CN104024476B - The manufacture method of the cold-rolled steel sheet of excellent corrosion resistance after chemical treatability and application - Google Patents
The manufacture method of the cold-rolled steel sheet of excellent corrosion resistance after chemical treatability and application Download PDFInfo
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- CN104024476B CN104024476B CN201280064512.3A CN201280064512A CN104024476B CN 104024476 B CN104024476 B CN 104024476B CN 201280064512 A CN201280064512 A CN 201280064512A CN 104024476 B CN104024476 B CN 104024476B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
Abstract
It is 100～5000mg/m to surface of cold-rolled steel plate with the adhesion amount of Zn2Mode implement Zn plating, after washing, make above-mentioned cold-rolled steel sheet contact with the aqueous solution containing P.Now, the P concentration containing P aqueous solution is 0.001～2g/L, and temperature is the scope of 30～60 DEG C.
Description
Technical field
The present invention relates to a kind of manufacture forming the good cold-rolled steel sheet of corrosion resistance after sufficient chemical conversion tunicle and application
Method.
Background technology
In recent years, as the countermeasure of global warming, in order to reduce the CO of automobile2How discharge capacity, carry out the light-duty of car body
Change for auto-maker, become problem.For the lightness of car body, it is most useful that the thin-walled property of used steel plate,
If but only reduced thickness of slab when the intensity of steel plate is identical, then the rigidity of steel plate would reduce, when now cannot guarantee collision
When the safety of passenger.Therefore, high-strength steel sheet is used to improve constantly as the trend of car body materials, this high intensity
Steel plate can reduce thickness of slab and utilize the high intensity of steel to make up the rigidity reduced because reducing thickness of slab, recently, by hot strength
The high-strength steel sheet of 1180MPa level also comes to life for the trend of vehicle body purposes.
In order to make steel plate high intensity, effectively add the alloying elements such as Si, Mn to the method carrying out solution strengthening, make
The method of crystal grain miniaturization, adds the precipitates such as Nb, Ti, V and forms the method that unit usually carries out precipitation strength, generate martensitic phase
The method etc. strengthened is carried out Deng the phase-change organization of hard.
Generally, the high intensity carried out by adding alloying element is owing to can cause the fall of ductility on the other hand
Low, so there is the shortcoming being difficult to make the extrusion forming of component shape.But, in solution strengthening, Si and other yuan
The impact of element phase comparison ductility reduction is less, so belonging to when guaranteeing ductility and realizing high intensity is effective unit
Element.Therefore, it can be said that for the steel plate taking into account processability and high intensity, adding of Si is the most required.
But, the equilibrium oxygen partial pres-sure of the oxide of Si is the lowest, and use in the manufacture of general cold-rolled steel sheet is continuous
Being oxidized easily in reducing atmosphere in annealing furnace, if therefore the steel plate containing Si being passed through continuous annealing furnace, then Si exists
Surface of steel plate is chosen oxidation and forms SiO2.If such surface is formed with SiO2Steel plate supply to the change before application
One-tenth processes, then SiO2The reaction of chemical synthesis treatment liquid and steel plate can be hindered, therefore there is the what is called not forming chemical conversion crystallization without covering
Part.Such after chemical conversion treatment, there is the water rinses after chemical conversion treatment sometimes of the steel plate without covering part the most
Rust occur, even if supposing the degree being not reaching to produce rust, the corrosion resistance of the steel plate after electrodeposition coating is the most excessively poor.Therefore
High strength cold rolled steel plate containing Si is used in vehicle body purposes is extremely difficult.
As the method for the chemical treatability improving such high strength cold rolled steel plate containing Si, propose all the time
A lot of methods.Such as, patent documentation 1 proposes surface and is formed with the cold-rolled steel of the oxide that atomic ratio [Si/Mn] is less than 1
Plate and as its manufacture method using the intrinsic standoff ratio of hydrogen in (Si/Mn) ratio of steel plate composition, annealing temperature, atmosphere and moisture as ginseng
Number specifies.But, in the method, increase along with the Si of steel plate composition measures, need to reduce annealing temperature, therefore to
When needing high annealing to desired intensity, stretching, it is necessary to improve the moisture ratio of atmosphere.But, on the contrary at surface of steel plate
Form Fe system oxide, so product cannot be become.That is, be for the main flow as current high-strength steel sheet containing 1.0%
The technology that the steel plate of the Si of left and right cannot be applied.
Patent documentation 2 proposes the steel plate to Si:0.05～2% and [Si]/[Mn]≤0.4 and defines surface of steel plate
The surface of steel plate coverage rate of the size of Si-Mn composite oxides and the number of per unit area and the oxide based on Si
High strength cold rolled steel plate.
Patent documentation 3 proposes the steel plate to Si:0.1～1% and [Si]/[Mn]≤0.4 and defines surface of steel plate
(Mn/Si) ratio, size and the number of per unit area of Mn-Si composite oxides and the steel plate of the oxide based on Si
The high strength cold rolled steel plate of surface coverage.
Patent documentation 4 proposes the steel plate to Si:0.1～2% and [Si]/[Mn]≤0.4 and defines surface of steel plate
(Mn/Si) ratio, size and the number of per unit area of Mn-Si composite oxides and the steel plate of the oxide based on Si
The high strength cold rolled steel plate of surface coverage.
The technology of patent documentation 2～4 can be applied to contain up to the steel plate of the Si of 2%, as the example of its manufacture method
Son, suppresses the dew point when acid washing conditions after hot rolling, continuous annealing as less than-40 DEG C.However, it is desirable to it is specific for meeting
The steel plate of Si/Mn ratio, has the little such shortcoming of degree of freedom of steel plate composition.It addition, if it is considered that the dew of the production line of reality
Point variation, makes dew point during continuous annealing the following is the most rambunctious for-40 DEG C, is therefore the technology being not suitable for volume production.
Patent documentation 5 proposes the steel plate to more than Si:0.4% and [Si]/[Mn] >=0.4 and defines surface of steel plate
The manufacture method of pickling is implemented after the cold-rolled steel sheet of the surface coverage of Si base oxide and annealing.
Patent documentation 6 proposes to the steel plate containing Si more than 0.5 mass %, after annealing with 2.0g/m2Above
The technology of grinding surface of steel plate.
Patent documentation 7 proposes by after the steel plate annealing of the Si containing 0.5～2.0%, pH0～4, temperature 10～
In the acid solution of 100 DEG C process 5～150 seconds, and carry out in the alkaline solution of pH10～14, temperature 10～100 DEG C 2～
The technology processed for 50 seconds.
The technology of patent documentation 5～7 is the technology of the oxide skin(coating) formed after removing annealing on surface, at patent documentation
In the example of 5, in order to remove Si base oxide, need to use the acid of high concentration, now, the passivation tunicle of base steel can be promoted on the contrary
Formation, therefore there is the shortcoming of effect that may not be improved chemical treatability.In patent documentation 6,7, need in production line
Region or the region of acid solution process → alkaline solution process of grinding are set, cause the increase of hugeization of equipment, cost,
Not-so-practical.
Proposing in patent documentation 8 by making surface of steel plate have adhesion amount is 10～2000mg/m2Plating Zn tunicle and
Make it have the crystalline orientation of regulation and take into account the technology of anti-stickness and chemical treatability.This technology is primarily to improve
Anti-stickness and carry out, for chemical treatability, even the Zn adhesion amount of trace, at facies posterior hepatis and the steel plate exposed division of Zn
Between also can form micella (microcell), show that chemical conversion treatment reaction in surface is active.But, high in the Si concentration of steel plate
In the case of, the major part of surface of steel plate is by SiO2Oxide cover, when this part is steel plate exposed division, it is difficult to say one be shaped as micro-
Born of the same parents.It addition, use sulfuric acid bath as electroplating bath, when the same terms proposed in by embodiment forms plating Zn tunicle, find because of
The kind of the alkaline degreaser before chemical conversion treatment and cannot fully defat.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 4-276060 publication
Patent documentation 2: No. 3934604 publications of Japanese Patent No.
Patent documentation 3: Japanese Unexamined Patent Publication 2005-290440 publication
Patent documentation 4: No. 3889768 publications of Japanese Patent No.
Patent documentation 5: Japanese Unexamined Patent Publication 2004-323969 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2003-226920 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2007-009269 publication
Patent documentation 8: Japanese Unexamined Patent Publication 2006-299351 publication
Summary of the invention
So, for the addition of the cold rolling of Si for realizing the purpose of high intensity on the premise of not making ductility reduction
For steel plate, the technology meeting chemical treatability still can not be said to be sufficient, and present situation is that high-strength steel sheet is applied to Automobile
There is obstruction in body.
It is an object of the invention to, for providing a kind of chemical treatability and application containing Si as the steel plate of intensified element
The manufacture method of the cold-rolled steel sheet of rear excellent corrosion resistance.
The present inventor etc. are conceived to form SiO at surface of steel plate2Time, because of in institute's forming part as steel plate main constituent
Fe does not dissolves, so not occurring chemical conversion crystallization to form the situation of reaction.It addition, the present inventor etc. consider by using someway
The dissolving reaction making surface of steel plate occurs then to be associated with chemical conversion crystallization and forms reaction.It addition, the present inventor etc. are additionally contemplates that
Metal Zn forms the zinc phosphate tunicle as chemical conversion tunicle by the reaction with chemical synthesis treatment liquid.Carry out the result studied,
The present inventor etc. confirm by surface of cold-rolled steel plate gives the thin Zn layer being only the q.s needed for formation zinc phosphate tunicle,
Even if thus be the cold-rolled steel sheet containing Si, also can carry out chemical conversion crystallization formed reaction, its result can shape after chemical conversion treatment
Become zinc phosphate tunicle.Should illustrate, above-mentioned Zn layer is not only the zinc layers of the one side being evenly affixed to surface of cold-rolled steel plate, also includes
Be attached to surface of cold-rolled steel plate unevenly and in the discontinuous zinc layers of surface of cold-rolled steel plate local stratification.
But, chemical conversion treatment is the general work carried out according to alkalescence defat → surface adjustment → parkerized order
Skill, in its neutral and alkali degreasing process, oil is constantly mixed into, and therefore in actual production line, degreasing power can be deteriorated.The present inventor etc.
Have been found that and will implement Zn plating and the steel plate only washed impregnated in and assume that the degreaser of this actual production line
In, then cannot fully remove and give the antirust oil etc. of steel plate and occur hydrophobic.And such there occurs that hydrophobic steel plate is in this state
Lower the poorest with the wettability of chemical synthesis treatment liquid, produce surface uneven, it is therefore important that by surface of steel plate after alkalescence defat
Oil point completely removes.From this viewpoint, find by implementing after Zn electroplate and wash, then make it and containing P aqueous solution
Contact, even if thus use assume that the degreaser of actual production line time, it is also possible to the oil removing steel plate divides, and obtains sufficiently
Water-wet rate.
The present invention completes based on above opinion, and its main idea is as follows.
[1] manufacture method of the cold-rolled steel sheet of excellent corrosion resistance after a kind of chemical treatability and application, it is characterised in that
It is 100～5000mg/m to surface of cold-rolled steel plate with the adhesion amount of Zn2Mode implement Zn plating, after washing, make above-mentioned cold rolling
The aqueous solution of scope that steel plate is 0.001～2g/L with the concentration containing P and above-mentioned P, temperature is 30～60 DEG C contacts.
[2] manufacture method of the cold-rolled steel sheet of excellent corrosion resistance after a kind of chemical treatability and application, it is characterised in that
It is 100～1000mg/m to surface of cold-rolled steel plate with the adhesion amount of Zn2Mode implement Zn plating, after washing, make above-mentioned cold rolling
The aqueous solution of scope that steel plate is 0.001～2g/L with the concentration containing P and above-mentioned P, temperature is 30～60 DEG C contacts.
According to the present invention, obtain the cold-rolled steel sheet of excellent corrosion resistance after chemical treatability and application.Even for because of
Surface is formed with the oxide of Si, Mn known as surface densification element and is difficult to shape in the coating process in automobile making
Become the steel plate of chemical conversion treatment tunicle, it is also possible to formed and be sufficiently melted into tunicle, obtain corrosion resistance after good application.
Detailed description of the invention
Generally, cold-rolled steel sheet be by by through cold rolling steel plate in hydrogeneous reducing atmosphere at the model of 700～900 DEG C
Enclose enforcement heat treatment and manufacture.But, by heating in reducing atmosphere, the easily oxidizable unit in steel plate composition can be produced
The phenomenon (following, to be sometimes referred to as surface densification) that element is thickened as oxide at surface of steel plate.As its representational oxide,
There is SiO2, MnO, Si-Mn system complex oxide.The part of these oxides of having surface of steel plate can hinder and utilize chemical synthesis treatment liquid
Steel plate etches and separates out the reaction of chemical conversion crystallization, and the part being formed without chemical conversion crystallization in surface of steel plate generation local is the most so-called
Without covering part, chemical treatability is poor.
On the other hand, if surface of steel plate to be implemented plating Zn, then cover the oxide of surface densification due to Zn, even if so
At the surface of steel plate that oxide exists, also there is the reaction of Zn and chemical synthesis treatment liquid.Even if it addition, it is thick surface cannot to be completely covered
The oxide changed, owing to the Zn around existed reacts with chemical synthesis treatment liquid, so also being able to be readily formed chemical conversion tunicle.
Here, during for common cold-rolled steel sheet, the Fe that element is steel plate composition reacted with chemical synthesis treatment liquid.But,
When surface implements plating Zn, this Zn becomes the element reacted with chemical synthesis treatment liquid.It addition, the phosphate crystal formed is generally
Cold-rolled steel sheet in formed phosphophyllite (Zn2Fe(PO4)2·4H2O).But, in the present invention, major part phosphate crystal is phosphorus
Zinc ore (Zn3(PO4)2·4H2O)。
In order to obtain the effect that this chemical treatability improves, needing to make Zn is 100mg/m at the adhesion amount of surface of steel plate2
Above.As it has been described above, in this technology, give the Zn on surface and form, owing to playing, the effect that chemical conversion treatment crystallizes, so needing
Fully cover surface of steel plate.That is, if less than 100mg/m2Adhesion amount, then Zn cannot fully cover surface of steel plate, sees not
Improvement to chemical conversion treatment.On the other hand, even if Zn attachment quantitative change is many, although no problem from the viewpoint of chemical conversion property, but
The purpose improved merely for the chemical conversion of cold-rolled steel sheet self, owing to the increase of Zn adhesion amount can cause cost to increase, more than institute
It is limited to 5000mg/m2.From the viewpoint of suppression cost increases further, preferably 1000mg/m2Below.
It is contemplated that the method that the various Zn of making are attached to surface of steel plate.But, the present invention most preferably utilizes electric plating method.
This is because the suitable adhesion amount of the Zn having effect in the present invention is 5000mg/m2Hereinafter, such as hot dipping method cannot
Tackle such flash plating to cover.
Common chemical conversion treatment is carried out according to alkalescence defat → surface adjustment → parkerized order.Initially
Alkaline degreasing process in, need to remove when coating the extrusion forming of the antirust oil of steel plate, automobile body outer board and frequently use
Pressurization washing oil etc..But, make to implement the steel plate direct impregnation of thin Zn plating in alkalescence degreaser, may not be by complete for oil
Full removing.When particularly several trolley bodies continuously flowed into being carried out alkalescence defat in the paint line etc. of auto-maker, can send out
Oil generation is mixed into or alkalescence degreaser deterioration etc..Therefore, steel plate occurs hydrophobic in the most fully enforcement defat sometimes
It is passed to follow-up surface adjust in operation.At such hydrophobic part, it is impossible to give surface well and adjust liquid, Jin Er
Follow-up phosphate treated operation occurs phosphate crystal coarsening or there is the part etc. not forming crystallization, to phosphate
Process and produce harmful effect.
Therefore, in the present invention, impregnated in containing in P (phosphorus) aqueous solution after implementing Zn plating.By soaking in containing P aqueous solution
Stain, so that the P of trace is attached to surface, even if also thus being able to fully in the case of the deterioration etc. that alkalescence degreaser occurs
Defat.Its mechanism is inferred as follows: if using general zinc sulfate to bathe as Zn electroplating bath, then sulfate radical is mixed into plating Zn quilt
In film, owing to this sulfate radical improves and the affinity of oil, so defat becomes difficulty.On the other hand, it is believed that if make containing P aqueous solution with
Steel plate contacts, then the sulfate radical existed on surface is rinsed, and then P trace ground is attached to surface, thus reduces affine with oily
Property.Therefore defat is improved.
The P concentration containing P aqueous solution contacted with steel plate is preferably the scope of 0.001～2g/L.This is because if less than
0.001g/L, the attachment that the cleaning performance of sulfate radical is little the most sometimes and P is on surface is insufficient.On the other hand, even if more than 2g/L,
Effect there will not be larger difference.
Temperature containing P aqueous solution is preferably the scope of 30～60 DEG C.If this is because less than 30 DEG C, then sulfate radical is clear
Washing the attachment with P to require time for, continuous annealing apparatus needs long and big equipment.On the other hand, if above 60 DEG C, although effect
Fruit fully, but is additionally required the equipment etc. for heating, is not suitable for economically.
The method making steel plate contact with the aqueous solution containing P is not particularly limited.It is for instance possible to use impregnation method, spraying square
Formula etc..Using spraying pressure, nozzle diameter, the steel plate distance etc. away from nozzle during spray pattern, making aqueous solution and steel as long as meeting
The sufficient condition of plate contact, is also not particularly limited for this condition.
Should illustrate, an object of the present invention is for there is SiO because of the surface of cold-rolled steel plate after annealing2Deng and not
The steel plate of chemical conversion tunicle can be formed, promote the formation of tunicle, therefore, it is adaptable to such as contain the high intensity of the Si of more than 0.5%
Cold-rolled steel sheet etc..But, by being 100～5000mg/m with the adhesion amount of Zn2Mode make Zn be attached to surface of steel plate, i.e.
After the Zn making trace is present in surface of steel plate and can make application, corrosion resistance improves, therefore, and the viewpoint of corrosion resistance after application
Set out, it is also possible to for general cold-rolled steel sheet.Therefore, the present invention is to guarantee chemical conversion treatment with all cold-rolled steel sheets as object
The technology of corrosion resistance after property and application.
Embodiment
The steel making technology using well-established law carries out melting to the steel with A～H that the one-tenth shown in table 1 is grouped into, and casts continuously
Make steel billet, then, after this steel billet is again heated to 1250 DEG C, implement finish rolling end temp be 850 DEG C, coiling temperature be 600
DEG C hot rolling, make the hot rolled plate of thickness of slab 3.0mm.After this hot rolled plate pickling, it is cold-rolled to thickness of slab 1.5mm, as material to be tested.
Use laboratory reduction heating simulator, by this material to be tested in the blanket of nitrogen containing 10vol% hydrogen with 800～850 DEG C
Scope at most implement 2 minutes heat treated, make annealed sheet (cold-rolled steel sheet).
Use containing ZINC SULFATE HEPTAHYDRATE: 1mol/L and utilize sulphuric acid to be adjusted to the aqueous solution of pH2.0, using yttrium oxide
Plate, as anode, is implemented plating to by annealed sheet obtained above (cold-rolled steel sheet), is made Zn be attached to surface.The adhesion amount of Zn leads to
Cross change electric current density and conduction time changes.Sample after enforcement plating is after washing, further at diphosphate sodium
(Na4P2O7·10H2O) aqueous solution impregnates 3 seconds.Solution is by P concentration: 0.5g/L, temperature: on the basis of 50 DEG C, for part
Sample, is evaluated also by change concentration and temperature.Should illustrate, in order to compare, be also prepared for plating is not carried out
The annealed sheet (cold-rolled steel sheet) of the unattached Zn in surface.
It follows that implement chemical conversion treatment shown below to by cold-rolled steel sheet derived above.
First, respectively with normal concentration build the commercially available alkaline degreaser of bath (Nihon Parkerizing (strain) makes,
Fine Cleaner FC-E2001) situation and assume to there occurs that deterioration is diluted to 2 times of situations carrying out building bath of normal concentration
In, cold-rolled steel sheet is impregnated 2 minutes, evaluates the water-wet rate of the steel plate after washing.It is the situation of more than 80% by water-wet rate
It is evaluated as zero, the situation less than 80% is evaluated as △, the situation of less than 50% is evaluated as ×, as the index of defat.
It follows that the degreaser that will be diluted with 2 times for above-mentioned normal concentration has carried out the cold-rolled steel sheet of defat, impregnated in
Surface adjusts in liquid (Nihon Parkerizing (strain) makes, PL-ZTH), in bath temperature: 43 DEG C, process time: the condition of 120 seconds
Under impregnated in phosphate treated liquid (Nihon Parkerizing (strain) make, PALBOND PB-L3080), carry out at chemical conversion
Reason.
SEM is used to observe the surface of cold-rolled steel plate after chemical conversion treatment with 300 times, 10 visual fields of multiplying power, according to generation
Become the presence or absence in region (without covering part) of crystallization and size and the inhomogeneities of crystalline state, carry out by following 5 stages
Evaluate and mark as chemical conversion treatment.
5 points: do not find without covering part, and crystallization is the most uniform.
4 points: though finding that crystallization is the most uneven, but do not find without covering part.
3 points: find small without covering part.
2 points: find bigger without covering part.
1 point: find many places bigger without covering part.
To the steel plate after chemical conversion treatment further to be coated with thickness: 20 μm implement commercially available ED application (Kansai Paint
(strain) makes, GT-10), incision intersects after cut channel in application face to utilize NT cutter (registered trade mark), warm saline (5%NaCl, 50
DEG C) in dipping 10 days.Sample after dipping is covered, with polyester tape, the cut channel portion that intersects, after carrying out strip operation, measures from cutting
The unilateral maximum stripping width of trace.Table 2～5 will be shown in the lump by result from above and condition.
[table 1]
From table 2～5, for steel A, B and C, owing to steel plate composition not containing substantial amounts of Si, even if so the most right
Good chemical treatability is implemented also to obtain in the example (comparative example 1～3) that Zn electroplates in surface, but it is big to peel off width, after application
Corrosion-resistant.
For comparative example 9,10 and example 1～8 (steel A) of the present invention, comparative example 11,12 and example 9～16 (steel B) of the present invention, than
Relatively example 13,14 and example 17～24 (steel C) of the present invention, it is known that if surface being given plating Zn, then after warm saline immersion test
Stripping width reduces, particularly 100mg/m2The level peeling off width under above adhesion amount is low and stable, corrosion-resistant after application
Property excellent.
Steel D～H is due to containing substantial amounts of Si, so in the example (comparative example 4～8) that surface is not implemented plating Zn, changing
Become and crystallization occurs without covering part, particularly in G, H of Si amount more than 1.5%, become almost without forming chemical conversion crystallization
The level that scoring is 1.
When implementing Zn plating, Zn adhesion amount is less than 100mg/m2Example (comparative example 15～24) in, still for nothing occurs
The level of the chemical conversion crystallization of covering part, and insufficient.
It is 100mg/m at Zn adhesion amount2In above example (example 25～64 of the present invention), all obtain not without covering part
Chemical conversion crystallization, chemical treatability is excellent.It addition, it is the lowest and stable to understand the stripping width after warm saline immersion test simultaneously,
It is little affected by the impact of composition of steel.
It addition, the example (comparative example 25) not contacted with the aqueous solution containing P after Zn electroplates is even if or connecing with the aqueous solution containing P
Touch but in the low example (comparative example 26,27) of its P concentration, example (comparative example 28,29) that temperature is low, building bath with normal concentration
Although degreaser in obtain sufficient defat, if but deterioration state on the paint line that simulation is actual is diluted to regulation
The degreaser of 2 times of concentration carries out defat, then occurs hydrophobic after defat.
On the other hand, the example in P concentration and treatment fluid temperature are the scope of the invention (example 65～69,70 of the present invention)
In, even dilution degreaser also obtains sufficient defat.
Industrial applicability
Even containing the high tensile strength cold-rolled steel sheet of the intensified elements such as a large amount of Si, the chemical treatability before its application is the best
Good, and the corrosion resistance after application is also good, is therefore best suitable for for such as body of a motor car purposes.
Claims (2)
1. the manufacture method of the cold-rolled steel sheet of excellent corrosion resistance after a chemical treatability and application, it is characterised in that to containing
The surface of cold-rolled steel plate having the Si of more than 0.5 mass % is 100～5000mg/m with the adhesion amount of Zn2Mode implement Zn electricity
Plating, the model that after washing, to make described cold-rolled steel sheet and concentration containing P and described P be 0.001～2g/L, temperature is 30～60 DEG C
The aqueous solution contact enclosed.
2. the manufacture method of the cold-rolled steel sheet of excellent corrosion resistance after a chemical treatability and application, it is characterised in that to containing
The surface of cold-rolled steel plate having the Si of more than 0.5 mass % is 100～1000mg/m with the adhesion amount of Zn2Mode implement Zn electricity
Plating, the model that after washing, to make described cold-rolled steel sheet and concentration containing P and described P be 0.001～2g/L, temperature is 30～60 DEG C
The aqueous solution contact enclosed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011285173A JP5853683B2 (en) | 2011-01-25 | 2011-12-27 | Method for producing cold-rolled steel sheet with excellent chemical conversion and post-coating corrosion resistance |
| JP2011-285173 | 2011-12-27 | ||
| PCT/JP2012/063102 WO2013099316A1 (en) | 2011-12-27 | 2012-05-16 | Method for producing cold-rolled steel sheet having excellent chemical conversion properties and excellent corrosion resistance after coating |
Publications (2)
| Publication Number | Publication Date |
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| CN104024476A CN104024476A (en) | 2014-09-03 |
| CN104024476B true CN104024476B (en) | 2016-10-26 |
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| CN201280064512.3A Active CN104024476B (en) | 2011-12-27 | 2012-05-16 | The manufacture method of the cold-rolled steel sheet of excellent corrosion resistance after chemical treatability and application |
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| Country | Link |
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| JP (1) | JP5853683B2 (en) |
| KR (1) | KR101639926B1 (en) |
| CN (1) | CN104024476B (en) |
| AR (1) | AR087284A1 (en) |
| TW (1) | TWI457465B (en) |
| WO (1) | WO2013099316A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014013623A1 (en) * | 2012-07-18 | 2014-01-23 | Ｊｆｅスチール株式会社 | Method for producing steel sheet having excellent chemical conversion properties and galling resistance |
| JP6079079B2 (en) * | 2012-09-18 | 2017-02-15 | Ｊｆｅスチール株式会社 | Cold rolled steel sheet and method for producing the same |
| JP5971155B2 (en) * | 2012-10-11 | 2016-08-17 | Ｊｆｅスチール株式会社 | Method for producing high-strength hot-dip galvanized steel sheet and high-strength hot-dip galvanized steel sheet |
| JP5637230B2 (en) * | 2013-02-28 | 2014-12-10 | Ｊｆｅスチール株式会社 | Manufacturing method of high-strength cold-rolled steel sheet |
| JP5817770B2 (en) * | 2013-03-26 | 2015-11-18 | Ｊｆｅスチール株式会社 | Method for producing high-strength cold-rolled steel sheet with excellent chemical conversion properties and corrosion resistance after coating, and good sliding properties |
| JP5928437B2 (en) * | 2013-11-05 | 2016-06-01 | Ｊｆｅスチール株式会社 | Method for producing high-strength cold-rolled steel sheet with excellent chemical conversion and post-coating corrosion resistance |
| CN114231822B (en) * | 2021-10-29 | 2022-11-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for improving surface coatability of cold-rolled automobile plate |
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| CN1099432A (en) * | 1993-06-29 | 1995-03-01 | 日本钢管株式会社 | Zinc coated steel sheet and method therefor |
| CN101358366A (en) * | 2008-09-02 | 2009-02-04 | 厦门大学 | Method for preparing high interfacial strength nickel-zinc plating steel belt |
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| JPS56116888A (en) * | 1980-02-21 | 1981-09-12 | Nippon Steel Corp | Cold rolled steel plate with excellent suitability for phosphate treatment and electrodeposition painting property |
| JPH0723545B2 (en) * | 1987-07-21 | 1995-03-15 | 川崎製鉄株式会社 | Method for producing Zn-based electroplated steel sheet having excellent chemical conversion treatability |
| JPH04276060A (en) | 1991-02-28 | 1992-10-01 | Sumitomo Metal Ind Ltd | Cold rolled steel sheet and its manufacture |
| JP3269121B2 (en) * | 1991-09-30 | 2002-03-25 | 日本鋼管株式会社 | High strength cold rolled steel sheet for deep drawing and method for producing the same |
| JPH067442A (en) * | 1992-06-23 | 1994-01-18 | Kazumasa Takemori | Blade-like needle |
| JP2003226920A (en) | 2002-02-06 | 2003-08-15 | Kobe Steel Ltd | METHOD OF PRODUCING HIGH Si-CONTAINING HIGH TENSILE STRENGTH STEEL SHEET HAVING EXCELLENT PHOSPHATE FILM TREATABILITY |
| JP4319559B2 (en) | 2003-04-10 | 2009-08-26 | 株式会社神戸製鋼所 | High-strength cold-rolled steel plate with excellent chemical conversion properties |
| JP3934604B2 (en) | 2003-12-25 | 2007-06-20 | 株式会社神戸製鋼所 | High strength cold-rolled steel sheet with excellent coating adhesion |
| JP4698971B2 (en) | 2004-03-31 | 2011-06-08 | 株式会社神戸製鋼所 | High-strength cold-rolled steel sheet with excellent coating film adhesion and workability |
| JP3889768B2 (en) | 2005-03-31 | 2007-03-07 | 株式会社神戸製鋼所 | High-strength cold-rolled steel sheets and automotive steel parts with excellent coating film adhesion and ductility |
| JP2006299351A (en) | 2005-04-21 | 2006-11-02 | Jfe Steel Kk | Steel sheet having excellent galling resistance and chemical conversion treatability |
| JP4655782B2 (en) | 2005-06-30 | 2011-03-23 | Ｊｆｅスチール株式会社 | Method for producing ultra-high-strength cold-rolled steel sheet having a tensile strength of 780 MPa or more that has high ductility and excellent chemical conversion properties |
| CN101519775B (en) * | 2008-02-28 | 2011-01-19 | 宝山钢铁股份有限公司 | Environmental-friendly chrome-free phosphating electrogalvanized sealed steel sheet and manufacturing method thereof |
| JP7023545B2 (en) | 2020-12-11 | 2022-02-22 | 株式会社サンセイアールアンドディ | Pachinko machine |
-
2011
- 2011-12-27 JP JP2011285173A patent/JP5853683B2/en active Active
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2012
- 2012-05-16 CN CN201280064512.3A patent/CN104024476B/en active Active
- 2012-05-16 KR KR1020147019016A patent/KR101639926B1/en active IP Right Grant
- 2012-05-16 WO PCT/JP2012/063102 patent/WO2013099316A1/en active Application Filing
- 2012-05-21 TW TW101117953A patent/TWI457465B/en not_active IP Right Cessation
- 2012-07-23 AR ARP120102665 patent/AR087284A1/en active IP Right Grant
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| CN1099432A (en) * | 1993-06-29 | 1995-03-01 | 日本钢管株式会社 | Zinc coated steel sheet and method therefor |
| CN101358366A (en) * | 2008-09-02 | 2009-02-04 | 厦门大学 | Method for preparing high interfacial strength nickel-zinc plating steel belt |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013099316A1 (en) | 2013-07-04 |
| CN104024476A (en) | 2014-09-03 |
| KR20140106676A (en) | 2014-09-03 |
| JP2012167362A (en) | 2012-09-06 |
| JP5853683B2 (en) | 2016-02-09 |
| TWI457465B (en) | 2014-10-21 |
| AR087284A1 (en) | 2014-03-12 |
| KR101639926B1 (en) | 2016-07-14 |
| TW201326459A (en) | 2013-07-01 |
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