred.In addition, state after sulfurized layer is elaborated.
Ni：0.01％～1.0％
Ni is identical with Cu, also is not only the element that improves anti-general corrosion property, but also is that (under the local corrosion environment) together forms the element that sulfurized layer improves anti-pitting attack property with S under the base plate environment in oil cargo tank.Ni through containing more than 0.01% can bring into play above-mentioned effect, even but the content of Ni surpasses 1.0%, and not only above-mentioned effect can be saturated, and can cause cost to increase.Therefore, making the content of Ni is 0.01%～1.0%.Be limited to 0.9% on preferred, be limited to 0.8% on preferred.Be limited to 0.05% under preferred, be limited to 0.1% under preferred.In addition, state after sulfurized layer is elaborated.
W: greater than 0% and less than 0.01%
W improves acid proof element, can improve anti-general corrosion property.In addition, W also exists with other elements compounding the sulfurized layer that improves anti-general corrosion property, in moistening hydrogen-sulfide environmental, together forms non-corrosibility with S to improve the effect of anti-pitting attack property.W through containing trace can obtain above-mentioned effect.But, if contain the W more than 0.01%, then can't obtain the effect that matches with cost, and might cause the deterioration of weldableness.Thereby the content that makes W is greater than 0%, less than 0.01%.In addition, state after sulfurized layer is elaborated.
Below the Al:0.1%
Al is the deoxidation effective elements to steel, but owing to contain Si in the present invention, therefore utilizes Si to carry out deoxidation.Thereby, may not utilize Al to carry out deoxidation treatment, therefore also can not contain Al.But, also can except contain Si, also contain Al and carry out complex deoxidization.In this case, if contain the Al more than 0.005%, then deoxidation effectively.On the other hand, if the content of Al surpasses 0.1%, then not only anti-general corrosion property significantly worsens, and because thickization of nitride can cause toughness decline.Thereby the upper limit that will contain the content of the Al under the situation of Al is made as below 0.1%.Be limited to 0.05% on preferred.
Oil cargo tank of the present invention has above-mentioned element with the erosion resistance steel, and surplus is made up of Fe and impurity.In addition, impurity is meant in industry when making steel, because a variety of causes of manufacturing process and the composition of mainly sneaking into from such raw materials such as ore, waste materials, allowed the present invention not being produced in the dysgenic scope.
As required, oil cargo tank of the present invention can contain the part that one or more kinds of units among Cr, Mo, Ti, Zr, Sb, Sn, Nb, V, B, Ca, Mg, the REM usually substitute Fe with the erosion resistance steel.
These elements can be divided into following 3 groups.
(i) the 1st group is a kind of or two or more in the following element: below the Cr:5.0%, below the Mo:1.0%, below the Ti:0.2%, below the Zr:0.2%, below the Sb:0.3% and below the Sn:0.3%.
(ii) the 2nd group is a kind of or two or more in the following element: below the Nb:0.1%, below the V:0.2% and below the B:0.01%.
(iii) the 3rd group is a kind of or two or more in the following element: below the Ca:0.01%, below the Mg:0.01% and below the REM:0.01%.
Below, to above-mentioned each element of every group profile.
(i) the 1st group: Cr, Mo, Ti, Zr, Sb and Sn
Below the Cr:5.0%
Can contain Cr as required.If contain Cr separately, then can reduce the erosion resistance in the acid environment, but contain compoundly as if itself and Cu, then can be formed on and do the higher rusty scale of protectiveness in the wet environment repeatedly, thereby improve anti-general corrosion property.But if the content of Cr surpasses 5.0%, then not only above-mentioned effect is saturated, and can cause weldableness decline, cost to increase.Thereby, the upper limit of the content of Cr is made as 5.0%.Be limited to 4.5% on preferred, be limited to 4.0% on preferred.In addition, for the effect that stably passes and contain Cr and produce, the content that preferably makes Cr is more than 0.5%.More preferably more than 1.0%.
Below the Mo:10%
Can contain Mo as required.Mo improves acid proof element, has the effect that improves the anti-general corrosion property in the wet environment repeatedly of doing of sour water.In addition, also has in moistening hydrogen-sulfide environmental the effect that the sulfurized layer that together forms non-corrosibility with S improves anti-pitting attack property.But even the content of Mo surpasses 1.0%, not only effect can be saturated, and can damage weldableness, and cost also can increase.Thereby the upper limit of the content of the Mo in the time of will containing Mo is made as 1.0%.Be limited to 0.5% on preferred, be limited to 0.4% on preferred.In addition, for the effect that stably passes and contain Mo and produce, preferably contain the Mo more than 0.01%.More preferably more than 0.1%, further be preferably more than 0.2%.
Below the Ti:0.2%
Can contain Ti as required.Ti has the effect of the intensity that improves steel.Ti also has the toughness that improves steel, through forming the effect that MnS that TiS suppresses to become the corrosive starting point generates, improves anti-general corrosion property and anti-pitting attack property.And, utilize the dispersion of TiN to suppress thickization of crystal grain, therefore, the toughness of the weld part of big heat input improves.But even the content of Ti surpasses 0.2%, not only above-mentioned effect can be saturated, and cost also will rise.Thereby the upper limit of the content of the Ti in the time of will containing Ti is made as 0.2%.Be limited to 0.15% on preferred, be limited to 0.1% on preferred.In addition, for the effect that stably passes and contain Ti and produce, preferably contain the Ti more than 0.005%.More preferably more than 0.01%, further be preferably more than 0.015%.
Below the Zr:0.2%
Can contain Zr as required.Zr is identical with Ti, has preferential formation sulfide and suppresses the effect that MnS generates.In addition, Zr and Ti are in a ratio of the element that be difficult for to form nitride, and have and form the such characteristic of sulfide more efficiently.But,, then can cause toughness to descend if the content of Zr surpasses 0.2%.Thereby the upper limit of the content of the Zr in the time of will containing Zr is made as 0.2%.Be limited to 0.15% on preferred, be limited to 0.1% on preferred.In addition, for the effect that stably passes and contain Zr and produce, preferably contain the Zr more than 0.005%.More preferably more than 0.01%, further be preferably more than 0.02%.
Below the Sb:0.3%
Can contain Sb as required.Sb has raising in the effect of doing the anti-general corrosion property under the wet environment repeatedly, and has the acid proof effect of raising.And, also have through improving the effect that the erosion resistance of pitting attack portion under the lower environment of pH improves anti-pitting attack property.But even the content of Sb surpasses 0.3%, above-mentioned effect also can be saturated.Thereby the upper limit of the content of the Sb in the time of will containing Sb is made as 0.3%.Be limited to 0.25% on preferred, be limited to 0.2% on preferred.In addition, for the effect that stably passes and contain Sb and produce, preferably contain the Sb more than 0.03%.More preferably more than 0.05%.
Sn
: below 0.3%
Can contain Sn as required.Sn is the element that improves the erosion resistance in the acid environment, has the effect of the anti-general corrosion property of raising under the wet environment repeatedly of doing of sour water.And, also have through improving the effect that the erosion resistance of pitting attack portion under the lower environment of pH improves anti-pitting attack property.But even the content of Sn surpasses 0.3%, not only above-mentioned effect can be saturated, and the toughness of the welding joint of mother metal and the input of big heat is remarkable variation also.Thereby the upper limit of the content of the Sn in the time of will containing Sn is made as 0.3%.Be limited to 0.25% on preferred, be limited to 0.2% on preferred.In addition, for the effect that stably passes and contain Sn and produce, preferably contain the Sn more than 0.01%.More preferably more than 0.02%, further be preferably more than 0.03%.
(ii) the 2nd group: Nb, V and B
Below the Nb:0.1%
Can contain Nb as required.Nb is the element with effect of the intensity that improves steel.But, surpass 0.1% as if the content of Nb, then the toughness variation.Thereby the upper limit of the content of the Nb in the time of will containing Nb is made as 0.1%.Be limited to 0.08% on preferred, be limited to 0.05% on preferred.In addition, for the effect that stably passes and contain Nb and produce, preferably contain the Nb more than 0.001%.More preferably more than 0.005%, further be preferably more than 0.01%.
Below the V:0.2%
Can contain V as required.V is the element with effect of the intensity that improves steel.But, surpass 0.2% as if the content of V, then toughness and weldableness variation.Thereby the upper limit of the content of the V in the time of will containing V is made as 0.2%.Be limited to 0.15% on preferred.In addition, for the effect that stably passes and contain V and produce, preferably contain the V more than 0.005%.More preferably more than 0.01%.
Below the B:0.01%
Can contain B as required.B is the element with effect of the intensity that improves steel.But, surpass 0.01% as if the content of B, then the toughness variation.Thereby the upper limit of the content of the B in the time of will containing B is made as 0.01%.Be limited to 0.008% on preferred, be limited to 0.005% on preferred.In addition, for the effect that stably passes and contain B and produce, preferably contain the B more than 0.0002%.More preferably more than 0.0005%, further be preferably more than 0.0008%.
(iii) the 3rd group: Ca, Mg and REM
Below the Ca:0.01%
Can contain Ca as required.Ca has following effect: when corrosion reaction, be dissolved in water and be alkalescence, thereby suppress the effect that the pH at steel interface descends.Therefore, the erosion resistance of naked steel and finish department improves.But even the content of Ca surpasses 0.01%, above-mentioned effect also can be saturated.Thereby the upper limit of the content of the Ca in the time of will containing Ca is made as 0.01%.Be limited to 0.008% on preferred, be limited to 0.005% on preferred.In addition, for the effect that stably passes and contain Ca and produce, preferably contain the Ca more than 0.0002%.More preferably more than 0.0005%, further be preferably more than 0.001%.
Below the Mg:001%
Can contain Mg as required.Mg is identical with Ca, and the pH at the steel interface when also having through the inhibition corrosion reaction descends and improves the effect of erosion resistance.But even the content of Mg surpasses 0.01%, its effect also can be saturated.Thereby the upper limit of the content of the Mg in the time of will containing Mg is made as 0.01%.Be limited to 0.008% on preferred, be limited to 0.005% on preferred.In addition, for the effect that stably passes and contain Mg and produce, preferably contain the Mg more than 0.0002%.More preferably more than 0.0005%, further be preferably more than 0.001%.
Below the REM:0.01%
Can contain REM as required.REM has the effect of the weldableness that improves steel.But even the content of REM surpasses 0.01%, not only above-mentioned effect can be saturated, and the cost of steel also will rise.Thereby the upper limit of the content of the REM in the time of will containing REM is made as 0.01%.Be limited to 0.008% on preferred, be limited to 0.005% on preferred.In addition, for the effect that stably passes and contain REM and produce, preferably contain the REM more than 0.0001%.More preferably more than 0.0005%, further be preferably more than 0.001%.
At this, REM be meant that 15 elements of lanthanon add Y and Sc and the general name of 17 elements, can contain a kind of or two or more in these elements.In addition, the content of REM is meant the total content of these elements.
(B) sulfurized layer
Sulfurized layer is through in steel, containing Cu, W, Ni or Mo, and under the base plate environment of oil cargo tank, uses and form.Thereby,, steel needn't be pre-formed sulfurized layer when dispatching from the factory.Through the base plate steel of using as oil cargo tank, though receive H at the use initial stage
2S and Cl
-Attack certain pitting attack can take place, but after during certain, just can form sulfurized layer.Sulfurized layer can be reduced in the H on the steel interface
2S concentration, the anode dissolution of inhibition steel wherein, particularly has the W sulfide of cation selective or also has Mo sulfide can suppress Cl
-See through.Thus, the development of pitting attack is slowed down, and erosion resistance improves.
In the analysis that utilizes EPMA (electron probe microanalyzer) to carry out, can form from inboard (steel side) order by clear and definite sulfurized layer according to Mo sulfide, Cu sulfide, W sulfide, Ni sulfide.It is generally acknowledged that sulfurized layer is following according to the reason that above-mentioned such order generates: if calculate the critical S that is used to form sulfide according to the solubleness of each sulfide and the Cu that estimates out by the pitting attack tempo, W, Ni, Mo ionic concn
2 -Concentration, then this concentration is the order of Mo, Cu, W, Ni.
In case formed sulfurized layer, also can on this sulfurized layer, be formed with the iron rust that the is formed on steel surface usually (layer of β-FeOOH).The iron rust layer does not reduce H
2The effect of S concentration, inhibition Cl
-The effect that sees through, but owing to utilize the H after the sulfurized layer blocking-up sees through the iron rust layer
2S and Cl
-, therefore can bring into play superior corrosion resistance.
Sulfurized layer also can sustain damage because of parts such as cleaning oil cargo tanks sometimes.Even in this case, also can form sulfurized layer once more through use, therefore, erosion resistance can not descend.
Sulfurized layer more than has been described, but steel of the present invention also can under situation about using under the general corrosion environment, can utilize the erosion resistance of mother metal self to suppress the corrosion development as the cargo tank top plate portion that does not form sulfurized layer.
(C) protection against corrosion tunicle
For the steel of the present invention of above explanation,, can reduce corrosion allowance even directly use also can show good anti-corrosion.But, utilizing the protection against corrosion tunicle that is formed by organic resin, metal to cover under its surperficial situation, the weather resistance of protection against corrosion tunicle improves, and erosion resistance further improves, and is suitable as the corrosion resistant steel for cargo oil tanks material more.
At this; As the protection against corrosion tunicle that forms by organic resin; The resin coating of ethene butyral system, epoxy system, polyurethane series, phthalic acid system etc. can be enumerated,, the plating tunicle, sprayed of Zn, Al etc. can be enumerated as the protection against corrosion tunicle that forms by metal.
In addition; It is generally acknowledged that the reason that the weather resistance of protection against corrosion tunicle improves is following:, can suppress heaving, peeling off of protection against corrosion tunicle that the base steel corrosion from protection against corrosion tunicle defective part causes as the corrosive result of remarkable inhibition as the steel of the present invention of substrate.
Can utilize usual method to carry out the above-mentioned protection against corrosion tunicle that utilizes and cover the processing of steel surface.In addition, may not implement the coating anticorrosive tunicle to whole of steel, also can be only to carrying out anti-corrosive treatment as the single face that is exposed to the steel of the face in the corrosive environment.Perhaps, also can be only to carrying out anti-corrosive treatment as a part that is exposed to the steel of the part in the corrosive environment.
(D) method of manufacture
Steel of the present invention can be made as follows.But steel method of manufacture of the present invention is not limited to this method of manufacture.
Making suppresses the amount of S lower and has implemented slab RH in the stage of system steel, DH, induction stirring etc., that have the composition of stipulating among the present invention.
In Heating temperature be about 1100 ℃～1200 ℃, the rolling draft in each road is more than 3%, final rolling temperature is under the condition about 700 ℃～900 ℃, and this slab is carried out hot rolling.After rolling end, naturally cooling in atmosphere is perhaps cooling off in the humidity province of the temperature more than the Ar3 point about at least 570 ℃ so that 5 ℃/s of speed of cooling is above, afterwards naturally cooling in atmosphere.Through above operation, can make steel of the present invention.In addition, above-mentioned temperature all is the temperature of the surface portion of steel.
Embodiment 1
23 kinds of steel that use the melting of vacuum melting stove to have the chemical constitution shown in the table 1 are processed after the bloom of 150kg, utilize usual method to carry out heat forged, are made into the piece that thickness is 60mm.
Table 1
Then, after 1120 ℃ are heated 1 hour down, carry out hot rolling, under 850 ℃, be finish-machined to thickness 20mm, in atmosphere, naturally cool to room temperature afterwards above-mentioned.
From above-mentioned thickness be each steel plate of 20mm to extract width be that 25mm, length are that 50mm, thickness are the test film of 4mm, offer the corrosion test of the cabin backboard face environment of having simulated actual tanker.In addition, this corrosion test has been supposed cargo hold gas phase portion.At this; Use steel for the routine test of the invention of steel grade 1 especially; Being the protection against corrosion tunicle that coating has formed about 200 μ m, on the protection against corrosion tunicle, mark the cross scar afterwards and a part of steel substrate is come out, and offer same corrosion test through the spraying modified epoxy.
Promptly; As in the top board test of Fig. 1, seeing; The preparation adding has to the Glass Containers of the ion exchanged water of 1/3 part of bottom; The lid of the vinylformic acid system of utilization is airtight with the open upper end of above-mentioned Glass Containers, and the test film that this lid obtains extraction is installed on its lower surface, and has gas supply port.
Then, the Glass Containers after airtight is arranged in the thermostatic bath, applies 56 days 50 ℃ * 20 hours → 25 ℃ * 4 hours temperature cycle.At this moment, the corrosive gases in the cargo hold is simulated by the gas phase portion in Glass Containers, is blown into the gas A of composition as follows through above-mentioned gas supply port.
[gas A] be the % meter by volume, 5%O
2-13%CO
2-0.01%SO
2-0.05%H
2S-remains N
2
After 56 days corrosion test, having tried to achieve with " mm/ " according to the minimizing quality of each test film is the corrosion speed (general corrosion speed) of unit.In the table 2 above-mentioned test-results is expressed as " test 1 ".In addition, in table 2, with steel (steel grade 1 (tunicle is arranged)), tried to achieve the corrosion speed of its steel substrate exposed division for the test that has formed the protection against corrosion tunicle.
Table 2
Embodiment 2
The test film identical with embodiment 1 used in this test, and the test of the base plate of real ship has been supposed in enforcement.
That is,, prepare to add the Glass Containers of the 10%NaCl solution that has 40 ℃, the corrosion test sheet is immersed in the solution as in the base plate test of Fig. 2, seeing.
Then, the Glass Containers after airtight is arranged in the thermostatic bath, has implemented 28 days dip test.Be blown into the gas B of composition as follows through gas supply port.
[gas B] be the % meter by volume, 5%O
2-13%CO
2-0.01%SO
2-0.2%H
2S-remains N
2
In addition,, reserve the circular portion that diameter is 5mm, oil coating (mixture of crude oil and rust) is simulated in part coating in addition be made into the corrosion test sheet through extracting on the test film that obtains from steel plate.
In the corrosion test sheet after test, will not have origination point corrosive part, be the coating part of simulated oil coating as benchmark, through using the degree of depth of micrometer MP corrosion generation portion, carried out measurement to the pitting attack degree of depth.At this, the value that the degree of depth in the pitting attack generation portion is maximum is as the pitting attack degree of depth.
After 28 days corrosion test, having tried to achieve with " mm/ " according to the pitting attack degree of depth of each test film is the pitting attack speed of unit.In the table 2 above-mentioned test-results is expressed as " test 2 ".In addition, identical with embodiment 1, in table 2, with steel (steel grade 1 (tunicle is arranged)), tried to achieve the corrosion speed of its steel substrate exposed division for the test that is formed with the protection against corrosion tunicle.
Embodiment 3
From the thickness that likewise is made into embodiment 1 be each steel plate of 20mm to extract width be that 40mm, length are that 50mm, thickness are the test film of 4mm, implement to have simulated the test of the environment in the pitting attack of cargo hold base plate.
That is,, in 30 ℃ 10%NaCl solution, add HCl, test film is immersed in p H is adjusted in 0.85 the solution as in the acid dipping of Fig. 3 test, seeing.Duration of test is 72 hours, for the deterioration that makes solution is an inferior limit to the influence that corrosion produces, just changes solution in per 24 hours.
After 72 hours corrosion test, having tried to achieve with " mm/ " according to the minimizing quality of each test film is the corrosion speed of unit.In the table 2 above-mentioned test-results is expressed as " test 3 ".In addition, identical with embodiment 1, in table 2, with steel (steel grade 1 (tunicle is arranged)), tried to achieve the corrosion speed of its steel substrate exposed division for the test that is formed with the protection against corrosion tunicle.
Also can learn according to the corrosion test result shown in the table 2, because comparative example 21 suitably do not add alloying element, therefore, in test 1, test 2 and test erosion resistance and insufficient in 3.In addition, because the P of comparative example 22 amount is improper, therefore, the erosion resistance in the test 3 is lower.
On the other hand, but knowledge capital invention example (1～20) all shows good anti-corrosion in test 1, test 2, test 3.
Utilizability on the industry
Adopt the present invention, can provide for the good oil cargo tank of the resistivity of general corrosion, local corrosion and use the erosion resistance steel.
Claims (7)
1. a corrosion resistant steel for cargo oil tanks material is characterized in that,
By quality % contain C:0.01%～0.2%, Si:0.01%～1.0%, Mn:0.05%～2.0%, P:0.002%～0.1%, below the S:0.01%, Cu:0.01%～2.0%, Ni:0.01%～1.0%, W: greater than 0% and less than 0.01%, below the Al:0.1%, surplus is made up of Fe and impurity.
2. corrosion resistant steel for cargo oil tanks material according to claim 1 is characterized in that,
By quality % contain below a kind of or two or more parts that substitute Fe in the following element: the Cr:5.0%, below the Mo:1.0%, below the Ti:0.2%, below the Zr:0.2%, below the Sb:0.3% and below the Sn:0.3%.
3. corrosion resistant steel for cargo oil tanks material according to claim 1 and 2 is characterized in that,
By quality % contain below a kind of or two or more parts that substitute Fe in the following element: the Nb:0.1%, below the V:0.2% and below the B:0.01%.
4. according to each described corrosion resistant steel for cargo oil tanks material in the claim 1～3, it is characterized in that,
By quality % contain below a kind of or two or more parts that substitute Fe in the following element: the Ca:0.01%, below the Mg:0.01% and below the REM:0.01%.
5. according to each described corrosion resistant steel for cargo oil tanks material in the claim 1～4, it is characterized in that,
The sulfide that has Cu, Ni and W on the surface perhaps also has the layer of the sulfide of Mo.
6. according to each described corrosion resistant steel for cargo oil tanks material in the claim 1～4, it is characterized in that,
The surface is covered by the protection against corrosion tunicle.
7. according to each described corrosion resistant steel for cargo oil tanks material in the claim 1～4, it is characterized in that,
Utilize the protection against corrosion tunicle across by the sulfide of Cu, Ni and W or the middle layer covering surfaces that also constitutes by the sulfide of Mo.
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| JP2010156698 | 2010-07-09 | ||
| JP2010-156698 | 2010-07-09 | ||
| PCT/JP2011/065595 WO2012005327A1 (en) | 2010-07-09 | 2011-07-07 | Corrosion-resistant steel material for cargo oil tank |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2012005327A1 (en) | 2013-09-05 |
| JP4941620B2 (en) | 2012-05-30 |
| KR20120035935A (en) | 2012-04-16 |
| WO2012005327A1 (en) | 2012-01-12 |
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