CN107109660A - The manufacture method of zinc-based metal plated steel sheet - Google Patents

The manufacture method of zinc-based metal plated steel sheet Download PDF

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Publication number
CN107109660A
CN107109660A CN201580061436.4A CN201580061436A CN107109660A CN 107109660 A CN107109660 A CN 107109660A CN 201580061436 A CN201580061436 A CN 201580061436A CN 107109660 A CN107109660 A CN 107109660A
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China
Prior art keywords
zinc
alkaline aqueous
aqueous solution
steel sheet
based metal
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Inventor
星野克弥
平章郎
平章一郎
古谷真
古谷真一
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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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc 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
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20—Other heavy metals

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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)

Abstract

The present invention provides a kind of manufacture method of zinc-based metal plated steel sheet, and methods described can remove the oxide of dezincify system coating surface by the contact with alkaline aqueous solution, further, it is possible to avoid the apparent problem caused by separating out the precipitate into alkaline aqueous solution.The manufacture method for the zinc-based metal plated steel sheet that the 1st invention for solving above-mentioned problem is related to is the manufacture method for the zinc-based metal plated steel sheet for having conversion zone on the surface of steel plate, and above-mentioned conversion zone is to include Zn4(SO4)1‑X(CO3)X(OH)6·nH2The oxide skin(coating) of crystal structure thing represented by O, it is used as the pre-treatment of above-mentioned conversion zone formation, following alkaline aqueous solutions are made to be contacted with zinc-based metal plated steel sheet more than 1.0 seconds, the alkaline aqueous solution contains the chelating agent for more than a kind in gluconic acid sodium salt, sodium glucoheptonate, sodium citrate, tartaric acid, arabonic acid, galactonic acid, D-sorbite, mannitol, glycerine, EDTA, sodium tripolyphosphate for adding up to more than 0.050mass%, and the pH of the alkaline aqueous solution is more than 10.0.

Description

The manufacture method of zinc-based metal plated steel sheet
Technical field
The present invention relates to the manufacture method for having zinc-based metal plated steel sheet of tool conversion zone.
Background technology
Zinc-based metal plated steel sheet is used in the extensive use centered on car body, household electrical appliances, building materials.On in such use Zinc-based metal plated steel sheet, set conversion zone, extrusion forming, raising corrosion resistance, the technology of the characteristic such as outward appearance to be in surface of steel plate Know.
But, for the zinc-based metal plated steel sheet before conversion zone is formed, all the time, had thickness less than in outermost layer 10nm Zn, the unnecessary oxide skin(coating) as the Al of impurity element etc..The unnecessary oxide skin(coating) can suppress such as trbasic zinc phosphate The reactivity of the chemical conversion treatments such as processing, chromate (Chromate) processing, needs to set to form sufficient conversion zone The reaction time of fixed length.
The increase in reaction time causes the operating costs such as cost of equipment, the increase of production line length, and electric power, natural gas Increase.
In this regard, by making steel plate be contacted with alkaline aqueous solution before conversion zone is formed, removing is present in zinc-based metal plated steel sheet table The unnecessary oxide skin(coating) of layer, the technology in shortening reaction time are known.
Recorded in patent document 1 make hot-dip galvanized steel sheet contacted with alkaline aqueous solution after with containing SiO2Chromate it is molten The technology that liquid is handled.
In addition, after being handled with alkaline aqueous solution, the technology that is intentionally formed oxide-film be also known.
The skill that oxide skin(coating) is formed after making hot-dip galvanized steel sheet be contacted with alkaline aqueous solution has been recorded in patent document 2,3 Art.
Recorded in patent document 4 and formed oxygen after being contacted on the surface for making alloyed hot-dip galvanized steel plate with alkaline aqueous solution The technology of compound layer.
Recorded in patent document 5 after being contacted on the surface for making hot-dip galvanized steel sheet with alkaline aqueous solution, formed and include Zn4 (SO4)1-X(CO3)X(OH)6·nH2The technology of the oxide skin(coating) of crystal structure thing represented by O.
Look-ahead technique document Prior Art
Patent document
Patent document 1：Japanese Unexamined Patent Publication 5-279868 publications
Patent document 2：Japanese Unexamined Patent Publication 2006-183074 publications
Patent document 3：Japanese Unexamined Patent Publication 2006-233280 publications
Patent document 4：Japanese Unexamined Patent Publication 2005-97741 publications
Patent document 5：Japanese Patent Application 2015-530230
The content of the invention
Brief summary of the invention
Invent problem to be solved
In the technology of patent document 1~5, it can be shortened for setting the anti-of conversion zone by the contact with alkaline aqueous solution Between seasonable.But, in usually used apparatus for continuous treatment, the precipitate for separating out Zn, Al into alkaline aqueous solution is attached to Deflection roll (deflecting roll), backing roll, produce impression, and then cause to be formed in conversion zone in surface of steel plate sometimes The apparent problems such as open defect are produced afterwards.
The present invention is to complete in view of the foregoing.It is an object of the present invention to provide a kind of system of zinc-based metal plated steel sheet Method is made, methods described can remove the unnecessary oxide skin(coating) of dezincify system coating surface by the contact with alkaline aqueous solution, and And, the apparent problem caused by separating out the precipitate into alkaline aqueous solution can be avoided.
Means for solving the problems
Further investigation of knowing clearly is repeated in order to solve above-mentioned problem in present inventor.As a result, find by Specific chelating agent is added in the alkaline aqueous solution used before conversion zone is formed, above-mentioned problem is can solve the problem that, so as to complete The present invention.More specifically, the present invention provides herein below.
The manufacture method for the zinc-based metal plated steel sheet that the 1st invention for solving above-mentioned problem is related to is that have on the surface of steel plate The manufacture method of the zinc-based metal plated steel sheet of conversion zone, it is characterised in that the conversion zone is to include Zn4(SO4)1-X(CO3)X(OH)6· nH2The oxide skin(coating) of crystal structure thing represented by O, as the pre-treatment for forming the conversion zone, makes following alkaline aqueous solutions Contacted with zinc-based metal plated steel sheet more than 1.0 seconds, the alkaline aqueous solution contain add up to more than 0.050mass% be selected from gluconic acid Sodium, sodium glucoheptonate, sodium citrate, tartaric acid, arabonic acid, galactonic acid, D-sorbite, mannitol, glycerine, More than a kind of chelating agent in EDTA, sodium tripolyphosphate, the pH of the alkaline aqueous solution is more than 10.0.
The manufacture method for the zinc-based metal plated steel sheet that the 2nd invention for solving above-mentioned problem is related to is described in the 1st invention The manufacture method of zinc-based metal plated steel sheet, it is characterised in that the pH of the alkaline aqueous solution is more than 12.6.
The effect of invention
According to the present invention, the oxide of dezincify system coating surface can be removed well by the contact with alkaline aqueous solution. Also, in the alkali process for shortening the conversion zone formation time, Al, Zn precipitate etc. can be reduced, so as to obtain Zinc-based metal plated steel sheet with the good conversion zone of outward appearance.
Brief description of the drawings
Fig. 1 is the schematic diagram for representing the metewand for evaluating open defect.
Embodiment
Hereinafter, embodiments of the present invention are illustrated.It should be noted that the invention is not restricted to following embodiment party Formula.In the present invention, so-called zinc-based metal plated steel sheet refers to that manufacture method is unrestricted, has in surface of steel plate and using zinc be used as main body The steel plate of envelope, includes steel plate that particle is dispersed with galvanized steel plain sheet, galvanized alloy steel plate, zinc coating etc..That is, zinc system coating bag Containing zinc coating, zn alloy coating, make particle be scattered in zinc formed by coating etc..
The present invention is the manufacture method of following zinc-based metal plated steel sheets, and the steel plate, which has to remove well, is present in zinc system The conversion zone of the unnecessary oxide skin(coating) on the surface of coating, i.e., include Zn4(SO4)1-X(CO3)X(OH)6·nH2Crystalline substance represented by O The oxide skin(coating) of body works.The present invention possesses following processes：For example, implementing the process of zinc system plating, being connect with alkaline aqueous solution Tactile process and formation includes Zn4(SO4)1-X(CO3)X(OH)6·nH2The work of the oxide skin(coating) of crystal structure thing represented by O Sequence.Hereinafter, each operation is illustrated.
- process of implementation zinc system plating-
First, the process for implementing zinc system plating is illustrated.In the process for implementing zinc system plating, implement zinc-plated side Method is not particularly limited, can be using usual ways such as galvanizing by dipping, electrogalvanizings.In addition, the processing bar of electrogalvanizing, galvanizing by dipping Part is not particularly limited, appropriate to use optimum condition.It should be noted that in the case of implementing galvanizing by dipping, from slag From the viewpoint of countermeasure, Al is preferably added in zinc-plated bath.In this case, the elemental composition beyond Al is not particularly limited.That is, In addition to Al, even if containing Pb, Sb, Si, Sn, Mg, Mn, Ni, Ti, Li, Cu etc., will not also damage the effect of the present invention.
Herein, the steel grade class for being carried out zinc-plated steel plate is not particularly limited, can be used mild steel, ultra-low carbon steel, IF steel, It with the addition of the various steel plates such as the high-tensile steel of various alloying elements.In addition, hot rolled steel plate, cold-rolled steel sheet can be used in above-mentioned steel plate Any of.The thickness of steel plate is not particularly limited.It should be noted that from for purposes such as car body, household electrical appliances, building materials From the viewpoint of, preferably 0.4~5.0mm.
In addition, in the process of implementation zinc system plating, after galvanizing by dipping is implemented, can also implement Alloying Treatment, make Into alloyed hot-dip galvanized steel plate.In the present invention, the condition of Alloying Treatment is not particularly limited, appropriate to be using optimum condition Can.
- the process contacted with alkaline aqueous solution-
Implement after the plating processing of zinc system, progress has used the contact of alkaline aqueous solution to handle.Make in contact processing The pH of alkaline aqueous solution is more than 10.0.When pH is less than 10.0, the removing of oxide skin(coating) becomes insufficient.If pH is 12.6 More than, then with the effect with the time of contact of aqueous alkali can be shortened, so it is preferred that.
On the other hand, from the viewpoint of the dissolving for preventing zinc system coating, the melanism for preventing appearance, pH is preferably Less than 14.0.
Contain the specific chelating agent for adding up to more than 0.050mass% in alkaline aqueous solution.If Al, Zn precipitate etc. Increase in alkaline aqueous solution, then the outward appearance of liquid turns into suspended liquid.In the present invention, make to contain in alkaline aqueous solution More than 0.050mass% chelating agent, can reduce Al, Zn precipitate etc..
Above-mentioned chelating agent is selected from gluconic acid sodium salt, sodium glucoheptonate, sodium citrate, tartaric acid, arabonic acid, galactolipin More than a kind in acid, D-sorbite, mannitol, glycerine, EDTA, sodium tripolyphosphate.From can with Al and Zn chelating and it is honest and clean From the viewpoint of valency, above-mentioned chelating agent is preferably gluconic acid sodium salt.
If total Al, the Zn's being less than in 0.050mass%, alkaline aqueous solution of chelator in alkaline aqueous solution Solubility increase becomes insufficient.From the viewpoint of precipitate from alkaline aqueous solution is reduced, contain in alkaline aqueous solution The amount of chelating agent is preferably more than 0.100mass%.On the other hand, chemically from the viewpoint of product cost, in alkaline aqueous solution The amount of the chelating agent contained is preferably below 10.0mass%.
From the viewpoint of the time of contact for shortening alkaline aqueous solution and steel plate, the temperature of alkaline aqueous solution is preferably 20 DEG C ~70 DEG C of scope, more preferably 40 DEG C~70 DEG C.
The species of alkaline assistant (alkali builder) is not limited.It should be noted that from reducing the viewpoint of cost Consider, preferably use the chemicals such as NaOH.In order to realize the pH of desired alkaline aqueous solution, alkaline assistant can be suitably adjusted Amount.In addition, in alkaline aqueous solution can also containing the material beyond the element contained in the zinc such as Zn, Al, Fe system plating solution, other into Point.
Alkaline aqueous solution is set not limited especially with the method that zinc-based metal plated steel sheet (the especially oxide skin(coating) on its top layer) is contacted It is fixed, have the method for making zinc-based metal plated steel sheet be impregnated in alkaline aqueous solution and being in contact with it, blow and spray alkaline aqueous solution and make its with it is zinc-plated It is method of steel plate contact etc..
The time for making zinc-based metal plated steel sheet be contacted with alkaline aqueous solution is more than 1.0 seconds.If the time of contact is less than 1.0 seconds, The oxide of dezincify system coating surface then can not be fully removed, therefore, for setting the shortening in reaction time of conversion zone to become It is insufficient.From the viewpoint of slave unit cost, productivity ratio, the time that zinc-based metal plated steel sheet is contacted with alkaline aqueous solution is set to be preferably 10.0 below the second.
, can be after the process of zinc system plating is implemented and real before or after alkaline aqueous solution processing in the present invention Apply skin-pass.For steel plate for the position that skin-pass roller is contacted, by the contact with roller, it is present in zinc system coating The unnecessary oxide skin(coating) of surface A l, Zn be removed, therefore, reactivity is improved.
- process of formation conversion zone-
Generally, make steel plate contacted with alkaline aqueous solution laggard water-filling wash, dry, then implement be used for set conversion zone, I.e., comprising Zn4(SO4)1-X(CO3)X(OH)6·nH2The processing of the oxide skin(coating) of crystal structure thing represented by O.
It is so-called to include Zn in the present invention4(SO4)1-X(CO3)X(OH)6·nH2The oxide of crystal structure thing represented by O Layer, refers to that zinc system coating is contacted and chemically reacted with chemical pretreatment solution, is consequently formed the reaction product in surface of steel plate Layer.As including Zn4(SO4)1-X(CO3)X(OH)6·nH2The formation processing of the oxide skin(coating) of crystal structure thing represented by O, For example, following process can be carried out：Oxide skin(coating) formation process, makes zinc-based metal plated steel sheet be contacted with the acid solution containing sulfate ion Afterwards, keep 1~60 second, then implement washing；Neutralisation treatment operation, makes the oxidation formed in above-mentioned oxide skin(coating) formation process The surface of nitride layer is contacted with alkaline aqueous solution, is kept in this condition more than 0.5 second, is then implemented washing, is dried.For alkalescence For the aqueous solution, containing being calculated as more than 0.01g/L P ion with P concentration, more than 0.1g/L carbon be calculated as with carbonate ions concentration Acid ion.In the present invention, there is Zn on the surface of steel plate4(SO4)1-X(CO3)X(OH)6·nH2Crystal structure represented by O Thing, the processing method is unrestricted.
Embodiment 1
Hereinafter, by embodiment, the present invention will be described.The scope of the technology of the present invention is not limited to following embodiment.
Implement galvanizing by dipping processing for thickness of slab 0.7mm, width 1100mm cold-rolled steel sheet, the steel plate formed after processing is entered Row skin-pass.Then, handled as the removing of oxide skin(coating), make steel plate and be adjusted to the alkali of the condition shown in table 1-1,1-2 Property the aqueous solution contact specify the time after, washed, dry.
Implement galvanizing by dipping processing and Alloying Treatment for thickness of slab 0.7mm, width 1100mm cold-rolled steel sheet, after processing The steel plate of formation carries out skin-pass, and, implement electrogalvanizing processing for thickness of slab 0.7mm, width 1100mm cold-rolled steel sheet, make After steel plate by above-mentioned processing is contacted according to same step with alkaline aqueous solution, washed, dried.
For by zinc-based metal plated steel sheet obtained from above-mentioned, evaluating the surface of the zinc system coating after alkaline aqueous solution processing The thickness of unnecessary oxide skin(coating), the open defect formed after conversion zone, and implement the suspended things contained in alkaline aqueous solution The measure of matter (SS).It should be noted that the pH of alkaline aqueous solution is measured using commercially available glass electrode.
Then, Zn is included as formation4(SO4)1-X(CO3)X(OH)6·nH2The oxide of crystal structure thing represented by O Layer processing, make steel plate be impregnated in be adjusted to containing 30g/L sodium acetate trihydrates, pH 1.5 sulfuric acid solution, use roller After rolling, kept for 10 seconds.Then, after being washed, dry.Then, using containing 9.8g/L pyrophosphoric acids and 0.48g/L carbonic acid The treatment fluid of sodium decahydrate carries out neutralisation treatment.
(1) measure of the thickness of unnecessary oxide skin(coating)
After contact with alkaline aqueous solution, the measure of thickness of the unnecessary oxide skin(coating) that is formed at zinc-based metal plated steel sheet uses Fluorescent x-ray analyzer.If the thickness (thickness of oxidation film) of oxide skin(coating) is below 4nm, can be evaluated is used for shorten The reaction time of conversion zone is set.If below 2nm, then it can be evaluated to further shorten the reaction time.
It is 30kV and 100mA by the voltage and current settings of bulb when determining, analyzing crystal is set as TAP, detects O-K Alpha ray.When measure O-K is Alpha-ray, in addition to its peak position, the intensity at background positions is also determined, so as to calculate The Alpha-ray net intensity of O-K.It should be noted that the time of integration at peak position and background positions is respectively 20 seconds.
In addition, on sample bench, it is set along with above-mentioned a series of sample and is divided into suitable size and is formed with film Thickness is the silicon wafer of 96nm, 54nm and 24nm silica envelope, is penetrated so as to can also calculate O-K α by these silica envelopes The intensity of line.Using above-mentioned data, oxide layer thicknesses and the standard curve of O-K alpha ray intensity are drawn, so as to calculate to aoxidize Silicon envelope conversion oxide layer thicknesses as material to be tested oxide layer thicknesses.
(2) after surface oxidation treatment open defect and thickness of oxidation film evaluation
Hot-dip galvanized steel sheet, alloyed hot-dip galvanized steel plate, electrogalvanizing for carrying out contacting processing with alkaline aqueous solution Steel plate, to be formed after the processing of oxide skin(coating) being implemented to surface, by visual observation and micro- sem observation evaluate open defect. That is, prepare the pH containing 5.0g/L ferrous sulfate, the aqueous solution of 50g/L sodium acetate heptahydrates with sulfuric acid being adjusted to 2.0 Obtained from treatment fluid, 3 μm of side is turned into thickness on the various clad steel sheets that contact processing is being carried out with alkaline aqueous solution Formula is coated with the treatment fluid, after being kept for 10 seconds, is washed, dried, and implements to form the processing of oxide skin(coating).It should be noted that Viewing area is 70mm × 150mm.Using the outward appearance sample shown in Fig. 1 as benchmark, given with 1~5 and give scoring, evaluated.4 Divide and represent good, 5 points of expressions are better.
(3) measure of suspended material (SS)
The alkaline aqueous solution after zinc-based metal plated steel sheet 100t processing is gathered, is carried out using aperture for 1 μm of membrane filter Suction filtration.Weight is determined after filter material is dried in 110 DEG C, mg/L is scaled.Manufacture when recording the value more than 10mg/L. If the steel plate treating capacity more than 10mg/L is more than 3000t, it can be evaluated from the viewpoint of productivity ratio to be good.In addition, right The steel plate more than 10mg/L is remained as after being handled in 5000t, is evaluated as (being designated as " ＞ in table 1-1,1-2 in the absence of suspended material 5000”).The measure is not implemented in No.1,54 and 56 for not carrying out aqueous alkali processing.
Table 1-1,1-2 will be shown in by result from above.It should be noted that No.15 and No.41 experimental condition Identical, No.20 is identical with No.28 experimental condition.
[table 1-1]
According to table 1-1,1-2, it is known that following item.
For No.1~57, the surface analysis removed using aqueous alkali after unnecessary oxide skin(coating) is implemented.
For not carrying out comparative example No.1,54 and 56 of alkaline aqueous solution contact processing, the thickness of oxide skin(coating) is 7 ~10nm, fails fully to remove.
Although No.2 and 3 is the contact implemented with alkaline aqueous solution but chelating agent is not added with from alkaline aqueous solution Viewpoint considers not sufficient example (comparative example).Oxide layer can fully be removed.However, the output increase of steel plate When, suspended material is generated in alkaline aqueous solution, makes appearance degradation.
Although No.4 and 11 is to implement the contact with the alkaline aqueous solution containing chelating agent but the concentration of chelating agent is not filled The example (comparative example) divided.Oxide layer can fully be removed.However, during the output increase of steel plate, in alkaline aqueous solution The middle suspended material of generation.
Although No.19 and 23 is to implement the contact with the alkaline aqueous solution containing chelating agent but time of contact short example Sub (comparative example).The thickness of oxide skin(coating) is 6~7nm, fails fully to remove.
Although No.27 and 34 is to implement the contact with the alkaline aqueous solution containing chelating agent but example low pH (compares Example).The thickness of oxide skin(coating) is 7nm, fails fully to remove.
The example of the present invention that it is the influence that pH is confirmed under conditions of 1.0 seconds in time of contact that No.24 and 28~33, which is,.If pH is More than 12.6, then even if time of contact can also to remove oxide-film to below 2nm within 1.0 seconds, used so as to further shorten In the reaction time for setting conversion zone.
Embodiment 2
For No.2~53,55,57, to including Zn4(SO4)1-X(CO3)X(OH)6·nH2Crystal structure thing represented by O Oxide skin(coating) analyzed.
(4)Zn4(SO4)1-X(CO3)X(OH)6·nH2O confirmation
Using diameter 0.15mm, long 45mm stainless steel brush and ethanol, wipe and include Zn4(SO4)1-X(CO3)X(OH)6· nH2The oxide skin(coating) of crystal structure thing represented by O, the ethanol that suction filtration is obtained, in the form of powdered ingredients extract envelope into Point.For gathering in powder form by film component, implement C's by heating up analysis using gas chromatography-mass spectrometry analysis instrument Quantitative analysis.The leading portion of gas chromatography-mass spectrometry analysis instrument is connected with thermal decomposition furnace.By the powder gathered in thermal decomposition furnace examination Sample inserts about 2mg, the temperature of thermal decomposition furnace is warming up to 500 DEG C from 30 DEG C with 5 DEG C/min of programming rate, will be in thermal decomposition furnace The gas of generation is delivered in gas chromatography-mass spectrometry analysis instrument with helium, analysis gas composition.Column temperature when GC/MS is determined It is set as 300 DEG C.
C existing forms
For similarly powdered and gather by film component, using gas chromatography-mass spectrometry analysis, analyze C presence Form.
Zn, S, O, H existing forms
Using x-ray photoelectron spectroscopy device, S, Zn, O existing forms are analyzed.Use AlKa monochromatization rays Source, implements to determine equivalent to the narrow spectrum (narrow) of Zn LMM, S 2p power spectrum.
P existing forms
Using X-ray absorption fine structure device, P existence is analyzed.Use high energy acclerator research aircraft Structure Photon Factory beam (beam line) BL27A, ZAFS (X-ray absorption end fine structure) is implemented in room temperature Measure.The radiating light of monochromatization is irradiated to the specimen surface Jing Guo degreasing, the full electricity of electric current metering is absorbed by using sample Sub- yield method (TEY) determines the absorption edge XANES (Near edge X-ray adsorption fine structure) of P-K shells.
The crystallization water is quantified
Using differential thermal balance is shown, less than 100 DEG C of weight decrement is determined.Measure has used about 15mg powdered samples.Will After in sample guide device.1000 DEG C, heat during record heating are warming up to from room temperature (about 25 DEG C) with 10 DEG C/min of programming rate Change again.
The determination of crystal structure
Implement similarly powdered and the X-ray diffraction by film component gathered, estimate crystal structure.Target uses Cu, Implement to determine under conditions of accelerating potential 40kV, tube current 50mA, sweep speed 4deg/min, 2~90 ° of scanning range.
Hereinafter, for No.2~38,40~53,55,57, obtained result is stated.
Gas chromatography-mass spectrometry analysis are carried out, as a result CO are able to confirm that between 150 DEG C~500 DEG C2Release, it is known that C Exist with the form of carbonate.
Analyzed using x-ray photoelectron spectroscopy device, as a result, observed near 987eV equivalent to ZnL MM's Peak, it is known that Zn exists with the state of zinc hydroxide.Similarly, peak equivalent to S 2p is observed near 171eV, it is known that S with The form of sulfate is present.
Analyzed using X-ray absorption fine structure device, as a result, observed near 2153,2158,2170eV Peak, it is known that P exists with the form of pyrophosphate.
According to the result for showing differential thermal balance, the weight that 11.2% is confirmed below 100 DEG C is reduced, it is known that contain crystallization Water.
The result of X-ray diffraction, 2 θ be 8.5 °, 15.0 °, 17.4 °, 21.3 °, 23.2 °, 26.3 °, 27.7 °, 28.7 °, 32.8 °, 34.1 °, 58.6 °, 59.4 ° are nearby observed diffraction maximum.
Result and composition ratio more than, charge balance, contain Zn4(SO4)0.95(CO3)0.05(OH)6· 3.3H2Crystal structure material represented by O.
Carried out for No.39 detailed by film analysis.
Gas chromatography-mass spectrometry analysis are carried out, as a result CO are able to confirm that between 150 DEG C~500 DEG C2Release, it is known that C Exist with the form of carbonate.
Analyzed using x-ray photoelectron spectroscopy device, as a result, observed near 987eV equivalent to ZnL MM's Peak, it is known that Zn exists with the state of zinc hydroxide.Similarly, peak equivalent to S 2p is observed near 171eV, it is known that S with The form of sulfate is present.
Analyzed using X-ray absorption fine structure device, as a result, observed near 2153,2158,2170eV Peak, it is known that P exists with the form of pyrophosphate.
According to the result for showing differential thermal balance, the weight that 9.4% is confirmed below 100 DEG C is reduced, it is known that contain the crystallization water.
The result of X-ray diffraction, 2 θ be 8.8 °, 15.0 °, 17.9 °, 21.3 °, 23.2 °, 27.0 °, 29.2 °, 32.9 °, 34.7 °, 58.9 ° are nearby observed diffraction maximum.
Result and composition ratio more than, charge balance, contain Zn4(SO4)0.8(CO3)0.2(OH)6·2.7H2O Represented crystal structure material.

Claims (2)

1. a kind of manufacture method of zinc-based metal plated steel sheet, the zinc-based metal plated steel sheet has conversion zone on the surface of steel plate, described zinc-plated It is that the manufacture method of steel plate is characterised by, the conversion zone is to include Zn4(SO4)1-X(CO3)X(OH)6·nH2Represented by O The oxide skin(coating) of crystal structure thing, as the pre-treatment for forming the conversion zone, makes following alkaline aqueous solutions and zinc-based metal plated steel sheet Contact more than 1.0 seconds, the alkaline aqueous solution contain add up to more than 0.050mass% be selected from gluconic acid sodium salt, glucoheptonic acid Sodium, sodium citrate, tartaric acid, arabonic acid, galactonic acid, D-sorbite, mannitol, glycerine, EDTA, sodium tripolyphosphate In more than a kind of chelating agent, the pH of the alkaline aqueous solution is more than 10.0.
2. the manufacture method of zinc-based metal plated steel sheet as claimed in claim 1, it is characterised in that the pH of the alkaline aqueous solution is More than 12.6.
CN201580061436.4A 2014-11-12 2015-11-09 The manufacture method of zinc-based metal plated steel sheet Pending CN107109660A (en)

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