CN104471115A - Method for producing steel sheet having excellent chemical conversion properties and galling resistance - Google Patents
Method for producing steel sheet having excellent chemical conversion properties and galling resistance Download PDFInfo
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- CN104471115A CN104471115A CN201280074788.XA CN201280074788A CN104471115A CN 104471115 A CN104471115 A CN 104471115A CN 201280074788 A CN201280074788 A CN 201280074788A CN 104471115 A CN104471115 A CN 104471115A
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- steel plate
- zinc
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- mucous membrane
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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
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
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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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Abstract
Provided is a method for producing a steel sheet having excellent chemical conversion properties and galling resistance. An electrolysis treatment is carried out in an aqueous solution containing a zinc ion and a nitrate ion using a steel sheet as a cathode to form a zinc oxide and/or a zinc hydroxide on the surface of the steel sheet in such a manner that the amount of the zinc oxide and/or the zinc hydroxide becomes 70 to 500 mg/m2 in terms of metal zinc content and the covering rate of the surface of the steel sheet becomes 60% or more. Subsequently, the steel sheet is washed with an aqueous solution containing phosphorus.
Description
Technical field
The present invention relates to the manufacture method being suitable as chemical convertibility that such as materials used in auto manufacturing uses and the excellent steel plate of resistent mucous membrane.
Background technology
Cold-rolled steel sheet widely uses in the fields such as automobile, household electrical appliances, building materials.Particularly in automotive field, consider from the requirement about thickness of slab precision, Flatness, use cold-rolled steel sheet.In addition, in recent years, from the CO reducing automobile
2quantity discharged and guarantee that the viewpoint of security is set out, as automotive sheet, the use of high strength cold rolled steel plate increases severely.
High tensile steel plate is added with the steel plate as element in steel such as Si, Mn, and these elements are formed with such as SiO in annealing process on surface of steel plate
2, MnSiO
4deng the oxide compound for representative.At this, if be conceived to chemical convertibility, then will be formed with SiO from the teeth outwards like this
2steel plate for chemical conversion treatment before application time, there is the part being called as so-called uncovering area (ス ケ) not forming chemical conversion treatment crystallization.Do not form the position being called as uncovering area of chemical conversion treatment crystallization if produced, then, when apply as automotive sheet, existence causes the possibility of the reduction of application adaptation after this, the reduction of erosion resistance, therefore not preferred.And known, such uncovering area significantly depends on the SiO on top layer
2amount.This is because, in the oxide compound formed in annealing process, MnSiO
4processable Deng Si-Mn composite oxides, but SiO
2be insoluble in the acid except hydrofluoric acid system, therefore, can not dissolve in the phosphoric acid forming chemical conversion treatment solution, hinder the reaction with chemical conversion treatment solution.
Then, if be conceived to resistent mucous membrane, then when carrying out stamping to high tensile steel plate, not only shaping load increases, and can produce owing to producing the high contact pressure portion of local the problem being called as sticking to mould.Think that sticking to mould produces as follows: steel plate time stamping comes in contact with the metal forming press tool with high contact pressure, slides, produce the adhesion of local thus, produce scratch due to the accumulation of adhesion or sliding resistance is increased.
Based on viewpoint as above, urgent expect to develop chemical convertibility and the excellent high tensile steel plate of resistent mucous membrane.
Relative to this, as the technology improving both the chemical convertibility of cold-rolled steel sheet and resistent mucous membrane, Patent Document 1 discloses and make one or more the metal in Ni, Mn, Co, Mo, Cu precipitate into technology in surface of cold-rolled steel plate discontinuously.
In addition, Patent Document 2 discloses and form the very thin tunicle of the zinc main body of 0 valency in lower floor, to form the technology of the amorphousness tunicle be made up of the zinc of divalent and the oxide compound of one or more the second element set that comprises in P, B, Si on upper strata in surface of cold-rolled steel plate.
In addition, Patent Document 3 discloses following technology: scatter the powder of one or more the metal oxide in Zn, Ni, Mn, Ti, Co, Mo, Al in surface of cold-rolled steel plate after, carry out temper rolling, surface of steel plate is formed and counts 1000mg/m with metal conversion
2following metal level.
But even if the method recorded in patent documentation 1 is applied to the cold-rolled steel sheet containing Si, also directly remain in the state on surface of steel plate in Si oxide compound, therefore, chemical convertibility is still bad.In addition, the elements such as Mo, Cu produce detrimentally affect to chemical convertibility, when chemical conversion treatment from steel plate stripping to chemical conversion treatment solution, also there is the problem of chemical convertibility deterioration.
In patent documentation 2, when the punching press of high tensile steel plate, the contact pressure of shaping load and local increases, therefore, give when the zinc of the divalent on upper strata occurs to destroy with the oxide skin comprising one or more the second element set in P, B, Si, press formability is hindered, resistent mucous membrane deterioration due to the zinc of 0 valency of lower floor and the adhesion of mould.In addition, in patent documentation 2, the surface of steel plate distributive law of above-mentioned tunicle is recited as less than 50%.Think when surface coverage is low like this, do not have chlamydate base steel sheet and contacting dies when difficult profiled parts such as two stiffening webs and cause adhesion, thus causing sticking to mould.
In patent documentation 3, powder and steel plate is closely sealed thinks to utilize the physics closing force produced by temper rolling.That is, the closing force of powder and steel plate is very low, and during punching press, particularly when the difficult-to-machine material that image height strength steel sheet is such, powder is violent from the disengaging steel plate, easily produces Stamping damage due to the powder accumulation departed from.In addition, describe in patent documentation 3: be dispersed in equably on surface of steel plate by making metal oxide and form uniform chemical conversion tunicle.But not recording the definition of scattering, is therefore indefinite, but it has been generally acknowledged that, count less than 50% with fraction of coverage, when fraction of coverage is low, when difficult profiled parts such as two stiffening webs, do not have chlamydate base steel sheet and contacting dies and cause adhesion, thus causing sticking to mould.
Therefore, the present inventor is studied to improve above-mentioned problem, has applied for patent documentation 4.That is, patent documentation 4 finds, forms zinc oxide and/or zinc oxyhydroxide by carrying out electrolysis treatment using steel plate as negative electrode in containing the aqueous solution of zine ion on surface of steel plate, tunicle amount is converted with metallic zinc and counts 70 ~ 500mg/m
2and when making fraction of coverage be more than 60%, be effective for raising chemical convertibility and resistent mucous membrane.
But, known in recent years, the CO in automobile manufacturing process
2in the trend of reduction, cost degradation, the low temperature development of chemical conversion treatment solution, only can not obtain good chemical convertibility with the tunicle formed in patent documentation 5.Specifically think, due to the low temperature of chemical conversion treatment solution, the etching of steel plate reduces, and the state on surface becomes more responsive, and therefore, the ability of dissolving above-mentioned tunicle reduces.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 3-236491 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-158858 publication
Patent documentation 3: Japanese Unexamined Patent Publication 3-086302 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2008-81808 publication
Summary of the invention
Invent problem to be solved
The present invention completes to advantageously solve the problem, and its object is to provide the manufacture method of chemical convertibility and the excellent steel plate of resistent mucous membrane.
For the method for dealing with problems
In order to solve the problem, the present inventor conducts in-depth research repeatedly.Result, the present inventor finds, on surface of steel plate, zinc oxide and/or zinc oxyhydroxide is formed, when being formed to be converted into metallic zinc amount for 70 ~ 500mg/m by carrying out electrolysis treatment using steel plate as negative electrode in the aqueous solution containing zine ion and nitrate ion
2and make fraction of coverage be more than 60%, and in the process that the laggard enforcement steel plate of electrolysis treatment contacts with the aqueous solution containing phosphorus, even if when chemical conversion treatment solution generation low temperature, be also effective for raising chemical convertibility and resistent mucous membrane.
The present invention completes based on above opinion, and its purport is as described below.
[1] manufacture method for chemical convertibility and the excellent steel plate of resistent mucous membrane, is characterized in that,
Electrolysis treatment is carried out using steel plate as negative electrode, to be converted into metallic zinc amount for 70 ~ 500mg/m in the aqueous solution containing zine ion and nitrate ion
2and the mode making the fraction of coverage of surface of steel plate reach more than 60% forms zinc oxide and/or zinc oxyhydroxide on described surface of steel plate,
Then, the aqueous solution containing phosphorus is utilized to contact described steel plate.
The manufacture method of the chemical convertibility [2] as described in above-mentioned [1] and the excellent steel plate of resistent mucous membrane, it is characterized in that, described steel plate contains the Si of more than 0.1 quality %.
The manufacture method of the chemical convertibility [3] as described in above-mentioned [1] or [2] and the excellent steel plate of resistent mucous membrane, is characterized in that, the phosphorus containing ratio of the described aqueous solution containing phosphorus is 5 ~ 5000 quality ppm.
The manufacture method of the chemical convertibility [4] according to any one of above-mentioned [1] ~ [3] and the excellent steel plate of resistent mucous membrane, is characterized in that, the pH of the described aqueous solution containing phosphorus is 4 ~ 12.
Invention effect
According to the present invention, chemical convertibility and the excellent steel plate of resistent mucous membrane can be obtained.Particularly, even if when chemical conversion treatment solution generation low temperature, also good chemical convertibility and resistent mucous membrane can be obtained.In addition, the present invention, for cold-rolled steel sheet, the high strength cold rolled steel plate performance effect particularly containing Si, as the effective technology of the chemical convertibility and resistent mucous membrane of taking into account high strength cold rolled steel plate, is industrially worth high.
Accompanying drawing explanation
Fig. 1 is the general principal view (embodiment) representing kinetic friction coefficient determinator.
Fig. 2 is the approximate three-dimensional map of the stiffening web shape and size represented in Fig. 1.
Embodiment
Below, the present invention is described in detail.
Be hot-rolled steel sheet and cold-rolled steel sheet as the steel plate of object in the present invention.Wherein, for the cold-rolled steel sheet used a large amount of in automotive field etc., the present invention is most suitable.In order to improve the impact of Addition ofelements owing to existing on surface of steel plate (such as high tensile steel plate) that each characteristics such as mechanical characteristics are added with various element in steel, the phosphate crystal sometimes during chemical conversion treatment becomes uneven.On the other hand, uniform chemical conversion treatment tunicle is often required for steel plate.From the viewpoint, apply the present invention to the above-mentioned steel plate being added with various element and there is value, by the present invention, stable chemical conversion treatment tunicle can be obtained.
The composition of the steel plate as object in the present invention is not particularly limited.Such as, preferably use Si content is the steel plate of more than 0.1 quality %.This is because, the Si content in steel is more than 0.1 quality %, usually forms Si oxide compound on surface of steel plate, significantly hinder chemical convertibility, therefore, the value applying process of the present invention is large.In addition, even if when punching press, when Si content is the steel plate of more than 0.1 quality %, the intensity of steel plate also increases, and therefore, easily causes sticking to mould, and by applying process of the present invention, sticking to mould is significantly suppressed.
Particularly when containing the Si of more than 0.3 quality % and the steel plate of Si content/Mn content >=0.4, in method in the past, chemical convertibility is significantly deteriorated.But by application the present invention, chemical convertibility becomes significantly good, therefore, even if, be also applicable to using the present invention for the steel plate of Si content/Mn content >=0.4 for the Si containing more than 0.3 quality %.
The invention is characterized in, in the aqueous solution containing zine ion and nitrate ion, carry out electrolysis treatment using steel plate as negative electrode, surface of steel plate is formed zinc oxide and/or zinc oxyhydroxide (following, to be also sometimes referred to as zinc system oxide compound).The zinc system oxide compound formed by catholyte facture has while be the very fine netted form of less than 1 μm, and by forming these zinc system oxide compounds on surface of steel plate, this netted tunicle form contributes to improving resistent mucous membrane.Mechanism resistent mucous membrane being improved about having netted tunicle form by zinc system oxide compound is still not clear, but can consider as follows.First, zinc system oxide compound is refractory metal, can suppress the adhesion of mould and steel plate, therefore not easily cause sticking to mould, can guarantee the punching press wet goods oil content given when punching press simultaneously, significantly can suppress the adhesion during oil-break caused by slip.
In addition, from the view point of the formation volume controlling zinc system oxide compound, catholyte process is also effective.
In the present invention, in the aqueous solution containing zine ion and nitrate ion, carry out electrolysis treatment using steel plate as negative electrode, surface of steel plate is formed zinc system oxide compound.Usually, when carrying out electrolysis treatment using steel plate as negative electrode in the aqueous solution only containing zine ion, precipitating metal zinc on surface of steel plate.Therefore, in the present invention, by adding nitrate ion further in containing the aqueous solution of zine ion, zinc system oxide compound can be formed on surface of steel plate.
Zine ion amount in the aqueous solution is 0.1 ~ 1mol/L, nitrate ion counts 0.1 ~ 1mol/L, current density for 1 ~ 30A/dm with nitric acid
2, liquid temperature is 30 ~ 70 DEG C, the relative velocity of plating solution be 0.5 ~ 2.0m/s is optimum range.By carrying out electrolysis treatment in above-mentioned scope, easily form zinc system of the present invention oxide compound.The compound of interpolation zine ion, nitrate ion is not particularly limited, as zine ion supplying compound, zinc sulfate, zinc chloride, zinc nitrate etc. can be enumerated, as the supplying compound of nitrate ion, can SODIUMNITRATE, saltpetre etc. be enumerated.
In addition, surface of steel plate being formed zinc system oxide compound can utilize x-ray photoelectron light-dividing device to confirm.By investigating the bonded energy of zinc, metallic zinc and zinc oxide/hydroxide can be distinguished.Specifically, the bonded energy of metallic zinc has peak near 494eV, and the bonded energy of zinc oxide and zinc hydroxide is respectively 499, have peak near 500eV.Therefore, zinc system of the present invention oxide compound does not have peak near 494eV, and only 499, observe peak near 500eV, known by this peak is zinc system oxide compound.In addition, the analysis of depth direction (from top layer through tunicle to base steel sheet interface) is being implemented by ion etching, in the present invention, at any one depth, zinc system oxide compound does not have peak near 494eV, only 499, observe peak near 500eV, tunicle entirety is zinc system oxide compound.
In addition, in the present invention, when surface of steel plate is formed zinc system oxide compound, its amount converts with metallic zinc and counts 70mg/m
2~ 500mg/m
2.This is one of most important condition in the present invention, like this, being defined as optimum quantity by the formation volume of the zinc system oxide compound by surface of steel plate, can giving full play to by forming zinc system oxide compound and the effect that produces, chemical convertibility and the excellent steel plate of resistent mucous membrane can be obtained.Be still not clear about the mechanism improving chemical convertibility by forming zinc system oxide compound, but can think due to, promote nucleation during chemical conversion treatment by forming zinc system oxide compound on surface of steel plate.In addition, by forming zinc system oxide compound on surface of steel plate, as mentioned above, the mould when punching press and the zinc system oxide compound formed between steel plate are high-melting-point, therefore have the effect suppressing adhesion.As a result, resistent mucous membrane improves.
70mg/m is less than in the formation volume of the zinc system oxide compound of surface of steel plate
2time, cannot fully providing chemical conversion processing time nucleation site, therefore, chemical convertibility improve effect little.On the other hand, the formation volume of the zinc system oxide compound of surface of steel plate is more than 500mg/m
2time, although the adhesion of mould when can suppress punching press and steel plate, zinc system oxide compound self is out of shape, and therefore, the disengaging amount of zinc system oxide compound increases, and the zinc system oxide compound of disengaging becomes sliding resistance.
For the foregoing reasons, the zinc system oxide compound for stable raising chemical convertibility and resistent mucous membrane is 70mg/m
2~ 500mg/m
2, be preferably 100 ~ 300mg/m
2.
It should be noted that, the formation volume of above-mentioned zinc system oxide compound measures the intensity of Zn by using fluorescent X-ray and comparatively calculates with the strength ratio that known Zn measures.
In addition, the fraction of coverage of the surface of steel plate of zinc system oxide compound is more than 60%.This is also one of important condition in the present invention.By making fraction of coverage be more than 60%, chemical convertibility and resistent mucous membrane can be improved.When fraction of coverage is less than 60%, when steel plate is subject to processing, press tool directly contacts with base steel sheet, therefore, produces small adhesion, and frictional coefficient increases, and press formability reduces.
It should be noted that, in the present invention, the fraction of coverage of zinc system oxide compound represents that zinc system oxide compound covers the area occupation ratio of surface of steel plate, specifically, about fraction of coverage, electron beam microscopic analyzer can be used to carry out 100 μm of square zinc element distributional analysiss, by mensuration area (10000 μm
2) calculated by the ratio that there is area of zinc.
Carry out electrolysis treatment using steel plate as negative electrode, surface of steel plate is formed zinc system oxide compound, then, above-mentioned steel plate is contacted with the aqueous solution containing phosphorus.This is also important condition.Common chemical conversion treatment is carried out according to alkali degreasing → surface modulation → parkerized order.In initial alkali degreasing operation, need the punching press cleaning wet goods that removing is coated on slushing oil on steel plate, frequently uses when automobile body outer board stamping.But, when particularly alkali degreasing being carried out for a large amount of vehicle bodies continuously transmitted in the paint line in car manufactures etc., consider that oil is mixed into or alkali degreasing liquid deterioration etc., therefore, even if by steel plate direct impregnation in alkali degreasing liquid, also not necessarily can except deoiling.According to circumstances, sometimes degreasing can not be implemented fully and surface modulation operation after being sent to by steel plate under the state of refusing water.Refuse water section at such, surface modulation liquid cannot be given exactly, and then in ensuing phosphatizing operation, the part etc. that phosphate crystal generation coarsening or existence do not form crystallization has detrimentally affect to phosphatizing.
Therefore, in the present invention, after steel plate is formed zinc system oxide compound tunicle, make it contact with the aqueous solution containing phosphorus (such as flooding).By flooding in containing the aqueous solution of phosphorus, adhering to the phosphorus of trace from the teeth outwards, thus, even if when considering the deterioration etc. of alkali degreasing liquid, also can carry out degreasing fully.Estimate about its mechanism, think to there is OH base in a part for zinc system oxide compound, OH base can improve the affinity with oil, is therefore difficult to carry out degreasing.Think in addition, when being given zinc system oxide compound by the electrochemical plating containing sulfuric acid, sulfate radical enters in Zn plating tunicle, and this sulfate radical can improve the affinity with oil, is therefore difficult to carry out degreasing.When making the aqueous solution containing phosphorus contact with steel plate, before oil with the bonding of OH base, OH base and P bonding, therefore, reduce with the affinity of oil, think in addition, when there is sulfate radical when forming zinc system oxide compound, the sulfate radical existed from the teeth outwards is washed off, and then micro-adhere to P, reduce the affinity with oil thus, therefore, degreasing improves.
As the aqueous solution containing phosphorus, as long as be not particularly limited containing phosphorus.As long as the aqueous solution containing at least one phosphorus compound be selected from phosphoric acid, condensed phosphoric acid, phosphorous acid, Hypophosporous Acid, 50 or their salt is not particularly limited.When enumerating concrete example, can enumerate: ortho-phosphoric acid, tetra-sodium, three metaphosphoric acids, four metaphosphoric acids, hexa metaphosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, triammonium phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tertiary sodium phosphate, trisodium phosphate, aluminum phosphate, ammonium hypophosphite, ammonium phosphite, triammonium phosphate etc.
5 ~ 5000 quality ppm are preferably containing the phosphorus containing ratio in the aqueous solution of phosphorus.When being less than 5 quality ppm, the effect that phosphorus is adsorbed onto on surface of steel plate is sometimes insufficient.In addition, during more than 5000 quality ppm, effect is saturated, sometimes causes liquid cost, treatment cost of waste liquor to increase.Be more preferably below 1000ppm.In addition, when time after treatment to oiling is long etc., cleaning spot is sometimes obvious, therefore, after cleaning in containing the aqueous solution of phosphorus, preferably re-starts common washing.In addition, phosphorus containing ratio is converted by phosphorus amount of metal and obtains.
The pH of the aqueous solution containing phosphorus is preferably 4 ~ 12.When being less than 4, zinc system oxide compound easily dissolves, and infringement improves the effect of resistent mucous membrane, chemical convertibility sometimes.On the other hand, when pH is more than 12, the meltage of zinc system oxide compound also can increase, and therefore, infringement improves the effect of resistent mucous membrane, chemical convertibility sometimes.In addition, pH is not in above-mentioned scope, can by adding the alkali such as the acid such as phosphoric acid, hydrochloric acid, sulfuric acid, sodium hydroxide of trace or dilute with water by pH regulator extremely above-mentioned scope.
The temperature of the aqueous solution containing phosphorus is preferably the scope of 20 ~ 70 DEG C.During lower than 20 DEG C, be sometimes difficult to complete phosphorus absorption at short notice.On the other hand, during more than 70 DEG C, not only phosphorus adsorption effect is saturated, and the aqueous solution containing phosphorus is easily dry, sometimes easily produces outward appearance unequal.In addition, about washing time, preferably carry out in the scope of 1 ~ 10 second.When being less than 1 second, can not fully complete during being adsorbed with of phosphorus.On the other hand, the process more than 10 seconds not only can cause manufacturing line and become extensive, and can zinc oxide be made to dissolve due to the aqueous solution containing phosphorus, sometimes cannot guarantee sufficient effect.
The method that such utilization contains the washing process of the aqueous solution of phosphorus is not particularly limited.Can enumerate: the method for dipping coated steel sheet, the method for carrying out spraying, the method etc. that is coated with of being undertaken by coating roll.Wherein, for the method for spraying for surface of steel plate, while with the treatment solution of a small amount of necessity, utilizing and within the shorter time, complete process with the effect that is multiplied of the flow effect of liquid, is therefore most preferred method.
[embodiment]
Use the steel plate A ~ F (thickness of slab is 1.2mm) with the composition shown in table 1, first, these steel plates are utilized to the solvent supersonic ripple degreasing of toluene, the oil content of removing surface of steel plate.Then, the electrolytic bath shown in table 2 forms and under electrolytic condition, carries out electrolysis treatment, surface of steel plate is formed zinc system oxide compound using steel plate as negative electrode.In addition, as a part for comparative example, use and do not carry out electroplating processes containing the electrolytic bath of nitrate ion, metallic zinc is separated out.
For the steel plate obtained by aforesaid method, use x-ray photoelectron light-dividing device, carry out depth analysis by sputter etching, investigating the material formed by electrolysis treatment is zinc system oxide compound or metallic zinc.Using the electrolytic bath not containing nitrate ion not carry out in the comparative example processed, confirming in the whole region of depth direction is metallic zinc, in addition, beyond above-mentioned comparative example, confirms to be zinc system oxide compound in the whole region of depth direction.
In addition, fluorescent X-ray is used to measure with the form of metallic zinc the amount of zinc system oxide compound and metallic zinc.At this, carry out metallic zinc plating in advance, make the calibration plate of the Zn intensity utilizing the Zn of ICP to measure and to utilize fluorescent X-ray, measure above-mentioned zinc amount.In addition, about the fraction of coverage of zinc system oxide compound, use electron beam microscopic analyzer, carry out 100 μm of square zinc element distributional analysiss, by the ratio (fraction of coverage) that there is area measuring areal calculation and go out zinc.
In addition, by method shown below, evaluate resistent mucous membrane and chemical convertibility.
(1) resistent mucous membrane evaluation
Evaluating resistent mucous membrane in order under the condition that the contact pressure of the stiffening web passage when assuming actual punching press is high, using the measuring friction coefficient device of Fig. 1, carry out dull and stereotyped same position sliding test repeatedly.As shown in Figure 1, be fixed on sample bench 2 from the measuring friction coefficient sample 1 cut for examination material, sample bench 2 is fixed on the upper surface of the sliding stand 3 that can move horizontally.Being provided with the sliding stand brace table 5 that can move up and down with the roller 4 be in contact with it at the lower surface of sliding stand 3, being arranged on sliding stand brace table 5 for the first load cell 7 by it upwards being pushed up the press load N measuring stiffening web 6 pairs of measuring friction coefficient samples 1.For measuring an end for making second load cell 8 of the sliding stand 3 sliding resistance F of movement in the horizontal direction be arranged on sliding stand 3 under the state of above-mentioned pressing force effect.In addition, the surface of sample 1 is coated with the punching press wash oil プ レ ト Application R352L that the chemical company of China fir village as lubricating oil manufactures, tests.The press load that resistent mucous membrane is tested is set as N:1200kgf, the drawing speed (horizontal movement velocity of sliding stand 3) of sample is set as 100cm/ minute.
Fig. 2 is the approximate three-dimensional map representing during resistent mucous membrane is evaluated the stiffening web shape and size used.The lower surface of stiffening web 6 with by be pressed on the surface of sample 1 slide in state dynamic.The shape of the stiffening web 6 shown in Fig. 2 is the slip direction length 12mm of width 10mm, sample, the curved surface that the bottom at slip direction two ends is 4.5mmR by curvature is formed, and the stiffening web lower surface of pressing sample has that width is 10mm, slip direction length is the plane of 3mm.When using this stiffening web, the frictional coefficient in stiffening web passage when can evaluate stamping.
About resistent mucous membrane evaluation test condition, to being applied on the surface by the punching press wash oil プ レ ト Application R352L that chemical company of China fir village manufactures before the test, maximum 40 sliding tests are repeatedly implemented at the same position of the sample 1 obtained, and utilize the number of times that can slide as the index of resistent mucous membrane.At this, about the number of times that can slide, setting in the self-braking mode of measuring friction coefficient device when there is steel plate and the adhesion of mould, i.e. sticking to mould, as set(ting)value, setting more than the mode stopped during 500kgf with sliding resistance F.
×: the number of times that can slide is less than 17 times (measuring friction coefficient device being stopped owing to there is sticking to mould).
Zero: the number of times that can slide is 17 times ~ 29 times (measuring friction coefficient device being stopped owing to there is sticking to mould).
◎: 30 times can be carried out and slide
At this, slip number of times is for 17 times sticking to mould does not occur and the cold-rolled steel sheet of 270MPa level that uses carries out occurring when above-mentioned resistent mucous membrane is evaluated the average time of sticking to mould with the press load of 400kgf to current, when can slide more than 17 times, think and sticking to mould can not occur in practical, therefore, using slip number of times be more than 17 times as benchmark.
(2) chemical convertibility evaluation
Use commercially available chemical conversion treatment medicament (the パ Le ボ Application De PB-L3065 system that Nihon Parkerizing Co., Ltd. manufactures), chemical conversion treatment is carried out under the condition of bath temperature 35 DEG C, 120 seconds time, carry out the surperficial SEM after chemical conversion treatment to observe, thus, the homogeneity of evaluating chemical conversion processing crystallization.At this, surperficial SEM observes and evaluates under the visual field of 300 times, and it evaluates area is about 0.1mm
2.The Evaluation for Uniformity of chemical conversion treatment crystallization is judged by following benchmark.
××: almost whole is not all being observed chemical conversion treatment crystallization.
×: on about half, do not observe chemical conversion treatment crystallization.
△: the small uncovering area observing more than 3 places.
Zero: observe 2 sentence under small uncovering area and/or more than 3 places coarsening crystallization.
◎: chemical conversion treatment crystallization is without uncovering area, and coarsening crystallization is 2 to sentence down.
In addition, the size of the small uncovering area of above-mentioned record is 200 μm
2below.In addition, coarsening crystallization is defined as the crystallization that the long limit of chemical conversion treatment crystallization is more than 15 μm.
The test-results obtained by aforesaid method and condition are shown in Table 2 in the lump.
Table 1
According to table 2, test No.1 ~ 20,24 ~ 28 all define zinc system oxide compound on surface of steel plate, do not observe the generation of metallic zinc.In addition we know following item.
(1) No.1 ~ 6 by changing conduction time, the amount of zinc system oxide compound are changed and the result comparing and obtain.Known, the comparative example 1,2 of No.1, No.2 due to the amount of zinc system oxide compound few, therefore, chemical convertibility is bad.In addition we know, the comparative example 3 of No.6 due to the amount of zinc system oxide compound many, therefore, resistent mucous membrane reduces.Known on the other hand, when example of the present invention 1 ~ 3 of No.3 ~ 5 that the amount of zinc system oxide compound is applicable to, resistent mucous membrane, chemical convertibility are all excellent.
(2) No.7 has and the No.4 roughly amount of the zinc system oxide compound of equal extent but the low comparative example 4 of fraction of coverage.Known, resistent mucous membrane and chemical convertibility bad.No.8 is under the power on condition same with No.7 but makes amount and the fraction of coverage example of the present invention 4 within the scope of the present invention of zinc system oxide compound by extending conduction time.Known, resistent mucous membrane and chemical convertibility good.
(3) No.4 and No.9 ~ 14 are examples of the situation not having to utilize the aqueous solution containing phosphorus to carry out washing process or the situation that phosphorus containing ratio is changed.Known, there is no to utilize that to carry out the chemical convertibility of the comparative example 5,6 of the No.9 and 10 washing process containing the aqueous solution of phosphorus bad.On the other hand, the example of the present invention 2,5 ~ 8 of No.4 and No.11 ~ 14 has utilized the aqueous solution containing phosphorus to carry out under the preferred conditions and has washed process, known, chemical convertibility and resistent mucous membrane excellent.
(4) example of the present invention 9 ~ 11 of No15 ~ 17 is the examples utilizing the aqueous solution containing phosphorus that the pH of washing process is changed.Known, all obtain good chemical convertibility and resistent mucous membrane.
(5) example of the present invention 2,12 ~ 14 of No.4 and No.18 ~ 20 is the examples making to change to the ion supplying compound in electrolytic bath.Known, all obtain good resistent mucous membrane and chemical convertibility when using any one compound.
(6) example of the present invention 2,15 ~ 19 of No.4 and No.24 ~ 28 is examples that the kind of steel plate is changed.Known, all obtain good chemical convertibility and resistent mucous membrane.
Utilizability in industry
According to the present invention, sticking to mould can be suppressed when can be provided in stamping, demonstrate the steel plate of good chemical convertibility when the chemical conversion treatment of then carrying out, can apply in field widely centered by body of a motor car purposes.
Label declaration
1 measuring friction coefficient sample
2 sample benchs
3 sliding stands
4 rollers
5 sliding stand brace tables
6 stiffening webs
7 first load cells
8 second load cells
9 guide rails
N press load
F sliding resistance
Claims (4)
1. a manufacture method for chemical convertibility and the excellent steel plate of resistent mucous membrane, is characterized in that,
Electrolysis treatment is carried out using steel plate as negative electrode, to be converted into metallic zinc amount for 70 ~ 500mg/m in the aqueous solution containing zine ion and nitrate ion
2and the mode making the fraction of coverage of surface of steel plate reach more than 60% forms zinc oxide and/or zinc oxyhydroxide on described surface of steel plate,
Then, described steel plate is contacted with the aqueous solution containing phosphorus.
2. the manufacture method of chemical convertibility as claimed in claim 1 and the excellent steel plate of resistent mucous membrane, it is characterized in that, described steel plate contains the Si of more than 0.1 quality %.
3. the manufacture method of chemical convertibility as claimed in claim 1 or 2 and the excellent steel plate of resistent mucous membrane, it is characterized in that, the phosphorus containing ratio of the described aqueous solution containing phosphorus is 5 ~ 5000 quality ppm.
4. the manufacture method of the chemical convertibility according to any one of claims 1 to 3 and the excellent steel plate of resistent mucous membrane, is characterized in that, the pH of the described aqueous solution containing phosphorus is 4 ~ 12.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2012/068744 WO2014013623A1 (en) | 2012-07-18 | 2012-07-18 | Method for producing steel sheet having excellent chemical conversion properties and galling resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104471115A true CN104471115A (en) | 2015-03-25 |
Family
ID=49948474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280074788.XA Pending CN104471115A (en) | 2012-07-18 | 2012-07-18 | Method for producing steel sheet having excellent chemical conversion properties and galling resistance |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20150014517A (en) |
| CN (1) | CN104471115A (en) |
| WO (1) | WO2014013623A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110945160A (en) * | 2017-07-25 | 2020-03-31 | 杰富意钢铁株式会社 | High-strength cold-rolled steel sheet and method for producing same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3292230B1 (en) * | 2015-05-07 | 2019-06-12 | Phosfan Ltd. | Method for applying ultrafine phosphate conversion crystal coatings |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5525431A (en) * | 1989-12-12 | 1996-06-11 | Nippon Steel Corporation | Zinc-base galvanized sheet steel excellent in press-formability, phosphatability, etc. and process for producing the same |
| JP2008081808A (en) * | 2006-09-28 | 2008-04-10 | Jfe Steel Kk | Steel sheet having excellent chemical conversion treatment property and galling resistance |
| CN101522945A (en) * | 2006-10-31 | 2009-09-02 | 杰富意钢铁株式会社 | Phosphate-treated galvanized steel sheet and method for producing the same |
| CN102216493A (en) * | 2008-12-16 | 2011-10-12 | 杰富意钢铁株式会社 | Galvanized steel sheet and method for manufacturing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2819427B2 (en) * | 1990-08-01 | 1998-10-30 | 新日本製鐵株式会社 | Galvanized steel sheet with excellent press formability and chemical conversion properties |
| JP5853683B2 (en) * | 2011-01-25 | 2016-02-09 | Ｊｆｅスチール株式会社 | Method for producing cold-rolled steel sheet with excellent chemical conversion and post-coating corrosion resistance |
-
2012
- 2012-07-18 KR KR1020147036256A patent/KR20150014517A/en not_active Application Discontinuation
- 2012-07-18 CN CN201280074788.XA patent/CN104471115A/en active Pending
- 2012-07-18 WO PCT/JP2012/068744 patent/WO2014013623A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5525431A (en) * | 1989-12-12 | 1996-06-11 | Nippon Steel Corporation | Zinc-base galvanized sheet steel excellent in press-formability, phosphatability, etc. and process for producing the same |
| JP2008081808A (en) * | 2006-09-28 | 2008-04-10 | Jfe Steel Kk | Steel sheet having excellent chemical conversion treatment property and galling resistance |
| CN101522945A (en) * | 2006-10-31 | 2009-09-02 | 杰富意钢铁株式会社 | Phosphate-treated galvanized steel sheet and method for producing the same |
| CN102216493A (en) * | 2008-12-16 | 2011-10-12 | 杰富意钢铁株式会社 | Galvanized steel sheet and method for manufacturing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110945160A (en) * | 2017-07-25 | 2020-03-31 | 杰富意钢铁株式会社 | High-strength cold-rolled steel sheet and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014013623A1 (en) | 2014-01-23 |
| KR20150014517A (en) | 2015-02-06 |
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Application publication date: 20150325 |
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| RJ01 | Rejection of invention patent application after publication |