CN107541722A - Zinc-based metal plated steel sheet phosphate solution, Zinc-based metal plated steel sheet treated with phosphate and its manufacture method - Google Patents
Zinc-based metal plated steel sheet phosphate solution, Zinc-based metal plated steel sheet treated with phosphate and its manufacture method Download PDFInfo
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- CN107541722A CN107541722A CN201710496204.2A CN201710496204A CN107541722A CN 107541722 A CN107541722 A CN 107541722A CN 201710496204 A CN201710496204 A CN 201710496204A CN 107541722 A CN107541722 A CN 107541722A
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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
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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
- 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
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/50—Controlling or regulating the coating processes
- C23C2/52—Controlling or regulating the coating processes with means for measuring or sensing
- C23C2/526—Controlling or regulating the coating processes with means for measuring or sensing for visually inspecting the surface quality of the substrate
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
Abstract
The invention discloses the Zn comprising 500~2000ppm2+, 50~1000ppm Ni+And 3000~40000ppm Mg2+Zinc-based metal plated steel sheet phosphate solution and the discoloration-resistant and the excellent Zinc-based metal plated steel sheet treated with phosphate of film adherability and its manufacture method using the solution.
Description
Technical field
Discoloration-resistant and film adhesion the present invention relates to a kind of zinc-based metal plated steel sheet phosphate solution and using the solution
The excellent Zinc-based metal plated steel sheet treated with phosphate of property and its manufacture method
Background technology
Process of the phosphate coating processing as application or lamination, is widely used in automobile and household electrical appliance etc..With regard to use
For zinc-based metal plated steel sheet in automobile and household electrical appliance etc., the application and film adhesion force of its own are low, therefore, typically pass through
Phosphate treated seeks the raising of application and film adherability.
In addition, when carrying out phosphate treated to zinc-based metal plated steel sheet using the phosphate solution of commercialization, although painting can be made
Dress adhesiveness is significantly improved, but film adherability improves seldom.It was by phosphate coating and laminated film in the past
Between be additionally formed the excellent PVC film of adhesion to overcome the problem.But most immediate cause environmental problem etc., at present lamination
The trend in steel plate field is stops using PVC film, thus, it is desirable to develop a kind of film that can improve phosphate coating itself
The technology of adhesiveness.
In addition, it is as described above, with the simplification of the membrane structure of laminate steel, in the base formed with phosphate coating
When surface discolouration is produced on plinth steel plate, the problem of this surface discolouration can be directly exposed to outside be present, therefore, there is still a need for opening
Send the technology for the discoloration-resistant that can improve phosphate coating.
The content of the invention
Technical problems to be solved
Multiple first purpose of the present invention are to provide a kind of zinc-based metal plated steel sheet phosphate solution, the resistance to change using the solution
Color and the excellent Zinc-based metal plated steel sheet treated with phosphate of film adherability and its manufacture method.
Technical scheme
An aspect of of the present present invention, there is provided a kind of zinc-based metal plated steel sheet phosphate solution, it includes 500~2000ppm Zn2 +, 50~1000ppm Ni+And 3000~40000ppm Mg2+。
Another aspect of the present invention, there is provided a kind of Zinc-based metal plated steel sheet treated with phosphate, it includes zinc-based metal plated steel sheet and formation
Phosphate coating at least one side of the zinc-based metal plated steel sheet, the phosphate coating based on laser microscope for
The three-dimensional table area ratio of bivariate table area is 1.7~8.8.
Another aspect of the present invention, there is provided a kind of manufacture method of Zinc-based metal plated steel sheet treated with phosphate, it includes following step
Suddenly：Prepare zinc-based metal plated steel sheet；Degreasing is carried out to the surface of the zinc-based metal plated steel sheet；Utilize plating of the surface conditioner to the degreasing
The surface of zinc system steel plate carries out surface adjustment processing；And adjust the zinc-plated of processing by surface described using phosphate solution
It is that phosphate coating is formed on the surface of steel plate, wherein, the phosphate solution includes 500~2000ppm Zn2+, 50~
1000ppm Ni+And 3000~40000ppm Mg2+。
Beneficial effect
The discoloration-resistant and film adherability of Zinc-based metal plated steel sheet treated with phosphate made according to the present invention are very excellent, from
And the base material of laminate steel can be preferably used as.
Further, Zinc-based metal plated steel sheet treated with phosphate made according to the present invention can also be preferably used as plastic layer compressed steel
The base material of plate.
Brief description of the drawings
Fig. 1 is the SEM image that the surface of each test piece to being manufactured in embodiment 1 is observed.
Fig. 2 is the SEM image that the surface of each test piece to being manufactured in embodiment 2 is observed.
Embodiment
, it is known that the needle-like shape phosphate crystal generally in epithelium is fine and when densely being formed, phosphate coating it is viscous
Attached property can be improved.Because grappling (anchoring) effect.
But the result of study of the present inventor is, although needle-like shape phosphate crystal as described above can be improved and applied
Adhesiveness between film, but the adhesiveness between film can be reduced on the contrary.Therefore, the present inventor is in order to provide a kind of and film
The excellent phosphate coating of adhesiveness and conduct in-depth research, its result obtains following knowledge and opinion.
(1) it is different from film, for film, in order to improve the film adherability of phosphate coating, it is necessary to make phosphoric acid
Salt crystallizes to maximize with the contact area of film.
(2) therefore, it is necessary to suitably control the form (morphology) of the phosphate crystal in phosphate coating, can be with
By phosphate crystal be formed as major axis length is shorter, slightly circle and thicker form in the direction of the width, without being created as pin
Shape, so as to make the contact area of phosphate crystal and film maximize.
(3), can be by appropriate as a method for forming the phosphate crystal with form as described above
The composition and phosphate treated condition of ground control phosphate solution are realized.
Below, the zinc-based metal plated steel sheet of one aspect of the present invention is described in detail with phosphate solution.
The zinc-based metal plated steel sheet of an aspect of of the present present invention includes 500~2000ppm Zn with phosphate solution2+, 50~
1000ppm Ni+And 3000~40000ppm Mg2+。
Zn2+：500~2000ppm
Zinc ion is the neccessary composition for forming phosphate crystal.When the content of zinc ion is too low, phosphate be present
Crystallization formed thick and it is uneven the problem of.Therefore, zinc ion preferably comprises more than 500ppm, more preferably comprising 800ppm with
On.But when the content of zinc ion is excessive, the phosphate crystal of very dense needle-like is formed, so as to there is film adhesion
Property reduce the problem of.Therefore, zinc ion preferably comprises below 2000ppm, more preferably comprising below 1700ppm.
Ni2+：50~1000ppm
Nickel ion is the composition added to improve the corrosion resistance of phosphate coating, heat resistance and film adherability.
In the present invention, in order to show this effect, nickel ion preferably comprises more than 50ppm, more preferably comprising more than 300ppm.But
It is, when the content of nickel ion is excessive, the phosphate crystal of very dense needle-like to be formed, so as to there is film adherability reduction
The problem of.Therefore, nickel ion preferably comprises below 1000ppm, more preferably comprising below 400ppm.
Mg2+：3000~40000ppm
Magnesium ion is the composition added to improve the corrosion resistance of phosphate coating, heat resistance and film adherability.Enter
One step, in the present invention, for phosphate crystal in phosphate coating be formed as major axis length it is shorter, in width
Upper slightly circle and thicker form, without being created as needle-like, magnesium ion is the composition for playing main function.In the present invention, it is
Such effect is shown, magnesium ion preferably comprises more than 3000ppm, more preferably comprising more than 5000ppm, further preferably include
More than 8000ppm.But when the content of magnesium ion is excessive, the excessively round phosphate crystal such as phosphophyllite tissue is formed, no
Only it is unfavorable for the raising of adhesion, the problem of reducing the physical properties such as corrosion resistance, heat resistance is also present.Therefore, magnesium ion is excellent
Choosing includes below 40000ppm, more preferably comprising below 30000ppm, further preferably comprising below 20000ppm.
Although species and its content only by suitably controlling the cation constituent in phosphate solution as described above
Can realizes the desired effect of the present invention, but by controlling following condition its effect is maximized simultaneously.
Preferably, the PO contained in the phosphate solution4 3-Concentration control be 5000~40000ppm.Work as phosphate
The PO contained in solution4 3-Concentration it is too low when, oxidation with free acid, reduction reaction deficiency, consequently, it is possible to making phosphate knot
Crystalline substance becomes thick.Therefore, the PO4 3-Concentration be preferably controlled to more than 5000ppm, more preferably control be more than 6000ppm.
But work as PO4 3-Excessive concentration when, phosphate coating becomes blocked up, and excessive etching can occur, consequently, it is possible to making
Adhesion strength between base material reduces.Therefore, the PO4 3-Concentration be preferably controlled to below 40000ppm, more preferably control be
Below 30000ppm.
NO is also included in the phosphate solution3 -, the NO3 -Concentration be preferably controlled to 5000~40000ppm.As above
Described nitrate ion plays a part of accelerator, can be with HNO3、NaNO3Form input.As the NO3 -Concentration mistake
When low, the thickness of phosphate coating becomes too thin, consequently, it is possible to reducing reaction.Therefore, the NO3 -Concentration preferably control
For more than 5000ppm, more preferably control is more than 6000ppm, still, works as NO3 -Excessive concentration when, phosphatic adhesion amount mistake
More, the size of crystal grain is excessively fine, consequently, it is possible to reducing adhesion.Therefore, the NO3 -Concentration be preferably controlled to
Below 40000ppm, more preferably control is below 30000ppm.
The acid of the phosphate solution is preferably 2~20 than (total acidity/free acidity).Acid is than being in solution management project
One of very important factor, when acid than it is too low when, it is not easy to produce etching, consequently, it is possible to being not easily formed phosphoric acid salted hide
Film.Therefore, the lower limit of the sour ratio is preferably 2, and more preferably 8.But when acid than it is excessive when, phosphatic adhesion amount is excessive,
The size of phosphate crystal grain is excessively fine, consequently, it is possible to reducing adhesion.Therefore, the upper limit of the sour ratio is preferably 20,
More preferably 15.
Below, the discoloration-resistant to another aspect of the present invention and the excellent phosphate-treated galvanized steel of film adherability
Plate is described in detail
The Zinc-based metal plated steel sheet treated with phosphate of one aspect of the present invention includes zinc-based metal plated steel sheet and is formed at zinc-plated system's steel
Phosphate coating at least one side of plate.Zinc-plated system's steel as the base material of the Zinc-based metal plated steel sheet treated with phosphate of the present invention
Plate, such as plated steel sheet, hot-dip galvanized steel sheet, alloyed hot-dip galvanized steel plate, hot dip galvanized zinc alloy steel plate can be used each
Kind zinc-based metal plated steel sheet.Now, in the present invention, to the species of the alloying element included in the coating layer of the zinc-based metal plated steel sheet
And composition range does not limit particularly.
The three-dimensional table area ratio for bivariate table area based on laser microscope of the phosphate coating is preferably
1.7~8.8, more preferably 2.0~7.2, it is further preferably 2.6~6.0.When the ratio is less than 1.7, although phosphate crystal
With than relatively round and thick form, but most phosphate crystal is relative to the lamination of zinc-based metal plated steel sheet and phosphate coating
Direction obliquely arranges so that and it is few with the contact area of film, so as to cause film adhesion force to be deteriorated.On the other hand, when described
When ratio is more than 8.8, phosphate crystal is formed as very dense needle-like so that and it is small with the contact area of film, so as to cause
Adhesiveness is deteriorated.
In the present invention, to the three-dimensional table area for bivariate table area based on laser microscope of phosphate coating it
The assay method of ratio does not limit particularly, for example, can determine by the following method.That is, using software image system
Analysis (analySIS) equipment of (Soft Image System) company, determined in 100 μ m, 100 μm of areal extent three-dimensional
Surface area and bivariate table area, so as to computational chart area ratio, specifically, phosphate knot can be determined by determining three-dimensional roughness
Brilliant height, and accumulated by analysis (analysis) equipment to determine the three-dimensional cross-sectional of phosphate crystal, so as to determine phosphorus
The three-dimensional table area of hydrochlorate epithelium, the perspective plane of phosphate crystal is determined by analysis (analysis) equipment, so as to
The bivariate table area of phosphate coating is determined, and the three-dimensional table area and two-dimensional surface of determined phosphate coating can be passed through
Product carrys out computational chart area ratio.
According to one, the average circularity of the phosphate crystal of the phosphate coating can be 0.47~0.96, preferably
It can be 0.50~0.85, more preferably can be 0.55~0.70.When average circularity is less than 0.47, phosphate crystal has
Typical salmoite (hopeite) form so that tailed off with the contact area of film, thus may become film adherability
Difference.On the other hand, when average circularity is more than 0.96, phosphate crystal is relative to zinc-based metal plated steel sheet and the layer of phosphate coating
Pressure direction obliquely arranges so that is tailed off with the contact area of film, consequently, it is possible to making film adhesion force be deteriorated.It is here, flat
Equal circularity refers to assume that the projected area of one and the phosphate crystal of each indefinite shape has the feelings of circle of the same area
Under condition, the numerical value that is averaged to the numerical value of its circumference divided by particle circumference, the value is closer to 1, then it represents that proper circle
The phosphate crystal of shape is more.
According to one, the quantity of the per unit area of the phosphate crystal of the phosphate coating can be 0.3~2.3
Individual/μm2, preferably can be 0.5~2.1/μm2, more preferably can be 0.8~1.9/μm2.When the particle of per unit area
Quantity is less than 0.3/μm2When, the size of phosphate crystal is excessively thick, is crushed consequently, it is possible to phosphate occurs in processing
Or the phenomenon crushed, on the other hand, when the amounts of particles of per unit area is more than 1.7/μm2When, the size of phosphate crystal
It is too small, so as to be difficult to ensure that sufficient adhesion amount, resistance to oxidation discolouration etc. thus can be caused to be deteriorated, it is difficult to which holding is filled with film
The adhesion divided.
According to one, the epithelium adhesion amount of the phosphate coating can be 0.3~2.3g/m2.When epithelium adhesion amount mistake
When low, desired film adherability may be difficult to ensure that.Therefore, the lower limit of the epithelium adhesion amount is preferably 0.3g/m2,
More preferably 1.0g/m2.But when epithelium adhesion amount is blocked up, durability is fragile, so as to may result in because of external impact
Phosphate coating easily comes off.Therefore, the upper limit of the epithelium adhesion amount is preferably 2.3g/m2, more preferably 1.5g/m2。
The discoloration-resistant and film adherability of the Zinc-based metal plated steel sheet treated with phosphate of the present invention are very excellent, so as to excellent
From the base material for making laminate steel.Further, the Zinc-based metal plated steel sheet treated with phosphate manufactured in the present invention can also be used preferably
Make the base material of plastic lamination steel plate.According to one, Zinc-based metal plated steel sheet treated with phosphate of the invention temperature be 50 DEG C, it is relatively wet
Spend under the conditions of the constant temperature and humidity for 95% after 24 hours, there can be less than 2.0 whiteness deviation (Δ L*) value.Wherein,
Whiteness deviation refers to by the whiteness difference before and after 24 hours.
Below, the discoloration-resistant to another aspect of the present invention and the excellent Zinc-based metal plated steel sheet treated with phosphate of film adherability
Manufacture method be described in detail.
First, zinc-based metal plated steel sheet is prepared.As previously described, the base material as Zinc-based metal plated steel sheet treated with phosphate of the invention
Zinc-based metal plated steel sheet, can use as plated steel sheet, hot-dip galvanized steel sheet, alloyed hot-dip galvanized steel plate, galvanizing by dipping close
The various zinc-based metal plated steel sheets such as golden steel plate, in of the invention, for the alloying element included in the coating layer of the zinc-based metal plated steel sheet
Species and composition range do not limit particularly.
Then, degreasing is carried out to the surface of the zinc-based metal plated steel sheet.This step is institute on the surface for remove zinc-based metal plated steel sheet
The step of oil of attachment.When oil be present on the surface of zinc-based metal plated steel sheet, phosphorus can not be formed well because hindering and etching
Hydrochlorate epithelium, therefore, the step are the step of implementation to prevent problem above.
Then, surface adjustment processing is carried out to the surface of the zinc-based metal plated steel sheet of the degreasing using surface conditioner.It is zinc-plated
Be steel plate after degreasing process, its surface almost loses activity a little in structure, therefore, is directly formed after degreasing process
During phosphate coating, coarse and thick epithelium can be obtained.Therefore, before phosphate coating is formed, it is preferable to carry out to described
The surface of the zinc-based metal plated steel sheet of degreasing applies free energy and makes the increased surface adjustment processing of quantity of active site.
In the present invention, the method that processing is adjusted to surface does not limit particularly, can be by by the zinc-plated of the degreasing
It is to be extruded (squeezing) after steel plate is impregnated in the surface conditioner to implement.
According to one, the surface conditioner used in the surface adjustment can be at titanium colloid (colloid) system activity
Manage agent.
According to one, the content of the titanium contained in the titanium colloid system active treating agent can be 0.05~0.6 weight %,
It is preferred that can be 0.2~0.4 weight %.When the content of the titanium is less than 0.05 weight %, phosphate crystal may become
Excessively thick, on the other hand, when the content of the titanium is more than 0.6 weight %, phosphate crystal may become excessively dense,
And it is likely to form as needle-like.
Then, phosphoric acid is formed on the surface of the zinc-based metal plated steel sheet that processing is adjusted by surface using phosphate solution
Salt epithelium.Now, the composition included in phosphate solution and acid than etc. as previously described.
In the present invention, do not limited particularly for the method for forming phosphate coating, can be by passing through table by described
The zinc-based metal plated steel sheet of face adjustment processing is impregnated in the phosphate solution or sprays phosphate solution in its surface to implement.
According to one, when forming the phosphate coating, the surface temperature of the zinc-based metal plated steel sheet can be 50~70
℃.When the surface temperature is less than 50 DEG C, because activity less causes to react slow progress, productivity thus may be reduced.But
It is, it is not only unfavorable in economic aspect when surface temperature is too high, and slurry (slurry) is largely generated because etching fast, because
This is not preferred.Therefore, the upper limit of the surface temperature of the zinc-based metal plated steel sheet is preferably controlled to 70 DEG C, and more preferably control is 60 DEG C.
Below, the present invention is more specifically illustrated by embodiment.It is to be noted, however, that following embodiments
It is only used for illustrating the present invention and making materialization of the present invention, is not intended to limit the interest field of the present invention.Because the present invention's
Interest field is determined by content and the content thus, it is possible to rationally derive described in claims.
(embodiment 1)
First, other conditions be all set to it is constant in the case of, only change phosphate solution in Zn2+Concentration, from
And totally 9 test pieces are made, the form (morphology) of phosphate crystal is observed obtained each test piece, and film is adhered to
Property is evaluated.Now, in all test piece manufactures, the Ni for including 350ppm has been used+, 10000ppm Mg2+、
20000ppm PO4 3-, 25000ppm NO3 -And acid is than the phosphate solution (Zn for 102+Concentration is recorded in table 1 below),
Surface conditioner has used the titanium colloid system active treating agent of the titanium containing 0.2 weight %, zinc-plated when forming phosphate coating
The surface temperature for being steel plate is 55 DEG C, and epithelium adhesion amount is 1.3~1.5g/m2。
Then, observed using sweep electron microscope (Scanning Electron Microscope, SEM) obtained
Each test piece surface, its result is shown in Fig. 1 and table 2 below.Wherein, Fig. 1 a~Fig. 1 g be respectively to test piece 1-1~
The SEM image that 1-7 surface is observed.
Then, the discoloration-resistant and film adherability of obtained test piece are evaluated.The specific of film adherability is commented
Valency method and evaluation criterion are as follows.On the surface of obtained each test piece after laminated film, cross-cut (cross-cut) into
5mm × 5mm, and the AEG-process (Erichsen) for implementing 8mm observes whether film at normal temperatures is peeled off afterwards, and in constant temperature and humidity
Placed 2 hours in machine (65 DEG C, 95%), whether viewing film is peeled off.The result of observation, if film is not peeled off completely,
" 5 " are evaluated as, if when being peeled off by force with the sharp object such as such as knife on working position, there is the possibility being stripped, then
" 4 " are evaluated as, if the stripping of film occurs at the position of cross-cut (cross-cut), " 3 " are evaluated as, if handed over
Pitch the position of cutting and the stripping of film occurs for the position of AEG-process, be then evaluated as " 2 ", in the event of the stripping of film,
Then it is evaluated as " 1 ".Its result is shown in table 2 below.
Table 1
| Test piece name | Test piece 1-1 | Test piece 1-2 | Test piece 1-3 | Test piece 1-4 | Test piece 1-5 | Test piece 1-6 | Test piece 1-7 |
| Zn2+Concentration (ppm) | 400 | 500 | 800 | 1000 | 1500 | 2000 | 3500 |
Table 2
With reference to table 2 it has been confirmed that meeting the Zn proposed in the present invention2+In example 1-1~1-5 of concentration, not only film
Adhesiveness is excellent, and with less than 2.0 excellent whiteness deviation.
In contrast, in comparative example 1-1, Zn2+Concentration be not up to the scope that proposes in the present invention, so as to because of phosphate
It is reactive insufficient and cause phosphate crystal to fail normal growth, the crystal size being consequently formed is small and is formed sparse,
Cause the quantity of per unit area also few.Thus, film adherability and resistance to oxidation discolouration are illustrated as very poor.In addition, than
Compared with example 1-2, Zn2+Concentration beyond the scope proposed in the present invention so that phosphate crystal is formed as typical salmoite
(hopeite) form, thus surface area ratio and average circularity show small.Thus, film adherability is shown as very poor.
(embodiment 2)
Then, other conditions be all set to it is constant in the case of, only change phosphate solution in Mg2+Concentration, from
And totally 10 test pieces are made, the form of phosphate crystal is observed to obtained each test piece, and film adherability is evaluated.
Now, in all test piece manufactures, the Ni for including 300ppm has been used+, 1000ppm Zn2+, 20000ppm PO4 3-、
25000ppm NO3 -And acid is than the phosphate solution (Mg for 102+Concentration is recorded in Table 3 below), other conditions with implementation
Example 1 is identical.The results are shown in Fig. 2 and table 4 below.Wherein, Fig. 2 a~Fig. 2 h are respectively that test piece 2-1~2-8 surface is entered
The SEM image of row observation.
Table 3
Table 4
With reference to table 4 it has been confirmed that meeting the Mg proposed in the present invention2+In example 2-1~2-6 of concentration, not only film
Adhesiveness is excellent, and with less than 2.0 excellent whiteness deviation.
Conversely, in comparative example 2-1, Mg2+Concentration be not up to the scope that proposes in the present invention, cause phosphate knot
Crystalline substance fails normal growth, and thus film adherability and resistance to oxidation discolouration are illustrated as very poor.In addition, in comparative example 2-2,
Mg2+Concentration beyond the scope proposed in the present invention so that most phosphate crystal is relative to zinc-based metal plated steel sheet and phosphorus
The laminating direction of hydrochlorate epithelium obliquely arranges, and so as to which surface area ratio shows very low, average circularity then shows very big.By
This, film adherability is shown as very poor.
Claims (14)
1. a kind of zinc-based metal plated steel sheet phosphate solution, the Zn comprising 500~2000ppm2+, 50~1000ppm Ni+And 3000
~40000ppm Mg2+。
2. zinc-based metal plated steel sheet phosphate solution according to claim 1, it is characterised in that contain in the phosphate solution
Some PO4 3-Concentration be 5000~40000ppm.
3. zinc-based metal plated steel sheet phosphate solution according to claim 1, it is characterised in that the phosphate solution also wraps
Containing NO3 -, the NO3 -Concentration be 5000~40000ppm.
4. zinc-based metal plated steel sheet phosphate solution according to claim 1, it is characterised in that the acid of the phosphate solution
Than being that total acidity/free acidity is 2~20.
5. a kind of Zinc-based metal plated steel sheet treated with phosphate, it includes zinc-based metal plated steel sheet and is formed at least the one of the zinc-based metal plated steel sheet
Phosphate coating on face, the three-dimensional table area for bivariate table area based on laser microscope of the phosphate coating it
Than for 1.7~8.8.
6. Zinc-based metal plated steel sheet treated with phosphate according to claim 5, it is characterised in that the phosphoric acid of the phosphate coating
The average circularity of salt crystallization is 0.47~0.96.
7. Zinc-based metal plated steel sheet treated with phosphate according to claim 5, it is characterised in that the phosphoric acid of the phosphate coating
The quantity of the per unit area of salt crystallization is 0.3~2.3/μm2。
8. Zinc-based metal plated steel sheet treated with phosphate according to claim 5, it is characterised in that the epithelium of the phosphate coating
Adhesion amount is 0.3~2.3g/m2。
9. Zinc-based metal plated steel sheet treated with phosphate according to claim 5, it is characterised in that temperature be 50 DEG C, it is relatively wet
Spend whiteness deviation (the Δ L after 24 hours under the conditions of the constant temperature and humidity for 95%*) it is less than 2.0.
10. a kind of manufacture method of Zinc-based metal plated steel sheet treated with phosphate, comprises the following steps：
Prepare zinc-based metal plated steel sheet；
Degreasing is carried out to the surface of the zinc-based metal plated steel sheet；
Surface adjustment processing is carried out to the surface of the zinc-based metal plated steel sheet of the degreasing using surface conditioner；And
Phosphate coating is formed on the surface of the zinc-based metal plated steel sheet that processing is adjusted by surface using phosphate solution,
The phosphate solution includes 500~2000ppm Zn2+, 50~1000ppm Ni+And 3000~40000ppm Mg2 +。
11. the manufacture method of Zinc-based metal plated steel sheet treated with phosphate according to claim 10, it is characterised in that the surface
The surface conditioner used in adjustment processing is titanium colloid system active treating agent.
12. the manufacture method of Zinc-based metal plated steel sheet treated with phosphate according to claim 10, it is characterised in that the titanium glue
The content of the titanium contained in system active treating agent is 0.05~0.6 weight %.
13. the manufacture method of Zinc-based metal plated steel sheet treated with phosphate according to claim 10, it is characterised in that the phosphoric acid
The sour ratio of salting liquid is that total acidity/free acidity is 2~20.
14. the manufacture method of Zinc-based metal plated steel sheet treated with phosphate according to claim 10, it is characterised in that forming institute
When stating phosphate coating, the surface temperature of the zinc-based metal plated steel sheet is 50~70 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2016-0079483 | 2016-06-24 | ||
| KR1020160079483A KR101830508B1 (en) | 2016-06-24 | 2016-06-24 | Phosphate-treated zinc-based plated steel sheet having excellent discoloration resistance and film adhesiveness |
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|---|---|
| CN107541722A true CN107541722A (en) | 2018-01-05 |
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| Country | Link |
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| JP (2) | JP6605538B2 (en) |
| KR (1) | KR101830508B1 (en) |
| CN (1) | CN107541722A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110057994A (en) * | 2019-05-05 | 2019-07-26 | 南通市产品质量监督检验所 | A kind of metallographic method identification steel product electrogalvanizing and hot galvanizing test method |
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|---|---|---|---|---|
| GB944897A (en) * | 1961-07-18 | 1963-12-18 | Amchem S A | Improvements in or relating to the formation of chemical conversion coatings upon metal surfaces |
| JP2680618B2 (en) * | 1987-08-19 | 1997-11-19 | メタルゲゼルシャフト アクチェンゲゼルシャフト | Metal phosphate treatment method |
| CN1369022A (en) * | 1999-08-09 | 2002-09-11 | 新日本制铁株式会社 | Zinc-based metal plated steel sheet treated with phosphate being excellent in formability and method for production thereof |
| CN1745196A (en) * | 2003-01-31 | 2006-03-08 | 杰富意钢铁株式会社 | Black zinc-plated steel sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002105667A (en) * | 2000-09-29 | 2002-04-10 | Kawasaki Steel Corp | Surface treated steel sheet having excellent press formability |
| JP4267213B2 (en) * | 2001-03-27 | 2009-05-27 | 新日本製鐵株式会社 | Zinc phosphate-treated zinc-coated steel sheet with excellent corrosion resistance and color tone |
| JP5119864B2 (en) * | 2006-10-31 | 2013-01-16 | Ｊｆｅスチール株式会社 | Phosphate-treated galvanized steel sheet and method for producing the same |
-
2016
- 2016-06-24 KR KR1020160079483A patent/KR101830508B1/en active IP Right Grant
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2017
- 2017-06-20 JP JP2017120404A patent/JP6605538B2/en active Active
- 2017-06-26 CN CN201710496204.2A patent/CN107541722A/en active Pending
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- 2019-09-09 JP JP2019163751A patent/JP2019203205A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB944897A (en) * | 1961-07-18 | 1963-12-18 | Amchem S A | Improvements in or relating to the formation of chemical conversion coatings upon metal surfaces |
| JP2680618B2 (en) * | 1987-08-19 | 1997-11-19 | メタルゲゼルシャフト アクチェンゲゼルシャフト | Metal phosphate treatment method |
| CN1369022A (en) * | 1999-08-09 | 2002-09-11 | 新日本制铁株式会社 | Zinc-based metal plated steel sheet treated with phosphate being excellent in formability and method for production thereof |
| CN1745196A (en) * | 2003-01-31 | 2006-03-08 | 杰富意钢铁株式会社 | Black zinc-plated steel sheet |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110057994A (en) * | 2019-05-05 | 2019-07-26 | 南通市产品质量监督检验所 | A kind of metallographic method identification steel product electrogalvanizing and hot galvanizing test method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2019203205A (en) | 2019-11-28 |
| JP2017226917A (en) | 2017-12-28 |
| JP6605538B2 (en) | 2019-11-13 |
| KR101830508B1 (en) | 2018-02-21 |
| KR20180001668A (en) | 2018-01-05 |
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