CN104024476A - Method for producing cold-rolled steel sheet having excellent chemical conversion properties and excellent corrosion resistance after coating - Google Patents
Method for producing cold-rolled steel sheet having excellent chemical conversion properties and excellent corrosion resistance after coating Download PDFInfo
- Publication number
- CN104024476A CN104024476A CN201280064512.3A CN201280064512A CN104024476A CN 104024476 A CN104024476 A CN 104024476A CN 201280064512 A CN201280064512 A CN 201280064512A CN 104024476 A CN104024476 A CN 104024476A
- Authority
- CN
- China
- Prior art keywords
- steel plate
- rolled steel
- cold
- steel sheet
- corrosion resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Electrolytic Zn plating is carried out on the surface of a cold-rolled steel sheet so that the adhesion amount of Zn is 100-5,000 mg/m<2>, and the resulting cold-rolled steel sheet is washed with water and then brought into contact with an aqueous solution containing P. In this connection, the P concentration of the aqueous solution containing P is 0.001-2 g/L and the temperature of the aqueous solution containing P is within the range of 30-60 DEG C.
Description
Technical field
The present invention relates to a kind of manufacture method that changes into fully the good cold-rolled steel sheet of erosion resistance after tunicle and application that forms.
Background technology
In recent years, as the countermeasure of Global warming, in order to reduce the CO of automobile
2quantity discharged, the lightness of how to carry out car body has become problem for auto-maker.For the lightness of car body, the thin-walled property of the steel plate that uses the most effectively, if but only reduce thickness of slab under the identical state of the intensity of steel plate, the rigidity of steel plate reduces, the security of the passenger in the time of now cannot guaranteeing to collide etc. in situation.Therefore, adopt high tensile steel plate to improve constantly as the trend of car body materials, this high tensile steel plate can reduce thickness of slab and utilize the high strength of steel to make up the rigidity reducing because reducing thickness of slab, recently, by the high tensile steel plate of tensile strength 1180MPa level, the trend for vehicle body purposes also comes to life.
In order to make steel plate high strength, effectively add the method that the alloying elements such as Si, Mn carry out solution strengthening, make the method for crystal grain miniaturization, add the method that the precipitate forming elements such as Nb, Ti, V carry out precipitation strength, generate that martensite equates the phase-change organization of hard and the method strengthened etc.
Conventionally, by adding high strength that alloying element carries out owing to can causing the reduction of ductility on the other hand, so there is the shortcoming of the extrusion forming that is difficult to make component shape.But in solution strengthening, it is less that Si and other elements compare the impact that ductility reduces, and is effective element so belong to when guaranteeing ductility and realizing high strength.Therefore, can say for the steel plate of taking into account processibility and high strength, the interpolation of Si is almost essential.
Yet, the equilibrium oxygen partial pres-sure of the oxide compound of Si is very low, easily oxidized in reducing atmosphere in the continuous annealing furnace using in the manufacture of general cold-rolled steel sheet, if therefore the steel plate that contains Si is passed into continuous annealing furnace, Si forms SiO in the selected oxidation of surface of steel plate
2.If such surface is formed with to SiO
2steel plate be supplied to the processing that changes into before application, SiO
2meeting obstruction chemical synthesis treatment liquid reacts with steel plate, therefore exists and does not form the uncovered part of what is called that changes into crystallization.Like this just there is rust changing into the washing stage that exists after processing the steel plate without cover part sometimes changing into after processing, even if supposition reaches the degree that produces rust, the erosion resistance of the steel plate after electrodeposition coating is non-constant also.Therefore it is very difficult the high strength cold rolled steel plate that contains Si being used in to vehicle body purposes.
Method as improving the chemical treatability of such high strength cold rolled steel plate that contains Si has proposed a lot of methods all the time.For example, in patent documentation 1, having proposed surface is formed with the cold-rolled steel sheet that atomic ratio [Si/Mn] is the oxide compound below 1 and as its manufacture method, the intrinsic standoff ratio of hydrogen and moisture in (Si/Mn) ratio of steel plate composition, annealing temperature, atmosphere is stipulated as parameter.But, in the method, along with the Si amount of steel plate composition increases, need to reduce annealing temperature, while therefore needing high temperature annealing in order to obtain desirable intensity, stretching, the essential moisture ratio that improves atmosphere.But forming Fe at surface of steel plate is on the contrary oxide compound, so cannot become product.That is be, for the technology as the steel plate of the Si that contains 1.0% left and right of the main flow of high tensile steel plate cannot be applied at present.
In patent documentation 2, proposed the steel plate of Si:0.05～2% and [Si]/[Mn]≤0.4 to stipulate the high strength cold rolled steel plate of the surface of steel plate fraction of coverage of the oxide compound that the size of Si-Mn composite oxides and the number of per unit area of surface of steel plate and the Si of take are main body.
In patent documentation 3, proposed the steel plate of Si:0.1～1% and [Si]/[Mn]≤0.4 to stipulate the high strength cold rolled steel plate of (Mn/Si) ratio, size and the number of per unit area of Mn-Si composite oxides and the surface of steel plate fraction of coverage of the oxide compound that the Si of take is main body of surface of steel plate.
In patent documentation 4, proposed the steel plate of Si:0.1～2% and [Si]/[Mn]≤0.4 to stipulate the high strength cold rolled steel plate of (Mn/Si) ratio, size and the number of per unit area of Mn-Si composite oxides and the surface of steel plate fraction of coverage of the oxide compound that the Si of take is main body of surface of steel plate.
The technology of patent documentation 2～4 can be applied to contain at most the steel plate of 2% Si, and as the example of its manufacture method, the dew point during by the acid washing conditions after hot rolling, continuous annealing suppresses for below-40 ℃.But, need to, for meeting the steel plate of specific Si/Mn ratio, have the little such shortcoming of degree of freedom of steel plate composition.In addition, if consider the dew point change of real production line, it is very rambunctious below that the dew point while making continuous annealing is-40 ℃, is therefore the technology that is not suitable for volume production.
The steel plate that has proposed and [Si]/[Mn] >=0.4 above to Si:0.4% in patent documentation 5 has been stipulated the cold-rolled steel sheet of surface coverage and the manufacture method of the rear enforcement of annealing pickling of the Si base oxide of surface of steel plate.
In patent documentation 6, proposed containing the steel plate of Si more than 0.5 quality %, after annealing with 2.0g/m
2the technology of above grinding surface of steel plate.
In patent documentation 7, proposed after the steel plate annealing that contains 0.5～2.0% Si, in the acidic solution of 10～100 ℃ of pH0～4, temperature, process 5～150 seconds, and the technology of carrying out processing for 2～50 seconds in the basic solution of 10～100 ℃ of pH10～14, temperature.
The technology of patent documentation 5～7 is the technology of removing the oxide skin forming on surface after annealing, in the example of patent documentation 5, in order to remove Si base oxide, need to use the acid of high density, now, can promote on the contrary the formation of the passivation tunicle of base steel, therefore have the shortcoming of the effect that may not be improved chemical treatability.In patent documentation 6,7, the region of grinding or the region that acidic solution processing → basic solution is processed need to be set in production line, cause hugeization of equipment, the increase of cost, not-so-practical.
In patent documentation 8, having proposed by making surface of steel plate have adhesion amount is 10～2000mg/m
2plating 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 mainly carried out in order to improve anti-stickness, for chemical treatability, even the Zn adhesion amount of trace also can form micella (microcell) between the facies posterior hepatis of Zn and steel plate exposed division, shows that surface changes into processing reaction and enlivens.But in the situations such as the Si of steel plate concentration height, the major part of surface of steel plate is by SiO
2oxide compound covers, and when this part is steel plate exposed division, is difficult to one and is shaped as micella.In addition, use sulfuric acid bath as plating bath, when the same terms proposing in by embodiment forms plating Zn tunicle, find because changing into the fully degreasing of kind of the alkaline degreasing fluid before processing.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 4-276060 communique
Patent documentation 2: No. 3934604 communique of Japanese Patent
Patent documentation 3: TOHKEMY 2005-290440 communique
Patent documentation 4: No. 3889768 communique of Japanese Patent
Patent documentation 5: TOHKEMY 2004-323969 communique
Patent documentation 6: TOHKEMY 2003-226920 communique
Patent documentation 7: TOHKEMY 2007-009269 communique
Patent documentation 8: TOHKEMY 2006-299351 communique
Summary of the invention
Like this, added for the cold-rolled steel sheet of Si for realizing high-intensity object under the prerequisite for not making ductility reduce, the technology that meets chemical treatability still can not say fully, and present situation is high tensile steel plate to be applied to car body have obstruction.
The object of the invention is to, for containing the steel plate of Si as strengthening element, provide the manufacture method of the cold-rolled steel sheet of excellent corrosion resistance after a kind of chemical treatability and application.
The inventor etc. are conceived to form SiO at surface of steel plate
2time, because the Fe as steel plate principal constituent in institute's forming section does not dissolve, so do not change into the situation that crystallization forms reaction.In addition, the consideration such as the inventor makes the solubilizing reaction of surface of steel plate occur can be associated with to change into crystallization to form reaction someway by adopting.In addition, the inventor waits and has also considered that Metal Zn is by forming as the zinc phosphate tunicle that changes into tunicle with reacting of chemical synthesis treatment liquid.The result of studying, the inventor etc. have confirmed by surface of cold-rolled steel plate being given only for forming the thin Zn layer of the required q.s of zinc phosphate tunicle, even thereby the cold-rolled steel sheet for containing Si, also can change into crystallization and form reaction, its result can form zinc phosphate tunicle after changing into processing.Should illustrate, above-mentioned Zn layer is not only the zinc layer of the one side that is evenly attached to surface of cold-rolled steel plate, also comprises being attached to unevenly surface of cold-rolled steel plate and at the discontinuous zinc layer of the local stratification of surface of cold-rolled steel plate.
Yet changing into processing is that in its neutral and alkali degreasing process, oil is constantly sneaked into according to alkaline degreasing → surface adjustment → parkerized general technology in sequence, therefore in actual production line, degreasing power can variation.If the discoveries such as the inventor are by having implemented, Zn electroplates and the steel plate that only carried out washing impregnated in the degreasing fluid of having supposed this actual production line, cannot fully remove to give the antirust wet goods of steel plate and occur hydrophobic.And such generation hydrophobic steel plate also poor with the wettability of chemical synthesis treatment liquid under this state, produce surface uneven, therefore importantly after alkaline degreasing, the oil content of surface of steel plate is removed completely.From this viewpoint, find by after electroplating and wash at enforcement Zn, then make it and contact containing the P aqueous solution, thereby even when the degreasing fluid of actual production line has been supposed in use, also can remove the oil content of steel plate, obtain sufficient water-wet rate.
The present invention completes based on above opinion, and its main idea is as follows.
[1] manufacture method for the cold-rolled steel sheet of excellent corrosion resistance after chemical treatability and application, is characterized in that, it is 100～5000mg/m that surface of cold-rolled steel plate be take to the adhesion amount of Zn
2mode implement Zn and electroplate, after washing, making above-mentioned cold-rolled steel sheet and the concentration that contains P and above-mentioned P is that 0.001～2g/L, temperature are that the aqueous solution of the scope of 30～60 ℃ contacts.
[2] manufacture method for the cold-rolled steel sheet of excellent corrosion resistance after chemical treatability and application, is characterized in that, it is 100～1000mg/m that surface of cold-rolled steel plate be take to the adhesion amount of Zn
2mode implement Zn and electroplate, after washing, making above-mentioned cold-rolled steel sheet and the concentration that contains P and above-mentioned P is that 0.001～2g/L, temperature are that the aqueous solution of the scope of 30～60 ℃ contacts.
According to the present invention, obtain the cold-rolled steel sheet of excellent corrosion resistance after chemical treatability and application.Even if be difficult in the coating process for the oxide compound because be formed with the Si, the Mn that are known as surface densification element on surface in automobile making form and change into the steel plate of processing tunicle, also can form and change into fully tunicle, obtain erosion resistance after good application.
Embodiment
Conventionally, cold-rolled steel sheet is to manufacture by the steel plate through cold rolling is implemented to thermal treatment the scope of 700～900 ℃ in hydrogeneous reducing atmosphere.But, by heating in reducing atmosphere, can produce easily oxidizable element in steel plate composition at surface of steel plate the phenomenon (following, to be sometimes referred to as surface densification) as oxide compound multiviscosisty.As its representational oxide compound, there is SiO
2, MnO, Si-Mn system complex oxide.Surface of steel plate exists the part of these oxide compounds to hinder and utilizes chemical synthesis treatment liquid by steel plate etching and separate out the reaction that changes into crystallization, produces that local not form the part that changes into crystallization be so-called without cover part at surface of steel plate, and chemical treatability is poor.
On the other hand, if surface of steel plate is implemented to plating Zn, due to the oxide compound of Zn covering surfaces multiviscosisty, so even if reacting of Zn and chemical synthesis treatment liquid also occurs the surface of steel plate existing at oxide compound.In addition, though the oxide compound of covering surfaces multiviscosisty completely, because the Zn and the chemical synthesis treatment liquid that around exist react, so also can easily form and change into tunicle.
Here, during for common cold-rolled steel sheet, the element reacting with chemical synthesis treatment liquid is the Fe of steel plate composition.But when effects on surface has been implemented plating Zn, this Zn becomes the element reacting with chemical synthesis treatment liquid.In addition, the phosphate crystal of formation forms phosphophyllite (Zn in common cold-rolled steel sheet
2fe (PO
4)
24H
2o).But in the present invention, most of phosphate crystal is hopeite (Zn
3(PO
4)
24H
2o).
The effect of improving in order to obtain this chemical treatability, need to make Zn is 100mg/m at the adhesion amount of surface of steel plate
2above.As mentioned above, in this technology, give at surperficial Zn and form owing to playing the effect of processing crystallization that changes into, so need fully to cover surface of steel plate.That is, be less than if 100mg/m
2adhesion amount, Zn cannot fully cover surface of steel plate, can't see the improvement that changes into processing.On the other hand, many even if Zn adheres to quantitative change, although from the viewpoint of changing into property, consider no problem, only for the object that changes into property improvement of cold-rolled steel sheet self, because the increase of Zn adhesion amount can cause cost to increase, so on be limited to 5000mg/m
2.The viewpoint increasing from further inhibition cost, is preferably 1000mg/m
2below.
Can consider that the various Zn of making are attached to the method for surface of steel plate.But, in the present invention, most preferably utilize electric plating method.This is because the suitable adhesion amount of the Zn having effect is in the present invention 5000mg/m
2below, for example hot dipping method cannot be tackled such flash plating and covered.
Commonly change into that to process be according to alkaline degreasing → surface adjustment → in sequence parkerized.In initial alkaline degreasing process, need to remove and coat the slushing oil of steel plate, the frequent pressurization washing oil using the etc. during extrusion forming of automobile body outer board.Yet, having made to implement the steel plate direct impregnation of thin Zn plating in alkaline degreasing fluid, oil may not be removed completely.While particularly several trolley bodies that continuously flow into being carried out to alkaline degreasing in paint line of auto-maker etc., can occur that oil is sneaked into or alkaline degreasing fluid deteriorated etc.Therefore, steel plate occurs fully not implementing degreasing to be passed in follow-up surface adjustment operation under hydrophobic state sometimes.At such hydrophobic part, cannot give well surface and adjust liquid, and then phosphate crystal coarsening occur in follow-up phosphatizing operation or have the part etc. that does not form crystallization, phosphatizing is produced to detrimentally affect.
Therefore, in the present invention, implement after Zn electroplates to impregnated in containing in P (phosphorus) aqueous solution.By flooding containing in the P aqueous solution, thereby make micro-P be attached to surface, even thus in the situation that there is the also fully degreasing such as deteriorated grade of alkaline degreasing fluid.To its mechanism, be inferred as follows: if use general zinc sulfate to bathe as Zn plating bath, sulfate radical is sneaked in plating Zn tunicle, because this sulfate radical improves and oily affinity, so degreasing change is difficult.On the other hand, think that the sulfate radical existing on surface is rinsed if make contact with steel plate containing the P aqueous solution, and then P is attached to surface micro-ly, thus reduction and oily affinity.Therefore improve degreasing.
The P concentration containing the P aqueous solution contacting with steel plate is preferably the scope of 0.001～2g/L.This is because if be less than 0.001g/L, and the cleaning performance of sulfate radical is little and P is insufficient in adhering to of surface sometimes.On the other hand, even if be greater than 2g/L, effect does not have larger difference yet.
Temperature containing the P aqueous solution is preferably the scope of 30～60 ℃.This is because if lower than 30 ℃, and adhering to of the cleaning of sulfate radical and P needs the time, and continuous annealing apparatus need to be grown and large equipment.On the other hand, if higher than 60 ℃, although effect is abundant, additionally need equipment for heating etc., be not suitable for economically.
Steel plate is not particularly limited with the method contacting containing the P aqueous solution.For example, can adopt impregnation method, spray pattern etc.Spraying pressure while adopting spray pattern, nozzle diameter, steel plate apart from the distance of nozzle etc., as long as meet the sufficient condition that the aqueous solution is contacted with steel plate, are also not particularly limited for this condition.
Should illustrate, one of object of the present invention is to have SiO for the surface of cold-rolled steel plate because of after annealing
2deng and can not form the steel plate that changes into tunicle, promote the formation of tunicle, therefore, be applicable to such as the high strength cold rolled steel plate that contains more than 0.5% Si etc.Yet, by take the adhesion amount of Zn, be 100～5000mg/m
2mode make Zn be attached to surface of steel plate, that is, make micro-Zn be present in surface of steel plate and can make erosion resistance after application improve, therefore, the viewpoint of erosion resistance from application, also can be for general cold-rolled steel sheet.Therefore, the present invention is the technology of guaranteeing erosion resistance after chemical treatability and application of take that all cold-rolled steel sheets are object.
Embodiment
The steel making technology that adopts well-established law carries out melting to the steel of the A～H that has the one-tenth shown in table 1 and be grouped into, steel billet is made in continuous casting, then, this steel billet is reheated after 1250 ℃, implement finish rolling end temp and be 850 ℃, coiling temperature and be the hot rolling of 600 ℃, make the hot-rolled sheet of thickness of slab 3.0mm.By after this hot-rolled sheet pickling, be cold-rolled to thickness of slab 1.5mm, as supplying examination material.Use the reduction heating simulator in laboratory, this confession examination material scope with 800～850 ℃ in the nitrogen atmosphere that contains 10vol% hydrogen is implemented at most to 2 minutes heat treated, make annealed sheet (cold-rolled steel sheet).
Use contains ZINC SULFATE HEPTAHYDRATE: 1mol/L and utilize sulfuric acid to be adjusted into the aqueous solution of pH2.0, and use iridium oxide plate as anode, to being implemented to electroplate by annealed sheet obtained above (cold-rolled steel sheet), make Zn be attached to surface.The adhesion amount of Zn is by changing current density and changing conduction time.Sample after enforcement is electroplated is after washing, further at diphosphate sodium (Na
4p
2o
710H
2o) in the aqueous solution, flood 3 seconds.Solution is to take P concentration: 0.5g/L, temperature: 50 ℃ is benchmark, for sample segment, also by changing concentration and temperature, evaluates.Should illustrate, in order to compare, the annealed sheet (cold-rolled steel sheet) of Zn is not adhered on the surface of also having prepared not implement to electroplate.
Next, the cold-rolled steel sheet by obtaining is above implemented to the shown below processing that changes into.
First, with normality, building commercially available alkaline degreasing fluid (Nihon Parkerizing (strain) system of bathing respectively, Fine Cleaner FC-E2001) deteriorated dilution has occurred for situation and hypothesis is that 2 times of normality are built in the situation of bath, cold-rolled steel sheet is flooded 2 minutes, evaluate the water-wet rate of the steel plate after washing.By water-wet rate, being that more than 80% average evaluation is zero, is △ by the average evaluation of less than 80%, by the average evaluation below 50%, be *, as the index of degreasing.
Next, the cold-rolled steel sheet that the degreasing fluid of 2 times with dilution is afore mentioned rules concentration has been carried out to degreasing, impregnated in surface and adjust liquid (Nihon Parkerizing (strain) system, PL-ZTH) in, bathing temperature: 43 ℃, treatment time: under the condition of 120 seconds, impregnated in phosphatizing liquid (Nihon Parkerizing (strain) system, PALBOND PB-L3080), in, change into processing.
Use SEM to observe and change into the surface of cold-rolled steel plate after processing with 300 times of multiplying powers, 10 visual fields, according to do not generate change into crystallization region (without cover part) have or not the ununiformity with size and crystalline state, by following 5 stages, evaluates as changing into process and marks.
5 minutes: do not find without cover part, and crystallization is also even.
4 minutes: though find that crystallization is slightly inhomogeneous, do not find without cover part.
3 minutes: find small in cover part.
2 minutes: find larger without cover part.
1 minute: find many places larger without cover part.
To changing into steel plate after processing further to be coated with thickness: 20 μ m implement commercially available ED application (Kansai Paint (strain) system, GT-10), utilize NT cutter (registered trademark) to intersect after cut channel in the incision of application face, in warm saline (5%NaCl, 50 ℃), dipping is 10 days.Sample after dipping is covered to the cut channel portion of intersecting with polyester tape, carry out after strip operation, measure and peel off width from the one-sided maximum of cut channel.Result by obtaining above and condition are shown in to table 2～5 in the lump.
[table 1]
From table 2～5, for steel A, B and C, owing to not containing a large amount of Si in steel plate composition, so even also obtain good chemical treatability in the example (comparative example 1～3) that effects on surface enforcement Zn does not electroplate, but it is large to peel off width, corrosion-resistant after application.
For comparative example 9,10 and the inventive example 1～8 (steel A), comparative example 11,12 and the inventive example 9～16 (steel B), comparative example 13,14 and the inventive example 17～24 (steel C), if giving, known effects on surface electroplates Zn, the width of peeling off after warm saline dip test reduces, particularly 100mg/m
2the level of peeling off width under above adhesion amount is low and stable, excellent corrosion resistance after application.
Steel D～H is owing to containing a large amount of Si, so implement in the example (comparative example 4～8) of plating Zn at effects on surface not, change in crystallization and occur without cover part, particularly at Si, measure in more than 1.5% G, H, the level that the scoring that becoming does not almost have formation to change into crystallization is 1.
When implementing Zn plating, Zn adhesion amount is less than 100mg/m
2example (comparative example 15～24) in, still for occurring the level that changes into crystallization without cover part, and insufficient.
At Zn adhesion amount, be 100mg/m
2in above example (inventive example 25～64), all obtain not without the crystallization that changes into of cover part, chemical treatability is excellent.In addition, simultaneously after known warm saline dip test to peel off width also low and stable, be subject to hardly the impact of composition of steel.
In addition, after Zn electroplates not with the example (comparative example 25) contact containing the P aqueous solution even or with contain that the P aqueous solution contacts but in the low example (comparative example 26,27) of its P concentration, example (comparative example 28,29) that temperature is low, although obtain sufficient degreasing in the degreasing fluid of building bath with normality, if but carried out degreasing in the degreasing fluid of 2 times that deterioration state dilution on the actual paint line of simulation is normality, after degreasing, would occur hydrophobic.
On the other hand, in P concentration and treatment solution temperature, be in the example (inventive example 65～69,70) in the scope of the invention, even dilution degreasing fluid also obtains sufficient degreasing.
Utilizability in industry
Even the high tensile strength cold-rolled steel sheet that contains the strengthening elements such as a large amount of Si, the chemical treatability before its application is also good, and the erosion resistance after application is also good, is therefore suitable for most for example body of a motor car purposes.
Claims (2)
1. a manufacture method for the cold-rolled steel sheet of excellent corrosion resistance after chemical treatability and application, is characterized in that, it is 100～5000mg/m that surface of cold-rolled steel plate be take to the adhesion amount of Zn
2mode implement Zn and electroplate, after washing, making described cold-rolled steel sheet and the concentration that contains P and described P is that 0.001～2g/L, temperature are that the aqueous solution of the scope of 30～60 ℃ contacts.
2. a manufacture method for the cold-rolled steel sheet of excellent corrosion resistance after chemical treatability and application, is characterized in that, it is 100～1000mg/m that surface of cold-rolled steel plate be take to the adhesion amount of Zn
2mode implement Zn and electroplate, after washing, making described cold-rolled steel sheet and the concentration that contains P and described P is that 0.001～2g/L, temperature are that the aqueous solution of the scope of 30～60 ℃ contacts.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-285173 | 2011-12-27 | ||
| 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 |
| 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 |
|---|---|
| CN104024476A true CN104024476A (en) | 2014-09-03 |
| CN104024476B CN104024476B (en) | 2016-10-26 |
Family
ID=48699402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP5853683B2 (en) |
| KR (1) | KR101639926B1 (en) |
| CN (1) | CN104024476B (en) |
| AR (1) | AR087284A1 (en) |
| TW (1) | TWI457465B (en) |
| WO (1) | WO2013099316A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114231822A (en) * | 2021-10-29 | 2022-03-25 | 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 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150014517A (en) * | 2012-07-18 | 2015-02-06 | 제이에프이 스틸 가부시키가이샤 | 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPS6425988A (en) * | 1987-07-21 | 1989-01-27 | Kawasaki Steel Co | Production of zn alloy electroplated steel sheet having superior chemical treatability |
| JPH05311326A (en) * | 1991-09-30 | 1993-11-22 | Nkk Corp | High strength cold rolled steel plate for deep drawing and production thereof |
| JPH067442A (en) * | 1992-06-23 | 1994-01-18 | Kazumasa Takemori | Blade-like needle |
| 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 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04276060A (en) | 1991-02-28 | 1992-10-01 | Sumitomo Metal Ind Ltd | Cold rolled steel sheet and its manufacture |
| 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
-
2012
- 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
- 2012-05-16 CN CN201280064512.3A patent/CN104024476B/en active Active
- 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
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPS6425988A (en) * | 1987-07-21 | 1989-01-27 | Kawasaki Steel Co | Production of zn alloy electroplated steel sheet having superior chemical treatability |
| JPH05311326A (en) * | 1991-09-30 | 1993-11-22 | Nkk Corp | High strength cold rolled steel plate for deep drawing and production thereof |
| JPH067442A (en) * | 1992-06-23 | 1994-01-18 | Kazumasa Takemori | Blade-like needle |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114231822A (en) * | 2021-10-29 | 2022-03-25 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| AR087284A1 (en) | 2014-03-12 |
| TW201326459A (en) | 2013-07-01 |
| KR101639926B1 (en) | 2016-07-14 |
| JP2012167362A (en) | 2012-09-06 |
| JP5853683B2 (en) | 2016-02-09 |
| TWI457465B (en) | 2014-10-21 |
| WO2013099316A1 (en) | 2013-07-04 |
| KR20140106676A (en) | 2014-09-03 |
| CN104024476B (en) | 2016-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104024476A (en) | Method for producing cold-rolled steel sheet having excellent chemical conversion properties and excellent corrosion resistance after coating | |
| EP1439240B2 (en) | Method for hot-press forming a plated steel product | |
| JP5650222B2 (en) | Method of manufacturing a steel member with a metal coating that provides protection against corrosion, and steel member | |
| CN110777319B (en) | Plating solution for highly corrosion-resistant highly formable hot-formed steel, hot-formed steel sheet, hot-dip plating production process, hot-stamped part, and application | |
| CN104551572A (en) | Production process of rolled electronic copper foil | |
| EP2963157B1 (en) | Process for producing high-strength cold-rolled steel sheet | |
| JP5817770B2 (en) | Method for producing high-strength cold-rolled steel sheet with excellent chemical conversion properties and corrosion resistance after coating, and good sliding properties | |
| CN104988456B (en) | A kind of production method of the very thin steel band of the double composite deposites of Cu Sn/Sn Au | |
| JP2000073183A (en) | Zinc system plated steel sheet excellent in formability and weldability and its production | |
| JP2006299351A (en) | Steel sheet having excellent galling resistance and chemical conversion treatability | |
| JP2006131971A (en) | Cold rolled steel sheet having excellent phosphate treatability and salt warm water resistance after coating | |
| JP2007138216A (en) | Cold-rolled steel sheet superior in chemical conversion treatment property and galling resistance, and manufacturing method therefor | |
| JP5928437B2 (en) | Method for producing high-strength cold-rolled steel sheet with excellent chemical conversion and post-coating corrosion resistance | |
| TWI279452B (en) | A Zn-plated steel sheet with an inorganic and organic composite plated layer excellent in corrosion resistance | |
| JP2007138213A (en) | Cold-rolled steel sheet superior in chemical conversion treatment property and galling resistance, and manufacturing method therefor | |
| CN104364410A (en) | High-strength steel sheet, high-strength hot-dip zinc-coated steel sheet, and methods for producing said steel sheets | |
| JP3778791B2 (en) | Pre-painting method and molded product | |
| JPH04314874A (en) | Steel sheet or steel material plated with zinc containing nickel and chromium as base for coating and production thereof | |
| JPS60138052A (en) | Cold rolled steel sheet having superior corrosion resistance after coating | |
| JPS6043498A (en) | Galvanized steel sheet having high corrosion resistance and its production | |
| JPH0718464A (en) | Production of highly corrosion-resistant electrogalvanized steel sheet excellent in chemical convertibility | |
| JPH08311691A (en) | Production of blackened steel sheet excellent in corrosion resistance | |
| JPH01149990A (en) | Surface treated steel sheet having superior workability and coating suitability | |
| JPH09263918A (en) | Production of high lubricty calvannealed steel sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |