CN102264937A - Corrosion-resistant steel material for crude oil tanker - Google Patents
Corrosion-resistant steel material for crude oil tanker Download PDFInfo
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- CN102264937A CN102264937A CN200980152637XA CN200980152637A CN102264937A CN 102264937 A CN102264937 A CN 102264937A CN 200980152637X A CN200980152637X A CN 200980152637XA CN 200980152637 A CN200980152637 A CN 200980152637A CN 102264937 A CN102264937 A CN 102264937A
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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
- C22C38/02—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
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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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
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
Abstract
Disclosed is a corrosion-resistant steel material for a tanker, which has excellent corrosion resistance in a corrosive environment produced in an oil tank in the tanker and also has excellent post-coating corrosion resistance in a corrosive environment produced in a ballast tank in the tanker. Specifically disclosed is a corrosion-resistant steel material for a crude oil tanker, which comprises (by mass%) 0.03 to 0.16% of C, 0.05 to 1.50% of Si, 0.1 to 2.0% of Mn, 0.025% or less of P, 0.01% or less of S, 0.005 to 0.10% of Al, 0.008% or less of N, more than 0.1% and not more than 0.5% of Cr, and 0.03 to 0.5% of Cu, and may additionally comprise, as an optional additive element, at least one element selected from W in an amount of 0.01 to 0.5%, Mo in an amount of 0.01 to 0.5%, Sn in an amount of 0.001 to 0.2%, Sb in an amount of 0.001 to 0.5%, Ni in an amount of 0.005 to 0.3% and Co in an amount of 0.005 to 0.3%, wherein Cu, W, Mo, Sn, Sb, Cr, Ni, Co, S and P are so contained as to meet a specific relationship.
Description
Technical field
The present invention relates to the oil tank portion (oil tank) of crude oil carrier (crude oil tanker) and the employed crude oil carrier of the different sites corrosion-resistant steel (corrosion-resistant steel product) of ballast tank portion corrosive environments (corrosion environment) such as (ballast tank), the general corrosion (general corrosion) that local corrosion of locating to take place in particular to the base plate that can reduce crude oil carrier oil tank portion (bottom plate) (local corrosion) and top board (top board) and side plate (side plate) are located to take place, and the corrosive crude oil carrier corrosion-resistant steel of the ballast tank portion application face at the oil tank portion base plate back side.
Background technology
Known, be filled in the interior rare gas element (inert gas) of oil tank (with O for preventing blast (explosion protection)
2: 5 volume %, CO
2: 13 volume %, SO
2: 0.01 volume %, surplus N
2The waste gas (exhaust gas) of boiler of forming for representative (boiler) or engine (engine) etc.) O that is contained in
2, CO
2, SO
2Or from crude oil evaporable H
2Corrosive gasess such as S (corrosive gas), the internal surface (back side of upperdeck (back side of upper deck)) on the top of crude oil carrier oil tank portion causes general corrosion.
And, above-mentioned H
2S forms solid S (elemental sulfur) owing to the katalysis (catalyst action) of the iron rust (iron rust) that produces because of corrosion is oxidized, exists with stratiform in iron rust.And above-mentioned corrosion product (corroded product) is peeled off easily, thereby is deposited on the bottom of petroleum tank.Therefore, in the dock inspection (dock inspection) of per oil tanker that carried out in 2.5 years, all to spend huge expense and carry out repairing on oil tank top (maintenance and repair) and sedimental removing.
On the other hand; thought in the past; because the effect of corrosion inhibition of the protective membrane from crude oil (protective film) that generates on the effect of corrosion inhibition (corrosion inhibition function) of crude oil itself and the petroleum tank internal surface, so the employed steel of the base plate of the petroleum tank of oil tanker do not corrode.But, recent findings, the local corrosion of bowl-type (bowl-shaped) also takes place in the steel that oil tank bottom plate uses.
As the reason of the local corrosion that causes above-mentioned bowl-type, can enumerate:
What (1) high density had been dissolved in existence is the condensed water (brine) of the salt of representative with sodium-chlor (sodium chloride);
(2) clean the disengaging of the crude oil protective membrane cause by over-drastic;
(3) high densityization of the sulfide that contains in the crude oil (sulfide);
(4) O that contains in the rare gas element of explosion-proof usefulness
2, CO
2, SO
2High densityization;
(5) participation of microorganism (microorganism) etc.,
But these all only are to infer, can't conclude clear and definite reason.
Suppress the effective means of aforesaid corrosive and be on steel surface, to implement recoat dress (heavy coating) thus make steel and the isolated method of corrosive environment.But the someone points out, because the surface covered of petroleum tank is huge, therefore petroleum tank is implemented application and need spend a large amount of constructions and inspection charge, in addition, and under the corrosive environment of petroleum tank, promoted on the contrary the to film corrosion of damaged portion of recoat dress.
Therefore, even proposed the steel that under the such environment of petroleum tank, also has erosion resistance.For example, disclose the good oil cargo tank of anti-general corrosion and anti-local corrosion (cargo oil tank) in the patent documentation 1 and used corrosion-resistant steel, it is in the steel of C:0.01～0.3 quality %, an amount of Si, Mn, P, S have been added, also add Ni:0.05～3 quality %, and optionally added Mo, Cu, Cr, W, Ca, Ti, Nb, V, B.And, disclose and contained H
2In the dried repeatedly wet environment of S, if the content of Cr surpasses 0.05 quality %, then erosion resistance and pitting corrosion resistance (pitting corrosion resistance) significantly reduce comprehensively, and therefore making the content of Cr is below the 0.05 quality %.
In addition, disclose in the patent documentation 2 and had good anti-general corrosion and anti-local corrosion and can suppress to contain the corrosion-resistant steel that petroleum tank that the corrosion product of solid S generates is used, it is in the steel of C:0.001～0.2 quality %, add an amount of Si, Mn, P, S and Cu:0.01～1.5 quality %, Al:0.001～0.3 quality %, N:0.001～0.01 quality %, also added at least a of Mo:0.01～0.2 quality % or W:0.01～0.5 quality %.
On the other hand, when lade not, the ballast tank of crude oil carrier plays the effect that can make mooring stability navigation (safety navigation), owing to inject seawater, so ballast tank is under the very harsh corrosive environment.Therefore; in order to realize the protection against corrosion of the employed steel of ballast tank, use the protection against corrosion utilize epoxy resin coating (epoxy type paint) the film formation and the electrolytic protection (electrolytic protection) of (protecting coating) usually simultaneously.
But even adopt above-mentioned protection against corrosion countermeasure, the corrosive environment of ballast tank still is under the harsh state.That is, when in ballast tank, injecting seawater,, therefore can suppress to be taken place by the corrosive of seawater thorough impregnation part because electrolytic protection plays a role.But when not injecting seawater in the ballast tank, electrolytic protection is inoperative fully, so owing to residual effect of adhering to salinity (residual attached saline metter) is subjected to heavy corrosion.
The employed steel in the position that is in harsh corrosive environment about ballast tank etc. have proposed several motions.For example, the erosion resistance low alloy steel that ballast tank is used is disclosed in the patent documentation 3, in its steel below C:0.20 quality %, interpolation Cu:0.05～0.50 quality %, W:0.01～improve element as erosion resistance less than 0.05 quality %, perhaps, further add among Ni, Ti, Zr, V, Nb, Ge, Sn, Pb, As, Sb, Bi, Te, the Be more than a kind or 2 kinds.In addition, the erosion resistance low alloy steel that ballast tank is used is disclosed in the patent documentation 4, add Cu:0.05～0.50 quality %, W:0.05～0.5 quality % in its steel below C:0.20 quality % and improve element as erosion resistance, also add among Ge, Sn, Pb, As, Sb, Bi, Te, the Be more than a kind or 2 kinds.In addition, disclose the erosion resistance low alloy steel that ballast tank is used in the patent documentation 5, in its steel below C:0.15 quality %, added Cu:0.05～less than 0.15 quality %, W:0.05～0.5 quality %.
In addition, a kind of ballast tank is disclosed in the patent documentation 6, wherein, coating tar epoxy coating (tar epoxy paint) on the corten material, pure epoxy coating (pure epoxy paint), no-solvent type epoxy coating (solventless epoxy paint), polyurethane coating anticorrosive coatings such as (urethane paint), described corten material is by adding P:0.03～0.10 quality % in the steel below C:0.15 quality %, Cu:0.1～1.0 quality %, Ni:0.1～1.0 quality % improve element as erosion resistance and obtain.Above-mentioned technology prolongs life-span of corrosion-proof coating by the erosion resistance of improving steel itself, realizes not having maintenanceization (maintenance-free) between the usage period at the boats and ships in 20～30 years.
In addition, proposed the steel that ballast tank is used in the patent documentation 7, it improves unit as erosion resistance and usually improves erosion resistance by adding Cr:0.2～5 quality % in the steel below C:0.15 quality %, thereby realizes the nothing maintenanceization of boats and ships.In addition, the anti-corrosion method of ballast tank has been proposed in the patent documentation 8, it is characterized in that, added Cr:0.2～5 quality % improve element as erosion resistance steel in the steel of use below C:0.15 quality % as constituting steel, and the oxygen concentration (oxygen gas concentration) that makes ballast tank inside reaches ratio below 0.5 with respect to the value in the atmosphere.
In addition, proposed in the patent documentation 9 to improve erosion resistance, thereby realized the nothing maintenanceization relevant with the protection against corrosion of boats and ships by adding Cr:0.5～3.5 quality % in the steel below C:0.1 quality %.In addition, in the patent documentation 10 steel for ship is disclosed, its by in the steel of C:0.001～0.025 quality %, add Ni:0.1～4.0 quality % improve anti-film damaging, thereby reduce to repair the maintenance cost of application etc.
In addition, shipping steel is disclosed in the patent documentation 11, it adds Cu:0.01～2.00 quality %, Mg:0.0002～0.0150 quality % in the steel of C:0.01～0.25 quality %, have erosion resistance thus under the environment for use of freight house (cargo hold for ore and coal) of outside plate, ballast tank, oil cargo tank, ore and the coal of boats and ships etc.
In addition, patent documentation 12 and 13 discloses steel product for cargo oil tank, it is by in the steel of C:0.01～0.2%, suppress the interpolation of Cr, Al, add Cu:0.05～2%, also compound interpolation P, Ni, W and Sn etc. improve general corrosion and local corrosive resistivity in crude oil corrosive environment (crude oil corrosion environment) and corrosive environment of sea water (seawater corrosion environment).
Patent documentation 1: TOHKEMY 2003-082435 communique
Patent documentation 2: TOHKEMY 2004-204344 communique
Patent documentation 3: Japanese kokai publication sho 48-050921 communique
Patent documentation 4: Japanese kokai publication sho 48-050922 communique
Patent documentation 5: Japanese kokai publication sho 48-050924 communique
Patent documentation 6: Japanese kokai publication hei 07-034197 communique
Patent documentation 7: Japanese kokai publication hei 07-034196 communique
Patent documentation 8: Japanese kokai publication hei 07-034270 communique
Patent documentation 9: Japanese kokai publication hei 07-310141 communique
Patent documentation 10: TOHKEMY 2002-266052 communique
Patent documentation 11: TOHKEMY 2000-017381 communique
Patent documentation 12: TOHKEMY 2005-325439 communique
Patent documentation 13: TOHKEMY 2007-270196 communique
Summary of the invention
As mentioned above, in the prior art, the employed steel of employed steel of oil tank portion and ballast tank portion of crude oil carrier are developed respectively under the most situation.But, the back side of the base plate of the oil tanker oil tank portion that naked state uses down, usually also be the ballast tank portion that application is used, therefore, can not consider respectively that the erosion resistance in the corrosive environment of erosion resistance in the corrosive environment in the oil tank portion and ballast tank portion is used as the characteristic that steel that oil tanker uses should have.
On the other hand, patent documentation 12 and 13 technology of being put down in writing are to be conceived to load seawater at the ballast tank that is positioned at the oil cargo tank outside when not loading crude oil, to take into account the technology that crude oil corrosive environment and corrosive environment of sea water are target.And for corrosive environment of sea water, the erosion resistance as after the variation of filming of the corrosion-proof coating of oil cargo tank outside surface is conceived to the erosion resistance that steel itself have.But in above-mentioned technology, any consideration is carried out in the improvement of the erosion resistance under the existence of just not filming.
But, in the technology of patent documentation 12 and 13, do not carry out any consideration, steel surface exist the erosion resistance of the state film to be application after the improvement of erosion resistance, very effective on the basis of realization crude oil carrier with the long lifetime of corrosion-resistant steel, though expect the exploitation of this technology, present practical situation are not have the technology that realizes above-mentioned long lifetime.
Therefore, the objective of the invention is to, a kind of crude oil carrier corrosion-resistant steel is provided, its H in oil tanker oil tank portion
2Have superior corrosion resistance under the caused corrosive environment of corrosive gasess such as S, and after also having good application under the corrosive environment of ballast tank portion erosion resistance.
The inventor for develop in oil tanker oil tank portion and arbitrary corrosive environment of ballast tank portion in have the oil tanker corrosion-resistant steel of superior corrosion resistance, and further investigate.It found that, by containing Cr: greater than 0.1 quality % and below 0.5 quality %, Cu:0.03～0.5 quality %, and contain and be selected from W:0.01～0.5 quality %, Mo:0.01～0.5 quality %, Sn:0.001～0.2 quality %, Sb:0.001～0.5 quality %, among Ni:0.005～0.3 quality % and Co:0.005～0.3 quality % more than a kind or 2 kinds as optional interpolation element, and make mentioned component satisfy certain specific relation, can access thus in oil tanker oil tank portion and arbitrary corrosive environment of ballast tank portion in demonstrate the oil tanker corrosion-resistant steel of superior corrosion resistance, thereby finished the present invention.
Promptly, the present invention is a kind of crude oil carrier corrosion-resistant steel, it is characterized in that, contain: C:0.03～0.16 quality %, Si:0.05～1.50 quality %, Mn:0.1～2.0 quality %, below the P:0.025 quality %, below the S:0.01 quality %, Al:0.005～0.10 quality %, below the N:0.008 quality %, C r: greater than 0.1 quality % and below 0.5 quality %, Cu:0.03～0.5 quality %, and, contain and be selected from W:0.01～0.5 quality %, Mo:0.01～0.5 quality %, Sn:0.001～0.2 quality %, Sb:0.001～0.5 quality %, among Ni:0.005～0.3 quality % and Co:0.005～0.3 quality % more than a kind or 2 kinds as optional interpolation element, and mentioned component is below 0.5 with the X value that following by satisfying (1) formula defines, by the Y value of following (2) formula definition is that mode below 0.5 contains, surplus is made of Fe and unavoidable impurities
X value=(1-0.8 * Cu
0.5) * { 1-(0.8 * W+0.4 * Mo)
0.3} * { 1-(0.8 * Sn+0.8 * Sb)
0.5} * { 1-(0.05 * Cr+0.03 * Ni+0.03 * Co)
0.3} * (1+S/0.01+P/0.05) ... (1)
Y value=(1-0.3 * Cr
0.3) * { 1-(0.8 * W+0.5 * Mo)
0.3} * { 1-(Sn+0.4 * Sb)
0.3} * { 1-(0.1 * Ni+0.1 * Co+0.05 * Cu)
0.3} * { 1+ (S/0.01+P/0.08)
0.3... (2)
At this, the above-mentioned symbol of element in various is represented the content (quality %) of each element.
Crude oil carrier corrosion-resistant steel of the present invention, it is characterized in that, contain be selected among W:0.01～0.5 quality %, Mo:0.01～0.5 quality %, Sn:0.001～0.2 quality % and the Sb:0.001～0.5 quality % more than a kind or 2 kinds as above-mentioned optional interpolation element.
In addition, crude oil carrier corrosion-resistant steel of the present invention is characterized in that, on the basis of above-mentioned optional interpolation element, also contains a kind or 2 kinds that is selected among Ni:0.005～0.3 quality % and the Co:0.005～0.3 quality %.
In addition, crude oil carrier corrosion-resistant steel of the present invention, it is characterized in that, on the basis that mentioned component is formed, also contain be selected among Nb:0.001～0.1 quality %, Ti:0.001～0.1 quality %, Zr:0.001～0.1 quality % and the V:0.002～0.2 quality % more than a kind or 2 kinds.
In addition, crude oil carrier corrosion-resistant steel of the present invention, it is characterized in that, on the basis that mentioned component is formed, also contain be selected among Ca:0.0002～0.01 quality %, REM:0.0002～0.015 quality % and the Y:0.0001～0.1 quality % more than a kind or 2 kinds.
In addition, crude oil carrier corrosion-resistant steel of the present invention is characterized in that, on the basis that mentioned component is formed, also contains B:0.0002～0.003 quality %.
In addition, crude oil carrier corrosion-resistant steel of the present invention is characterized in that, forms the primer coating film that contains Zn on the surface of above-mentioned steel.
In addition, crude oil carrier corrosion-resistant steel of the present invention is characterized in that, forms epoxies on the surface of above-mentioned steel and films.
The invention effect
According to the present invention, can be provided in the corrosive environment of oil tanker oil tank portion, at naked state, implemented zinc rich primer application (zinc primer coating) or implemented all have good anti-general corrosion and anti-local corrosion under arbitrary state in the state of zinc rich primer and epoxies application, even and in the corrosive environment of ballast tank portion, implemented the zinc rich primer application or implemented zinc rich primer and the state of epoxies application under also have good application after the steel of erosion resistance.Therefore, the steel of the present invention building material that can be suitable as oil tanker oil tank portion and ballast tank portion uses.
Description of drawings
Fig. 1 is the figure that the explanation general corrosion is tested employed testing apparatus.
Fig. 2 is the figure of the employed testing apparatus of explanation local corrosion test.
Embodiment
One-tenth with steel of the present invention is grouped into the reason that is limited to above-mentioned scope to be described.
C:0.03～0.16 quality %
C is an effective elements aspect the intensity that improves steel, in the present invention, in order to ensure desirable intensity, needs to add more than the 0.03 quality %.On the other hand, surpass 0.16 quality %, the toughness (toughness) of weldability (weldability) and welding heat affected zone is reduced if add.Therefore, C adds in the scope of 0.03～0.16 quality %.Be preferably 0.05～0.15 quality %, more preferably 0.10～0.15 quality %.
Si:0.05～1.50 quality %
Si is the element that adds as reductor (deoxidizing agent), also is the element that improves the intensity of steel.Therefore, in the present invention, add more than the 0.05 quality % in order to ensure desirable intensity.But, surpass 1.50 quality % if add, the toughness of steel is reduced.Therefore, making Si is the scope of 0.05～1.50 quality %.Be preferably 0.20～1.50 quality %, more preferably 0.30～1.20 quality %.
Mn:0.1～2.0 quality %
Mn is the element that improves the intensity of steel, in the present invention, adds more than the 0.1 quality % in order to obtain desirable intensity.On the other hand, surpass 2.0 quality %, toughness and weldability are reduced if add.Therefore, making Mn is the scope of 0.1～2.0 quality %.Be preferably 0.5～1.6 quality %, more preferably 0.7～1.5 quality %.
Below the P:0.025 quality %
P is the harmful element that makes the toughness reduction of steel at grain boundary segregation, and expectation reduces its content as far as possible.Particularly, surpass 0.025 quality % if contain P, then toughness significantly reduces.In addition, surpass 0.025 quality %, then bring detrimentally affect to erosion resistance if contain P.Therefore, making P is below the 0.025 quality %.Be preferably below the 0.015 quality %.More preferably below the 0.010 quality %, more preferably below the 0.008 quality %.
Below the S:0.01 quality %
S forms non-metallic inclusion (non-metal inclusion) MnS and becomes the starting point of local corrosion, is the harmful element that makes anti-local corrosion reduction, and expectation reduces its content as far as possible.Particularly, surpass 0.01 quality %, then cause the remarkable reduction of anti-local corrosion if contain.Therefore, make S on be limited to 0.01 quality %.Be preferably below the 0.005 quality %, more preferably below the 0.001 quality %.
Al:0.005～0.10 quality %
Al is the element that adds as reductor, in the present invention, needs to add more than the 0.005 quality %.But if add to surpass 0.10 quality %, then the toughness of steel reduces, therefore make Al on be limited to 0.10 quality %.Be preferably 0.01～0.06 quality %, more preferably 0.02～0.05 quality %.
Below the N:0.008 quality %
N is the harmful element that toughness is reduced, and expectation reduces its content as far as possible.Particularly, surpass 0.008 quality % if contain, then flexible reduces increase, therefore makes to be limited to 0.008 quality %.Be preferably below the 0.005 quality %, more preferably below the 0.004 quality %.
Cr: greater than 0.1 quality % and below 0.5 quality %
Cr carries out along with corrosive and moves in the rusty scale, by blocking-up Cl
-Intrusion to rusty scale suppresses Cl
-To the enrichment of the interface of rusty scale and matrix.In addition, when coating contained the priming paint of Zn, forming with Fe was the Cr at center and the composite oxides of Zn, thereby can make Zn continue for a long time to exist at surface of steel plate, therefore can significantly improve erosion resistance.Particularly, above-mentioned effect, become in improvement oil tanker oil tank bottom plate portion the back side ballast tank like this, and the environment of the contact with sea water of containing salt under erosion resistance aspect be effective, by the steel that contain Cr are implemented to contain the Zn prime treatment, compare with the steel that do not contain Cr thus, can significantly improve erosion resistance.If Cr content be 0.1 quality % with the next effect that can't fully obtain above-mentioned Cr, on the other hand, surpass 0.5 quality % then the toughness of weld part reduced if add Cr.Therefore, make Cr greater than 0.1 quality % and the scope below 0.5 quality %.Particularly under the situation that requires good toughness of welded zone, preferred Cr amount is 0.11～0.20 quality %, more preferably 0.11～0.16 quality %.
Cu:0.03～0.5 quality %
Cu is the element that improves the intensity of steel, and is present in the corrosion of invar and in the rust that generates, has the effect that improves erosion resistance.If add less than 0.03 quality % then can't fully obtain above-mentioned effect, on the other hand, if add that the flexible that surpasses 0.5 quality % then may cause welding heat affected zone reduces and the surface crack (surface cracking) when making etc.Therefore, Cu adds in the scope of 0.03～0.5 quality %.Be preferably 0.04～0.20 quality %, more preferably 0.04～0.15 quality %.
Steel of the present invention, except that mentioned component, also need to contain be selected among W, Mo, Sn, Sb, Ni and the Co more than a kind or 2 kinds as optional interpolation element.
W:0.01～0.5 quality %
W has the effect of the spot corrosion that suppresses oil tanker oil tank portion base plate, in addition, also has improvement for the erosion resistance of the general corrosion of oil tanker upperdeck portion with improve ballast tank portion and take place so repeatedly by the effect of the erosion resistance after the application under the corrosive environment of salt solution (salt water) dipping and high humidity (high moistness).Above-mentioned effect shows when interpolation 0.01 quality % is above.But, if surpass 0.5 quality % then above-mentioned effect is saturated.Therefore, W adds in the scope of 0.01～0.5 quality %.Be preferably the scope of 0.02～0.3 quality %.0.03～0.10 quality % more preferably.
Think that W has the aforesaid reason of improving the erosion resistance effect and is, in the rust that generates following steel plate corrosion, generate WO
4 2-, because this WO
4 2-Existence, suppress chloride ion (chloride ion) and invade surface of steel plate.Think that in addition the position that descends at the pH of the anode portion (anode section) of surface of steel plate etc. generates FeWO
4, because this FeWO
4Existence, chloride ion is suppressed to the intrusion of surface of steel plate, consequently the corrosion of steel plate is inhibited effectively.And thinking, because WO
4 2-To the caused restraining effect of the absorption of steel surface (inhibiting action), the corrosion of steel is suppressed.
Mo:0.01～0.5 quality %
Mo not only suppresses the spot corrosion of oil tanker oil tank portion base plate, and has improvement to the erosion resistance of the general corrosion of oil tanker upperdeck portion with the effect of the erosion resistance after improving application under the corrosive environment that salt water retting and high humidity take place repeatedly of ballast tank portion.Above-mentioned effect shows when above adding 0.01 quality %, still, if surpass 0.5 quality % then above-mentioned effect is saturated.Therefore, Mo adds in the scope of 0.01～0.5 quality %.Be preferably the scope of 0.03～0.4 quality %.0.03～0.10 quality % more preferably.
In addition, think that Mo has the aforesaid reason of improving the erosion resistance effect and is, identical with W, in the rust that generates in the corrosion of following steel plate, generate MoO
4 2-, because this MoO
4 2-Existence, suppress chloride ion and invade surface of steel plate, the result is that the corrosion of steel plate is effectively suppressed.
Sn:0.001～0.2 quality %, Sb:0.001～0.5 quality %
Sn and Sb have the effect of the spot corrosion that suppresses oil tanker oil tank portion base plate, in addition, also has improvement to the erosion resistance of the general corrosion of oil tanker upperdeck portion with the effect of the erosion resistance after improving application under the corrosive environment that salt water retting and high humidity take place repeatedly of ballast tank portion.Above-mentioned effect more than adding Sn:0.001 quality %, Sb:0.001 quality % shows when above.On the other hand, Sn surpasses 0.2 quality %, interpolation Sb surpasses 0.5 quality % then above-mentioned effect is saturated if add.Therefore, Sn adds in the scope of 0.001～0.2 quality %, Sb adds in the scope of 0.001～0.5 quality %.For Sn, be preferably 0.005～0.10 quality %, more preferably 0.01～0.06 quality %.In addition, for Sb, be preferably 0.02～0.15 quality %, more preferably 0.03～0.10 quality %.
Ni:0.005～0.3 quality %, Co:0.005～0.3 quality %
Ni and the Co rust particle granular by generating has the effect of the erosion resistance under erosion resistance of significantly improving under the naked state (no-coating) and the state of having implemented the epoxies application on zinc rich primer is filmed.Therefore, when wanting further to improve erosion resistance, preferably contain these elements auxiliaryly.Above-mentioned effect more than adding Ni:0.005 quality %, Co:0.005 quality % shows when above.On the other hand, surpass 0.3 quality % even adding Ni surpasses 0.3 quality %, add Co, above-mentioned effect is also saturated.Therefore, preferably in above-mentioned scope, add Ni and Co respectively.For Ni, be preferably 0.01～0.2 quality %, more preferably 0.03～0.15 quality %.In addition, for Co, be preferably 0.01～0.2 quality %, more preferably 0.03～0.15 quality %.
Steel of the present invention contain at proper range on the basis of mentioned component, and also needing to make it is below 0.5 and by the Y value that following (2) formula defines to be that mode below 0.5 contains to satisfy X value by the definition of following (1) formula.
X value=(1-0.8 * Cu
0.5) * { 1-(0.8 * W+0.4 * Mo)
0.3} * { 1-(0.8 * Sn+0.8 * Sb)
0.5} * { 1-(0.05 * Cr+0.03 * Ni+0.03 * Co)
0.3} * (1+S/0.01+P/0.05) ... (1)
Y value=(1-0.3 * Cr
0.3) * { 1-(0.8 * W+0.5 * Mo)
0.3} * { 1-(Sn+0.4 * Sb)
0.3} * { 1-(0.1 * Ni+0.1 * Co+0.05 * Cu)
0.3} * { 1+ (S/0.01+P/0.08)
0.3... (2)
At this, each symbol of element in the above-mentioned formula is represented the content (quality %) of these elements.
At this, above-mentioned (1) formula is to estimate the formula that each composition is given the influence that the corrosion in the oil tanker oil tank brings, and the coefficient of the composition that erosion resistance improves is represented with negative (minus), in addition, the coefficient of the composition of erosion resistance variation is represented with just (plus).Therefore, the corrosion resistance of steel that the value of X is more little is good more.The inventor investigates the relation of the erosion resistance of the value of above-mentioned X and the steel under the corrosive environment in the oil tanker oil tank, found that, if X is 0.5 with the excellent corrosion resistance under the corrosive environment in the next oil tanker oil tank, if but X surpasses 0.5 then above-mentioned erosion resistance variation.Therefore, need to make the X value be 0.5 to be carried out to the branch design to get off to steel of the present invention.Further preferred X value is below 0.4.
In addition, above-mentioned (2) formula is to estimate the formula that each composition is given the influence that erosion resistance is brought after the application of ballast tank, and is identical with above-mentioned (1) formula, and the coefficient of the composition that erosion resistance improves is represented to bear, in addition, make the coefficient of composition of erosion resistance variation just to represent.Therefore, the corrosion resistance of steel that the value of Y is more little is good more.The inventor to the application of the value of above-mentioned Y and the steel under the corrosive environment in the ballast tank after the relation of erosion resistance investigate, found that, if Y is 0.5 with excellent corrosion resistance after the application under the corrosive environment in the next ballast tank, if but Y surpasses 0.5 then above-mentioned erosion resistance variation.Therefore, need to make the Y value be 0.5 to be carried out to the branch design to get off to steel of the present invention.Further preferred Y value is below 0.4.
In addition, steel of the present invention, in order to demonstrate the spot corrosion that suppresses oil tanker oil tank portion base plate and the general corrosion of oil tanker upperdeck portion effectively by few interpolation number of elements, and improve the effect of the erosion resistance after the application under the corrosive environment that salt water retting and high humidity take place so repeatedly in ballast tank portion, preferably contain and be selected from the above-mentioned optional interpolation element, W:0.01～1.0 quality % particularly, Mo:0.01～0.5 quality %, among Sn:0.001～0.2 quality % and Sb:0.001～0.5 quality % more than a kind or 2 kinds, secondly, preferably contain a kind or 2 kinds that is selected among Ni and the Co.
In addition, steel of the present invention, in order to improve the intensity of steel, can be on the basis of mentioned component, following ranges contain be selected among Nb, Ti, Zr and the V more than a kind or 2 kinds.
Nb:0.001～0.1 quality %, Ti:0.001～0.1 quality %, Zr:0.001～0.1 quality % and V:0.002～0.2 quality %
Nb, Ti, Zr and V are the element with the effect that improves steel strength, can optionally add according to desirable strength.In order to obtain above-mentioned effect, preferably add the above V of 0.001 quality % above Nb, Ti, Zr and 0.002 quality % respectively.But, surpass 0.1 quality %, add V and surpass 0.2 quality % if add Nb, Ti, Zr, then toughness reduces, and therefore, preferably adds Nb, Ti, Zr, V respectively in above-mentioned scope.In addition, for Nb, be preferably 0.004～0.05 quality %, more preferably 0.005～0.02 quality %.For Ti, be preferably 0.002～0.03 quality %, more preferably 0.002～0.01 quality %.For Zr, be preferably 0.001～0.05 quality %, more preferably 0.002～0.01 quality %.For V, be preferably 0.003～0.15 quality %, more preferably 0.004～0.1 quality %.
In addition, steel of the present invention, in order to improve intensity or to improve toughness, can also be on the basis of mentioned component, following scope contain be selected among Ca, REM and the Y more than a kind or 2 kinds.
Ca:0.0002～0.01 quality %, REM:0.0002～0.015 quality % and Y:0.0001～0.1 quality %
Ca, REM and Y all have the flexible effect of improving welding heat affected zone, can add as required.By adding more than the Ca:0.0002 quality %, more than the REM:0.0002 quality %, can accessing above-mentioned effect more than the Y:0.0001 quality %, if surpass 0.1 quality % above 0.01 quality %, interpolation REM above 0.015 quality %, interpolation Y but add Ca, then cause flexible to reduce on the contrary, therefore, preferably in above-mentioned scope, add Ca, REM, Y respectively.In addition, for Ca, be preferably 0.001～0.005 quality %, more preferably 0.001～0.003 quality %.For REM, be preferably 0.0005～0.015 quality %, more preferably 0.001～0.010 quality %.For Y, be preferably 0.0001～0.05 quality %, more preferably 0.0002～0.01 quality %.
And steel of the present invention can contain B in following scope on the basis of mentioned component.
B:0.0002～0.003 quality %
B is the element that improves the intensity of steel, can add as required.In order to obtain above-mentioned effect, preferably add more than the 0.0002 quality %.But, surpass 0.003 quality % then the toughness reduction if add.Therefore, preferably in the scope of 0.0002～0.003 quality %, add B.Be preferably 0.0002～0.002 quality %, more preferably 0.0002～0.0015 quality %.
Use has the of the present invention oil tanker steel of the former material of steel of mentioned component composition by above-mentioned method manufacturing, it is characterized in that, the erosion resistance of not only not having under the state of application (anti-general corrosion, anti-local corrosion) is good, and the erosion resistance after the application is also good.Particularly, crude oil carrier steel of the present invention, converting in Zn content, to make the glue spread of the coating such as priming paint that contain Metal Zn or Zn compound (below, be generically and collectively referred to as " zinc rich primer ") be 1.0g/m
2More than, form zinc rich primer and film, can significantly improve anti-local corrosion and anti-general corrosion thus.Preferably convert and count 10g/m with average Zn content
2More than.15g/m more preferably
2More than.The relation of the Zn content of thickness that zinc rich primer is filmed and steel surface depends on the Zn containing ratio in the zinc rich primer, if count more than the 10 μ m with average application thickness usually, then whole steel surface can be covered,, 1.0g/m at least can both be guaranteed regardless of the kind of zinc rich primer
2Above glue spread.In addition, from improving the viewpoint of erosion resistance, the upper limit of the thickness of zinc rich primer is not special to be provided with, if thicken but film, then cutting property and weldability reduce, and therefore, have under the situation of cutting, welding operation behind the coating zinc rich primer, the thickness of preferred zinc rich primer is below the 100 μ m, more preferably below the 50 μ m.For example, also can after being implemented shot peening, surface of steel plate implement above-mentioned zinc rich primer application.
In addition, crude oil carrier steel of the present invention by being coated with epoxy resin coating etc. on the steel surface of no application or on the steel surface after the above-mentioned zinc rich primer application, can form epoxies and film.Thus, compare with the situation of existing steel for ship, can further improve anti-local corrosion and anti-general corrosion, and, particularly during ballast tank under being used for the harsh corrosive environment that causes by seawater etc., can access erosion resistance after the more suitably application, for example improve the effect of the anti-swelling property of filming.
At this, epoxies is filmed and is not particularly limited, and can use various redixs.For example can use modified epoxy, tar epoxy etc.In addition, the thickness that redix is filmed is not particularly limited, but from the viewpoint of painting cost and operability, is preferably below the 500 μ m, more preferably below the 350 μ m, can suitably select according to needed characteristic.
Embodiment
To have the various steel meltings that the one-tenth of the No.1 shown in the table 1～36 is grouped into vacuum melting furnace or converter, thereby make steel ingot or steel billet (steel slab), with gained steel ingot or steel billet reheat to 1200 ℃, implement finishing temperature (finishing temperature) then and be 800 ℃ hot rolling, make the Plate Steel that thickness of slab is 16mm.The steel plate of No.1～36 that as above obtain is offered following 3 kinds of corrosion resistance tests.
(1) the general corrosion test of the environment of simulation oil tanker upperdeck
In order to estimate erosion resistance to the general corrosion at the oil tanker upperdeck back side, cut the rectangle small pieces of wide 25mm * long 48mm * thick 4mm from the Plate Steel of above-mentioned No.1～36, shot peening (shot blasting) is implemented on its surface, thereby make the corrosion test sheet of naked state, use corrosion testing apparatus shown in Figure 1 (corrosion test equipment) to carry out the general corrosion test.This corrosion testing apparatus is made of corrosion test groove (corrosion test chamber) 2 and temperature control panel (temperature-controlled plate) 3, implantation temperature remains on 40 ℃ water 6 in corrosion test groove 2, then, in above-mentioned water 6, import CO by 12 volume %
2, 5 volume % O
2, 0.01 volume % SO
2, 0.3 volume % H
2S, surplus N
2The mixed gas (mixed gas) that constitutes (importing gas (introduced gas) 4), (supersaturated vapor) is full of in the corrosion test groove 2 with oversaturated water vapor, thereby reproduces the corrosive environment at the crude oil carrier upperdeck back side.Then, by being built-in with the temperature control panel 3 of well heater (heater) and refrigerating unit (cooling system), the corrosion test sheet 1 of the top rear face that is arranged on above-mentioned Thoughs given repeatedly 180 days temperature variation, generate dew (dewcondensation water) by the surface that makes test film 1 and cause general corrosion, wherein, the said temperature variation was 1 circulation in 4 hours with 30 ℃ * 4 hours+50 ℃ one-tenth.Among Fig. 1,5 expressions are from the discharge gas (emission gas) of Thoughs.
After the above-mentioned test, for each test film, try to achieve the thickness of slab decrement that causes by corrosion by the quality change before and after the test, with this thickness of slab decrement with respect to the value of the comparative steel of No.36 be average evaluation 60% below be anti-general corrosion very good (◎), will surpass 60% and the average evaluation below 70% be well (zero), will be anti-general corrosion poor (*) above 70% average evaluation.
(2) pittingtest of the environment of simulation oil tanker oil tank portion base plate
In order to estimate erosion resistance to the spot corrosion of oil tanker oil tank portion base plate, cut the foursquare small pieces of wide 50mm * long 50mm * thick 15mm from the steel plate of No.1～36 identical with the employed steel plate of the test of (1), shot peening is implemented on its surface, and the coating thickness that makes mineral-type (inorganic system) zinc rich primer then respectively is the coating of 2 grades of 0 μ m (not having coating), 15～25 μ m.
Then, with non-corrosibility coating (masking) implemented to cover in the end face and the back side of above-mentioned 4 kinds of small pieces, be coated with from the mud that contains oil composition (sludge) of the oil tanker collection of reality preparation corrosion test sheet (corrosion coupon) then on the surface (right face) that becomes corrosion test by the test face.At this moment, be coated on the sulphur mixing mud that has mixed 50 quality % sulphur in the mud, only evenly be coated with mud in other part by the part of central part 2mm Φ of test face.In this test film, the part that has been coated with sulphur mixing mud becomes the corrosive starting point, promotes local corrosion, therefore can more correctly hold steel product ingredient, priming paint and their the combination influence that inhibition brings to local corrosion.
Afterwards, above-mentioned test film is offered 1 month corrosion test of dipping in the experimental liquid 12 of corrosion testing apparatus shown in Figure 2.Above-mentioned corrosion testing apparatus is the device of two stratotypes of corrosion test groove 8, thermostatic bath 9, injects the experimental liquid 12 that the local corrosion identical with actual petroleum tank base plate can take place in corrosion test groove 8, and test film 7 be impregnated in wherein.Above-mentioned experimental liquid 12 uses the artificial seawater (artificial seawater) that will stipulate among the ASTM D1141 as test mother liquor (test mother water), and importing is adjusted to 5 volume %O in this liquid
2+ 10 volume %H
2The intrinsic standoff ratio of S, and surplus is by N
2The mixed gas that gas constitutes (importing gas 10) and the liquid that obtains.In addition, adjust, the temperature of experimental liquid 12 is remained on 50 ℃ by temperature to the water 13 that injects thermostatic bath (constant-temperature bath) 9.In addition, import gas 10, therefore often experimental liquid 12 is stirred owing to supply with continuously.Among Fig. 2,11 expressions are from the discharge gas of Thoughs.
After the above-mentioned corrosion test, remove the rust that generates on the test film surface, visual observation etch state then, and measure the depth of corrosion of local corrosion generating unit by hydrobarometer (depth meter), is that average evaluation below 40% is anti-local corrosion very good (◎) with depth of corrosion with respect to the value of the comparative steel of No.36, to and be good (zero) at the average evaluation below 50% above 40%, will be anti-local corrosion bad (*) above 50% average evaluation.
(3) the application post-etching test of simulation ballast tank environment
In order to estimate the erosion resistance after the application under the ballast tank environment, cut the test film of wide 50mm * long 150mm * thick 5mm from the steel plate of No.1～36 identical with the employed steel plate of the test of (1), after the test film surface carried out shot peening, implement the surface treatment of following condition A, B, make the exposure test sheet.
Condition A: the two-layer tunicle that forms zinc rich primer (about 15 μ m) and tar epoxy coating (about 200 μ m) on the test film surface
Condition B: the individual layer tunicle that forms tar epoxy coating (about 200 μ m) on the test film surface
In addition, to having the above-mentioned condition A that films and the test film of B, give the cut of going up from filming to the in-line (in a straight line) of the long 80mm of matrix surface (scratch) with cutter (utility knife).
Then, above-mentioned test film is offered following corrosion test, this corrosion test is 1 circulation with (keeping 1 day in the artificial seawater of 30 ℃ of temperature) → (keeping 1 day down and in the moistening atmosphere of relative humidity 98～99% for 40 ℃ in temperature), and carry out 60 circulations (120 days) repeatedly, the corrosive cycle of the environment of the ballast tank of conduct simulation actual ship is tested (corrosion cycle test) thus.The evaluation of the erosion resistance of each test film is as follows: to having the condition A that films and the test film of B, measure the swelling area of filming that takes place around the cut, is that average evaluation below 50% is an erosion resistance very good (◎) after the application with its ratio with respect to the value of the comparative steel of No.36, to and be good (zero) at the average evaluation below 70% above 50%, will be erosion resistance bad (*) after the application above 70% average evaluation.
The corrosion resistance test result of above-mentioned (1)～(3) is grouped into the X value and the Y value of trying to achieve with the one-tenth by each steel plate is shown in table 2.Can confirm by table 2, satisfy the Plate Steel that one-tenth of the present invention was grouped into and satisfied condition No.1～30 of X value and Y value, in whole corrosion tests of (1)～(3), all demonstrate than target level good anti-corrosion, wherein, above-mentioned target level is represented with respect to the ratio of basic steel (No.36) with the Plate Steel of No.1～30, relative therewith, the Plate Steel of No.31～35 of the condition of discontented unabridged version invention, in more than one the corrosion test in office, all be observed the corrosion above target level, wherein, above-mentioned target level is represented with respect to the ratio of No.36 steel with the Plate Steel of No.31～35.
Steel of the present invention also are suitable in addition boats and ships and ground petroleum tank etc. except that being used for crude oil carrier.
Label declaration
1,7: test film
2,8: the corrosion test groove
3: temperature control panel
4,10: import gas
5,11: discharge gas
6,13: water
9: thermostatic bath
12: experimental liquid
Table 2
Annotate: each erosion resistance is that the basis is estimated with the steel of No.36.
Claims (8)
1. crude oil carrier corrosion-resistant steel, it contains C:0.03～0.16 quality %, Si:0.05～1.50 quality %, Mn:0.1～2.0 quality %, below the P:0.025 quality %, below the S:0.01 quality %, Al:0.005～0.10 quality %, below the N:0.008 quality %, Cr: greater than 0.1 quality % and below 0.5 quality %, Cu:0.03～0.5 quality %, and, contain and be selected from W:0.01～0.5 quality %, Mo:0.01～0.5 quality %, Sn:0.001～0.2 quality %, Sb:0.001～0.5 quality %, among Ni:0.005～0.3 quality % and Co:0.005～0.3 quality % more than a kind or 2 kinds as optional interpolation element, and mentioned component is below 0.5 with the X value that satisfies by the definition of following (1) formula, by the Y value of following (2) formula definition is that mode below 0.5 contains, surplus is made of Fe and unavoidable impurities
X value=(1-0.8 * Cu
0.5) * { 1-(0.8 * W+0.4 * Mo)
0.3} * { 1-(0.8 * Sn+0.8 * Sb)
0.5} * { 1-(0.05 * Cr+0.03 * Ni+0.03 * Co)
0.3} * (1+S/0.01+P/0.05) ... (1)
Y value=(1-0.3 * Cr
0.3) * { 1-(0.8 * W+0.5 * Mo)
0.3} * { 1-(Sn+0.4 * Sb)
0.3} * { 1-(0.1 * Ni+0.1 * Co+0.05 * Cu)
0.3} * { 1+ (S/0.01+P/0.08)
0.3... (2)
At this, the symbol of element in the above-mentioned formula is represented the quality % content of each element.
2. crude oil carrier corrosion-resistant steel as claimed in claim 1, its contain be selected among W:0.01～0.5 quality %, Mo:0.01～0.5 quality %, Sn:0.001～0.2 quality % and the Sb:0.001～0.5 quality % more than a kind or 2 kinds as described optional interpolation element.
3. crude oil carrier corrosion-resistant steel as claimed in claim 2, it also contains a kind or 2 kinds that is selected among Ni:0.005～0.3 quality % and the Co:0.005～0.3 quality % on the basis of described optional interpolation element.
4. as each described crude oil carrier corrosion-resistant steel in the claim 1～3, its on the basis that described one-tenth is grouped into, also contain be selected among Nb:0.001～0.1 quality %, Ti:0.001～0.1 quality %, Zr:0.001～0.1 quality % and the V:0.002～0.2 quality % more than a kind or 2 kinds.
5. as each described crude oil carrier corrosion-resistant steel in the claim 1～4, its on the basis that described one-tenth is grouped into, also contain be selected among Ca:0.0002～0.01 quality %, REM:0.0002～0.015 quality % and the Y:0.0001～0.1 quality % more than a kind or 2 kinds.
6. as each described crude oil carrier corrosion-resistant steel in the claim 1～5, it also contains B:0.0002～0.003 quality % on the basis that described one-tenth is grouped into.
7. as each described crude oil carrier corrosion-resistant steel in the claim 1～6, wherein, form the primer coating film that contains Zn on the surface of described steel.
8. as each described crude oil carrier corrosion-resistant steel in the claim 1～7, wherein, form epoxies on the surface of described steel and film.
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| JP2009-035217 | 2009-02-18 | ||
| PCT/JP2009/071841 WO2010074307A1 (en) | 2008-12-24 | 2009-12-22 | Corrosion-resistant steel material for crude oil tanker |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201035333A (en) | 2010-10-01 |
| KR101147950B1 (en) | 2012-05-24 |
| KR20100137017A (en) | 2010-12-29 |
| EP2377963A4 (en) | 2015-08-05 |
| KR20120008089A (en) | 2012-01-25 |
| CN102264937B (en) | 2013-10-30 |
| EP2377963A1 (en) | 2011-10-19 |
| JP4502075B1 (en) | 2010-07-14 |
| JP2010216005A (en) | 2010-09-30 |
| EP2377963B1 (en) | 2019-03-13 |
| TWI404807B (en) | 2013-08-11 |
| WO2010074307A1 (en) | 2010-07-01 |
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