CN106048449A - Coating steel material with excellent corrosion resistance - Google Patents

Coating steel material with excellent corrosion resistance Download PDF

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Publication number
CN106048449A
CN106048449A CN201610203844.5A CN201610203844A CN106048449A CN 106048449 A CN106048449 A CN 106048449A CN 201610203844 A CN201610203844 A CN 201610203844A CN 106048449 A CN106048449 A CN 106048449A
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steel
corrosion resistance
film
coating
corrosion
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阪下真司
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Kobe Steel Ltd
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Kobe Steel Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • 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
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • 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
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

The invention provides a coating steel material with excellent corrosion resistance capable of inhibiting seawater pollution, corrosion resistance and corrosion resistance which are affected by corrosion effects such as splashing sea salt particles and the like, and the steel material base steel material for coating contains c/o particles :0.04 -0.30%, si = 30% :0.05 -1 0%, mn: 1 -2 :is greater than 0% and less than 0.04%, s is higher than 0% and less than 0.04% or less., al: 0.5wt % -20%, cu: 0.05 -1. 0%, Cu: 0.05 -1, cr: 0.05 -1, 0%, n: 001 -0.00015%, n: 001 -0.00015%, and contains ti: 0.005 -0.1%, nb is greater than 0.5%, nb is greater than 0.5%, nb is less than or equal to 1%, nb is less than or equal to 1%, nb is :0.005 -0.1% any one or both of the following:, the surface layer contains zn: 20 -200 g/min. m2, cu: 0. 3 -20. 0 g m2, and contains cr: 0.3-20.0 g m2, ni: 0.3 -20 m2 of any one or more of two or more of two or more of two or more of two or more.

Description

The application steel of excellent corrosion resistance
Technical field
The present invention relates to the application steel of steel structure for boats and ships, marine structure, bridge etc., in detail, Particularly relate to the application steel of the excellent corrosion resistance used under the corrosive environment that sea water or splashing sea salt particle are main cause Material.
Background technology
The many structure components as various works of steel, but as boats and ships, marine structure, bridge etc. by sea When the structure component of works of water impact uses, steel can by the corrosiveness of sea water etc., exist reduce because of thickness of slab and Perforation etc. causes works intensity to reduce such problem.
The corrosion that such steel cause because of sea water, when steel being served only for the position being impregnated in completely in sea water, Can be prevented by electric protection, but near the neighborhood, sea on sea etc. the most not by the position of Seawater immersion, electricity is anti- Corruption is the most inoperative, exposes to the open air in the violent corrosive environment of the spittle formation of sea water, prevents from having any problem with electric protection.
It addition, using steel as the structure component of the ballast box of boats and ships use time, ballast box needs according to delivery load Injecting, discharge sea water, therefore its inner surface will not be in the state being immersed in sea water often, it is impossible to fully obtains electric protection effect.
Additionally, the works by inshore metal bridge beam etc. also can expose the atmospheric corrosion ring formed at splashing sea salt particle to the open air In border, when therefore the structure component as such works uses steel, the application of electric protection may not effectively situation be very Many.
So, in the works of the boats and ships affected by sea water, marine structure, bridge etc., the application of electric protection Can not say certain effective, the most all the time, use the surface at steel to form anticorrosive coating film by anticorrosive coating more.Make For the coating for anticorrosive coating, it is possible to enumerate epoxy resin, chlorinated rubber system, acrylic resin, polyurethane resin and The various anticorrosive paints such as fluororesin system, the most with good grounds environment uses optimal application system so that it is the situation that multiple stratification uses.
But, deterioration or any outside mechanicalness effect that anticorrosive coating film can cause due to ultraviolet and occur Damage.In the flaw portion of such anticorrosive coating film, because corrosion of steel progress, so needing the maintenance of periodicity.But, at ship In the works of oceangoing ship, marine structure, bridge etc., due to the examination and maintenance of the state of anticorrosive coating, there is a need to build foot hands The eminence of frame, marine or baroque place etc., the very difficult place of examination and maintenance of the state of anticorrosive coating is the most very Many.So, from guaranteeing safety and reducing from the viewpoint of maintenance load, the corrosion with the flaw portion of anticorrosive coating film as starting point Suppression becomes very important technical problem.
As the countermeasure of such problem, by adjustment and the improvement of manufacture method of the chemical composition of steel, make steel The corrosion resistance of self improves, and contributes to suppressing the technology of the corrosion in the flaw portion of anticorrosive coating film, a large amount of by patent documentation 1,2 etc. Propose.By using these technology, although the corrosion resistance of application steel positively improves, but present situation is requirement corrosion resistance Further raising.
Particularly in the ballast box of boats and ships, in the place that film is peeled off, the erosion corrosion amount of 1 year also can reach 1mm, for Corrode the harshest environment, the corrosion in the flaw portion of strong expectation suppression anticorrosive coating film.It addition, in recent years, the use of boats and ships The requirement that the time limit extends improves, and in boats and ships, the application life-span of the ballast box that application deterioration is the most violent exceedes the longevity of existing 15 year The upswing in demand of lifeization.
The most in recent years, from the viewpoint of environment of preserving our planet is such, do not discharge as greenhouse gases The clean energy resource of carbon dioxide attract attention, deepwater wind-power electricity generation, wave-activated power generation, the generating of tide ocean current, the temperature difference are sent out The exploitation of the generation technology of electricity, solar electrical energy generation etc. advances.
It uses environmental condition, it may also be envisaged that for having harsher than the beach of conventional works, briny environment Corrosive probability, thus it is required to be applicable to the corrosion resistant aseptic technic of harsher environmental condition.It addition, realizing These time, the inspection of the painting state of steel and repaste the upkeep operation difficulties such as dress, therefore go out from the viewpoint of life cycle cost Send out, the upswing in demand that anti-corrosion life extends further, it is desirable to develop and improve higher than the corrosion resistance of conventional application steel Technology.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2010-229526 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2012-92404 publication
Summary of the invention
The problem that invention is to be solved
The present invention is formed in view of above-mentioned existing practical situation, and its problem is, it is provided that a kind of excellent corrosion resistance Application steel, it can suppress to be affected by the corrosiveness of sea water, splashing sea salt particle etc. and corrode.
Its problem is particularly in the medium plate of more than thickness of slab 3mm, steel plate, shaped steel, it is provided that a kind of corrosion resistance is excellent Different application steel, even if its conduct is under corrosive environment of sea water, or are the corrosive environment of main cause at splashing sea salt particle Under works structure with component use, corrosion resistance also will not occur problem.
For solving the means of problem
The application steel of the excellent corrosion resistance of the present invention are characterised by, are containing matrix steel and to be formed at described The application steel of the surface layer on the surface of matrix steel, described matrix steel in terms of quality % containing C:0.04～ 0.30%, Si:0.05～1.0%, Mn:0.1～2.5%, P: higher than 0% and below 0.04%, S: higher than 0% and Less than 0.04%, Al:0.005～0.20%, Cu:0.05～1.0%, Cr:0.05～1.0%, N:0.001～0.015%, and And containing any one in Ti:0.005～0.1%, Nb:0.005～0.1% or two kinds, surplus is by Fe and inevitably Impurity is constituted, it addition, described surface layer contains Zn:20～200g/m2, Cu:0.3～20.0g/m2, and containing Cr:0.3～ 20.0g/m2, Ni:0.3～20.0g/m2In any one or two kinds.
Additionally, it is preferred that described matrix steel in terms of quality % possibly together with Ni:0.01～6.0%, Co:0.01～5.0%, Mo:0.01～2.0%, W:0.01～2.0% any one or two or more.
Additionally, it is preferred that described matrix steel in terms of quality % possibly together with Mg:0.0005～0.01%, Ca:0.0005～ 0.01%, any one in REM:0.0005～0.01% or two or more.
Additionally, it is preferred that described matrix steel in terms of quality % possibly together with Sn:0.001～0.2%, Sb:0.001～0.2%, In Se:0.001～0.2% any one or two or more.
Additionally, it is preferred that described matrix steel in terms of quality % possibly together with B: higher than 0% and below 0.01%, V: be higher than 0% and below 0.1%, Zr: higher than 0% and below 0.1%, Zn: any one in higher than 0% and below 0.1% Or it is two or more.
Invention effect
The application steel of the excellent corrosion resistance according to the present invention, are i.e. used in by sea water, splashing sea salt particle etc. The impact of corrosiveness and steel in the harsh corrosive environment of the high boats and ships of the probability corroded, marine structure, bridge etc. Works, it is also possible to play good corrosion resistance.
Detailed description of the invention
In surface is implemented with the steel of application, it is known that if the film that its surface is formed perfects, then the corrosion of steel Inhibition is big, additionally, by selected suitable application system, it is possible to obtain high antiseptic effect.But, there is any defect in film Time and film generation matrix steel expose flaw time, the corrosion of matrix steel is then sent out with this film flaw portion as starting point Raw, a stepping exhibition of going forward side by side.
The present inventor goes forward side by side one for suppressing the corrosion of such matrix steel with film flaw portion as starting point The method of stepping exhibition is studied.Its results verification arrives, in film flaw portion, except the exposed division at matrix steel occurs corruption Beyond erosion reaction, the corrosion factor such as water, chloride ion also can invade the interface of film and matrix steel from described flaw portion, and There is to be coated with underfilm corrosion in the inside of film, and find the erosion progress of itself and the matrix steel in film flaw portion and expand closely Relevant.
It addition, in surface is implemented with the steel of application, it is known that by making to contain at the interface of film with matrix steel The layer having Zn is formed, and utilizes the anode loss protection effect of Zn, can suppress erosion progress and the film deterioration in film flaw portion, be coated with Dress corrosion resistance improves.From this foothold, in application steel, by the coating etc. of inorganic zinc primer, make containing The surface layer of Zn is formed on matrix steel, to realize corrosion resistance raising.
As the effect being formed at matrix steel and the layer at the interface of film, although there is anode loss protection effect to bring Erosion progress suppression and film degradation inhibiting, but the present inventor is ground for the protectiveness of further control corrosion rate product Study carefully.It was found that it is except Cu and Cr, in any one or the matrix steel of two kinds that are added with the most in right amount in Ti or Nb, By being formed in addition to containing Zn on its surface, possibly together with appropriate Cu, additionally contain in Cr and Ni any one or The surface layer of two kinds, thus, in addition to the anode loss protection effect of the Zn in film flaw portion, additionally it is possible to concertedness ground obtains The protectiveness of corrosion product improves effect, it is possible to significantly inhibit the erosion progress from film flaw portion, it is possible to make application use The corrosion resistance of steel is greatly improved, thus completes the present invention.
Also have, it is known that by adding Cu and Cr etc. in matrix steel, the protectiveness as the rust of corrosion product carries Height, corrosion resistance improves, but in the present invention, in addition to making the chemical composition of above-mentioned matrix steel suitably change, by entering One step carries out the layer being located at film with the interface of matrix steel, is i.e. formed at suitableization of the surface layer on the surface of matrix steel, The protectiveness of the corrosion product in film flaw portion significantly improves, it is possible to obtain anticorrosion effect.
Hereinafter, the present invention is explained based on embodiment.Further, the matrix steel of the application steel of the present invention is constituted Material, in addition to surface layer, the application for its surface illustrates the most in order.
<one-tenth of matrix steel is grouped into>
Matrix steel, in addition to excellent corrosion resistance, in addition it is also necessary to as the structure mechanical property of component necessity, and And need to meet weldability.From these viewpoints, in addition to described Cu, Cr, Ti, Nb, it is also desirable to suitably adjust Si, The content of Mn, Al, P, S.Hereinafter, the restriction reason for the composition range of these various addition element illustrates.Further, single Position all describes as %, the meaning of expression quality %.
C:0.04～0.30%
C is for ensuring that the basic addition element required for the intensity of matrix steel.In order to obtain as matrix steel Generally required strength characteristics, at least needs to be allowed to containing more than 0.04%.But, if make C contain superfluously, then molten in acid The generation quantitative change of the cementite worked as negative electrode point in liquid is many, promotes corrosion reaction, and corrosion resistance deteriorates.It addition, toughness Deteriorate the most in the lump.In order to avoid such harmful effect generation caused because of the superfluous interpolation of C, even if the content of C is also required to more Suppression is 0.30%.Therefore, the content of C is in the range of 0.04～0.30%.Further, the preferred lower limit of the content of C is 0.045%, more preferably more than 0.05%.It addition, the preferred upper limit of the content of C is 0.29%, more preferably 0.28% with Under.
Si:0.05～1.0%
Si is for deoxidation and to guarantee the element required for intensity, if being the most at least allowed to containing more than 0.05%, then no Act on to these.But, if be allowed to contain superfluously higher than 1.0%, then weldability deterioration.Therefore, the scope of the content of Si It is 0.05～1.0%.Further, the preferred lower limit of the content of Si is 0.08%, more preferably more than 0.10%.It addition, Si The preferred upper limit of content is 0.95%, more preferably less than 0.90%.
Mn:0.1～2.5%
Mn also with Si again it is for deoxidation and guarantee the element required for intensity, if its content is less than 0.1%, the most not Can ensure that the minimum intensity of steel as structure component.But, if be allowed to contain superfluously higher than 2.5%, the most tough Property deterioration.Therefore, the content of Mn is in the range of 0.1～2.5%.Further, the preferred lower limit of the content of Mn is 0.15%, more excellent Elect more than 0.2% as.It addition, the preferred upper limit of the content of Mn is 2.4%, more preferably less than 2.3%.
P: higher than 0% and below 0.04%
If P be surplus contain, then make toughness and weldability deterioration element, the upper limit of the permissible level of P is 0.04%. The content of preferably P is the fewest, and the preferred upper limit of the content of P is 0.038%, and more preferably less than 0.035%.But It is industrially to make the P in matrix steel reach 0% and have any problem.
S: higher than 0% and below 0.04%
If S is also to make toughness and the element of weldability deterioration at most containing quantitative change, the upper limit of the content allowed is 0.04%.S The preferred upper limit of content be 0.038%, more preferably less than 0.035%.But, industrially make matrix steel In S reach 0% and have any problem.
Al:0.005～0.20%
Al also with described Si, Mn again it is be used for deoxidation and guarantee the element required for intensity.In order to effectively play this The effect of sample, needs to be allowed to containing more than 0.005%.But, if being allowed to containing higher than 0.20%, then damage weldability, therefore The content of Al is in the range of 0.005～0.20%.Further, the preferred lower limit of the content of Al is 0.008%, more preferably More than 0.010%.It addition, the preferred upper limit of the content of Al is 0.19%, more preferably less than 0.18%.
Cu:0.05～1.0%
Cu is solid-solution in ferrite, except make the anode of the matrix steel exposed division in film flaw portion activity degree reduce with Outward, also there is the effect forming fine and close scale film at matrix steel surface, be that the corrosion resistance in film flaw portion improves required The element wanted.In order to play such effect, at least need to be allowed to containing more than 0.05%.But, if be allowed to superfluously containing, Then making weldability and hot-workability deterioration, therefore the content of Cu needs to be less than 1.0%.Therefore, the content of Cu in the range of 0.05～1.0%.Further, the preferred lower limit of the content of Cu is 0.06%, and preferred lower limit is 0.07%.It addition, Cu The preferred upper limit of content is 0.95%, and the preferred upper limit is 0.90%.
Cr:0.05～1.0%
It is solid-solution in as Cr with Cu in ferrite, except making the activity of the anode of the matrix steel exposed division in film flaw portion Beyond degree reduces, also there is the effect forming fine and close scale film at matrix steel surface, be the corrosion resistance in film flaw portion Element required for raising.In order to play such effect, at least need to be allowed to containing more than 0.05%.But, if superfluous ground Be allowed to containing, then make weldability and hot-workability deterioration, therefore the content of Cr needs to be less than 1.0%.Therefore, the content of Cr Scope is 0.05～1.0%.Further, the preferred lower limit of the content of Cr is 0.06%, and preferred lower limit is 0.07%.Separately Outward, the preferred upper limit of the content of Cr is 0.95%, and the preferred upper limit is 0.90%.
N:0.001～0.015%
N forms the fine dispersion particle of nitride in steel, for improving the corrosion resistance of matrix steel and guaranteeing intensity It it is effective element.In order to obtain such effect, the content of N needs to be more than 0.001%.But, if content is superfluous, then remove Beyond having undesirable effect the toughness of matrix steel, also damaging weldability, the upper limit therefore making the content of N is 0.015%. Therefore, the content of N is in the range of 0.001～0.015%.Further, the preferred lower limit of the content of N is 0.0015%, more preferably It is more than 0.002%.It addition, the preferred upper limit of the content of N is 0.014%, more preferably less than 0.013%.
Any one or two kinds in Ti:0.005～0.1%, Nb:0.005～0.1%
Ti and Nb, with under the coexisting of Cu and Cr, has the effect forming fine and close scale film at matrix steel surface, is Element required for corrosion resistance raising.In order to play such effect, it is allowed to the most respectively containing more than 0.005%.But, If be allowed to superfluously containing, then make weldability and hot-workability deterioration, therefore the content of Ti and Nb be respectively necessary for 0.1% with Under.The preferred lower limit of the content of Ti and Nb is respectively 0.006%, and preferred lower limit is 0.007%.It addition, Ti and Nb The preferred upper limit of content is respectively 0.095%, and the preferred upper limit is 0.09%.
It is above constituting the restriction of the composition range of the necessary addition element of the matrix steel of the application steel of the present invention Reason, surplus is Fe and inevitable impurity.As inevitable impurity, it is possible to enumerate O, H etc., these elements are not damaging Even containing under the degree of all characteristics of evil matrix steel.But, the total content suppression of these inevitable impurity exists Less than 0.1%, preferably less than 0.09%, thus enable that the corrosion resistance of the present invention manifests effect maximization.
If it addition, constitute the present invention application steel matrix steel in, containing element shown below the most more Effectively.Illustrate sequentially for the restriction reason containing composition range during these elements.
Any in Ni:0.01～6.0%, Co:0.01～5.0%, Mo:0.01～2.0%, W:0.01～2.0% One or more
Ni, Co, Mo, W are solid-solution in ferrite, have the effect that the activity degree making dissolving react reduces, for corrosion resistance Raising be effective element.It addition, appropriate Ni, Co, Mo, W are also effective for the strength characteristics improving matrix steel, it it is root According to the element needing interpolation.This performance this effect, is allowed to the most respectively containing more than 0.01%.But, if these elements Content superfluous, then make weldability and hot-workability deterioration, be therefore allowed to containing sometimes, Ni is less than 6.0%, Co be 5.0% with Under, Mo and W is less than 2.0%.Ni, Co, Mo, W is made to be respectively 0.02% containing preferred lower limit sometimes, more preferably More than 0.03%.It addition, making Ni contain the preferred upper limit sometimes is 5.9%, more preferably less than 5.8%.Co is made to contain sometimes The preferred upper limit be 4.9%, more preferably less than 4.8%.Mo and W is made to be respectively containing the preferred upper limit sometimes 1.9%, more preferably less than 1.8%.
Any one in Mg:0.0005～0.01%, Ca:0.0005～0.01%, REM:0.0005～0.01% Or it is two or more
Mg, Ca, REM are in using environment, and the effect that the pH of the surface neighborhood with suppression steel reduces, for making corrosion resistant It is effective element that erosion property improves further.This acts through these elements and through corrosion dissolution and reacts with hydrion and sent out Wave.In order to effectively play such effect, it is allowed to the most respectively containing more than 0.0005%.But, if the containing of these elements Amount surplus, then make weldability and hot-workability deterioration, when therefore containing these elements, be 0.0005～0.01%.Make Mg, Ca, REM are respectively 0.0006% containing preferred lower limit sometimes, and further preferred lower limit is respectively 0.0007%.Another Aspect, makes Mg, Ca, REM be respectively 0.0095% containing the preferred upper limit sometimes, and the further preferred upper limit is respectively 0.009%.
Any one or two kinds in Sn:0.001～0.2%, Sb:0.001～0.2%, Se:0.001～0.2% with On
Sn, Sb, Se are effective addition element for the raising of corrosion resistance.By making these elements contain respectively More than 0.001%, corrosion resistance raising effect is played effectively.But, if the content of these elements is superfluous, then make welding Property and hot-workability deterioration, therefore make these elements containing sometimes, be 0.001～0.2%.Make more excellent containing sometimes of Sn, Sb, Se The lower limit of choosing is respectively 0.002%, and further preferred lower limit is respectively 0.003%.On the other hand, make Sn, Sb, Se containing sometimes The preferred upper limit be respectively 0.19%, the further preferred upper limit is respectively 0.18%.
B: higher than 0% and below 0.01%, V: higher than 0% and below 0.1%, Zr: higher than 0% and 0.1% Below, Zn: in higher than 0% and below 0.1% any one or two or more
B, V, Zr and Zn etc. be also to intensity improve effective element, it is possible to be allowed to as required containing.These add unit Even if element adds the most slightly, if contained, strength-enhancing effect the most also can be shown, such as, by making B contain More than 0.0001%, make V, Zr, Zn contain more than 0.001%, strength-enhancing effect can obtain more really manifesting.But, if making These element surplus ground contain, then base metal tenacity and weldability deterioration, therefore make these elements restricted containing content sometimes.Make B, containing being less than 0.01% sometimes, makes V, Zr, Zn be respectively less than 0.1% when containing.Additionally make that B contains sometimes preferred on Being limited to 0.0095%, the further preferred upper limit is 0.009%.It addition, the preferred upper limit making V, Zr, Zn contain sometimes is 0.095%, the further preferred upper limit is 0.09%.
<tissues of matrix steel>
Need not be particularly limited to for constituting the tissue of the matrix steel of the application steel of the present invention, but in order to be filled The mechanical property divided, it is recommended that for comprising the tissue of ferrite and pearlite, or comprise the tissue of ferrite and bainite.
<manufacture methods of matrix steel>
In order to positively manufacture the matrix steel of the application steel constituting the present invention, for example, it is preferable to pass through following description Method manufacture.Firstly, for the molten steel from converter or electric furnace steel tapping to casting ladle, RH vacuum degasser is used to adjust to this The one-tenth of bright defined is grouped into, and carries out temperature adjustment and carry out double refining.Thereafter, with continuous casting process, ingot casting method etc. Common casting method makes steel ingot.Further, as structure component, special in order to ensure the machinery required for steel Property and the fundamental characteristics such as weldability, recommend killed steel is preferably used as deoxy forms, more preferably use Al killed steel.
<surface layer>
For the application steel of the present invention, implement containing Zn:20～200g/m on the surface of matrix steel2, Cu: 0.3～20.0g/m2, and also containing Cr:0.3～20.0g/m2, Ni:0.3～20.0g/m2In any one or two kinds Surface layer.
The Zn of surface layer, has the effect suppressing the corrosion of matrix steel to carry out by anode loss protection effect, this The effect of sample is 20g/m at the Zn adhesion amount of surface layer2Played time above.The preferred lower limit of Zn adhesion amount is 25g/ m2, more preferably 30g/m2Above.It addition, if Zn adhesion amount is the most to a certain degree, the most not only anode loss protection effect is saturated, And easily peel off from matrix steel, therefore exist and sacrifice the antisepsis situation that effectively period shortens.From this viewpoint Setting out, Zn adhesion amount is recommended as 200g/m2Below.The preferred upper limit of Zn adhesion amount is 190g/m2, more preferably 180g/m2 Below.
It addition, make Cu and Cr in the surface layer of the chemical composition of the scope containing described content, Cu and Ni, Cu and Ni and When Cr coexists, the rust more densification miniaturization of the corrosion product as steel in film flaw portion can be made, play and suppress The effect that the corrosion factor such as water, chloride ion invades to rusty scale, therefore the corrosion reaction of matrix steel is inhibited, and has very much Help corrosion resistance improve.
Such effect is 0.3g/m by making the adhesion amount of the Cu of surface layer2Above, then make in Cr and Ni any one Kind or two kinds containing 0.3g/m2Manifest above.The preferred adhesion amount of Cu, Cr and Ni of surface layer is respectively 0.4g/m2With On, more preferably 0.5g/m2Above.But, if the adhesion amount of Cu, Cr and Ni is too much, then surface layer and matrix steel Adhesive force reduces, and surface layer is easily peeled off from matrix steel.In order to avoid such harmful effect, it is recommended that Cu, Cr and Ni's is attached The amount of wearing is respectively 20.0g/m2Below.The preferred upper limit of the adhesion amount of Cu, Cr and Ni is respectively 19.5g/m2Hereinafter, one is entered Step is preferably 19.0g/m2Below.
As the method forming this surface layer, it is possible to illustrate Zn powder, Cu powder, Cr powder and Ni powder, with silicic acid The solvent mixing that Arrcostab etc. are suitable, sprays and brushes.Alternatively, it is also possible to the Zn-Cu-Cr making suitable composition closes The powder of gold, Zn-Cu-Ni alloy or Zn-Cu-Cr-Ni alloy etc., is used for common primary coat operation by this alloy powder.At this moment, Suitable pigment can also be added as needed on.Or the spraying processes such as flame wire spraying and electric arc spraying can also be used, make Zn, Cu, Cr, Ni are that desired adhesion amount forms surface layer.Further, as the pre-treatment of formation surface layer, preferred substrate steel Material surface removes oxide skin etc. in advance with shot-peening etc..
It addition, in order to ensure the adhesive strength of surface layer Yu matrix steel, preferably make the roughness of matrix steel surface reach More than roughness to a certain extent, if but rough surface is spent slightly, then and bubble enters recess and produces surface layer and matrix steel The part that material does not touch, adhesive strength is likely to decrease on the contrary.From this viewpoint, it is recommended that the surface of matrix steel is in advance Reach the surface roughness of appropriateness.
As the concrete surface roughness of matrix steel, such as, it is recommended that 10 of JIS B 0601:2001 defined put down All roughness Rzjis are that 10 μm are to 80 μm.Further, the adjustment of the surface roughness of matrix steel, such as according to common spray Ball processes then can be implemented with blasting treatment etc..
<application>
The application steel of the present invention, implement application again on described surface layer and carry out practicality.As for application Coating, can be with rated epoxy system, chlorinated rubber system, acrylic resin system, fluororesin system and polyurethane resin system etc. Coating, it is possible to use this multiple coating makes film multiple stratification.
Such as, as the coating for forming epoxy resin film, if used as the coating of anticorrosive paint, as long as Contain the coating of epoxy resin as vehicle, use which kind of coating can, be not particularly limited.As concrete coating, Epoxy coating, modified epoxy resin paint, tar epoxy coating etc. can be illustrated.
It addition, as the coating for forming chlorinated rubber system film, if with chlorinated resin for main material Coating, then use which kind of coating can, be not particularly limited.As concrete coating, it is possible to illustrate with chlorinated rubber and chlorine Changing the chlorinated resins such as polyolefin is the coating of main material.
It addition, as forming the coating of acrylic resin film, it is possible to illustrate common acrylic resin coating, Acrylic emulsion cold coating, acroleic acid polyurethane system emulsion coatings, acrylic acid silicon-type emulsion coatings, acrylic lacquer etc. Coating.
It addition, as the coating for forming fluororesin coating film, it is possible to illustrate polyflon coating, perfluoroalkoxy The coating of base cold coating, fluorinated ethylene propylene cold coating etc..
It addition, as the coating for forming polyurethane resin film, it is possible to illustrate polyurethane resin coating, the poly-ammonia of polyester The coating such as ester resin paint, moisture-cure polyurethane resin coating, epoxy-polyurethane coating, modified epoxy polyurethane resin coating.
When the thickness of these films is crossed thin, antiseptic effect is insufficient, if but the most blocked up, then it is susceptible to film and peels off, because of This recommends to reach optimal thickness according to practicality.From this viewpoint, the thickness of application in terms of dry film thickness, such as, is recommended It is the thickness of 100～1000 μm.
It addition, restrict the most especially for forming the coating process of film, the common paintings such as spraying and brushing can be suitable for Dress method.But, need, for moderately cleaning as the matrix steel surface being coated material, such as, to push away before application Recommend the attachment salt concentration being made steel surface by cleaning, reach 50mg/m with NaCl conversion2Hereinafter, preferably 10mg/m2With Under.
As the form of the application steel of the present invention, include, for example steel plate, steel pipe, bar steel, wire rod, shaped steel etc..Separately Outward, as purposes, include, for example as freighter, combination vessel, the passenger boats such as oil tanker, container ship, bulk carrier, the ship of warship etc. The structural elements of the ballast box of oceangoing ship uses, in addition, it is possible to enumerate for upper deck, bridge, hatch board, crane, various pipe arrangement, The steel structure of the various boats and ships such as stair, handrail.
It addition, if marine structure, then the works exploiting oil and natural gas on ocean can be set forth in, in ocean In headed by the float type equipment producing storage shipment etc. that carries out oil, combustion gas etc., the wind-power electricity generation in ocean, wave The generating relevant device such as generating, sea current generating, thermo-electric generation, solar electrical energy generation.It addition, in bridge field, it is possible to example Show that splashing salt component is about higher than 0.1mdd:mg/dm2Bridge steel plate material in the high splashing salinity environment of/day.
[embodiment]
Hereinafter, enumerate embodiment and further illustrate the present invention, but the present invention is not limited by following embodiment, certainly at energy The scope enough meeting front purport described later can certainly suitably be changed enforcement, and these are all contained in the technology of the present invention In the range of.
[for the making of examination material]
The steel being grouped into the various one-tenth shown in vacuum melting furnace melting table 1, become the steel ingot of 50kg.By obtained steel Ingot carries out hot rolling after being heated to 1150 DEG C, becomes the former material of steel of thickness of slab 10mm.Cutting size from the former material of steel is 150mm × 70mm The test film of × 5mm.The one side as 150mm × 70mm scope in test face of the total Test sheet for cutting implements shot-peening Process, 10 the mean roughness Rzjis making JIS B 0601:2001 defined are 30 ± 10 μm, carry out washing and After acetone cleans, carry out application.
In the one side of 150mm × 70mm scope of the test film implementing described bead, formed suitably containing Zn, The surface layer of Cu, Cr, Ni.This surface layer by spray following experimental liquid and formed, this coating fluid with alkyl silicate as solvent, Suitably it is mixed with metal Zn, Ni metal, metal Cr and the powder of W metal,.Further, Zn, Cu, Cr and Ni are suitably adjusted to coating Addition and the coating weight of liquid and make the adhesion amount of Zn, Cu, Cr and Ni of surface layer change.
For forming the face of 150mm × 70mm scope of the surface layer containing described Zn, Cu etc., spray modified epoxy tree Fat system coating and implement application.The thickness of this application is calculated as 200 ± 20 μm with dry film thickness.Additionally, make modified epoxy system The coated face of coating is dried, forms the film flaw of the through steel matrix of long 80mm, wide 3mm in this application face.
Whole test films is using formation described application face defective as test face, and the face silicon beyond test face seals Glue is coated to, for examination in following corrosion testing.
[corrosion tests]
As the corrosion testing under the corrosive environment of simulated seawater, use the combined-circulation test of artificial sea water: implement CCT.Cycling condition is, carries out 1) the artificial sea water spraying of 35 DEG C, 1.5 hours；2) temperature 60 C, relative humidity 20%RH, 2.5 Hour；3) temperature 50 C, relative humidity 95%RH, 2.5 hours repeatedly.
Further, the temperature and humidity making each interprocedual changes until stable transit time is 0.5 hour.During test it is 3 months.Sample supplies examination by each for the No.1 to No.49 shown in table 23.
The evaluation of the progress extent deteriorated as the film from film flaw portion and corrode, tries to achieve and terminated later certainly at CCT Corroded area and corrosion depth in the film flaw portion of test film.About corroded area, it is due to film from film flaw portion Lower corrosion causes the area of the total of the area of the part of paint blister and the area in film flaw portion, for each 3 test films Meansigma methods.
About corrosion depth, measure film flaw portion and the corrosion depth of periphery thereof, try to achieve the maximum of each 3 test films Value.Further, the measurement of corrosion depth is the film of disbonded test sheet after CCT terminates, by 10% diammonium hydrogen citrate water After catholyte in solution carries out de-rust process, implement to measure with depth gauge.
[combined-circulation result of the test]
Combined-circulation is tested: corroded area and the corrosion depth tried to achieve after CCT are as shown in table 2.Further, each sample Corroded area and corrosion depth, be formed on common steel the sample of the No.1 of common Zn priming paint corroded area and Corrosion depth represents respectively as relative value when 100.
The evaluation criterion of corroded area and corrosion depth is as follows.Corroded area, corrosion depth are by following manner table Show, i.e. relative value is more than 80 and representing with A less than 90, and relative value is more than 70 and representing with AA less than 80, relative value Representing with AAA less than 70, corroded area, corrosion depth are the sample of A～AAA in overall merit for qualified, are evaluated as The application steel of excellent corrosion resistance.
The corroded area of No.1～No.12 and the relative value of corrosion depth are 90 to 100, the corrosion resistance in film flaw portion Insufficient.No.2, No.6 and No.7, although containing Zn, Cu, the Cr that present invention provide that in surface layer, but the Cu content of steel The most very few, the corrosion resistance that therefore cannot fully obtain film flaw portion improves.
No.3 and No.8 contains Zn, Cu, the Cr that present invention provide that at surface layer, but the Cr content of matrix steel is the most very few, Therefore the corrosion resistance that cannot fully obtain film flaw portion improves.
Though No.4 and No.5 contains Zn, Cu, the Cr that present invention provide that at surface layer, but the Ti content of matrix steel or Nb contain Measuring very few, the corrosion resistance that therefore cannot fully obtain film flaw portion improves.
It addition, the matrix steel of No.9 with No.10 become to be grouped into the regulation being satisfied by the present invention, but the Zn of surface layer or Cu is very few, and the corrosion resistance that therefore cannot fully obtain film flaw portion improves.
Zn and Cu being grouped into surface layer that become of the matrix steel of No.11 with No.12 is satisfied by the regulation of the present invention, but Cr or Ni of surface both layer is the most very few, and the corrosion resistance that therefore cannot fully obtain film flaw portion improves.
Relative to these comparative examples, all meet the sample of No.13～No.49 of the regulation of the present invention, corroded area and Relative value's both suppression of corrosion depth, less than 90, play the corrosion resistance in the film flaw portion of excellence.
Particularly any one in making Ni, Co, Mo and W or the matrix steel of two or more S12～S18 contained in right amount On material, being formed with the sample of No.18～No.27 of the surface layer that present invention provide that, the inhibition of corroded area is notable.
Wherein, any one in the most in right amount containing Sn, Sb and Se or the matrix steel of two or more S28, S29 On, the inhibition of the corroded area having the sample of No.40～No.42 of the surface layer that present invention provide that is more notable.
It addition, appropriate containing Mg, Ca and REM in any one or the matrix steel of two or more S19～S21 On, the inhibition of the corrosion depth having the sample of No.28～No.31 of the surface layer that present invention provide that is notable.
Wherein, any one in the most in right amount containing Sn, Sb and Se or the matrix steel of two or more S30～S32 On, the inhibition of the corrosion depth having the sample of No.43～No.46 of the surface layer that present invention provide that is more notable.
As previously discussed, the application steel of the present invention all play the resistance to of excellent film flaw portion under briny environment Corrosivity, is suitable as exposing the structural elements in sea water, splashing sea salt particle to the open air.
[table 1]
[table 2]

Claims (5)

1. the application steel of an excellent corrosion resistance, it is characterised in that be containing matrix steel and to be formed at described matrix The application steel of the surface layer on the surface of steel, described matrix steel are following steel, containing C in terms of quality %: 0.04～0.30%, Si:0.05～1.0%, Mn:0.1～2.5%, P: higher than 0% and below 0.04%, S: higher than 0% also Below 0.04%, Al:0.005～0.20%, Cu:0.05～1.0%, Cr:0.05～1.0%, N:0.001～0.015%, And containing any one in Ti:0.005～0.1%, Nb:0.005～0.1% or two kinds, surplus is by Fe and inevitable Impurity constitute,
Further, described surface layer contains Zn:20～200g/m2, Cu:0.3～20.0g/m2, and containing Cr:0.3～20.0g/ m2, Ni:0.3～20.0g/m2In any one or two kinds.
The application steel of excellent corrosion resistance the most according to claim 1, wherein, described matrix steel are in terms of quality % Possibly together with any one in Ni:0.01～6.0%, Co:0.01～5.0%, Mo:0.01～2.0%, W:0.01～2.0% Or it is two or more.
The application steel of excellent corrosion resistance the most according to claim 1 and 2, wherein, described matrix steel are with matter Any one possibly together with in Mg:0.0005～0.01%, Ca:0.0005～0.01%, REM:0.0005～0.01% of amount % meter Plant or two or more.
The application steel of excellent corrosion resistance the most according to any one of claim 1 to 3, wherein, described matrix steel Material in terms of quality % possibly together with any one in Sn:0.001～0.2%, Sb:0.001～0.2%, Se:0.001～0.2% Or it is two or more.
The application steel of excellent corrosion resistance the most according to any one of claim 1 to 4, wherein, described matrix steel Material in terms of quality % possibly together with B: higher than 0% and below 0.01%, V: higher than 0% and below 0.1%, Zr: higher than 0% also Below 0.1%, Zn: in higher than 0% and below 0.1% any one or two or more.
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