CN100424213C - Marine steel material superior in corrosion resistance - Google Patents
Marine steel material superior in corrosion resistance Download PDFInfo
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- CN100424213C CN100424213C CNB200510087933XA CN200510087933A CN100424213C CN 100424213 C CN100424213 C CN 100424213C CN B200510087933X A CNB200510087933X A CN B200510087933XA CN 200510087933 A CN200510087933 A CN 200510087933A CN 100424213 C CN100424213 C CN 100424213C
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Abstract
The invention provides a marine steel material having superior corrosion resistance, which can be practically used even without being painted or electrolytically protected, particularly, a marine steel material showing superior durability to crevice corrosion, in damp air atmosphere such as in an upper part inside a ballast tank, at which electrolytic protection does not work, and on an upper deck of a crude oil tank. The marine steel material comprises each of 0.01-0.20% C, 0.01-0.50% Si, 0.01-2.0% Mn, 0.05-0.50% Al, 0.01-5.0% Cu and 0.01-5.0% Cr, further each of P controlled to 0.020% or less (including 0%) and S controlled to 0.010% or less (including 0%), and the balance Fe with unavoidable impurities.
Description
Technical field
The present invention relates to a kind of in boats and ships such as crude oil tanker, freighter, vessel, passenger boat, warship as primary structure with the anti-corrosion steel of boats and ships that material uses, particularly relate to the salinity that is exposed to seawater formation and the steel for ship of the corrosion resistance excellent under the high temperature wet environment.
Background technology
The steel that use with material (for example, outside plate, ballast tank, oil tank etc.) as its primary structure in above-mentioned various boats and ships are under the environment owing to salinity that is exposed on seawater formation and high temperature humidity, so often be subjected to corrosion damage.Such corrosion might cause and leaking and casualty such as sinking, so be necessary steel are implemented some corrosion protection measures.As practiced corrosion protection means so far, (a) application and (b) electric anticorrosion etc. known well by people.
Wherein, in coating process, because the possibility height that holiday exists, and also can cause coating injured sometimes, so the situation that the matrix steel expose is many owing to the collision in the manufacturing process etc. by multiple application representative.In such steel exposed portions serve, understand the local and concentrated steel that erode, early stage leakage will take place in the petroleum-type liquid fuel that is loaded.
On the other hand, electric anticorrosion is very effective for the part that is immersed in fully in the seawater, but is subjected to position that seawater splashes etc. in the atmosphere owing to do not form the necessary circuit of corrosion protection, so corrosion protection result can not be fully played.Also have, the sacrificial anode that corrosion protection is used consume unusually or come off disappear in, fierce corrosion is arranged sometimes immediately.
Outside the above-mentioned technology,, the technology of patent documentation 1 has for example been proposed also as improving the corrosion proof technology of steel self.In this technology, disclose a kind ofly by suitable adjustment chemical composition of steel, and form the material of corrosion resistance excellent, even the anti-corrosion steel of the also operable shipbuilding of not application.Also have, in patent documentation 2, disclose a kind ofly, improve the coating steel for ship in work-ing life by suitably regulating the chemical constitution of steel.These technology be we can say and compared in the past, can guarantee solidity to corrosion in a way.
But about the solidity to corrosion under more severe corrosive environment, it is enough still can not to say so, and still requires further to improve solidity to corrosion.Particularly, in the contact part of foreign matter and steel,, reduced in the life-span owing to the grade corrosion (so-called crevice corrosion) of formed [crack] part of the pars affecta of constructional reason or erosion shield becomes very remarkable.Be inadequate about this a part of solidity to corrosion in the technical scheme that is proposed so far.
[patent documentation 1] spy opens the scope of 2001-17381 communique claim etc.
[patent documentation 2] spy opens the scope of 2002-26605 communique claim etc.
Summary of the invention
The present invention is conceived to above-mentioned situation, even its purpose is to provide a kind of unreal steel for ship that applies the corrosion resistance excellent that dress and electric anticorrosion also can practicability, particularly the electric anticorrosion effect less than ballast tank in top and moist atmosphere environment such as oil tank upperdeck under, for the steel for ship of performance excellent durabilities such as crevice corrosion.
In order to achieve the above object and the development steel for ship of the present invention, have following main points, contain the C:0.04～0.18% (meaning of quality %, down together), Si:0.01～0.50%, Mn:0.10～1.8%, Al:0.05～0.40%, Cu:0.05～4.00%, Cr:0.05～4.50%, Ni:0.05～4.50%, Ti:0.008～0.20%, Ca:0.0010～0.015%, and the content that suppresses P and S is P:0.020% following (comprising 0%) and S:0.010% following (comprising 0%), surplus is Fe and unavoidable impurities, and the content of Cr [Cr] is 1～50 with the ratio ([Cr]/[Al]) of the content [Al] of Al.
Also have in steel for ship of the present invention, according to necessity, make it also contain (1) Mg:0.0005～0.020%, (2) Co:0.01～5.0%, (3) Se:0.005～0.50%, (4) Sb:0.01～0.50% and/or Sn:0.01～0.50% are in (5) B:0.0001～0.010%, V:0.01～0.50% and Nb:0.003～0.50% more than any one, according to the kind of ingredient, the characteristic of steel for ship also can be further improved.
Use in the steel in shipbuilding of the present invention, when making its Al that contains specified rate simultaneously and Cr, by suitably adjusting chemical constitution, even unreally apply dress and electric anticorrosion also can obtain the steel for ship of the corrosion resistance excellent of practicability, realized that particularly a kind of raising is to crack corrosive solidity to corrosion, and the electric anticorrosion effect less than ballast tank in top and moist atmospheric environment such as oil tank upperdeck under, for the steel for ship of the excellent weather resistance of performances such as crevice corrosion.Such steel for ship outside such use, can be used for the materials such as outside plate as boats and ships such as crude oil tanker, freighter, vessel, passenger boat, warships.
Description of drawings
Fig. 1 is the explanatory view that is illustrated in the face shaping of the test film A that uses in the Kesternich test.
Fig. 2 is the explanatory view that is illustrated in the face shaping of the test film B that uses in the Kesternich test.
Fig. 3 is the explanatory view that is illustrated in the face shaping of the test film C that uses in the Kesternich test.
Fig. 4 is the explanatory view that is illustrated in the face shaping of the test film D that uses in the Kesternich test.
Fig. 5 is the explanatory view that is illustrated in the face shaping of the test film E that uses in the Kesternich test.
Fig. 6 is the explanatory view that is illustrated in the face shaping of the test film F that uses in the Kesternich test.
Embodiment
Present inventors have carried out constantly research with keen determination in order to address the above problem.The result is, found by making its Al that contains specified rate simultaneously and Cr, and suitably adjusted chemical constitution, just can solve the shipbuilding steel of above-mentioned problem, finished the present invention.
In steel of the present invention, make it contain Al simultaneously and Cr is crucial, which these compositions are short of, and all can not reach purpose of the present invention.Each action effect about these compositions is narrated below, and by using these elements simultaneously, the reason that solidity to corrosion is improved can be carried out following consideration.
Al has the effect that forms stable oxide corrosion protection film on steel surface.The Al3 of corrosion dissolution from steel
+Ion and dissolved oxygen etc. combine and form the Al oxide compound, and these Al oxide compounds are piled up from the teeth outwards and formed the corrosion protection film.The corrosion protection result of this protective membrane can not be said so very abundant at the perchloride environment of boats and ships.On the other hand, Cr and above-mentioned Al form the stable oxide protective membrane equally from the teeth outwards, and performance is to the corrosion protection result of steel, but the corrosion protection result of independent Cr oxide compound can not be said very abundant.
Above-mentioned Al protective oxide layer is that stability is very high in about neutral region of about 5～8.5 in the pH value, and its solvability uprises when the pH value surpasses 8.5.Steel for ship is exposed to seawater wherein, and its pH value is about 8 in cleaning, in its pH value of marine site of breeding such as marine alga with alkalify arrival about 9.5.Also have, in the position that the corrosive cathodic reaction takes place, because the OH that the dissolved oxygen reduction generates
-Ion is so the pH value has the tendency of rising.Therefore, under ship environment, the Al oxide compound may not stably exist, on the contrary easily dissolving and can't obtain its protectiveness under many circumstances.To this, because the Cr oxide compound is at alkaline Domain Stability height, the Cr ion of oligodynamical passes through hydrolysising balance; has the effect that the pH value is descended; so, suppressed the rise dissolving of the Al oxide compound that caused of seawater pH value, brought into play the effect of guaranteeing its protectiveness.Therefore, by an amount of coexistence of Cr oxide compound and Al oxide compound, the corrosion protection result of steel can increase at double.
Such effect makes it obtain performance by being controlled to be proper content described later, but especially suitably controls ratio ([Cr]/[Al]: mass ratio) for good of these content.That is, this value ([Cr]/[Al]) is when being lower than 1, and then the corrosive homogeneity becomes insufficient easily, and the anti-crevice corrosion above 50 becomes insufficient.The value of this [Cr]/[Al] is preferably about 10～35.
Steel of the present invention in order to satisfy its fundamental characteristics as steel, need suitably be adjusted compositions such as C, Si, Mn, Cu, P, S.The reason that these composition ranges limit, the action effect with above-mentioned Al, each element of Cr is described below.
C：0.04～0.18％
C is in order to ensure the necessary element of the strength of materials.For obtain as the structural member of boats and ships minimum intensity, be (also will determine) about about 400MPa according to the thickness that uses steel, it is contained more than 0.04% is necessary.But, make its excessive containing above 0.18%, then can worsen toughness.So the content range of C is 0.04～0.18%.Also have, the content preferred lower limit of C is 0.08%.Have, the content preferred upper limit of C is 0.16% again.
Si：0.10～0.50％
Si is for deoxidation and guarantees the necessary element of intensity, discontented 0.10% minimum intensity that can not guarantee as structural member.But, make its excessive containing above 0.50%, then can worsen weldability.Also have, the content preferred upper limit of Si is for better below 0.40%, 0.30%.
Mn：0.10～1.8％
Mn and Si are for deoxidation equally and guarantee that intensity is necessary, discontented 0.10% minimum intensity that can not guarantee as structural member.But, make its excessive containing above 1.8%, then can worsen toughness.Also have, the content preferred upper limit of Mn is 1.6%.
Al：0.05～0.40％
As mentioned above, Al has the effect that forms stable oxide corrosion protection film from the teeth outwards.The content of Al reduces the then Al of corrosion dissolution
3+Ion disperses in seawater and can not pile up on steel surface, also just can not make it form the corrosion protection film.For make its give full play to Cr oxide compound coexistence under anti-corrosion effect, Al is contained more than 0.05% is necessary.If common steel, the content of Al surpasses 0.10% problem that has the weldability that toughness of welded zone descends slightly to be taken place, but steel of the present invention, by C, Si, P, S are in the suitable scope, even the content of Al is 0.10% to surpass～0.40% scope, also can guarantee to have and in the past the equal weldability of steel.But the content of Al surpasses 0.40% and excessive containing then can be damaged its weldability.Therefore, the content range of Al is 0.05～0.40%.Also have, the content preferred lower limit of Al is for better more than 0.08%, 0.10%.
Cu：0.05～4.00％
Cu helps to form fine and close surperficial rusty scale protective membrane and significantly improves corrosion proof effective element.Also have, the rusty scale protective membrane by containing the formed densification of Cu, with the anti-corrosion protective membrane of stable oxide of Al oxide compound and the coexistence of Cr oxide compound increases exponentially the protectiveness of mother metal (steel), makes the excellent solidity to corrosion of its performance.In order to bring into play such effect, it is contained more than 0.05% be necessary, still, excessive containing then can be worsened weldability and hot workability, so be preferably below 4.00%.
Cr：0.05～4.50％
Cr and Al form the stable oxide protective membrane equally from the teeth outwards and bring into play the effect of steel corrosion protection.Above-mentioned as the present invention institute, coexist by making Al oxide compound and Cr oxide compound, can improve the solidity to corrosion of steel tremendously, in order to bring into play such effect, it is contained more than 0.05% is necessary.But excessive containing then can be worsened weldability, so be necessary below 4.50%.
P: (comprise 0%) below 0.020%
P is the element that toughness and weldability are worsened, and should suppress its content as much as possible.The upper limit to 0.020% that allows of P content is if surpass then can not guarantee weldability as steel for ship.So the content of P is below 0.020%.Also have, the preferred upper limit of the content of P is 0.015%.
S:0.010% following (comprising 0%)
S and P are the element that toughness and weldability are worsened equally, should suppress its content as much as possible.The upper limit to 0.010% that allows of S content is if surpass then can not guarantee weldability as steel for ship.So the content of S is below 0.010%.Also have, the preferred upper limit of the content of S is 0.008%.
Basal component in the steel for ship of the present invention is as described above, and surplus is made of Fe and unavoidable impurities (for example O etc.), and the composition that does not damage steel characteristics outside these (for example, Zr, N etc.) also can allow to exist.But these allow the composition of existence, and its content is crossed at most can worsen toughness, so should be controlled at below about 0.1%.
Also have, in steel for ship of the present invention, outside the mentioned component, according to necessity, make it also contain (1) Ni:0.01～5.0%, in Co:0.01～5.0% and Ti:0.005～0.20% more than any one, (2) Ca:0.0005～0.020% and/or Mg:0.0005～0.020%, (3) Se:0.01～0.50%, (4) Sb:0.01～0.50% and/or Sn:0.01～0.50%, (5) B:0.0001～0.010%, in V:0.01～0.50% and Nb:0.003～0.50% more than any one, (6) Zn:0.001～0.10% grade also is effective, according to the kind of ingredient, the characteristic of steel for ship also can further improve.
In Ni:0.05～4.50%, Co:001～5.0% and Ti:0.008～0.20%
More than
Any among Ni, Co and the Ti all is to improve corrosion proof effective element.Wherein, Ni and Co help to form fine and close surperficial rusty scale protective membrane and significantly improve corrosion proof effective element.In order to make the such effect of its performance, preferably contain more than the Ni:0.05%, more than the Co:0.01%, still excessive containing then can be worsened weldability and hot workability, so be preferably below the Ni:4.50%, below the Co:5.0%.When making it contain Co, more preferably be limited to 0.05% down, be limited to 4.50% on more preferably.
Ti helps the densification of surperficial rusty scale protective membrane to form, and improves the closure of its environment, thereby increases substantially solidity to corrosion, and suppress the corrosion of inside, crack, the element that anti-crevice corrosion is improved.In order to ensure desired solidity to corrosion under such environment, it is contained be good more than 0.008%, still can worsen processibility and weldability above 0.20% excessive containing then.The preferred upper limit of Ti is 0.15%.
Ca:0.0010～0.015% and/or Mg:0.0005～0.020%
Ca and Mg are the effects that demonstrates rising pH value by dissolving, suppress to have taken place the caused pH value reduction of the local anodic hydrolytic action of dissolved of iron, thereby suppress corrosion reaction, improve corrosion proof effective element.Such effect is by containing more than the Ca:0.0010%, effectively being brought into play more than the Mg:0.0005.But Ca surpasses 0.015%, Mg surpassed for 0.020% excessive containing then and can worsen its processibility and weldability.Preferred lower limit when containing Mg is 0.0010%, and preferred upper limit is 0.015%.
Se：0.005～0.50％
Thereby the pH value of the position that Se is inhibition, and the corrosive solubilizing reaction has taken place reduces the inhibition corrosion reaction, and performance improves the element of solidity to corrosion effect.By making it contain such Se, partial pH value changes difficult the generation, thereby has the inhomogeneity effect of the corrosion of raising.Also have, move [the crack portion] that confined, the easy local pH of generation value reduces,, make its effect (effect that suppresses local corrosion) performance effectively according to above-mentioned reason at material.In order to ensure desired solidity to corrosion under such environment, the content of Se is good more than 0.005%.But surpassing for 0.50% excessive containing then can worsen processibility and weldability.In view of the above, the content of Se is 0.005～0.50%.Also have, the preferred lower limit of Se content is better more than 0.008%, 0.010%.Have, the preferred upper limit of Se content is for better below 0.45%, 0.40% again.
Sb:0.01～0.50% and/or Sn:0.01～0.50%
Sb and Sn help Cu, Ni, Ti etc. to generate the densification formation of rusty scale protective membrane and the pH value reduction effect that Se, Ca, Mg etc. produce, thereby improve corrosion proof element.In order to bring into play such effect, making it contain any is good more than 0.01%.But excessive containing then can be worsened processibility and weldability, so be good below 0.50%.When making it contain these elements, preferred lower limit is 0.02%, and preferred upper limit is 0.40%.
Any in B:0.0001～0.010%, V:0.01～0.50% and Nb:0.003～0.50%
More than one
In steel for ship, according to suitable position, have the requirement of higher intensity sometimes, these elements are the elements that improve intensity necessity.Wherein, B is contained more than 0.0001% then can improve hardenability, effective to improving intensity, still can worsen base metal tenacity, so not good above 0.010% excessive containing then.It is effective to improving intensity that V is contained more than 0.01%, surpasses the 0.50% excessive flexible that then can cause steel that contains and worsen, so not good.Nb is contained can be effective to improving intensity more than 0.003%, surpasses the 0.50% excessive toughness of then causing steel that contains and worsen.Also have, the preferred lower limit of these elements, B is 0.0003%, and V is 0.02%, and Nb is 0.005%.Also have preferred upper limit, B is 0.0090%, and V is 0.45%, and Nb is 0.45%.
Zn：0.001～0.100％
Zn and salinity and sulphur react, and form the beds of precipitation of zinc chloride and zinc sulphide at steel surface, thereby the moisture contact steel matrix that has in the blocking-up environment suppresses the corrosive effect.In material moves the coating that is limited or the part of crack, zinc chloride and zinc sulphide can not diffuse in the seawater and go, but are easy to precipitate on steel surface, and therefore, particularly the inhibition corrosive effect of under the coating or crack part is big.
In order to ensure reaching so desired solidity to corrosion of effect, the content of Zn is to be necessary more than 0.001%.But surpassing for 0.10% excessive containing then can worsen processibility and weldability.In view of the above, Zn content is 0.001～0.10%.Also have, the preferred lower limit of Zn content is for better more than 0.003%, 0.005%.Have, the preferred upper limit of Zn content is for better below 0.09%, 0.08% again.
When steel of the present invention being welded formation welding structure thing, when using common welding conditions or wlding to weld, the concentration of above-mentioned effective element changes at the welding joint place, and therefore the solidity to corrosion of weld part is not found sometimes.Particularly, the content of Al, Cu and Cr all is lower than in 0.3 at the ratio (content of the content/mother metal of deposited metal) of deposited metal and mother metal, the effect that the solidity to corrosion that is produced by these elements interpolations significantly improves does not occur, and the solidity to corrosion of deposited metal part is insufficient.Also have, because this ratio surpasses 3.0 toughness that can worsen weld part, so be thought of as not good from the angle of physical strength.Therefore, this ratio is recommended to be adjusted into 0.3～3.0, and preferable range is 0.5～2.0.
Also have, about the corrosion proof effective element Ni of raising, Co, Ti, Ca, Mg, Se, Sb, Sn, the Zn beyond Al, the Cr, when adding these, the ratio of the content of deposited metal and mother metal (content of the content/mother metal of deposited metal) is recommended to be adjusted into 0.3～3.0, and preferable range is 0.5～2.0.
Steel for ship of the present invention, basically the unreal dress steel self that apply also can be brought into play excellent solidity to corrosion, but as required, also can with tar epoxy coating shown in the embodiment as described later or the representational multiple anti-corrosion application beyond it, other anti-corrosion method such as zinc rich paint, shop primer uses simultaneously.When implementing such anticorrosive coating, shown in the embodiment, the solidity to corrosion of coating self (application solidity to corrosion) also can become good as described later.
Below, for embodiment the present invention is carried out specific description, the present invention is not limited by following embodiment, in meeting forward and backward described design scope, add that suitable to implement certainly after changing also be possible, these any one all be contained within the technical scope of the present invention.
[embodiment]
Embodiment 1
The steel of the chemical constitution shown in the following table 1～3 carry out melting by converter, are made into various steel plates by continuous casting and hot rolling.Resulting steel plate is cut and surfacing, be made into the test film (test film A) of 100 * 100 * 25 (mm) size at last.The face shaping of test film A as shown in Figure 1.
See below＜table 1～3 〉
Also have, as shown in Figure 2, the big test film (identical with above-mentioned test film A) of the small test sheet and 100 * 100 * 25 (mm) of 4 20 * 20 * 5 (mm) is joined, be made into the test film B that has formed crack portion.This small test sheet that forms the crack is the steel of identical chemical constitution with big test film, and surperficial and above-mentioned test film A has carried out surfacing equally.Next offer the aperture of φ 5mm at the center of small test sheet, base material side (big test film side) is offered screw hole, fixes with M4 plastics screw.
Have, having used mean thickness is comprehensive tar epoxy (priming paint: test film C (Fig. 3) zinc rich primer) that sprayed of 250 μ mm again.Corrosion protection is impaired with filming in order to investigate below, corrosive when the matrix steel expose progress degree, the one side of test film C make deeply with icking tool the icking tool that reaches (steel) matrix hinder (long: 100mm, wide: about 0.5mm).
Test in each chemical constitution shown in above-mentioned table 1～3 is used in the material, has carried out corrosion test with each 5 test film A, test film B, test film C respectively.The corrosion test method of this moment is as described below.
[corrosion test method]
Analog electrical corrosion protection effect less than ballast tank in moist atmospheric environment such as top, make it adhere to the sea salt particle and keep wet and carried out corrosion test (corrosion test A).Also have, the seawater 7.5ml that gathers in Bingku county Jia Guchuan city is dropped on the test face substantially uniformly, and make and pass through the exsiccant test film in temperature: horizontal positioned is corroded in 50 ℃, the Thoughs of the steady temperature humidity of humidity: 95%RH.Test period is 6 months, and each month appends seawater 5.0ml and drop on the test face.In this test, used above-mentioned test film A and test film B, its anti-general corrosion, corrosion homogeneity and anti-crevice corrosion are estimated.
Also have, simulated the corrosive environment of the upperdeck in the oil tank, test film is horizontally set on temperature remains in 50 ℃ the Thoughs, with the speed of 1L/min by by 5vol%O
2-10vol%CO
2-0.01vol%SO
2-0.3vol%H
2The corrosive gases that S forms corrodes (corrosion test B) to test film.At this moment, the humidity in the Thoughs is controlled at more than the 98%RH, and keeps moisture state, so that be in the steam-laden state always.Test period is 6 months.This test, each month appends seawater 5.0ml and drops on the test face.In this test, used above-mentioned test film A and test film C, its anti-general corrosion, corrosion homogeneity and application solidity to corrosion are estimated.
(1) for test film A, the changes in weight before and after the test is converted into the reduction D-ave (mm) of average thickness of slab, calculate the mean value of 5 test films, estimate the anti-general corrosion of each test with material.Also have, use the maximum depth of erosion D-max (mm) of contact pin type 3 d shape testing device determination test sheet A, [D-ave (mm)] carries out standardization (that is, calculating D-max/D-ave) by average thickness of slab reduction, and the corrosive homogeneity is made evaluation.Also have, weight determination after the test and measurement of plate thickness are carried out after utilizing katholysis [JISK8284] to remove corrosion product such as iron rust in the diammonium hydrogen citrate aqueous solution.
(2) for test film B, crack portion (contact surface) has been carried out visual inspection, whether investigated has crevice corrosion to take place, when crevice corrosion is identified, remove corrosion product with above-mentioned katholysis, use the contact pin type 3 d shape testing device to measure maximum crevice corrosion depth D-crev (mm).
(3) for implementing the test film C (hindering) that application is handled with icking tool, hinder with kind of calliper and icking tool vertical direction coating swell width, the width that swells of maximum is defined as maximum value in 5 test films.
The metewand of above-mentioned anti-general corrosion (D-ave), corrosion homogeneity (D-max/D-ave), anti-crevice corrosion (D-crev), application solidity to corrosion (swell area occupation ratio and maximum swells width) is as shown in table 4 below.Corrosion test result is shown in following table 5～7.
See below＜table 4～7 〉
Can carry out next step investigation according to these results.At first, in any corrosion test, when the content of Al, Cu and Cr all is discontented with foot proper range given to this invention (No.2～6), compare with always common iron (No.1), anti-general corrosion is improved slightly.But the corrosion proof effect of improving of corrosion homogeneity and application does not obtain confirming.
With respect to this, contain under the situation of an amount of Al, Cu and Cr (No.7～55), improve because the composite effect that the interpolation of these elements produces, any one solidity to corrosion all have significantly, corrosion homogeneity, anti-crevice corrosion and application solidity to corrosion also are improved.Corrosion proof raising like this is considered to owing to the stable oxide corrosion protection film of Al oxide compound and Cr oxide compound coexistence and contains the composite effect that the provide protection of the rusty scale protective membrane of the densification that Cu forms produces.
Wherein as can be known, on the basis of using Al, Cu and Cr at the same time, contain Ni, Co, Ti, Ca, Mg etc. again and improve corrosion proof element (N0.11～15), thereby the anti-general corrosion of steel is improved significantly.Particularly, by containing Ca and Mg, the raising of corrosion homogeneity and anti-crevice corrosion obtains confirming (No.14～15), is inferred as owing to these elements have the restraining effect that local pH is reduced and has suppressed partial corrosion.
In addition, confirmed by containing Ni, Co or Ti, and improved the corrosion proof effect of application (No.11～13 etc.), be inferred as because the composite effect of the embroidery layer densification of these elements has stoped the corrosive of coating damage part to make progress.
Have, contain Se by making it, significantly improved solidity to corrosion (No.35,36 etc.), this is because Se to the inhibition effect that the local pH value changes, helps the corrosion proof raising for local corrosions such as crevice corrosions.Also have, No.7,8,9, results such as 10 also clearly show, by the ratio of suitable adjustment ([Cr]/[Al]), obtain the excellent results that various solidity to corrosions significantly improve.
More have, make its test that contains Zn, obtained the further result of raising of application solidity to corrosion and anti-crevice corrosion with material (No.44,45,46 etc.).For example, on the basis of Al, Cu and Cr, add the No.45 of an amount of Zn again, compare, the result who all is improved on the anti-crevice corrosion in ballast tank and the application solidity to corrosion at the back side, deck on the oil tank with the No.8 that only adds Al, Cu and Cr.Add by Zn as mentioned above and improves solidity to corrosion, be inferred to be the zinc chloride that on the surface of steel, forms and the beds of precipitation of zinc sulphide and blocked the moisture in the environment, thereby have the effect of inhibition corrosive effect.
Embodiment 2
The steel of chemical constitution carry out melting by converter shown in the following table 8, make various steel plates by continuous casting and hot rolling.Resulting steel plate is cut off and surfacing, be made into the test film D ' of 300 * 150 * 25 (mm) size at last.Use the welding material of the chemical ingredients shown in the table 9, carry out union-melt weld, made connector test sheet D (Fig. 4) as shown in the figure with 2 D '.Also have, the line of all welding materials directly is 4.8mm, and groove is shaped as the V font.The heat input suitably is adjusted into from 1 to 10KJ/mm.
Also have, the small test sheet of 2 60 * 60 * 5 (mm) is joined, be made into the test film E (Fig. 5) that has formed crack portion.The chemical constitution that forms the small test sheet of using in the crack is identical with the mother metal of test film D, and surperficial and above-mentioned test film D has carried out surfacing equally.Next offer the aperture of φ 10mm at the center of small test sheet, base material side (big test film side) is offered screw hole, fixes with M8 plastics screw.
Have, having used mean thickness is comprehensive tar epoxy (priming paint: test film F (Fig. 6) zinc rich primer) that sprayed of 250 μ mm again.Corrosion protection is impaired with filming in order to investigate below, corrosion when the matrix steel expose progress degree, in the one side of test film F, along the direction of and level vertical with welding line with icking tool make the icking tool that reaches matrix deeply hinder (length: 200mm, wide: about 0.5mm).
For the connector test sheet that uses mother metal shown in the previous table 8,9 and welding material to make, use each 5 test film D, test film E and test film F to carry out corrosion test respectively.At this moment corrosion test method (exposure test of real ship) is as described below.
[corrosion test method]
The test that is made into is installed in respectively on the base plate of VLCC oil tank inner face with material, each 5 of each test film D～F, after the common navigation in 5 years, has investigated the corrosion condition of each test with material.After the exposure in 5 years,, in the diammonium hydrogen citrate aqueous solution, utilize katholysis [JISK8284] to remove corrosion products such as iron rust for test film D.Also have, for test film E, take off and form the small test sheet that crack portion uses, corrosion products such as having removed iron rust uses the same method.
(1) for test film D, the changes in weight before and after the test is converted into the reduction D-ave (mm) of average thickness of slab, calculate the mean value of 5 test films, estimate the anti-general corrosion of each test with material.Also have, use the maximum depth of erosion D-max (mm) of contact pin type 3 d shape testing device experiment with measuring sheet D, [D-ave (mm) carries out standardization (that is, calculating D-max/D-ave), and the corrosive homogeneity has been made evaluation by average thickness of slab reduction.
(2) for test film E, use the contact pin type 3 d shape testing device, measured the maximum crevice corrosion depth D-crev (mm) of big test film side.
(3) for implementing the test film F (hindering) that application is handled with icking tool, the coating of the direction of hindering perpendicular to icking tool with kind of calliper swell width, the width that swells of maximum is defined as maximum value in 5 test films.
Above-mentioned anti-general corrosion (average thickness of slab reduction: D-ave), the metewand of corrosion homogeneity (D-max/D-ave), anti-crevice corrosion (D-crev), application solidity to corrosion (maximum swells width) is as shown in table 10 below.Corrosion test result is as shown in table 11 below.Also have, in table 11, I (Al) is the Al content of the Al content/mother metal of deposited metal, and I (Cu) is the Cu content of the Cu content/mother metal of deposited metal, and I (Cr) is the Cr content of the Cr content/mother metal of deposited metal.
The content of the Al of weld part, Cu or Cr does not satisfy No.56, No.57 and the No.58 of relational expression (1), (2) or (3), and its anti-general corrosion excellence is still corroded homogeneity and the application solidity to corrosion does not obtain gratifying result.This is the result that the part at welding metal has corrosion to carry out.With respect to this, satisfy No.59～66 of this ratio relation formula (1), (2) or (3), for any corrosive property, all confirmed to have and improved corrosion proof result, demonstrated excellent solidity to corrosion as welded construction.
Also have, present embodiment is that the weld part with union-melt weld is an evaluation object, but other welding process such as dressing electric-arc welding and electroslag welding also can access identical effect.Also have, the welding material of use is not limited only to the scope of table 9, and welding conditions also is not limited only to present embodiment.
[table 1]
[table 2]
[table 4]
[table 5]
[table 6]
Claims (5)
1. the steel for ship of a corrosion resistance excellent, it is characterized in that, by percentage to the quality, contain C:0.04～0.18%, Si:0.1～0.50%, Mn:0.10～1.8%, Al:0.05～0.40%, Cu:0.05～4.00%, Cr:0.05～4.50%, Ni:0.05～4.50%, Ti:0.008～0.20%, and the content of P and S suppressed be: P:0.020% is following and comprise 0%, S:0.010% is following and comprise 0%, also contain in Ca:0.0010～0.015% and Mg:0.0005～0.020% more than one in addition
Surplus is Fe and unavoidable impurities,
Wherein ratio [Cr]/[Al] of Cr content [Cr] and Al content [Al] is 1～50.
2. steel for ship according to claim 1 is characterized in that, by percentage to the quality, also contains Co:0.01～5.0%.
3. steel for ship according to claim 1 is characterized in that, by percentage to the quality, also contains Se:0.005～0.50%.
4. steel for ship according to claim 1 is characterized in that, by percentage to the quality, also contains Sb:0.01～0.50% and/or Sn:0.01～0.50%.
5. steel for ship according to claim 1 is characterized in that, by percentage to the quality, also contains in B:0.0001～0.010%, V:0.01～0.50% and Nb:0.003～0.50% more than any one.
Applications Claiming Priority (5)
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| JP2004-222372 | 2004-07-29 | ||
| JP2004222372 | 2004-07-29 | ||
| JP2004222372A JP2006037201A (en) | 2004-07-29 | 2004-07-29 | Marine steel material superior in corrosion resistance |
| JP2004307130 | 2004-10-21 | ||
| JP2004-307130 | 2004-10-21 |
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| CN (1) | CN100424213C (en) |
Cited By (2)
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| CN102605277A (en) * | 2011-01-18 | 2012-07-25 | 株式会社神户制钢所 | Steel material for structural member having excellent corrosion resistance |
| CN105401045A (en) * | 2015-11-10 | 2016-03-16 | 太仓捷公精密金属材料有限公司 | Abrasion-resistant anti-corrosion material |
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Also Published As
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| CN1904118A (en) | 2007-01-31 |
| JP2006037201A (en) | 2006-02-09 |
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