CN106467950A - Coating steel and its manufacture method - Google Patents

Coating steel and its manufacture method Download PDF

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Publication number
CN106467950A
CN106467950A CN201610421302.5A CN201610421302A CN106467950A CN 106467950 A CN106467950 A CN 106467950A CN 201610421302 A CN201610421302 A CN 201610421302A CN 106467950 A CN106467950 A CN 106467950A
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mass
steel
coating
compound
content
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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
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • 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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • 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
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
    • 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
    • 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
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • 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
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of 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
    • C22C38/18—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
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • 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
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • 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
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/50—Form of the coating product, e.g. solution, water dispersion, powders or the like where organic solvent or water can be used as alternative

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Heat Treatment Of Steel (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

It is an object of the invention to provide the coating steel of excellent resistance to salt water can be maintained for long periods.The coating steel of the present invention, it is characterized in that, it is the coating steel of the coating possessing matrix steel and being formed at this matrix steel surface, wherein, coating has the average thickness of more than 8 μm and less than 105 μm, and containing Al compound, Cr compound, Cu compound and Fe compound, above-claimed cpd is oxide, oxyhydroxide or combinations thereof.Coating preferably comprises below more than Al oxide, hydroxyl oxidize Al or combinations thereof 0.08 mass % and 10.5 mass %, more than Cr oxide 0.08 mass % and below 10.5 mass %, more than Cu oxide 0.08 mass % and below 10.5 mass % and the Fe as Fe oxide and hydroxyl oxidize Fe3O4And alpha-feooh amounts to more than 29.5 mass %.In addition, as Fe3O4And the mean diameter of alpha-feooh, it is respectively preferably more than 4.5nm and below 22nm.

Description

Coating steel and its manufacture method
Technical field
The present invention relates to coating steel and its manufacture method.
Background technology
Steel are used as the component of various works mostly, when for becoming main in sea water and/or sudden sea salt particle During works in the beach such as the ship used under the corrosive environment of reason, marine structure, bridge, sea water, sometimes Make intensity decreases because producing minimizing, formation of etch pit of thickness of slab etc..Ballast tank (the ballast of especially known ship Tank) it is exposed in harsh corrosive environment.In addition, in recent years, from the viewpoint of saving earth environment from damage, as not discharging The clean energy resource generation technique of greenhouse gases carbon dioxide, deepwater wind-power electricity generation, wave-activated power generation, tidal power generating, sea The generation technologies such as stream generating, temperature difference generating, solar power generation attract attention.It is contemplated that this kind of deepwater works are also deposited In the probability being exposed to the corrosive environment harsher than the works in conventional beach, sea water.Therefore, for their steel Material needs to improve resistance to salt water by anticorrosion technique.
As anticorrosion technique, such as electrical anticorrosion, surface treatment etc. can be enumerated.As above-mentioned surface treatment, can enumerate Form coating corrosion-proof coating by application, coating anticorrosion spraying plating etc. is formed by spraying plating.It is also known that shape The rust becoming steel surface plays a role as the protection epithelium improving resistance to salt water, therefore further contemplates the surface treatment in steel The middle method using rust.And then it is also proposed that the improvement of steel itself and by the improvement of steel itself with surface treatment combine Method.
Electrical anticorrosion as one of anticorrosion technique is the method suppressing to corrode in the operation of electrode potential, and it is to carrying The resistance to salt water of the steel that height impregnated in sea water often is effective, and it often not impregnated in the steel of sea water to raising Resistance to salt water is less effective.As the concrete example of the not effective steel of raising to resistance to salt water using electrical anticorrosion, can Enumerate the steel in the marine portion of works on the ocean be for example exposed to the corrosive environment caused by the spittle etc. of sea water, especially sea The steel of face near zone, the reply loading load of ship and the injection of sea water and the inner surface of the ballast tank of draining are repeated Steel etc..In addition, as other concrete examples, also can enumerate that to be exposed to by the microgranule that the salinity from sea water is formed be sea salt Steel of works such as sudden and close with the seashore the repeating dry environment and moist environment metal bridge beam of particle etc..So, Electrical anticorrosion is to for the ballast tank of ship, steel of deepwater works less effective.
In addition, the corrosion-proof coating as other anticorrosion techniques is following method：For response environment using with The various resin such as epoxy resin, chlorinated rubber, acrylic resin, polyurethane resin, fluororesin is as the anticorrosion of main constituent Coating, and the film of single or multiple lift is formed on steel, thus improve resistance to salt water.But, above-mentioned film reason ultraviolet Caused deterioration, damage caused by arbitrary external mechanical acts on etc. and easily produce flaw, stripping, there is steel in result Material exposes and promotes the risk corroded.For example, the film that sometimes also can make the corrosion ballast tank in ship for the abrasion amount of 1 year is peeled off Position reach 1mm.Therefore, corrosion-proof coating needs regularly to be checked after application, repastes the maintenance such as dress, but, then Application needs to expend very high cost, duration.In addition, for the works such as ship, marine structure, bridge, due to difficulty On close to marine, no foothold and the complicated position of inaccessible eminence, structure etc., therefore cannot easily carrying out The inspection stated, the position of maintenance are also more.Therefore, from the viewpoint of the period maintaining resistance to salt water is short, corrosion-proof coating has When also and impracticable to the steel for the ballast tank of ship, deepwater works.
And then, the anticorrosion spraying plating as other anticorrosion techniques uses the metal more cheap than steel or the conjunctions such as zinc, aluminum, magnesium Gold is formed sprayed as depositing materials in steel surface and is obtained using this sprayed sacrificial anode effect anti-corrosion Erosion acts on.But, this anticorrosion spraying plating plays corrosion-resisting function by sprayed consumption it is therefore desirable to pass through regularly Spraying plating is maintaining sprayed average thickness, so, close with works due to being difficult to again, is therefore not easy to carry out again The position of spraying plating is also many.Therefore, same with corrosion-proof coating, from the viewpoint of the period maintaining resistance to salt water is short, anticorrosion Also to for the ballast tank of ship, steel of deepwater works impracticable when being sprayed with.
On the other hand it is known that：Corrosive environment of sea water is formed at steel surface comprise α-FeOOH, β- FeOOH, γ-FeOOH, Fe3O4The protection envelope invading as suppression corrosive substance Deng the rust of Fe compound plays a role, slightly The corrosion of micro- suppression steel.However, for the rust formed in common steel, because the particle diameter of Fe compound is larger, Compactness is short of, the intrusion inhibition of therefore corrosive substance little it is impossible to resistance to salt water is significantly increased.In addition, it is just above-mentioned For rust, due to relatively low with the adaptation of steel, therefore it be easily peeled off and come off.Therefore, utilize in the surface treatment of steel The method of rust does not also referred to as go up so practical.
And then, it is also proposed that by the improvement of steel itself, the changing of steel itself in addition to the above-mentioned surface treatment to steel The anticorrosion technique that good and surface treatment is combined.Specifically it is proposed that for example using the application steel with specific composition Method (with reference to Japanese Unexamined Patent Publication 2012-122117 publication), using the tool being covered by the protective rust containing special metal Method (with reference to Japanese Unexamined Patent Publication 2014-5499 publication) of the steel being made up of specified chemical etc..But, by above-mentioned conventional Method, maintain the period of excellent resistance to salt water also insufficient.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2012-122117 publication
Patent documentation 2：Japanese Unexamined Patent Publication 2014-5499 publication
Content of the invention
Invention technical problem to be solved
The present invention is completed based on situation as above, and its technical problem is that offer can remain excellent resistance to for long periods Salt coating steel and its manufacture method.
For solving the means of technical problem
The present inventor etc. to the steel in corrosive environment of sea water promote corrosion mechanism carry out detailed survey, and to conventional The different novel anticorrosion technology of the surface treatment such as corrosion-proof coating is studied.Result：As described above, in seawater corrosion ring The rust being formed by Fe compound being formed at steel surface in border will not be greatly improved resistance to salt water, and easily peels off from steel And come off, it is practical for also not claiming therefore for the surface treatment as steel.However it has been found that the surface in matrix steel The coating steel being formed with containing Fe compound and having the coating of suitable average thickness can maintain salt tolerant for long periods Aqueouss.Additionally, it was found that：Contain Cu compound by making above-mentioned coating, so that the compactness of above-mentioned coating improves, and By containing Al compound and Cr compound, such that it is able to make corrosive substance innoxious, these results are：Make corrosive substance Intrusion to matrix steel is significantly inhibited such that it is able to improve resistance to salt water.
That is, the invention completing to solve above-mentioned technical problem is a kind of coating steel it is characterised in that it possesses base Body steel and the coating being formed at this matrix steel surface, wherein, above-mentioned coating has more than 8 μm and less than 105 μm Average thickness, and containing Al compound, Cr compound, Cu compound and Fe compound, above-claimed cpd is oxide, hydroxyl Oxide or combinations thereof.
This coating steel is contained with the Fe compound of the excellent adhesion of matrix steel such that it is able to carry by making coating High coating and the adaptation of matrix steel.In addition, there is the average thickness of above range by making coating, such that it is able to press down The intrusion of corrosive goods confrontation matrix steel material processed.Result can maintain excellent resistance to salt water for a long time.In addition, steel should be coated to For, the Al compound contained by coating can fix corrosive chloride and innoxious, and Cr compound can fix corrosivity Sulfate and innoxious, and Cu compound can improve the compactness of coating, thus makes corrosive goods confrontation matrix steel material Intrusion be significantly inhibited, therefore can improve resistance to salt water.
Above-mentioned coating preferably comprises：Al oxide, hydroxyl oxidize Al or combinations thereof；Cr oxide；Cu oxide； And the Fe as above-mentioned Fe oxide and hydroxyl oxidize Fe3O4And alpha-feooh.Now, as Al oxide, hydroxyl oxidize Al Or the content of combinations thereof, more than preferably 0.08 mass % and below 10.5 mass %.In addition, containing as Cr oxide Amount, more than preferably 0.08 mass % and below 10.5 mass %.And then, as the content of Cu oxide, preferably 0.08 matter Below amount more than % and 10.5 mass %.And then, as Fe3O4And the total content of alpha-feooh, preferably 29.5 mass % with On.And then, as above-mentioned Fe3O4And the mean diameter of alpha-feooh, preferably respectively more than 4.5nm and below 22nm.
By making, coating contains Al oxide and/or hydroxyl oxidize Al is used as Al compound, such that it is able to promote further Enter corrosive muriatic fixation.In addition, being used as Cr compound by making coating contain Cr oxide, such that it is able to enter one Step promotes the fixation of corrosive sulfate.And then, it is used as Cu compound by making coating contain Cu oxide, such that it is able to Make coating finer and close.These results can improve resistance to salt water further.And then, by making the above-claimed cpd in coating Content be specified quantitative, thus while improving resistance to salt water, coating caused by can suppressing because of temperature change when using Crackle on layer is formed.And then, especially excellent by making coating contain in Fe compound and matrix steel adaptations Fe3O4And alpha-feooh is as Fe oxide and hydroxyl oxidize Fe, and their mean diameter is made to be above range, thus can To improve compactness and the adaptation with matrix steel of coating further.Result can improve resistance to salt water further and be somebody's turn to do The persistence of resistance to salt water.
Above-mentioned matrix steel preferably have following composition：C：More than 0.008 mass % and below 0.32 mass %, Si： More than 0.05 mass % and below 2.0 mass %, Mn：More than 0.08 mass % and below 3.0 mass %, P：0.001 mass % Above and below 0.05 mass %, S：Below 0.05 mass %, Al：More than 0.001 mass % and below 1.6 mass %, N： More than 0.001 mass % and below 0.015 mass % and surplus：Fe and inevitable impurity.So, above-mentioned by making Matrix steel have above-mentioned composition, such that it is able to improve resistance to salt water further.
Preferably：Above-mentioned matrix steel have P：More than 0.004 mass % and below 0.05 mass % and Al：0.008 Composition more than quality % and below 1.6 mass %, above-mentioned matrix steel also contain Cu：More than 0.08 mass % and 2.2 matter Amount below % and Cr：More than 0.08 mass % and below 3.0 mass %, and contain Mo further：More than 0.008 mass % and Below 2.2 mass % and W：At least one in more than 0.008 mass % and below 2.2 mass %.So, by making above-mentioned base The content of the P of body steel is specified quantitative, so that the protectiveness of above-mentioned coating improves.In addition, by making above-mentioned matrix steel P and Al content be specified quantitative, such that it is able to improve resistance to salt water further.And then, contained by making above-mentioned matrix steel Cu and Cr of specified quantitative, so that the compactness of coating improves further.And then, by making above-mentioned matrix steel with specified quantitative Containing at least one in Mo and W, thus Mo and/or W is solid-solution in ferrite and so that the activity degree that melting is reacted is reduced.These knots Fruit can more carry out improving resistance to salt water.
Above-mentioned matrix steel preferably also contain Ni：More than 0.008 mass % and below 5.2 mass % and Co：0.008 matter At least one in below amount more than % and 5.0 mass %.So, by make matrix steel with specified quantitative contain further Ni and At least one in Co, such that it is able to improve resistance to salt water and intensity further.
Above-mentioned matrix steel preferably also contain Mg：More than 0.0004 mass % and below 0.01 mass %, Ca：0.0004 matter Measure below more than % and 0.01 mass % and rare earth metal：In more than 0.0004 mass % and below 0.01 mass % at least 1 kind.So, by making matrix steel with specified quantitative further containing at least one in Mg, Ca and rare earth metal, thus can Reduced with the pH suppressing the near surface of matrix steel, result can improve resistance to salt water further.
Above-mentioned matrix steel preferably also contain Sn：More than 0.0008 mass % and below 0.2 mass %, Sb：0.0008 matter Measure below more than % and 0.2 mass % and Se：At least one in more than 0.0008 mass % and below 0.2 mass %.So, By making matrix steel with specified quantitative further containing at least one in Sn, Sb and Se, such that it is able to improve salt water resistance further Property.
Above-mentioned matrix steel preferably also contain Ti：More than 0 mass % and below 0.2 mass %, Nb：More than 0 mass % and Below 0.2 mass %, Zr：More than 0 mass % and below 0.2 mass %, V：More than 0 mass % and below 0.2 mass % and B： At least one in more than 0 mass % and below 0.01 mass %.So, contained further with specified quantitative by making matrix steel There is at least one in Ti, Nb, Zr, V and B, such that it is able to improve intensity further.
Another invention completing to solve above-mentioned technical problem is a kind of manufacture method of coating steel, and it possesses： Prepare the operation of matrix steel；Al compound, Cr compound, Cu compound and Fe compound are scattered in solvent by preparation The operation of coating formation compositionss；And above-mentioned coating formation compositionss are coated on the surface of above-mentioned matrix steel Operation, above-claimed cpd is oxide, oxyhydroxide or combinations thereof, forms average thickness and be in above-mentioned working procedure of coating More than 8 μm and less than 105 μm of coating.
Here " average thickness " refers to the meansigma methodss of the thickness in arbitrary 10 points mensure." mean diameter " refers to：Use Field emission transmission electron microscope (FE-TEM) observes the Fe in the section of coating with suitable multiplying power3O4And alpha-feooh Particle, the meansigma methodss of the positive diameter of a circle being homalographic with the sectional area of any 10 particles.
Invention effect
This coating steel and its manufacture method can provide the coating steel being capable of the excellent resistance to salt water of longer-term maintenance.
Brief description
Fig. 1 is the schematic etch figures in the test face representing test film used in embodiments of the invention.
Specific embodiment
<Coating steel>
Hereinafter, the embodiment of the coating steel to the present invention and its manufacture method illustrates.This coating steel possesses Matrix steel and be formed at this matrix steel surface coating.
(matrix steel)
As matrix steel, it is not particularly limited, it is possible to use known steel.As matrix steel, preferably have By forming as follows：C (carbon)：More than 0.008 mass % and below 0.32 mass %, Si (silicon)：More than 0.05 mass % and 2.0 matter Amount below %, Mn：More than 0.08 mass % and below 3.0 mass %, P (phosphorus)：More than 0.001 mass % and 0.05 mass % with Under, S (sulfur)：Below 0.05 mass %, Al (aluminum)：More than 0.001 mass % and below 1.6 mass %, N (nitrogen)：0.001 matter Measure below more than % and 0.015 mass %, surplus：Fe (ferrum) and inevitable impurity.This coating steel is by making matrix steel Material contains P, Al and N of specified quantitative, thus to easily and reliably can remain excellent for a long time by the synergism with coating Different resistance to salt water.In addition, this coating steel is by making C, Si, Mn, S and N that matrix steel contain specified quantitative, thus acceptable To easily and reliably meet the easness as the mechanical property required by the material of works, welding.Hereinafter, each composition is entered Row explanation.
[C (carbon)]
C in matrix steel is present to ensure that the intensity of this coating steel and effective element.As the C in matrix steel Content lower limit, preferably 0.008 mass %, more preferably 0.02 mass %, more preferably 0.03 mass %.Another Aspect, as the upper limit of the content of C, preferably 0.32 mass %, more preferably 0.29 mass %, more preferably 0.28 matter Amount %.When the content of C is less than above-mentioned lower limit, there is the risk of the intensity decreases of this coating steel.On the contrary, the content in C surpasses When crossing the above-mentioned upper limit, the generation quantitative change of the cementite playing a role as negative electrode site in corrosive environment is many, thus promotes rotten Erosion reaction, result exists makes risk that the resistance to salt water of this coating steel reduces and the risk that toughness also reduces.
[Si (silicon)]
Si in matrix steel is present to ensure that the deoxidation of matrix steel and the intensity of this coating steel and effective element. As the lower limit of the content of the Si in matrix steel, preferably 0.05 mass %, more preferably 0.08 mass %, further preferably For 0.10 mass %.On the other hand, as the upper limit of the content of Si, preferably 2.0 mass %, more preferably 1.95 mass %, More preferably 1.90 mass %.When the content of Si is less than above-mentioned lower limit, existing insufficient guarantees above-mentioned matrix steel Deoxidation and this coating steel intensity risk.On the contrary, when the content of Si exceedes the above-mentioned upper limit, there are this coating steel difficult Risk with welding.
[Mn (manganese)]
Same with Si, the Mn in matrix steel is present to ensure that the deoxidation of matrix steel and the intensity of this coating steel have The element of effect.As the lower limit of the content of the Mn in matrix steel, preferably 0.08 mass %, more preferably 0.15 mass %, More preferably 0.2 mass %.On the other hand, as the upper limit of the content of Mn, preferably 3.0 mass %, more preferably 2.9 Quality %, more preferably 2.8 mass %.When the content of Mn is less than above-mentioned lower limit, there are this coating steel cannot guarantee The risk of the intensity required by works.On the contrary, when the content of Mn exceedes the above-mentioned upper limit, there is the toughness fall of this coating steel Low risk.
[P (phosphorus)]
P in matrix steel is to improve the protectiveness of above-mentioned coating and improving the salt tolerant of this coating steel further Aqueouss and effective element.As the lower limit of the content of the P in matrix steel, preferably 0.001 mass %, more preferably 0.004 mass %, more preferably 0.008 mass %, particularly preferably 0.017 mass %.On the other hand, containing as P The upper limit of amount, preferably 0.05 mass %, more preferably 0.045 mass %, more preferably 0.04 mass %.Containing in P When amount is less than above-mentioned lower limit, there is the risk that the resistance to salt water of this coating steel reduces.On the contrary, the content in P exceedes on above-mentioned In limited time, there is the toughness risk reducing of this coating steel and the risk being difficult to welding.
[S (sulfur)]
S in matrix steel is so that the toughness of this coating steel is reduced and be difficult to the element welding.Therefore, matrix steel The content of the S in material is more few more preferred, and the content being industrially difficult to make S is 0 mass %.Accordingly, as the S in matrix steel Content the upper limit, preferably 0.05 mass %, more preferably 0.045 mass %, more preferably 0.04 mass %.Another Aspect, as the lower limit of the content of S, is not particularly limited, for example, 0.0001 mass %.
[Al (aluminum)]
Al in matrix steel is to form stable oxide in corrosive environment of sea water and improving this quilt further Cover the resistance to salt water of steel and effective element.In addition, same with above-mentioned Si and Mn, Al is also for guaranteeing matrix steel The intensity of deoxidation and this coating steel and effective element.As the lower limit of the content of the Al in matrix steel, preferably 0.001 Quality %, more preferably 0.008 mass %, more preferably 0.010 mass %.On the other hand, as Al content upper Limit, preferably 1.6 mass %, more preferably 1.45 mass %, more preferably 1.4 mass %.It is less than in the content of Al When stating lower limit, exist and cannot fully obtain the above-mentioned raising of the resistance to salt water of this coating steel, the guaranteeing and matrix steel of intensity The risk of the effect of the deoxidation of material.On the contrary, when the content of Al exceedes the above-mentioned upper limit, there is the wind that this coating steel is difficult to solder to Danger.
[N (nitrogen)]
N in matrix steel is to improve this quilt for by forming the fine dispersion particle of nitride in matrix steel Cover resistance to salt water and the effective element of intensity of steel.As the lower limit of the content of the N in matrix steel, preferably 0.001 matter Amount %, more preferably 0.0015 mass %, more preferably 0.002 mass %.On the other hand, as the upper limit of the content of N, It is preferably 0.015 mass %, more preferably 0.014 mass %, more preferably 0.013 mass %.It is less than in the content of N When stating lower limit, there is the resistance to salt water of this coating steel and the risk of intensity decreases.On the contrary, the content in N exceedes the above-mentioned upper limit When, there is the toughness risk reducing of this coating steel and the risk being difficult to welding.
[surplus]
In the composition of matrix steel, preferably make balance of Fe (ferrum) in addition to mentioned component and inevitably miscellaneous Matter.As this inevitable impurity, such as O (oxygen), H (hydrogen) etc. can be enumerated.Inevitable impurity in matrix steel As long as total content does not damage all characteristics of this coating steel, then it is not particularly limited.As in specific matrix steel can not The upper limit of the total content of the impurity avoiding, preferably 0.1 mass %, more preferably 0.09 mass %, more preferably 0.05 Quality %, particularly preferably 0.01 mass %.By make inevitable impurity total content be above range, such that it is able to enter One step improves the resistance to salt water of this coating steel.
Matrix steel more preferably contain element shown below further.Hereinafter, each element is illustrated.
[Cu (copper)]
Cu in matrix steel is that the resistance to salt water improving this coating steel by improving the compactness of coating is had The element of effect.As the lower limit of the content of the Cu in matrix steel, preferably 0.08 mass %, more preferably 0.12 mass %, More preferably 0.15 mass %.On the other hand, as the upper limit of the content of Cu, preferably 2.2 mass %, more preferably 1.95 mass %, more preferably 1.90 mass %.When the content of Cu is less than above-mentioned lower limit, there is the resistance to of this coating steel The risk of salt reduction.On the contrary, when the content of Cu exceedes the above-mentioned upper limit, exist be difficult to this coating steel welding, Hot worked risk.
[Cr (chromium)]
Same with Cu, the Cr in matrix steel is to the salt water resistance improving this coating steel by making coating finer and close The effective element of property.As the lower limit of the content of the Cr in matrix steel, preferably 0.08 mass %, more preferably 0.12 matter Amount %, more preferably 0.15 mass %.On the other hand, as the upper limit of the content of Cr, preferably 3.0 mass %, more excellent Elect 2.9 mass %, more preferably 2.8 mass % as.When the content of Cr is less than above-mentioned lower limit, there are this coating steel The risk that resistance to salt water reduces.On the contrary, when the content of Cr exceedes the above-mentioned upper limit, there is the weldering being difficult to this coating steel Connect, hot worked risk.
[Mo (molybdenum) and W (tungsten)]
Mo and W in matrix steel is to have by being solid-solution in ferrite to make the activity degree that melting is reacted reduce respectively The element of effect.Therefore, contain Mo and/or W by making matrix steel, so that the resistance to salt water of this coating steel carries further High.In addition, contain appropriate Mo and/or W by making matrix steel, so that the intensity of this coating steel also improves.
As the lower limit of the content of the Mo in matrix steel, preferably 0.008 mass %, more preferably 0.02 mass %, More preferably 0.03 mass %.On the other hand, as the upper limit of the content of Mo, preferably 2.2 mass %, more preferably 1.9 mass %, more preferably 1.8 mass %.When the content of Mo is less than above-mentioned lower limit, there is the salt tolerant of this coating steel Aqueouss, the risk of intensity decreases.On the contrary, when the content of Mo exceedes the above-mentioned upper limit, there is the weldering being difficult to this coating steel Connect, hot worked risk.
As the lower limit of the content of the W in matrix steel, preferably 0.008 mass %, more preferably 0.02 mass %, enter One step is preferably 0.03 mass %.On the other hand, as the upper limit of the content of W, preferably 2.2 mass %, more preferably 1.9 matter Amount %, more preferably 1.8 mass %.W content be less than above-mentioned lower limit when, exist this coating steel resistance to salt water, The risk of intensity decreases.On the contrary, when the content of W exceedes the above-mentioned upper limit, exist be difficult to this coating steel welding, heat plus The risk of work.
[Ni (nickel) and Co (cobalt)]
Matrix steel are preferably further containing at least one in Ni and Co.Ni and Co in matrix steel is to make this respectively The element that the resistance to salt water of coating steel and intensity improve further.
As the lower limit of the content of the Ni in matrix steel, preferably 0.008 mass %, more preferably 0.02 mass %, More preferably 0.03 mass %, particularly preferably 0.08 mass %.On the other hand, as the upper limit of the content of Ni, preferably For 5.2 mass %, more preferably 4.9 mass %, more preferably 4.8 mass %, particularly preferably 1 mass %.Ni's When content is less than above-mentioned lower limit, there is the resistance to salt water of this coating steel, the risk of intensity decreases.On the contrary, the content in Ni surpasses When crossing the above-mentioned upper limit, exist and be difficult to the welding of this coating steel, hot worked risk.
As the lower limit of the content of the Co in matrix steel, preferably 0.008 mass %, more preferably 0.02 mass %, More preferably 0.03 mass %, particularly preferably 0.04 mass %.On the other hand, as the upper limit of the content of Co, preferably For 5.0 mass %, more preferably 4.9 mass %, more preferably 4.8 mass %, particularly preferably 1 mass %.Co's When content is less than above-mentioned lower limit, there is the resistance to salt water of this coating steel, the risk of intensity decreases.On the contrary, the content in Co surpasses When crossing the above-mentioned upper limit, exist and be difficult to the welding of this coating steel, hot worked risk.
[Mg (magnesium), Ca (calcium) and rare earth metal (REM)]
Matrix steel are preferably further containing at least one in Mg, Ca and rare earth metal.Mg, Ca in matrix steel And rare earth metal is following element respectively：Melted by itself corrosion and react with hydrion, thus suppress matrix steel The pH of near surface reduce, result makes the resistance to salt water of this coating steel improve further.
As the lower limit of the content of the Mg in matrix steel, preferably 0.0004 mass %, more preferably 0.006 matter Amount %, more preferably 0.0007 mass %, particularly preferably 0.0009 mass %.On the other hand, as the content of Mg The upper limit, preferably 0.01 mass %, more preferably 0.0095 mass %, more preferably 0.009 mass %, particularly preferably 0.003 mass %.When the content of Mg is less than above-mentioned lower limit, there is the risk that the resistance to salt water of this coating steel reduces.On the contrary, When the content of Mg exceedes the above-mentioned upper limit, exist and be difficult to the welding of this coating steel, hot worked risk.
As the lower limit of the content of the Ca in matrix steel, preferably 0.0004 mass %, more preferably 0.0006 matter Amount %, more preferably 0.0007 mass %, particularly preferably 0.0013 mass %.On the other hand, as the content of Ca The upper limit, preferably 0.01 mass %, more preferably 0.0095 mass %, more preferably 0.009 mass %, particularly preferably 0.004 mass %.When the content of Ca is less than above-mentioned lower limit, there is the risk that the resistance to salt water of this coating steel reduces.On the contrary, When the content of Ca exceedes the above-mentioned upper limit, exist and be difficult to the welding of this coating steel, hot worked risk.
As the lower limit of the content of the rare earth metal in matrix steel, preferably 0.0004 mass %, more preferably 0.0006 mass %, more preferably 0.0007 mass %, particularly preferably 0.001 mass %.On the other hand, as rare earth The upper limit of the content of metalloid, preferably 0.01 mass %, more preferably 0.0095 mass %, more preferably 0.009 matter Amount %, particularly preferably 0.003 mass %.When the content of rare earth metal is less than above-mentioned lower limit, there are this coating steel The risk that resistance to salt water reduces.On the contrary, when the content of rare earth metal exceedes the above-mentioned upper limit, exist and be difficult to this coating steel The welding of material, hot worked risk.
[Sn (stannum), Sb (antimony) and Se (selenium)]
Matrix steel are preferably further containing at least one in Sn, Sb and Se.Sn, Sb and Se in matrix steel is respectively It is the element making the resistance to salt water of this coating steel improve further.
As the lower limit of the content of the Sn in matrix steel, preferably 0.0008 mass %, more preferably 0.002 matter Amount %, more preferably 0.003 mass %, particularly preferably 0.008 mass %.On the other hand, as Sn content upper Limit, preferably 0.2 mass %, more preferably 0.19 mass %, more preferably 0.18 mass %, particularly preferably 0.1 matter Amount %.When the content of Sn is less than above-mentioned lower limit, there is the risk that the resistance to salt water of this coating steel reduces.On the contrary, Sn's When content exceedes the above-mentioned upper limit, exist and be difficult to the welding of this coating steel, hot worked risk.
As the lower limit of the content of the Sb in matrix steel, preferably 0.0008 mass %, more preferably 0.002 matter Amount %, more preferably 0.003 mass %, particularly preferably 0.008 mass %.On the other hand, as Sb content upper Limit, preferably 0.2 mass %, more preferably 0.19 mass %, more preferably 0.18 mass %, particularly preferably 0.10 matter Amount %.When the content of Sb is less than above-mentioned lower limit, there is the risk that the resistance to salt water of this coating steel reduces.On the contrary, Sb's When content exceedes the above-mentioned upper limit, exist and be difficult to the welding of this coating steel, hot worked risk.
As the lower limit of the content of the Se in matrix steel, preferably 0.0008 mass %, more preferably 0.002 matter Amount %, more preferably 0.003 mass %, particularly preferably 0.008 mass %.On the other hand, as Se content upper Limit, preferably 0.2 mass %, more preferably 0.19 mass %, more preferably 0.18 mass %, particularly preferably 0.10 matter Amount %.When the content of Se is less than above-mentioned lower limit, there is the risk that the resistance to salt water of this coating steel reduces.On the contrary, Se's When content exceedes the above-mentioned upper limit, exist and be difficult to the welding of this coating steel, hot worked risk.
[Ti (titanium), Nb (niobium), Zr (zirconium), V (vanadium) and B (boron)]
Matrix steel are preferably further containing at least one in Ti, Nb, Zr, V and B.Ti, Nb, Zr, V in matrix steel And B is the element making the intensity of this coating steel improve further respectively.
As the content of the Ti in matrix steel, preferably greater than 0 mass %.As the lower limit of the content of Ti, more preferably 0.001 mass %, more preferably 0.008 mass %.On the other hand, as the upper limit of the content of Ti, preferably 0.2 matter Amount %, more preferably 0.19 mass %, more preferably 0.18 mass %, particularly preferably 0.10 mass %.Containing in Ti When amount is less than above-mentioned lower limit, there is the risk of the intensity decreases of this coating steel.On the contrary, the content in Ti exceedes the above-mentioned upper limit When, there is the toughness risk reducing of matrix steel and the risk of the welding being difficult to this coating steel.
As the content of the Nb in matrix steel, preferably greater than 0 mass %.As the lower limit of the content of Nb, more preferably 0.001 mass %, more preferably 0.008 mass %.On the other hand, as the upper limit of the content of Nb, preferably 0.2 matter Amount %, more preferably 0.19 mass %, more preferably 0.18 mass %, particularly preferably 0.10 mass %.Containing in Nb When amount is less than above-mentioned lower limit, there is the risk of the intensity decreases of this coating steel.On the contrary, the content in Nb exceedes the above-mentioned upper limit When, there is the toughness risk reducing of matrix steel and the risk of the welding being difficult to this coating steel.
As the content of the Zr in matrix steel, preferably greater than 0 mass %.As the lower limit of the content of Zr, more preferably 0.001 mass %, more preferably 0.06 mass %.On the other hand, as the upper limit of the content of Zr, preferably 0.2 matter Amount %, more preferably 0.19 mass %, more preferably 0.18 mass %, particularly preferably 0.10 mass %.Containing in Zr When amount is less than above-mentioned lower limit, there is the risk of the intensity decreases of this coating steel.On the contrary, the content in Zr exceedes the above-mentioned upper limit When, there is the toughness risk reducing of matrix steel and the risk of the welding being difficult to this coating steel.
As the content of the V in matrix steel, preferably greater than 0 mass %.As the lower limit of the content of V, more preferably 0.001 mass %, more preferably 0.02 mass %.On the other hand, as the upper limit of the content of V, preferably 0.2 matter Amount %, more preferably 0.19 mass %, more preferably 0.18 mass %, particularly preferably 0.10 mass %.Content in V During less than above-mentioned lower limit, there is the risk of the intensity decreases of this coating steel.On the contrary, when the content of V exceedes the above-mentioned upper limit, deposit In the toughness risk reducing of matrix steel and the risk of the welding being difficult to this coating steel.
As the content of the B in matrix steel, preferably greater than 0 mass %.As the lower limit of the content of B, more preferably 0.0001 mass %, more preferably 0.00015 mass %.On the other hand, as the upper limit of the content of B, preferably 0.01 Quality %, more preferably 0.0095 mass %, more preferably 0.009 mass %, particularly preferably 0.001 mass %.In B Content be less than above-mentioned lower limit when, there is the risk of the intensity decreases of this coating steel.On the contrary, the content in B exceedes on above-mentioned In limited time, there is the toughness risk reducing of matrix steel and the risk of the welding being difficult to this coating steel.
Particularly preferably：Matrix steel have C：More than 0.008 mass % and below 0.32 mass %, Si：0.05 matter Measure below more than % and 2.0 mass %, Mn：More than 0.08 mass % and below 3.0 mass %, P：More than 0.004 mass % and Below 0.05 mass %, S：Below 0.05 mass %, Al：More than 0.008 mass % and below 1.6 mass %, Cu：0.08 matter Measure below more than % and 2.2 mass %, Cr：More than 0.08 mass % and below 3.0 mass %, N：More than 0.001 mass % and Below 0.015 mass %, surplus：Fe and the composition of inevitable impurity, and contain Mo：More than 0.008 mass % and 2.2 Below quality % and W：At least one in more than 0.008 mass % and below 2.2 mass %.In addition, more preferably making matrix steel Ni, Co, Mg, Ca, rare earth metal, Sn, Sb, Ti, Nb, Zr, V, B, Se or combinations thereof is also contained in addition to above-mentioned element.Base Body steel are particularly preferred：As above-mentioned Ni etc., containing at least one in Ni and Co, and containing in Sn, Sb and Se at least 1 kind.In addition, matrix steel it is also particularly that：As above-mentioned Ni etc., containing at least one in Mg, Ca and rare earth metal, And containing at least one in Sn, Sb and Se.
(coating)
Coating contains Al compound, Cr compound, Cu compound and Fe compound, and above-claimed cpd is oxide, hydroxyl Base oxide or combinations thereof.That is, coating contains Al oxide and/or hydroxyl oxidize Al, Cr oxide and/or hydroxyl oxygen Change Cr, Cu oxide and/or hydroxyl oxidize Cu and Fe oxide and/or hydroxyl oxidize Fe.
As the lower limit of the average thickness of coating, it is 8 μm, is preferably 14 μm, is more preferably 21.5 μm.On the other hand, As the upper limit of the average thickness of coating, it is 105 μm, is preferably 80 μm, is more preferably 60 μm.Average thickness in coating It is impossible to fully suppress the intrusion of corrosive goods confrontation matrix steel material, and there is the resistance to of this coating steel less than during above-mentioned lower limit The risk of salt reduction.On the contrary, when the average thickness of coating exceedes the above-mentioned upper limit, hold because of temperature change when using Easily form crackle in coating, there is the wind of the local corrosion generation progress being exposed to the matrix steel on surface because of above-mentioned crackle Danger.
[Al compound]
Al compound contained by coating is innoxious by fixing corrosive chloride, thus suppression is to matrix steel The intrusion of material, result makes the resistance to salt water of this coating steel improve.In Al compound contained by coating, as hydroxyl oxygen Change Al, AlOOH etc. can be enumerated, as Al oxide, Al can be enumerated2O3Deng.
As the lower limit of the content of the Al compound in coating, preferably 0.08 mass %, more preferably 0.4 matter Amount %, more preferably 0.8 mass %.On the other hand, as the upper limit of the content of Al compound, preferably 10.5 matter Amount %, more preferably 6.0 mass %, more preferably 2.5 mass %, particularly preferably 1.2 mass %.In Al compound When content is less than above-mentioned lower limit, there is the risk that the resistance to salt water of this coating steel reduces.On the contrary, the content in Al compound surpasses When crossing the above-mentioned upper limit, easily form crackle in coating because of temperature change when using, result has generation matrix steel The risk of local corrosion.
[Cr compound]
Cr compound contained by coating is innoxious by fixing corrosive sulfate, thus suppression is to matrix steel The intrusion of material, result makes the resistance to salt water of this coating steel improve.In Cr compound contained by coating, as hydroxyl oxygen Change Cr, CrOOH etc. can be enumerated, as Cr oxide, CrO can be enumerated2、CrO3、Cr2O3Deng.As Cr compound, preferably Cr Oxide, more preferably Cr2O3.
When coating contains Cr oxide, as the lower limit of the content of the Cr oxide in coating, preferably 0.08 Quality %, more preferably 0.4 mass %, more preferably 0.8 mass %.On the other hand, as the content of Cr oxide The upper limit, preferably 10.5 mass %, more preferably 3.5 mass %, more preferably 1.2 mass %.In containing of Cr oxide When amount is less than above-mentioned lower limit, there is the risk that the resistance to salt water of this coating steel reduces.On the contrary, the content in Cr oxide exceedes During the above-mentioned upper limit, form crackle because of temperature change when using in coating, there is the risk that local corrosion occurs progress.
[Cu compound]
Cu compound contained by coating suppresses invading of corrosive goods confrontation matrix steel material by making coating fine and close Enter, result makes the resistance to salt water of this coating steel improve.In Cu compound contained by coating, as Cu oxide, can Enumerate CuO, Cu2O etc..
When coating contains Cu oxide, as the lower limit of the content of the Cu oxide in coating, preferably 0.08 Quality %, more preferably 0.4 mass %, more preferably 0.8 mass %.On the other hand, as the content of Cu oxide The upper limit, preferably 10.5 mass %, more preferably 3.5 mass %, more preferably 1.2 mass %.In containing of Cu oxide When amount is less than above-mentioned lower limit, there is the risk that the resistance to salt water of this coating steel reduces.On the contrary, the content in Cu oxide exceedes During the above-mentioned upper limit, easily form crackle in coating because of temperature change when using, result has the office producing matrix steel The risk of portion's corrosion.
[Fe compound]
Fe compound contained by coating can improve coating and the adaptation of matrix steel.Contained by coating In Fe compound, as hydroxyl oxidize Fe, alpha-feooh, β-FeOOH, γ-FeOOH etc. can be enumerated, as Fe oxide, can Enumerate Fe2O3、Fe3O4Deng.As Fe compound, Fe preferably therein3O4And alpha-feooh, more preferably Fe3O4And α- The combination of FeOOH.
Contain alpha-feooh and/or Fe in coating3O4When, as the Fe in coating3O4And the total content of alpha-feooh Lower limit, preferably 29.5 mass %, more preferably 35 mass %, more preferably 40 mass %.On the other hand, as upper State the upper limit of total content, be not particularly limited, for example, 99.5 mass %, be preferably 97.5 mass %, more preferably 95.5 quality %.When above-mentioned total content is less than above-mentioned lower limit, the adaptation of coating and matrix steel reduces, and exists and cannot grow Phase maintains the risk of the resistance to salt water of this coating steel.On the contrary, when above-mentioned total content exceedes the above-mentioned upper limit, the Al in coating The content of compound, Cr compound and Cu compound becomes insufficient, and result has the resistance to salt water reduction of this coating steel Risk.
When coating contains alpha-feooh, as the lower limit of the content of the alpha-feooh in coating, preferably 8 matter Amount %, more preferably 28 mass %.On the other hand, as the upper limit of the content of alpha-feooh, preferably 90 mass %, more preferably For 65 mass %, more preferably 55 mass %.In addition, containing Fe in coating3O4When, as the Fe in coating3O4's The lower limit of content, preferably 10 mass %, more preferably 28 mass %, more preferably 38 mass %.On the other hand, as Fe3O4Content the upper limit, preferably 95 mass %, more preferably 75 mass %, more preferably 52 mass %.In Fe3O4 And the content of alpha-feooh is when being respectively less than above-mentioned lower limit, the adaptation of coating and matrix steel reduces, and exists and cannot tie up for a long time Hold the risk of the resistance to salt water of this coating steel.On the contrary, in Fe3O4And the content of at least one party in alpha-feooh exceed above-mentioned During the upper limit, the content of Al compound, Cr compound and Cu compound in coating becomes insufficient, and result has this coating steel The risk that the resistance to salt water of material reduces.
When coating contains alpha-feooh, as the lower limit of the mean diameter of alpha-feooh, preferably 4.5nm, more excellent Elect 12nm, more preferably 15.5nm as.On the other hand, as the upper limit of the mean diameter of alpha-feooh, preferably 22nm, More preferably 19nm.In addition, containing Fe in coating3O4When, as Fe3O4Mean diameter lower limit, preferably 4.5nm, more It is preferably 8nm, more preferably 13nm.On the other hand, as Fe3O4Mean diameter the upper limit, preferably 22nm, more excellent Elect 18nm as.In Fe3O4And the mean diameter of at least one party in alpha-feooh be less than above-mentioned lower limit when, in the formation of coating When the volume of coating can be made significantly to shrink because of the evaporation of interparticle solvent, thus there is the wind defect such as cracking Danger.Result：The suppression using coating, corrosive substance being invaded in matrix steel becomes insufficient, exists because of above-mentioned crackle And there is the risk of corrosion, produce matrix steel in the near interface with coating in the local corrosion being exposed to the matrix steel on surface The risk of the corrosion of material.In addition, make coating peel off and come off because of the corrosion of above-mentioned matrix steel, sometimes also existing makes corruption Lose the risk carrying out further.On the contrary, in Fe3O4And the mean diameter of at least one party in alpha-feooh is when exceeding the above-mentioned upper limit, Easily produce gap between particle, so that the compactness of coating is reduced, result：Corrosive substance is easily between above-mentioned particle Invade and in matrix steel, thus there is the risk that the resistance to salt water of this coating steel reduces.
Particularly preferably：Coating contains Al oxide and/or hydroxyl oxidize Al, Cr oxide, Cu oxide and makees Fe for above-mentioned Fe oxide and hydroxyl oxidize Fe3O4And alpha-feooh.Now, as Al oxide and/or hydroxyl oxidize Al Content, more than preferably 0.08 mass % and below 10.5 mass %.In addition, as the content of Cr oxide, preferably 0.08 More than quality % and below 10.5 mass %.And then, as the content of Cu oxide, more than preferably 0.08 mass % and 10.5 Below quality %.And then, as Fe3O4And the total content of alpha-feooh, more than preferably 29.5 mass %.And then, as above-mentioned Fe3O4And the mean diameter of alpha-feooh, preferably respectively more than 4.5nm and below 22nm.Meet these by making coating Part, such that it is able to improve the resistance to salt water of this coating steel and the persistence of this resistance to salt water further.
From the viewpoint of the resistance to salt water improving with the adaptation of matrix steel, improving this coating steel, coating is excellent Choosing containing in addition to above-mentioned Al compound, Cr compound, Cu compound and Fe compound other metal oxyhydroxides and/ Or other metal-oxides.As other metal-oxides above-mentioned, such as SiO can be enumerated2、TiO2、ZrO2、Nb2O5、Ta2O5、 V2O5、La2O3、Ce2O3Deng.But, coating can also contain only Al compound, Cr compound, Cu compound and Fe compound And make other metal-oxides above-mentioned and the content of other metal oxyhydroxides be essentially 0 mass %.In addition, coating Can contain except above-mentioned Al compound, Cr compound, Cu compound, Fe compound, above-mentioned metal-oxide and metal hydroxy Composition beyond oxide.
(form of coating steel and purposes)
As the form of this coating steel, such as steel plate, steel pipe, bar steel, wire rod, shape steel etc. can be enumerated.In addition, this is coating Steel are under the corrosive environment that often impregnated in sea water, under the corrosive environment that often not impregnated in sea water, especially fly here sea salt Particle, the spittle become the corrosion that all can suppress under the corrosive environment of main cause caused by sea water etc..Accordingly, as this coating steel The purposes of material, can enumerate such as ship, marine structure, bridge etc..As above-mentioned ship, such as oil tanker, container can be enumerated Freighter, combination vessel, passenger boat, the warships etc. such as ship, bulk freighter (bulker).When this coating steel is used for ship, can be suitable for Various for ballast tank, upper deck, bridge, hatch board (hatchcover), crane, various pipe arrangement, step, railing etc. Portion's steel construction etc..In addition, as above-mentioned marine structure, can enumerate for example：Excavate oil on ocean, the excavation of natural gas sets Apply；The float type facility of the production of petroleum and natural gas, storage, shipment etc. is carried out on ocean；Carry out in deepwater wind-force Generating association facility of generating, wave-activated power generation, tidal power generating, ocean current generating, temperature difference generating, solar power generation etc. etc..And then, When this coating steel is used for bridge, sudden environment more than the sudden salt component of 0.1mdd for the salt component can be suitable as Bridge steel plate material.
<The manufacture method of coating steel>
The manufacture method of this coating steel possesses：Prepare the operation (matrix steel preparatory process) of matrix steel；Preparation will Al compound, Cr compound, Cu compound and Fe compound are scattered in the operation of the coating formation compositionss of solvent (preparation section)；And above-mentioned coating formation compositionss are coated on operation (the coating work on the surface of above-mentioned matrix steel Sequence).Hereinafter, each operation is illustrated.
(matrix steel preparatory process)
In this operation, prepare the matrix steel with required composition.As the manufacture method of matrix steel, have no especially Limit, the common steel producing method with converter steel method, Electric Cooker steel method etc. as representative can be adopted.Hereinafter, to matrix steel Concrete manufacture method illustrate.First, RH is used to the molten steel in ladle from converter or electric furnace steel tapping (Ruhrstahl-Heraeus) vacuum degasser is adjusted to required composition, and adjusts to carry out secondary fine by temperature Refining.Afterwards, make steel ingot using the common casting method such as continuous casting process, ingot casting method, thus obtain matrix steel.Said Classification that is bright, carrying out as the deoxy forms based on matrix steel, from guaranteeing mechanical property, welding easness etc. to for structure From the viewpoint of fundamental characteristics required by the steel of thing, preferably killed steel, more preferably Al killed steel.
(preparation section)
In this operation, Al compound, Cr compound, Cu compound and Fe compound are scattered in solvent and prepare coating Layer formation compositions.In this operation, other above-mentioned metal oxyhydroxides and/or other metal-oxides can be made to enter One step is scattered in solvent.As above-mentioned solvent, it is not particularly limited, the organic solvents such as such as alkyl silicate, water etc. can be enumerated, Wherein, preferably organic solvent, more preferably alkyl silicate.As the solid component concentration of coating formation compositionss, It is not particularly limited, more than for example, 10 mass % and below 60 mass %.For coating formation compositionss, due to The each composition being scattered in solvent is difficult to stably carry out chemical reaction, therefore the composition generally in addition to solvent be directly becoming by The composition of coating.Therefore, by adjusting the composition of each composition, the particle diameter of coating formation compositionss, such that it is able to easily and It is reliably formed the coating of required composition.
(working procedure of coating)
In this operation, coating formation compositionss are coated on the surface of matrix steel, on the surface of matrix steel Form coating.As the method on the surface that coating formation compositionss are coated on matrix steel, it is not particularly limited, can Enumerate and make it more than such as 70 DEG C after being for example coated using spraying etc. and less than 150 DEG C dry methods etc..Said Bright, by adjusting the solid component concentration of coating formation compositionss, coating weight used in this operation, such that it is able to easy And it is reliably formed the coating of required average thickness.
Process before in advance the surface of matrix steel being carried out preferably before this operation.As above-mentioned pre-treatment, can enumerate Such as grinding, using shot-peening etc. except surface attachments such as descale, salinity etc..In this operation, particularly preferably make matrix steel The salinity adhesion amount on material surface is few as much as possible, specifically, is preferably scaled less than 0.1g/m with such as NaCl2.
In addition, as above-mentioned pre-treatment, from the viewpoint of the adaptation guaranteeing coating and matrix steel, further preferably right Matrix steel give the process of the surface roughness of appropriateness.As the method for the surface roughness that matrix steel are given with appropriateness, Known method can be adopted, such as bead, blasting treatment etc. can be enumerated.Surface as specific matrix steel The lower limit of roughness, preferably 10 μm.On the other hand, as the upper limit of the surface roughness of matrix steel, preferably 80 μm.? When the surface roughness of matrix steel is less than above-mentioned lower limit, there is the risk of the adaptation reduction of coating and matrix steel.Phase Instead, when the surface roughness in matrix steel exceedes the above-mentioned upper limit, coating formation compositionss coating after matrix steel The recess of material brings bubble into, and result forms coating and the not closely sealed part of matrix steel, thus there is the wind of adaptation reduction Danger.Here, " surface roughness " refers to：According to JIS-B0601：2001 " geometrical property method (the GPS)-superficiality of product Shape：Contour curve mode-term, definition and surface texture parameter " measures the 10 points of mean roughness (Rz) obtaining, and will evaluate Length is set to 12.5mm, cutoff λ c is set to the value of 2.5mm.
Embodiment
Hereinafter, enumerate embodiment the coating steel of the present invention and its manufacture method are further illustrated, but, this Invention was not also limited by following embodiments originally, and the scope that certainly also can address purport described later on meeting is carried out suitably Implement again after change, they are also all contained in the technical scope of the present invention.
[making of coating steel]
Using vacuum fusion stove, melting is carried out to the steel with composition shown in table 1 and table 2, respectively obtain the steel of 50kg Ingot.By each Heating Steel Ingots of gained to after 1,150 DEG C, carry out hot rolling, be respectively prepared the steel former material of average thickness 10mm.From each steel Former material cuts the test film of 150 × 70 × 5 [mm], and these test films are set to matrix steel B1～B54.One side by test film The test face of being set to, implements shot-peening in the way of making this test face be finally reached 30 μm of Rz, afterwards, is washed and acetone to it Cleaning.After cleaning, the quality of determination test piece and thickness, the quality of matrix steel before being set to test and thickness.As Fig. 1 Shown, the region of 140 × 60 [mm] of the inner side of more than the 5mm of each of test face is set to pilot region A, to this trial zone Grid point X of the 5 × 13=65 point at the interval of 10mm in length and breadth in the A of domain carries out the mensure of the thickness of test film.In addition, from test face The back side carry out the mensure of above-mentioned thickness using ultrasound wave thickness of slab meter.Afterwards, using following method, quilt is formed on test film Coating.
Table 1
Table 2
The Fe of required mean diameter will be adjusted to3O4And the powder of alpha-feooh and other metal oxyhydroxides and other The powder mixing of metal-oxide, and so that it is scattered in as in the alkyl silicate of solvent, being prepared into coating formation group Compound.The solid component concentration of coating formation compositionss is set to 40 mass %.On the surface of test film in the way of spraying Coating layer formation compositions, afterwards so as to be dried in 100 DEG C of exsiccator, thus obtain the examination possessing coating Test piece.This test film is set to coating steel No.2～No.65.It is explained, the composition of coating is formed by coating to be used The mixing ratio of each composition of compositionss, can be by the solid in addition to solvent in coating formation compositionss being adjusted The composition of composition is considered as the composition of coating.In addition, the average thickness of coating is by the coating of coating formation compositionss Measure and to be adjusted, and be measured using electromagnetism film thickness gauge.After the formation of coating, by the test face of test film except examination Test the region B beyond region and the Teflon of the face in addition to test face (registered trade mark) covers.It is explained, except pilot region Region B in addition is the region that the distance from each side is less than 5mm.Afterwards, following corrosion testings are carried out.Show in table 3 and table 4 Go out coating steel No.1～matrix steel of No.65 and the composition of coating.It is explained, do not formed in coating steel No.1 Coating.In addition, " other compositions " of table 3 and table 4 represent other metal-oxides above-mentioned and other metal oxyhydroxides.
Table 3
Table 4
[corrosion testing]
The corrosion testing of the corrosive environment being formed by sea water as simulation, the combined-circulation implementing using artificial seawater is rotten Corrosion test (Cyclic Corrosion Testing：CCT).Specifically, the test face to test film, repeats (I) 35 DEG C artificial seawater spray 1.5 hours, (II) places 2.5 hours under temperature 60 C, humidity 20%RH, (III) in temperature 50 DEG C, place (I)～(III) of 2.5 hours under humidity 95%RH.It is explained, so that temperature and humidity is become in (I)～(III) During change, make be set to 0.5 hour the transfer time needed for conditional stability.In addition, being set to 84 days during test.And then, test film makes With each 3, it is set to N=3.
After CCT terminates, the mass change of determination test piece and corrosion depth.First, after CCT terminates, using 10% Fructus Citri Limoniae Katholysis in sour hydrogen two aqueous ammonium removes coating and the corrosion product of test film, afterwards, is washed and third Ketone cleans.After cleaning, the quality of determination test piece, the quality of the matrix steel after being set to test.By the matrix after test The difference of the quality of matrix steel before the quality of steel and test is set to the etching extent caused by corrosion, by 3 test films Meansigma methodss are set to average amount.In addition, to 65 shown in Fig. 1 grid point X, using ultrasound wave thickness of slab meter from the examination of test film Test the back side measurement thickness in face.Matrix steel after obtaining the thickness of matrix steel before the test of each grid point X and testing The difference of thickness, is set to the corrosion depth of this grid point X.Measure the respective corrosion of 65 grid point X of 3 test films Depth, the maximum of the corrosion depth of 195 points of grid point X is set to maximum corrosion depth.
To coating steel No.1～No.65, obtain and the average amount of coating steel No.1 and maximum corrosion depth are divided It is not set to relative value when 100, and be divided into A～E according to following benchmark.Average amount and the relative value of maximum corrosion depth All represent that numerical value is less, resistance to salt water is more excellent.
A：Relative value with respect to No.1 is less than 55
B：Relative value with respect to No.1 is more than 55 and less than 70
C：Relative value with respect to No.1 is more than 70 and less than 85
D：Relative value with respect to No.1 is more than 85 and less than 95
E：Relative value with respect to No.1 is more than 95
In addition, to coating steel No.1～No.65, according to following benchmark with the excellent order of resistance to salt water be divided into A～ F, is set to overall merit.A, B, C, D, E and F can be evaluated as " qualified " by overall merit, and G is evaluated as " unqualified ". Evaluation result is shown in Table 5.
A：The evaluation of average amount and maximum corrosion depth is A
B：One side of the evaluation of average amount and maximum corrosion depth is A, and the opposing party is B
C：The evaluation of average amount and maximum corrosion depth is B
D：One side of the evaluation of average amount and maximum corrosion depth is C, and the opposing party is more than B
E：The evaluation of average amount and maximum corrosion depth is C
F：The evaluation of average amount and maximum corrosion depth is below D.Wherein, average amount and maximum corrosion are deep Except the situation of the equal E of evaluation of degree
G：The evaluation of average amount and maximum corrosion depth is E
【Table 5】
Coating steel No.1, No.10 and No.11 are equivalent to the comparative example of the present invention, and overall merit is G, and resistance to salt water is Unqualified.Hereinafter, each comparative example is studied.
Coating steel No.1 assumes that the situation of the common steel not possessing coating.Although coating steel No.1 is in corruption Form the envelope of rust in corrosion test in surface, but do not obtain sufficient resistance to salt water.
Coating steel No.10 and No.11 is the too small comparative example of the average thickness of coating and excessive comparative example, all not Obtain sufficient resistance to salt water.
On the other hand, be equivalent to meet coating steel No.2～9 of the embodiment of the composition of the present invention and No.12～ For No.65, the relative value of average amount and maximum corrosion depth equal less than 95, play excellent resistance to salt water.Hereinafter, right Each embodiment is studied.
Coating steel No.12～No.17 is using the base containing C, Si, Mn, P, S, Al, N, Fe and inevitable impurity The embodiment of body steel B1～6.Hereinafter, by also referred to as basic for the above-mentioned composition of matrix steel composition 1.Coating steel No.12 The resistance to salt water of～No.17 is more excellent than the coating steel of comparative example, but, it is minimum in an embodiment.
Coating steel No.2～No.9 is to employ to be set to specified quantitative and contain Cu the content of P and Al of basic composition 1 And the embodiment of the matrix steel B7 of Cr and Mo and/or W.Hereinafter, the above-mentioned composition of matrix steel is also referred to as basic group Become 2.The resistance to salt water of coating steel No.2～No.9 is more excellent than the coating steel of comparative example, but has substantially employing It is minimum in the embodiment of matrix steel of composition 2.
Coating steel No.18～No.65 is using the matrix steel B7～B64 with basic composition 2 and by coating Al compound, the species of Cr compound, Cu compound and Fe compound, content and mean diameter be adjusted to appropriate scope Embodiment.Specifically, the Al oxide containing specified quantitative and/or hydroxyl oxidize Al be as Al compound, containing specified quantitative , as Cr compound, the Cu oxide containing specified quantitative is as Cu compound for Cr oxide.In addition, being contained altogether with specified quantitative Fe3O4And alpha-feooh is as Fe compound, above-mentioned Fe3O4And the mean diameter of alpha-feooh is respectively more than 4.5nm and 22nm Below.Compared with above-mentioned coating steel No.2～No.9, the average amount of coating steel No.18～No.65 and maximum are rotten At least average amount in erosion depth is excellent.Hereinafter, coating steel No.18～No.65 is studied.
Coating steel No.18～No.20 is the embodiment employing the matrix steel B7～B9 only with basic composition 2. Compared with above-mentioned coating steel No.2～No.9, the average amount of coating steel No.18～No.20 is dropped further Low.
Coating steel No.21～No.23 is to employ the base also containing Ni and/or Co with specified quantitative in addition to basic composition 2 The embodiment of body steel B10～B12.Compared with above-mentioned coating steel No.18～No.20, coating steel No.21～No.23 Maximum corrosion depth reduced further.
Coating steel No.24～No.29 is to employ also to contain Mg, Ca and/or REM with specified quantitative in addition to basic composition 2 Matrix steel B13～B18 embodiment.Compared with above-mentioned coating steel No.18～No.20, coating steel No.24～ The maximum corrosion depth of No.29 is reduced further.
Coating steel No.30～No.34 be employ except basic composition 2 outer also with specified quantitative contain Ni and/or Co and Mg, The embodiment of the matrix steel B19～B23 of Ca and/or REM.Compared with above-mentioned coating steel No.18～No.20, coating steel The average amount of material No.30～No.34 and maximum corrosion depth are reduced further.
Coating steel No.35～No.40 is to employ also to contain Sn, Sb and/or Se with specified quantitative in addition to basic composition 2 The embodiment of matrix steel B24～B29.Compared with above-mentioned coating steel No.18～No.20, coating steel No.35～ The maximum corrosion depth of No.40 is reduced further.
Coating steel No.41～No.44 be employ except basic composition 2 outer also with specified quantitative contain Ni and/or Co and Sn, The embodiment of the matrix steel B30～B33 of Sb and/or Se.Compared with above-mentioned coating steel No.18～No.20, coating steel The average amount of No.41～No.44 and maximum corrosion depth are reduced further.
Coating steel No.45～No.48 is to employ also to contain Mg, Ca and/or REM with specified quantitative in addition to basic composition 2 Embodiment with the matrix steel B34～B37 of Sn, Sb and/or Se.Compared with above-mentioned coating steel No.18～No.20, quilt The maximum corrosion depth covering steel No.45～No.48 is significantly reduced.
Coating steel No.49～No.53 be employ except basic composition 2 outer also with specified quantitative contain Ni and/or Co and Mg, The embodiment of the Ca and/or REM and matrix steel B38～B42 of Sn, Sb and/or Se.With above-mentioned coating steel No.18～ No.20 compares, and the average amount of coating steel No.49～No.53 and maximum corrosion depth are reduced, especially the most further Big corrosion depth is significantly reduced.Coating steel No.49～No.53 given play to inferior to coating steel No.63 described later and The excellent resistance to salt water of No.65.
Coating steel No.54～No.55 be employ in addition to basic composition 2 also with specified quantitative contain Ti, Nb, Zr, V and/ Or the embodiment of the matrix steel B43～B44 of B.Compared with above-mentioned coating steel No.18～No.20, coating steel No.54 The average amount of～No.55 and maximum corrosion depth slightly reduce.
Coating steel No.56～No.57 be employ except basic composition 2 outer also with specified quantitative contain Ni and/or Co and Ti, The embodiment of the matrix steel B45～B46 of Nb, Zr, V and/or B.Compared with above-mentioned coating steel No.18～No.20, it is coated to The maximum corrosion depth of steel No.56～No.57 is reduced further.
Coating steel No.58 and No.64 is to employ also to contain Mg, Ca and/or REM with specified quantitative in addition to basic composition 2 Embodiment with matrix steel B47 and B53 of Ti, Nb, Zr, V and/or B.With above-mentioned coating steel No.18～No.20 phase The maximum corrosion depth of coating steel No.58 and No.64 is reduced ratio further.In addition, with above-mentioned coating steel No.18～No.20 compares, and the average amount of the coating steel No.64 of the matrix steel V containing specified quantitative also obtains further Reduce.
Coating steel No.59～No.60 be employ except basic composition 2 outer also with specified quantitative contain Ni and/or Co and Mg, The embodiment of the Ca and/or REM and matrix steel B48～B49 of Ti, Nb, Zr, V and/or B.With above-mentioned coating steel No.18 ～No.20 compares, and the average amount of coating steel No.59～No.60 and maximum corrosion depth are reduced further.
Coating steel No.61 be employ in addition to basic composition 2 also with specified quantitative contain Sn, Sb and/or Se and Ti, Nb, The embodiment of the matrix steel B50 of Zr, V and/or B.Compared with above-mentioned coating steel No.18～No.20, coating steel The maximum corrosion depth of No.61 is reduced further.
Coating steel No.62 be employ except basic composition 2 outer also with specified quantitative contain Ni and/or Co and Sn, Sb and/or The embodiment of the Se and matrix steel B51 of Ti, Nb, Zr, V and/or B.Compared with above-mentioned coating steel No.18～No.20, quilt Cover the average amount of steel No.62 and maximum corrosion depth is reduced further.
Coating steel No.63 and No.65 be employ except basic composition 2 outer also with specified quantitative contain Ni and/or Co and Mg, The embodiment of matrix steel B52 and B54 of Ca and/or REM and Sn, Sb and/or Se and Ti, Nb, Zr, V and/or B.With above-mentioned Coating steel No.18～No.20 compares, and the average amount of coating steel No.63 and No.65 and maximum corrosion depth are entered One step reduces, and especially maximum corrosion depth is significantly reduced.Coating steel No.63 and No.65 plays the most in an embodiment Excellent resistance to salt water.
So may determine that：By possessing the coating of the composition meeting the present invention, such that it is able to improve resistance to salt water.Separately Outward, judge：Contain basic composition 1 by making matrix steel, such that it is able to improve resistance to salt water further, and by containing base This composition 2, thus further improve resistance to salt water.And then, judge：By making matrix steel also with spy in addition to basic composition 2 Quantitative containing at least arbitrary in Ni and/or Co and Mg, Ca and/or REM and Sn, Sb and/or Se and Ti, Nb, Zr, V and/or B Kind, such that it is able to improve resistance to salt water further, contain these whole elements particularly by with specified quantitative, such that it is able to notable Ground improves resistance to salt water.
Judged by above result：The coating steel of the present invention play excellent resistance to salt water in briny environment, and Can be suitable for exposing to the open air the works in sea water, sudden sea salt particle.In addition, the manufacture method of the coating steel of the present invention This coating steel can be provided.
Industrial applicability
This coating steel and its manufacture method can improve the coating steel that can maintain excellent resistance to salt water for long periods.
Symbol description
A pilot region
Region beyond B pilot region
X grid point

Claims (9)

1. a kind of coating steel are it is characterised in that be the coating possessing matrix steel and being formed at this matrix steel surface Coating steel, wherein, described coating has the average thickness of more than 8 μm and less than 105 μm, and contains Al compound, Cr Compound, Cu compound and Fe compound,
Described compound is oxide, oxyhydroxide or combinations thereof.
2. coating steel according to claim 1, wherein, described coating contains：
Al oxide, hydroxyl oxidize Al or combinations thereof：More than 0.08 mass % and below 10.5 mass %,
Cr oxide：More than 0.08 mass % and below 10.5 mass %,
Cu oxide：More than 0.08 mass % and below 10.5 mass % and
Fe as described Fe oxide and hydroxyl oxidize Fe3O4And alpha-feooh：Amount to more than 29.5 mass %,
Described Fe3O4And the mean diameter of alpha-feooh is respectively more than 4.5nm and below 22nm.
3. coating steel according to claim 1 and 2, wherein, described matrix steel have following composition：
C：More than 0.008 mass % and below 0.32 mass %,
Si：More than 0.05 mass % and below 2.0 mass %,
Mn：More than 0.08 mass % and below 3.0 mass %,
P：More than 0.001 mass % and below 0.05 mass %,
S：Below 0.05 mass %,
Al：More than 0.001 mass % and below 1.6 mass %,
N：More than 0.001 mass % and below 0.015 mass % and
Surplus：Fe and inevitable impurity.
4. coating steel according to claim 3, wherein, described matrix steel have
P：More than 0.004 mass % and below 0.05 mass % and
Al：Composition more than 0.008 mass % and below 1.6 mass %,
Also contain
Cu：More than 0.08 mass % and below 2.2 mass % and
Cr：More than 0.08 mass % and below 3.0 mass %,
And at least one in containing further as follows：
Mo：More than 0.008 mass % and below 2.2 mass % and
W：More than 0.008 mass % and below 2.2 mass %.
5. the coating steel according to claim 3 or 4, wherein, described matrix steel also contain following at least one：
Ni：More than 0.008 mass % and below 5.2 mass % and
Co：More than 0.008 mass % and below 5.0 mass %.
6. the coating steel according to claim 3,4 or 5, wherein, described matrix steel also contain following at least 1 Kind：
Mg：More than 0.0004 mass % and below 0.01 mass %,
Ca：More than 0.0004 mass % and below 0.01 mass % and
Rare earth metal：More than 0.0004 mass % and below 0.01 mass %.
7. the coating steel according to any one of claim 3～6, wherein, during described matrix steel also contain as follows At least one：
Sn：More than 0.0008 mass % and below 0.2 mass %, Sb：More than 0.0008 mass % and below 0.2 mass % and Se：More than 0.0008 mass % and below 0.2 mass %.
8. the coating steel according to any one of claim 3～7, wherein, during described matrix steel also contain as follows At least one：
Ti：More than 0 mass % and below 0.2 mass %,
Nb：More than 0 mass % and below 0.2 mass %,
Zr：More than 0 mass % and below 0.2 mass %,
V：More than 0 mass % and below 0.2 mass % and
B：More than 0 mass % and below 0.01 mass %.
9. a kind of manufacture method of coating steel, it possesses：
The operation of preparation matrix steel,
Al compound, Cr compound, Cu compound and Fe compound are scattered in the coating formation group of solvent by preparation The operation of compound and
Described coating formation compositionss are coated on the operation on the surface of described matrix steel,
Described compound is oxide, oxyhydroxide or combinations thereof,
Form the coating that average thickness is more than 8 μm and less than 105 μm in described working procedure of coating.
CN201610421302.5A 2015-08-19 2016-06-14 Coating steel and its manufacture method Pending CN106467950A (en)

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