CN109477222A - Trbasic zinc phosphate handles galvanized steel plain sheet and its manufacturing method - Google Patents

Trbasic zinc phosphate handles galvanized steel plain sheet and its manufacturing method Download PDF

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Publication number
CN109477222A
CN109477222A CN201780046955.2A CN201780046955A CN109477222A CN 109477222 A CN109477222 A CN 109477222A CN 201780046955 A CN201780046955 A CN 201780046955A CN 109477222 A CN109477222 A CN 109477222A
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Prior art keywords
galvanized steel
zinc phosphate
trbasic zinc
plain sheet
steel plain
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CN201780046955.2A
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CN109477222B (en
Inventor
星野克弥
荒川真吾
今井克德
今村真人
古谷真
古谷真一
松田武士
土本和明
松崎晃
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JFE Steel Corp
JFE Engineering Corp
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NKK Corp
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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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • 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
    • C23C22/73—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 characterised by the process
    • C23C22/76—Applying the liquid by spraying
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Coating With Molten Metal (AREA)

Abstract

The present invention provides and is used in the integration of components in recent years, when the automobile components that the complication of shape continues to develop, and the scratch of mold caused by the cracking of molded product when also can suitably inhibit as compression moulding, the trbasic zinc phosphate with excellent compression moulding handle galvanized steel plain sheet.It is, with the galvanized steel plain sheet of trbasic zinc phosphate system envelope, the adhesion amount of trbasic zinc phosphate system envelope is 1.0~2.0g/m at least single side2, Mn content is that 3.0~8.0 mass %, Ni contents are 0.7~1.3 mass %, and the three-dimensional arithmetic average roughness Sa of envelope surface is 0.05~0.12 μm, and three-dimensional maximum concave-convex surface height Sz is 0.4~0.9 μm.Sliding properties, the mold of trbasic zinc phosphate processing galvanized steel plain sheet are scratch resistance to be improved have high compression moulding, and, coating adhesion and coating after excellent corrosion resistance uneven without appearance.

Description

Trbasic zinc phosphate handles galvanized steel plain sheet and its manufacturing method
Technical field
That the present invention relates to resistances to sliding when compression moulding is small, it is uneven with excellent compression moulding and without appearance, Corrosion resistance also excellent trbasic zinc phosphate processing galvanized steel plain sheet and its manufacturing method after coating adhesion and coating.
Background technique
Plated steel sheet is widely used for the field of wide scope centered on car body purposes, right at these on the way Apply compression moulding in fact to for using.However, plated steel sheet has compression moulding poor for cold-rolled steel sheet The shortcomings that.The reason is that resistance to sliding of the plated steel sheet in compacting tool set is higher than cold-rolled steel sheet.That is, being asked there are following Topic: the high part of resistance to sliding at compacting tool set and reinforcing rib (bead), plated steel sheet become to be not easy to flow into compacting Mold, it is prone to the fracture of steel plate.
To solve the problems, such as above-mentioned galvanized steel plain sheet, it has been suggested that be formed with the galvanized steel of trbasic zinc phosphate system envelope in galvanizing surface Plate, and by it for practical.
In addition, in order to further increase the compression moulding of the above-mentioned galvanized steel plain sheet with trbasic zinc phosphate system envelope, patent text Offer the technology for the roughness that 1 discloses the surface of steel plate after control zinc-plated processing.Equally, patent document 2 discloses control and is formed The technology of the long side length of the trbasic zinc phosphate crystal of trbasic zinc phosphate system envelope.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2003-171775 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2003-221675 bulletin
Summary of the invention
Problems to be solved by the invention
In recent years, among car body purposes etc., as the complication of the integration of components, shape continues to develop, Mold caused by there is the cracking of molded product when occurring as compression moulding according to the shape of molded product abrades (die Galling) the problem of.For inhibition abrasive for this mold, even if forming trbasic zinc phosphate system envelope, simultaneously on galvanized steel plain sheet And the long side length of the roughness of surface of steel plate and trbasic zinc phosphate crystal is controlled as patent document 1,2, also it is still Insufficient.
Therefore, it is an object of the present invention to solve above-mentioned project in the prior art, and provides and is used in recent years zero In the case where automobile components that the integration of component, the complication of shape continue to develop etc., also can suitably it inhibit by suppressing Mold caused by the cracking of molded product when molding abrades, with excellent compression moulding, and without appearance unevenness, coating is close Also excellent trbasic zinc phosphate handles galvanized steel plain sheet to corrosion resistance after conjunction property and coating.In addition, other objects of the present invention are, provide The manufacturing method of the trbasic zinc phosphate processing galvanized steel plain sheet with above-mentioned excellent properties can steadily be manufactured.
Means for solving the problems
The present inventor has made intensive studies to solve the above subject, as a result, it has been found that, in galvanized steel sheet surface The trbasic zinc phosphate system envelope of regulation adhesion amount containing appropriate Mn and Ni is formed, and by the rough surface of the trbasic zinc phosphate system envelope Degree control is 0.05 μm≤Sa≤0.12 μm, 0.4 μm≤Sz≤0.9 μm, and thus, it is possible to solve the above subject.Still further, it was discovered that By carrying out trbasic zinc phosphate processing using blowing and spraying for the treatment fluid from nozzle, and at this moment, blowed and sprayed from nozzle with defined Angle blows and sprays treatment fluid to galvanized steel plate face, is above-mentioned three-dimensional thick thus, it is possible to control the surface roughness of trbasic zinc phosphate system envelope Rugosity (Sa, Sz).
The present invention is made based on above-mentioned cognition, is the gist of the invention below.
[1] trbasic zinc phosphate handles galvanized steel plain sheet, described to have the galvanized steel plain sheet of trbasic zinc phosphate system envelope at least single side Trbasic zinc phosphate processing galvanized steel plain sheet is characterized in that the adhesion amount of trbasic zinc phosphate system envelope is 1.0~2.0g/m2, Mn content is 3.0~8.0 mass %, Ni contents are 0.7~1.3 mass %, the three-dimensional arithmetic average roughness Sa of envelope surface is 0.05~ 0.12 μm and three-dimensional maximum concave-convex surface height Sz is 0.4~0.9 μm.
[2] manufacturing method of trbasic zinc phosphate processing galvanized steel plain sheet is that trbasic zinc phosphate described in above-mentioned [1] handles galvanized steel plain sheet Manufacturing method, the manufacturing method be characterized in that, from nozzle and to the galvanized steel plain sheet of logical plate blow and spray containing nickel ion and manganese from Thus the trbasic zinc phosphate treatment fluid of son carries out trbasic zinc phosphate processing, will when blowing and spraying trbasic zinc phosphate treatment fluid from the nozzle to galvanized steel plain sheet The treatment fluid in galvanized steel plain sheet longitudinal direction for galvanized steel plate face blows and sprays angle (that is, in galvanized steel plain sheet long side side Upwards, the treatment fluid injection direction of nozzle and galvanized steel plate face angulation) it is set as 30~80 °.
[3] manufacturing method of the trbasic zinc phosphate processing galvanized steel plain sheet as described in above-mentioned [2], which is characterized in that galvanized steel plain sheet The nozzle for blowing and spraying trbasic zinc phosphate treatment fluid is the gap nozzle being arranged along steel plate width direction.
The effect of invention
Trbasic zinc phosphate processing galvanized steel plain sheet of the invention is used in the integration of components in recent years, the complication of shape not When in the case where automobile components of disconnected development etc., caused by the cracking of molded product when also can suitably inhibit as compression moulding Mold scratch, with excellent compression moulding and uneven without appearance, excellent corrosion resistance after coating adhesion and coating. In addition, can steadily manufacture the trbasic zinc phosphate processing galvanized steel plain sheet with above-mentioned excellent properties using the manufacturing method of the present invention.
Detailed description of the invention
[Fig. 1] Fig. 1 is the explanatory diagram for showing the summary of measuring friction coefficient device used in embodiment.
[Fig. 2] Fig. 2 is the shape for showing reinforcing rib used in the device of Fig. 1, the explanatory diagram of size.
[Fig. 3] Fig. 3 is the shape for showing other reinforcing ribs used in the device of Fig. 1, the explanatory diagram of size.
[Fig. 4] Fig. 4 schematically shows the case where blowing and spraying trbasic zinc phosphate treatment fluid from gap nozzle in method of the invention One embodiment, Fig. 4 (A) are to observe obtained by gap nozzle to scheme from side, and Fig. 4 (B) is narrow from logical plate direction upstream observation It stitches and schemes obtained by nozzle.
Specific embodiment
Trbasic zinc phosphate of the invention handles galvanized steel plain sheet, is at least to have trbasic zinc phosphate system envelope in the one side of steel plate (plating clad can) Galvanized steel plain sheet.
Herein, galvanized steel plain sheet refers to so-called pure galvanized steel plain sheet, but due to generally can not usually in zinc-plated envelope Contain dissolved element (Fe and other composition of steel) from steel plate as plating impurity with avoiding, because sharing other kinds of plating Layer and the equipment such as measuring cell (cell) and mixed impurity (Ni, Sn, Al etc.), therefore being set as galvanized steel plain sheet also includes zinc-plated quilt Film contains the galvanized steel plain sheet of mentioned component.
In addition, galvanoplastic can be used in the formation of zinc coating, it is possible to use melting plating method is not particularly limited.
1.0~2.0g/m is set as in the adhesion amount for the trbasic zinc phosphate system envelope that zinc-plated face is formed2.If envelope adhesion amount is lower than 1.0g/m2Even if being also unable to give full play then in the case where applying oil condition by trbasic zinc phosphate system envelope bring oil retentivity, in addition, becoming Mold must not can avoid directly to contact with the zinc coating exposed from trbasic zinc phosphate system envelope surface, therefore by the shape of trbasic zinc phosphate system envelope At and the improvement effect of bring compression moulding becomes inadequate.On the other hand, if envelope adhesion amount is greater than 2.0g/m2, then Trbasic zinc phosphate system envelope needs to be formed for a long time, not only increased costs, but also the frictional resistance on surface increases, therefore, instead Compression moulding is set to be deteriorated.
In the present invention, in order to improve compression moulding and then improve the corrosion resistance after coating adhesion and coating, and The Mn of Ni and 3.0~8.0 mass % containing 0.7~1.3 mass % in trbasic zinc phosphate system envelope.Although not knowing trbasic zinc phosphate system Which kind of Ni contained in envelope and Mn be present in trbasic zinc phosphate crystal (Zn in the form of3(PO4)2·4H2O/Hopeite (phosphorus zinc Mine)) in, but due to even if contain Ni and Mn can not detect Hopeite by X-ray diffraction pattern, therefore, it is considered that Ni and Mn exists in the form of replacing Zn.
By making the Ni containing 0.7 mass % or more in trbasic zinc phosphate system envelope, corrosion resistant after coating adhesion, coating can get The improvement of corrosion.On the other hand, if Ni content is greater than 1.3 mass %, cost is increased, and is in addition easy to produce appearance unevenness It is even.
In addition, can further improve compression moulding by making the Mn containing 3.0 mass % or more in trbasic zinc phosphate system envelope Property, and improvement effect the tendency to become bigger with the more more then compression mouldings of Mn content.However, if containing 8.0 matter are greater than The Mn of % is measured, then the adaptation between electrocoating paint is deteriorated, and the corrosion resistance after coating is also deteriorated.
In the present invention, it will be controlled by the surface roughness of the trbasic zinc phosphate Crystallization of trbasic zinc phosphate system envelope in specific model In enclosing.That is, being 0.05~0.12 μm by the control of the three-dimensional arithmetic average roughness Sa as defined in ISO25178, by three-dimensional maximum table Height of concave convex Sz control in face is 0.4~0.9 μm.Even if as a result, in zero for being applied to that sliding distance is long, to be prone to oil consumption most In the case where part, remain to obtain excellent compression moulding.
In order to which the roughness of trbasic zinc phosphate Crystallization will be utilized to control, manage within the above range, treatment fluid is for phosphoric acid The contact method of coated steel sheet when zinc processing is important, and will be hereinafter described in detail to this.
Why three-dimensional arithmetic average roughness Sa is set as 0.05~0.12 μm, is in order to by the holding for improving oil Property, to even if also can in the case where being applied to the long components of sliding distance or surface pressing is easy to the components of rising Obtain stable sliding properties.If three-dimensional arithmetic average roughness Sa is lower than 0.05 μm, the recess kept to oil is small, nothing Method sufficiently obtains the improvement effect of compression moulding.On the other hand, if three-dimensional arithmetic average roughness Sa is more than 0.12 μm, when When the sliding of steel plate and mold, the resistance that surface is planarized becomes larger, therefore coefficient of friction increases, and will be unfavorable for being pressed into Type.
In addition, being only insufficient within the above range by three-dimensional arithmetic average roughness Sa control, it is also necessary to will be three-dimensional Maximum concave-convex surface height Sz control is at 0.4~0.9 μm.That is, from the viewpoint of oil retention when sliding, while controlling micro- The three-dimensional arithmetic average roughness Sa and three-dimensional maximum concave-convex surface height Sz of zonule are important.If three-dimensional maximum surface Height of concave convex Sz is lower than 0.4 μm, then in the case where sliding distance is long, recess portion is flattened, and is unable to give full play fuel-displaced holding Property.On the other hand, if three-dimensional maximum concave-convex surface height Sz is more than 0.9 μm, since the shape of recess portion deepens, therefore not to recess portion Sufficient pressure can be generated, adequately oil can not be played and keep effect.
Electron beam three-dimensional roughness resolver can be passed through by the roughness parameter of trbasic zinc phosphate crystal bring micro concavo-convex It measures.In addition, it is possible to use atomic force microscope (AFM) measurement.Using these means along surface Scanning Electron beam or Probe can find out the distribution of the height of surface and parallel direction from the displacement of secondary (reflection) electronic signal of gained or probe, Roughness parameter can be calculated from the result.For the shape from the observable micro concavo-convex in direction perpendicular to surface of steel plate It is micro- using above-mentioned electron beam three-dimensional roughness resolver or electric field radioactive scanning electron for shape, size, distribution Mirror is observed and is measured.
Using electron beam three-dimensional roughness resolver (such as (strain) Elionix system " ERA-8800FE ") measurement three In the case where tieing up arithmetic average roughness Sa and three-dimensional maximum concave-convex surface height Sz, measurement strip for example below may be set to Part.Measurement is with acceleration voltage 5kV, WD 15mm progress, and the sampling interval in direction is set as 1~5nm in face when measurement.For phosphoric acid The high sample of amount of zinc adhesion implements gold vapor deposition to avoid electrification caused by being irradiated by electron beam.In each of flat Position cuts out the coarse of 500 or more of long 12 μm or so from the scanning direction and direction normal thereto of electron beam and writes music Line measures the number and average height of fine protrusion per unit length.For determination part, it is set as appointing in each sample 10 positions of choosing.Using the subsidiary analysis software of device, from above-mentioned roughness curve calculate three-dimensional arithmetic average roughness Sa, The surface roughness parameters such as three-dimensional maximum concave-convex surface height Sz.If electron beam is irradiated in sample surface, the dirt of carbon main body Dye is promoted, and is embodied in determination data sometimes.It is this to influence to be easy to become in the case where measurement region is small as previously described It obtains significantly.Therefore, during data parse, the half of the length (12 μm) in direction will be measured as cut-off (cut-off) Wavelength and carry out Spline ultrafiltration (spline hyperfiltering), to remove above-mentioned influence.The correction of the present apparatus is using next From VLSI standard (strain) SHS film scale standard (scale 18nm, 88nm, 450nm) of US National research institute NIST.
It is to be appreciated that for the roughness of above-mentioned tiny area, as the cold-rolled steel sheet of raw material, galvanized steel plain sheet it is thick The influence of rugosity is small.The reason for this is that since measured length is 12 μm or so, it is very small, therefore the concave-convex ingredient of trbasic zinc phosphate crystal With significantly affecting.
Trbasic zinc phosphate processing galvanized steel plain sheet of the invention can be manufactured according to method as the followings, but be not limited to the preparation method.
Firstly, carrying out surface adjustment processing to the steel plate through zinc-plated processing.The treatment fluid used as surface adjustment, Liquid can be adjusted for the commercial surface based on titanium colloid, treatment fluid can be made to be attached to surface in a manner of impregnating, be sprayed etc..So Trbasic zinc phosphate processing is carried out afterwards, but in the present invention, in order to obtain the desired surface of micro concavo-convex bring by trbasic zinc phosphate crystal Roughness makes trbasic zinc phosphate treatment fluid and galvanized steel plain sheet face contact with ad hoc approach, forms trbasic zinc phosphate system envelope.In addition, in order to make Contain Ni and Mn in trbasic zinc phosphate system envelope, uses the trbasic zinc phosphate treatment fluid for being added with nickel ion and manganese ion.
As the composition of trbasic zinc phosphate treatment fluid, in order to by the control of envelope adhesion amount within the specified scope and from cost cutting From the perspective of, such as it is preferably set to following compositions.That is, being preferably set to phosphate ion: 10~30g/L, nitrate ion: 1.0~ 15g/L, zinc ion: 0.1~8.0g/L, nickel ion: 0.1~8.0g/L, manganese ion: 0.1~8.0g/L.
By continuously blowing and spraying trbasic zinc phosphate treatment fluid from nozzle (preferably gap nozzle) to the galvanized steel plain sheet of logical plate, thus into The processing of row trbasic zinc phosphate.By control at this time, trbasic zinc phosphate treatment fluid to galvanized steel plate face blow and spray angle, can will be by trbasic zinc phosphate crystalline substance The micro concavo-convex bring surface roughness control of body is the three-dimensional roughness present invention provide that in range.Specifically, in self-spray When mouth blows and sprays trbasic zinc phosphate treatment fluid to galvanized steel plain sheet, by the place in the galvanized steel plain sheet longitudinal direction for galvanized steel plate face Reason liquid blows and sprays angle (contact angle) and is set as 30~80 °, be controllable to as a result, present invention provide that surface roughness.It is so-called to blow and spray Angle (contact angle), refers in galvanized steel plain sheet longitudinal direction, the treatment fluid injection direction (hole axle of nozzle bore) of nozzle and plating Zinc steel plate surface angulation can not obtain sufficient surface roughness, another if the treatment fluid blows and sprays angle lower than 30 ° On the one hand, if more than 80 °, surface roughness appropriate is had exceeded.Above-mentioned mechanism is unclear, but thinks that trbasic zinc phosphate crystal exists The side that trbasic zinc phosphate treatment fluid is supplied to is grown up, to influence three-dimensional roughness.
Downstream side or upstream side of the trbasic zinc phosphate treatment fluid injection direction (hole axle of nozzle bore) of nozzle towards logical plate direction And form trbasic zinc phosphate treatment fluid blows and sprays angle.However, when making the trbasic zinc phosphate treatment fluid injection direction direction of nozzle lead to plate direction In the case where upstream (that is, in the case that angulation is acute angle between the upstream side and treatment fluid injection direction in logical plate direction), Return to ejection section once again in the presence of the treatment fluid sprayed to become difficult to ensure defined treatment conditions, therefore Fig. 4 as be described hereinafter It is shown, preferably make the treatment fluid injection direction of nozzle towards the downstream in logical plate direction (that is, the downstream side in logical plate direction and treatment fluid Angulation is acute angle between injection direction).
In general, galvanized steel plain sheet carries out logical plate in the horizontal direction in trbasic zinc phosphate process for producing line, therefore in galvanized steel plain sheet In the case that two sides carries out trbasic zinc phosphate processing, in top position and the lower position for carrying out the galvanized steel plain sheet of logical plate with horizontal direction Nozzle is respectively configured, to blow and spray upper surface from treatment fluid to galvanized steel plain sheet, lower surface.
In order to equably blow and spray treatment fluid in the width direction of galvanized steel plain sheet, grow trbasic zinc phosphate crystal equably, spray Mouth is preferably set to the gap nozzle set up along steel plate width side.
Fig. 4 shows the embodiment for the case where blowing and spraying trbasic zinc phosphate treatment fluid by gap nozzle, and Fig. 4 (A) is from side It observes and schemes obtained by gap nozzle, Fig. 4 (B) is to observe to scheme obtained by gap nozzle from the upstream side in logical plate direction.In Fig. 4,10 It is galvanized steel plain sheet for gap nozzle, 11, gap nozzle 10 is arranged along steel plate width direction.The gap nozzle can be in logical plate direction On be provided spaced apart it is multiple.
For gap nozzle 10, make treatment fluid injection direction (hole axle 100 of nozzle bore) towards galvanized steel plain sheet 11 The downstream in logical plate direction, and the treatment fluid in the galvanized steel plain sheet longitudinal direction for galvanized steel plate face blows and sprays angle, θ (in galvanized steel plain sheet longitudinal direction, the treatment fluid injection direction and galvanized steel plate face angulation of nozzle) is set as 30~80 ° Range.
Condition is blowed and sprayed as the trbasic zinc phosphate treatment fluid using gap nozzle 10, usually, it is proper that by gap nozzle 10 The injection liquid measure that the distance between galvanized steel plain sheet 11 is set as the width of the every 1m of 10~1000mm, gap nozzle is set as 5~100L/ Min, jet pressure are set as 0.1~5.0kgf/cm2Left and right.
Embodiment
Implement electrogalvanizing using steel plate of the common method to the plate thickness 0.7mm after cold rolling through annealing then to be impregnated in 3 seconds in 3.0g/L, 40 DEG C of surface adjustment treatment fluid (it uses Japanese Parkerizing (strains) to make " PL-ZN "), thus Implement surface adjustment processing.Next, will have the trbasic zinc phosphate treatment fluid formed as shown in table 1 to blow with defined as shown in table 2 Spray angle degree is blowed and sprayed from gap nozzle to galvanized steel plain sheet, and trbasic zinc phosphate system envelope is consequently formed.
It should be noted that gap nozzle is blowed and sprayed at trbasic zinc phosphate with the prominent form of Fig. 4 as using the gap nozzle Reason liquid blows and sprays condition, and the injection liquid measure that the distance between gap nozzle and steel plate are set as the every 1m width of 50mm, gap nozzle is set 0.5kgf/cm is set as 50L/min, jet pressure2。
[table 1]
PO4(g/L) 15.7
Zn(g/L) 1.4
Ni(g/L) 0.5~1.3
Mn(g/L) 0.5~3.5
NO3(g/L) 2.5
For gained trbasic zinc phosphate handles galvanized steel plain sheet, the adhesion amount composition surface of measurement trbasic zinc phosphate system envelope is thick Rugosity coefficient of friction, and it is uneven to corrosion resistance, appearance after sliding properties (compression moulding), coating adhesion, coating It is even to be evaluated.These above-mentioned measurements and evaluation are carried out in the following manner.
(1) measurement of the adhesion amount of trbasic zinc phosphate system envelope and Ni concentration (Ni content), Mn concentration (Mn content)
Only trbasic zinc phosphate system envelope is dissolved using 2 mass %+ ammonium hydroxide of ammonium dichromate, 14 mass % solution, by dissolution front and back Calculating envelope adhesion amount of poor quality.In addition, by ICP apparatus for analyzing luminosity in the liquid dissolved with trbasic zinc phosphate system envelope The concentration of Mn, Ni carry out quantitative analysis, and the Ni concentration and Mn concentration of trbasic zinc phosphate system envelope are calculated from the assay value.
(2) by the measurement of trbasic zinc phosphate crystal bring micro concavo-convex shape
Electron beam three-dimensional roughness resolver ((strain) Elionix society system " ERA-8800FE ") is used.With adding for 5kV Fast voltage, 15mm WD be measured, the sampling interval in direction is set as 1~5nm in face when measurement.For phosphoric acid amount of zinc adhesion More sample, to avoid carrying out golden vapor deposition by the electrification that electron beam irradiation generates.In flat part from the electronics of each position The scanning direction of beam and 12 μm of direction cut-out length or so of 500 or more roughness curves normal thereto, measure every list The fine protrusion number and average height of bit length.Arbitrarily select 10 positions as determination part in each sample.Utilize dress Subsidiary analysis software is set, it is high to calculate three-dimensional arithmetic average roughness Sa, three-dimensional maximum concave-convex surface from above-mentioned roughness curve Spend the surface roughness parameters such as Sz.If electron beam is irradiated in sample surface, the pollution of carbon main body is promoted, is embodied in sometimes In determination data.It is this to influence to be easy to become significant in the case where measurement region is small as so herein.Therefore, it is parsed in data During, the half that will measure the length (12 μm) in direction carries out Spline ultrafiltration as cut-off (cut-off) wavelength, to remove Go the influence.The correction of the present apparatus uses the VLSI Standard Co., Ltd SHS film scale from US National research institute NIST Standard (scale 18nm, 88nm, 450nm).
(3) measurement of coefficient of friction
To evaluate compression moulding, the coefficient of friction of each material to be tested measures in the following manner.Fig. 1 is to show used rub Wipe the explanatory diagram of the summary of factor detection device.In said device, by from it is being acquired for test material, be used to measure coefficient of friction Sample 1 is fixed on sample platform 2, which is fixed on the upper surface for the sliding stand 3 that can be moved horizontally.The following table of sliding stand 3 In face, being arranged has sliding stand supporting station 5 with the roller 4 of the following table face contact of sliding stand 3, can moving up and down, the first meter (it is used for by raising sliding stand supporting station 5 force snesor 7, and applies to by reinforcing rib 6 to measuring friction coefficient sample 1 The pushing load N added is measured) it is installed on sliding stand supporting station 5.Second dynamometric sensing is installed in an end of sliding stand 3 (it is used in the state of applying above-mentioned pushing force device 8, to the resistance to sliding F for moving sliding stand 3 in the horizontal direction It is measured).It is to be appreciated that the antirust of Sugimura chemical industry (strain) manufacture is cleaned oil " Preton as lubricating oil R352L " is coated on the surface of sample 1, and is tested.
Fig. 2, Fig. 3 are the shape for showing reinforcing rib used, the perspective view of size.The lower surface of reinforcing rib 6 is to be pushed State in the surface of sample 1 is slided.The shape of reinforcing rib 6 shown in Fig. 2 is the glide direction length 5mm of width 10mm, sample, The lower part at glide direction both ends is made of the curved surface of radius of curvature 1.0mmR, and the reinforcing rib lower surface that sample is pushed has width The plane of 10mm, glide direction length 3mm.The shape of reinforcing rib 6 shown in Fig. 3 is the glide direction length of width 10mm, sample 59mm, glide direction both ends lower part are made of the curved surface of curvature 4.5mmR, and the reinforcing rib lower surface that sample is pushed has width The plane of 10mm, glide direction length 50mm.
The measurement of coefficient of friction carries out under the conditions of as shown below two.
[condition 1]
Using reinforcing rib shown in Fig. 2, pushes load N and be set as: 400kgf, the hauling speed (level of sliding stand 3 of sample Movement speed) it is set as: 100cm/min.
[condition 2]
Using reinforcing rib shown in Fig. 3, pushes load N and be set as: the hauling speed (level of sliding stand 3 of 400kgf, sample Movement speed) it is set as: 20cm/min.
Friction coefficient μ between material to be tested and reinforcing rib is calculated using formula μ=F/N.
(4) the scratch resistance evaluation of mold
Using measuring friction coefficient device shown in FIG. 1, other than measuring coefficient of friction, repeat to implement 50 slidings examination It tests, investigation coefficient of friction increases number of repetition when 0.01 or more, occurs using the number of repetition as mold scratch critical heavy Again it counts, it is scratch resistance thus to evaluate mold.Here, if can not observe 0.01 or more repeating to implement 50 sliding tests Coefficient of friction increase, then be evaluated as 50 times or more.[condition 1] of experimental condition and above-mentioned " measurement of (3) coefficient of friction " It is identical.
(5) evaluation of coating adhesion
Coating adhesion is evaluated using secondary hydration resistant test.
According to car body manufacturing process, after carrying out common alkali degreasing, being adjusted followed by surface, in Japan Dipping 2 minutes in the phosphate treated liquid " PB-WL35 " of Parkerizing (strain) manufacture.Then, using Kansai Paint Co., " GT100 electrocoating paint " (bath temperature: 28~30 °) of Ltd. manufacture, electricity consumption deposition voltage 250V are powered 180 seconds and implement Electrodeposition coating toasts 20 minutes at 170 DEG C, forms electrodeposition coating (film thickness: 20 μm) and is used as material to be tested.With wide 2mm's Pocket knife carries out crosscutting (cross-cut) to the material to be tested film, takes out after impregnating 10 in 50 DEG C of pure water, uses grid glue Band carries out disbonded test, observes the removing situation of film.Also, the situation that the film survival rate after disbonded test is 95% or more Be evaluated as " 〇 ", the film survival rate after disbonded test be 85% or more, lower than 95% the case where be evaluated as " △ ", disbonded test The case where film survival rate afterwards is lower than 85% is evaluated as "×".
(6) after coating corrosion resistance evaluation
According to car body manufacturing process, after carrying out common alkali degreasing, being adjusted followed by surface, in Japan Dipping 2 minutes in the phosphate treated liquid " PB-WL35 " of Parkerizing (strain) manufacture.Then, using Kansai Paint Co., " GT100 electrocoating paint " (bath temperature: 28~30 °) electricity consumption deposition voltage 250V of Ltd. manufacture is powered 180 seconds and implements Electrodeposition coating toasts 20 minutes at 170 DEG C, forms electrodeposition coating (film thickness: 15 μm) and is used as material to be tested.With pocket knife to institute State material to be tested film carry out it is crosscutting after, under cycling condition discussed below carry out combined-circulation corrosion test, by hereafter Shown expanded width is measured, to evaluate corrosion resistance after coating.It is to be appreciated that for corrosion resistance after electrodeposition coating For, since the influence of Zn plating amount is also larger, it is 40g/m that Zn plating adhesion amount is made in this test2Sample into Row evaluation.
Brine spray 2 hours (5%NaCl, 35 °) → dry 4 hours (60 DEG C, 25%RH) → 2 hours wet (50 DEG C, 95%RH)
Each material to be tested is taken out after carrying out the combined-circulation corrosion test of 120 circulations under above-mentioned cycling condition, to next It is measured from maximum 5 points of the unilateral expanded width of transverse portions, using average value as expanded width, which is 0mm or more, it is evaluated as "○" lower than the case where 5mm, is evaluated as " △ " for 5mm or more, lower than the case where 7mm, be 7mm's or more Situation is evaluated as "×".
(7) the non-uniform evaluation of appearance
By visual observation and the appearance of micro- sem observation (multiplying power × 10) evaluation trbasic zinc phosphate processing galvanized steel plain sheet is uneven.Observation Area is 70mm × 150mm.Evaluation criteria is as shown below, and scoring as 4 or more is then " good ".
Scoring 1: 50% or more the area ratio exists with visually certifiable obvious uneven.
Scoring 2: though 50% or more the area ratio exists with visually certifiable obvious unevenly and can not visually confirm It is certifiable obvious uneven with micro- sem observation.
Scoring 3: 20% or more the area ratio exists lower than 50% with visually certifiable obvious uneven.
Scoring 4: though 20% or more the area ratio, exist lower than 50% with visually certifiable obvious uneven and with visual It can not confirm but certifiable obvious uneven with micro- sem observation.
Scoring 5: there is no certifiable obvious uneven with visual or micro- sem observation.
The above measurement and evaluation result are shown in table 2 and table 3 together with trbasic zinc phosphate treatment conditions.
According to table 2 and table 3, sliding properties, the mold of the trbasic zinc phosphate processing galvanized steel plain sheet of example of the present invention are scratch resistance to be changed It is apt to and high compression moulding can be obtained, in addition also uneven there is no appearance, corrosion resistance is also after coating adhesion and coating Excellent.
[table 2]
[table 3]
Description of symbols
1 measuring friction coefficient sample
2 sample platforms
3 sliding stands
4 rollers
5 sliding stand supporting stations
6 reinforcing ribs
7 first load cells
8 second load cells
9 tracks
10 gap nozzles
11 galvanized steel plain sheets
100 nozzle hole axles
N pushes load
F resistance to sliding

Claims (3)

1. trbasic zinc phosphate handles galvanized steel plain sheet, to have the galvanized steel plain sheet of trbasic zinc phosphate system envelope, the phosphoric acid at least single side Zinc handles galvanized steel plain sheet and is characterized in that,
The adhesion amount of trbasic zinc phosphate system envelope is 1.0~2.0g/m2, Mn content is that 3.0~8.0 mass %, Ni contents are 0.7 ~1.3 mass %,
The three-dimensional arithmetic average roughness Sa of envelope surface is 0.05~0.12 μm and three-dimensional maximum concave-convex surface height Sz is 0.4~0.9 μm.
2. trbasic zinc phosphate handles the manufacturing method of galvanized steel plain sheet, the system of galvanized steel plain sheet is handled for trbasic zinc phosphate described in claim 1 Method is made, the manufacturing method is characterized in that,
The trbasic zinc phosphate treatment fluid containing nickel ion and manganese ion is blowed and sprayed to the galvanized steel plain sheet of logical plate from nozzle, thus carries out phosphoric acid Zinc processing,
It is when blowing and spraying trbasic zinc phosphate treatment fluid from the nozzle to galvanized steel plain sheet, the galvanized steel plain sheet for galvanized steel plate face is long Treatment fluid on edge direction blow and spray angle (that is, in galvanized steel plain sheet longitudinal direction, the treatment fluid injection direction and galvanized steel of nozzle Plate face angulation) it is set as 30~80 °.
3. the manufacturing method of trbasic zinc phosphate processing galvanized steel plain sheet as claimed in claim 2, which is characterized in that blowed and sprayed to galvanized steel plain sheet The nozzle of trbasic zinc phosphate treatment fluid is the gap nozzle along the setting of steel plate width direction.
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