CN1034681C - Method for making manganese-containing zinc phosphate layer on surface of zinc-plated steel - Google Patents

Method for making manganese-containing zinc phosphate layer on surface of zinc-plated steel Download PDF

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CN1034681C
CN1034681C CN90106684A CN90106684A CN1034681C CN 1034681 C CN1034681 C CN 1034681C CN 90106684 A CN90106684 A CN 90106684A CN 90106684 A CN90106684 A CN 90106684A CN 1034681 C CN1034681 C CN 1034681C
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content
charged ion
positively charged
described method
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CN1049531A (en
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乔格·里索普
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Henkel Two Jsc
Henkel AG and Co KGaA
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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
    • C23C22/18—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
    • C23C22/05—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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/364—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 fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C23C22/365—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 fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations

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

Abstract

In a process for phosphatizing electrolytically and/or hot-dip galvanized steel strip, the steel strip is briefly treated with acidic phosphatizing solutions which contain, in addition to zinc and phosphate ions, manganese and nickel cations and anions of oxygen-containing acids with an accelerator effect. The weight ratio of nickel cations to nitrate anions is ajusted to between 1:10 and 1:60 and the weight ratio of manganese cations nitrate anions is adjusted to between 1:1 and 1:40.

Description

The method that contains the manganese zinc phosphate layer in the surface of galvanized steel manufacturing
The present invention relates to wherein form the zinc phosphate layer that contains manganese and nickel in the method to electroplating and/or the galvanized steel band of melt impregnation carries out phosphated method.The above-mentioned zinc phosphate layer that contains manganese and nickel is to use aqueous solution, by spraying method, sprays that method and/or pickling process apply.
The phosphated method on iron, steel, zinc and alloy thereof and aluminium surface is early existing reported in literature (ullmanns Encylopadie der technischenchemie in this area, 4th Edi-tion, volume 15, pages 686 and 687), phosphated purpose being carried out on these surfaces is to improve the clinging power of coating and strengthen corrosion resistance.
WARoland and k-HGottwald be at " Metalloberflache ", 42nd, and the Zinc phosphate coating of having mentioned the manganese modification in 1988/6 can be used as the adhesion primer of modern coating.The present invention has stated that except that zine ion and nickel ion mn ion is used for the low phosphated method of zinc, in particular for the steel sheet of surface modification, strengthens its corrosion resistance really.In phosphoric acid zinc coating, infiltrate manganese and cause forming the strong littler tightr crystal of alkali resistant ability.Enlarged the working range of phosphatizing groove simultaneously; Aluminium also can be compound in steel by phosphatization and form thin layer on electricity or the galvanized steel of melt impregnation, and its performance index are closed the common requirement of symbol.
From DE, 32,45, known method of electro-galvanizing metal objects especially Galvanized Steel Strip being carried out short period of time phosphoric acid processing with phosphate solution among the 411A1, wherein phosphate solution is except that containing zinc and phosphate anion, also contains other metallic cation and/or has the oxygen acid root negatively charged ion of accelerator effect.The weight of the unit surface of the zinc phosphate layer that forms in these methods is less than 2g/m 2Employed acid phosphatase salts solution middle-jiao yang, function of the spleen and stomach ion Zn 2+Content be about 1～2.5g/l, the free acid content scope is 0.8～3 point, the sour ratio of total acid content and free acid amount is 5～10, the treatment time is no more than 5 minutes substantially.
Preferably use the phosphatizing groove that contains Silver Nitrate, wherein Zn 2+/ NO 3 -Weight ratio remained on PO 1: 1～1: 8 4 3-/ NO 3 -Weight ratio remained on 1: 0.1～1: 2.5.
From EP, 0,106,495, the known a kind of phosphatization method of A1 has wherein formed nickeliferous and zinc phosphate layer manganese, and wherein the existence of fluorion is absolutely necessary, and the upper limit of concentration of nitrate ion is 10g/l.
EPO112,826, B1 is about nickelic phosphatizing method, need be 5.2: 1～16: 1 in the mol ratio of this nickel and zinc.
In addition, EPO has mentioned the phosphatization method in 175,606, wherein, has used iron content phosphatizing groove.In addition, use many organism as accelerator, existing of manganese is dispensable.And, need to regulate zinc and nickel and nickel and iron certainty ratio really.
The actual at present plating of using and/or the phosphatizing method of the galvanized steel band of melt impregnation also have limitation, wish it is eliminated.Yet, need to form unit plane weight less than 2g/m in order to improve corrosion resistance 2Phosphate coating.The coating poor adhesion is because the weight of unit surface is bigger.Particularly when phosphoric acid salt and coated material distortion, in the actual method of using, the phosphatizing time was generally more than 2 seconds, and its linear velocity is about 60～120m/min.
As everyone knows, use nickeliferous cationic phosphate solution can improve bounding force and corrosion resistance nature, yet, have been found that in finishing the present invention the concentration of raising nickel can be improved corrosion resistance nature, but caused containing the zinc phosphate layer blackening of manganese and nickel.
The objective of the invention is to utilize 2～30 seconds processing phases, avoid on the zinc phosphate layer on plating and/or the melt impregnation surface of galvanized steel, occurring the black phenomenon of color, keep its resistance to corrosion simultaneously.From document, learn,, significantly reduce nickel content by replacing with manganese, to obtain the erosion resistance and the bounding force of coating, the three cation technology that adopted of automobile industry and the continuous phosphatization of steel band for example.In order to reach this purpose, in treating processes, form tight successive phosphate coating, and have gratifying deformation performance and be absolutely necessary.Therefore the present invention has a mind to reduce the weight of phosphate coating, does not but damage the homogeneity of the meticulous crystallizing layer in Galvanized Steel Strip surface and the strong erosion resistance of zinc phosphate layer.The term according to the present invention, " the galvanized steel band of electricity and/or melt impregnation " also comprises usually said zinc alloy, { for example, " zinc coating DIFFUSION TREATMENT " zinc alloy ZNE (electrochemical plating, wherein contain 10～13% nickel) or nickelalloy ZFE (electrochemical plating wherein contain Fe).
Above-mentioned purpose is by electricity and/or melt impregnation Galvanized Steel Strip are carried out fast processing with the acid phosphatase salts solution, the phosphate coating that forms manganese and nickel reaches, wherein the phosphatizing time is 2～30 seconds, and temperature range is 40～70 ℃, and phosphate solution meets the following conditions:
Positively charged ion Zn 2+Content 0.02～0.75g/l
Positively charged ion Mn 2+Content 0.2～2.0g/l
Positively charged ion Ni 2+Content 0.1～2.0g/l
Negatively charged ion PO 4 3-10～20g/l
Anion N O 3 -Content 0.5～30g/l
Free acid content scope 1.6～3.0 points
Total acid content scope 12～40 points
Positively charged ion Ni in aforesaid method 2+With anion N O 3 -Weight ratio be adjusted in 1: 10～11: 60 scopes in, positively charged ion Mn 2+With anion N O 3 -Weight ratio be adjusted in 1: 1～1: 40 scope in.
The definition of above parameter and measure Chr, Ries is at " uberwachung vonPhos Phatierungsbadern ", and Galvanotechnik 59 (1968), NO.1, (Eugen G.Leuze-Verlag has been described in detail in SauLgau) pp.37-39.For example, the definition of free acid point is with dimethyl yellow, and tropeolin-D and tetrabromophenol sulfonphthalein are the milliliter number of the 0.1N NaoH that consumed of indicator titration 10Ml phosphatizing groove solution.The total acid implication of counting is to be the milliliter number of the 0.1n NaoH that consumed when phenolphthalein just begins to become magenta of indicator titration phosphatizing groove solution with phenolphthalein.
Therefore, in the methods of the invention, it is necessary making up above-mentioned all parameters.
Positively charged ion Zn 2+Concentration maintain low-down limited range, a spot of zine ion adds in the treatment trough at first, to quicken to set up cation balance.When Galvanized Steel Strip is used the superphosphate solution-treated, separate out zinc very soon.If the zinc content before carrying out phosphatization in the phosphate-treated solution surpasses 0.75g/l, the coating binding property that obtains so subsequently is with variation.Under certain condition, zinc content can increase in treating processes in the phosphatizing groove, and this is because positively charged ion Zn 2+Separate out from the Galvanized Steel Strip surface regularly, increased the content of zinc like this, but can not influence this implementation of processes.So obtained positively charged ion Zn according to experiment 2+Content range be 1.1～3g/l, preferably at 1.1～2.2g/l.
If mn ion content is lower than 0.2g/l, manganese content in the zinc phosphate layer reduces, thereby makes that after the electric osmose, the bounding force of matrix and coating can not meet the demands.On the other hand, if manganese content is higher than 2.0g/l, then further do not improve for the coating of back fork-like farm tool used in ancient China.Yet the concentration of high manganese will have precipitation to produce with making and can not get stable solution in the phosphatizing liquid.
If had positively charged ion nickel and manganese simultaneously coating coated with after, the bounding force of phosphoric acid zinc coating and erosion resistance are all good unusually.
If phosphate radical anion content is less than 10g/l in the treatment solution, then form defective zinc phosphate layer, on the contrary,, can not receive especially good effect if phosphate content surpasses 20g/l, therefore using high-load phosphate radical is non-remunerative economically.
The weight ratio that an importance of the present invention is positively charged ion nickel and negatively charged ion nitrate radical and the weight ratio of positively charged ion manganese and negatively charged ion nitrate radical.Reported in literature, positively charged ion nickel and manganese can improve the erosion resistance of zinc phosphate layer, but also can make the color blackening.Though for automobile industry, color is not a subject matter, aspect the family expenses products production, the tone of zinc phosphate layer is extremely important, because under latter event, coating subsequently often is very thin.
Another important indicator of the present invention is the bonderize time.Although in automobile industry, the treatment time surpasses 120 seconds usually, when carrying out the Galvanized Steel Strip phosphatization, wishes all that under any circumstance the treatment time is no more than 1 minute.Within the scope of the present invention, in 2～30 seconds treatment times, the optimum handling time is 3～20 seconds.
Can make phosphoric acid zinc coating on Galvanized Steel Strip, this coating outside surface is bright, although contain nickel.Simultaneously, general manganese replaces nickel, and nickel content can be lower and do not damage corrosion resistance nature than prior art, and this is ecological and economic aspect is all very important, because narrated first and contain manganese three cation technology and be used for fan-shaped steel band.
In embodiment preferred of the present invention, electricity and/or melt impregnation Galvanized Steel Strip are carried out parkerized method are characterised in that phosphate solution satisfies following condition:
Positively charged ion Zn 2+Content 0.4～0.6g/l
Positively charged ion Mn 2+Content 0.9～1.1g/l
Positively charged ion Ni 2+Content 0.6～0.9g/l
Negatively charged ion PO 4 3-Content 12～16g/l
Anion N O 3 -Content 10～30g/l
Another embodiment preferred is that the weight ratio of positively charged ion nickel and negatively charged ion nitrate radical is adjusted in 1: 20～1: 60 scope among the present invention.In finishing process of the present invention, finding can have detrimentally affect to the phosphatization process when nitrate ion content is too high, also same phenomenon can occur when nickel content is too low, and it has disadvantageous effect to erosion resistance.In another embodiment preferred of the present invention, the weight ratio of positively charged ion manganese and negatively charged ion nitrate radical is adjusted in 1: 6～1: 20 scope in, say that more specifically this weight ratio has desirable influence to the wet adhesion of coating.
The particularly important is present method and be not only applicable to the galvanized steel band of melt impregnation and carry out phosphatization, be applicable to that also electrochemical plating carry out the phosphatization of galvanized steel band.For the electro-galvanizing steel band, the existence of negatively charged ion fluorine there is no need in the practice, although the existence of fluorine is to not influence of phosphatization.Yet if adopt the galvanized steel band of melt impregnation, fluorion is used in suggestion, when particularly needing the complexing of aluminium negatively charged ion.Therefore the characteristics of another embodiment preferred of the present invention are that the content of fluorine in the bonderize liquid is 0.1～1.0g/l, are preferably in 0.4～0.6g/l.
In practice, phosphatization operates under the medium high-temperature of 40～70 ℃ of scopes to be carried out, and temperature is suitable especially 55～65 ℃ of these scopes.The method of the coating processing liquid of any technical feasibility all is suitable, more specifically says, can adopt spraying technology and dipping method to implement method of the present invention.
Before carrying out the phosphate solution processing, water-wet must be used, for the object on the operate continuously band always the case fully in the galvanized surface of electricity and/or melt impregnation.If cover with oil in order to preserve with the anticorrosion galvanizing layer surface, then before carrying out phosphatizing, should with known appropriate means top oil be removed the wettable galvanized metal surfaces known pre-treatment of process before carrying out the phosphate solution processing of water then earlier.In DE-OS2038105 and DE-OS2043085 detailed description the appropriate pretreatment method, according to these bibliographical informations, pending parkerized metallic surface can be with the titanium salt that contains activator and sodium phosphate and other organism such as alkyl phosphate or polycarboxylic solution-treated.As titanium component, preferably use especially titanyl sulfate of water miscible titanium compound such as potassium titanium fluorochemical, the ortho-phosphoric acid disodium often uses as sodium phosphate.Titanium-containing compound and sodium phosphate use with certain proportion, and wherein titanium content accounts for 0.005% of titanium compound and sodium phosphate summation at least.
As prior art such as DE-OS32,45411 is described, and for method of the present invention, the zinc phosphate layer that method is thus obtained is carried out passivation and is good in following technological process.For example such passivating process can use antimony chromic acid or chromic acid and phosphate mixture fork-like farm tool used in ancient China to realize.Being generally 0.01～1.0g/l in this chromic acid concentration, is the water rinse step between phosphatizing step and post-processing step.
Utilize the method for the invention, can obtain weight per unit area less than 2g/m 2Phosphoric acid zinc coating, this zinc phosphate layer has continuously meticulous crystalline texture, and makes electro-galvanizing and/or melt impregnation Galvanized Steel Strip have the bright gray face of ideal uniform.Through the parkerized steel band then available thin phosphate layer of need not painting again or varnish, in the course of processing that may deform, this zinc phosphate layer with the high weight per unit area that traditional method obtains has better properties, and the organic coating that back fork-like farm tool used in ancient China applies, its bounding force has been compared obvious improvement with prior art.
In another embodiment preferred of the present invention, if adopt the electro-galvanizing steel band, then producing weight per unit area is 0.7～1.6g/m 2Zinc phosphate layer.If adopt the melt impregnation Galvanized Steel Strip, the generation weight per unit area is 0.8～1.6g/m 2The phosphoric acid layer, this point is very favorable.
The method according to this invention for example sprays by known method, floods and/or sprays-soak and the combination of described method, applies the zinc phosphate layer that contains manganese and nickel.
In another embodiment preferred of the present invention, when handle electroplating steel band, sour ratio, promptly the ratio of total acid content and free acid be adjusted in 25: 1～10: 1 scope in, preferably in 15: 1～10: 1 scopes.
The characteristics of another embodiment of the invention are anion N O in the phosphatizing liquid 3 -Content range is 1.0～30g/l.
By the upper layer of the inventive method preparation, any field that can be used to use phosphate coating.A kind of useful especially application is the preparation that is used for the particularly electric Dipping of coating for metal surfaces.
Embodiment
In the ordinary method treating processes, comprise following step:
1. clean and oil removing
Use contains the alkaline cleaner (RIDOLINE for example of tensio-active agent C72), handled 5～20 seconds down at 50～60 ℃ with spraying process.
2. flushing
3. activation
Use contains titanium salt reagent (for example FIXODINE 950) and sprayed 2～4 seconds down at 20～40 °.
4. phosphatizing
Its composition sees Table 1.
5. flushing
6. post-passivation is handled
Use contain chromium or do not contain the post-passivation agent of chromium (for example DEOXYL YTE 41B or DEOXYLYTE80) in 20～50 ℃ the spray or flooded 2～6 seconds.
7. extruding
With the squeezed fluid wheel float gage liquid is removed compacting coating then.
8. dry
Steel band after the extruding is with the heat drying of itself.
Galvanizing steel (every zinc coating thickness is 7.5 μ m) and melt impregnation galvanized steel (every zinc bed thickness 10 μ m) are carried out surface treatment.Weight per unit area at the surperficial phosphate layer of galvanizing steel (ZE) is 0.6～1.6g/m 2, and be 0.8～1.6g/m with the weight per unit area of the phosphate layer of melt impregnation surface of galvanized steel 2
The composition embodiment treatment trough parameter 1234 Comparative Example F S of table 1 phosphatizing groove 1)(point) 2.3 2.7 2.6 2.6 2.4GS 2)(point) 17 22 14 16 15m 2+G/l 0.5 0.5 0.5 0.5 0.9Mn 2+G/1 1.0 0.5 1.0 0.8 0.0Ni 2+G/l 0.6 0.2 0.3 0.6 0.2F -G/l 0.1 0.0 0.1 0.1 0.0P 4- 3-G/l 13.0 13.0 16.0 14.0 13.0NO 3G/l 7.0 4.0 20.0 30.0 1.6 temperature ℃ 55 58 60 58 56 times (second) 56665 1The FS=free acid 2The GS=total acid
As treating parkerized matrix, can select for use the galvanized steel of two-sided electrochemical plating (zinc of 7.5/7.5um) to change climatic test P1210 with VW tests, also can select for use melt impregnation galvanized steel (zinc of 10/10um) to carry out SaltSprayTest, the layer analysis of galvanizing steel (by the atomic absorption spectrum quantitative analysis):
Element embodiment comparative example
1 2 3 4
％ ％ ％ ％ ％
Manganese 5.1 3.9 4.5 5.7 0.0
Nickel 0.6 0.2 0.8 0.4 0.1
Zinc 40.5 40.8 38.6 40.4 45.9
Weight *1.0 1.1 0.9 1.0 1.2
Ash in the bright ash of the surface bright ash of the bright ash of bright ash *Average weight per unit area, according to DIN50942, g/m 2
Use embodiment 1,3 and 4 and the sheet material that obtains of case of comparative examples, change the weather corrosion test by VW standard P 1210, test period is 15～30 days, carries out salt-fog test 1008 hours by DIN50021SS.
Use standard K ET priming paint FT857042 (BASF Lacke of manufacturers and Farben AG) to be used for the VWP1210 test as coating; Use polyester priming paint BASF general number 21110 (4um) and Unitect polyester Deckiack number 5092935002 (16um) to carry out salt-fog test.
1.VW change climatic test P1210
15 days
Embodiment 1 embodiment 3 embodiment 4 comparative example areas are pressed DIN mO/gO mO/gO mO/gO mO/gO
53209 otch are pressed DIN 0.5 0.3 0.3 0.1
VW standard K 2 K2-K5-6 is pressed in 53167 rockfalls
30 days
Embodiment 1 embodiment 3 embodiment 4 comparative example areas are pressed DIN mO/gO mO/gO mO/gO mO/gO
53209 otch are pressed DIN 1.1 0.6 0.8 1.7
VW standard K 3 K3 K4 K9 are pressed in 53167 rockfalls
2. salt-fog test
Embodiment 1 embodiment 3 areas are pressed DIN mO/gO mO/gO
53209 otch are pressed DIN 2.2 0.0
53167 (mm) T-is bent to test 10 01 according to ECCA-T7 (1985).
When determining the foam degrees of coating according to DIN53209, coatingsurface forms how much being weighed by the foam degrees fork-like farm tool used in ancient China of bubble.According to described standard, the foam degrees that forms is that notice is calculated the number of steeping on the per unit area and the big or small fork-like farm tool used in ancient China of bubble is determined.By characteristic character and numeral foam degrees, with the foaming number on the representation unit area; Size by feature number of words and character representation foaming.
Characteristic symbol and digital MO represent not have blistery to exist, and m5 then represents by the foaming number on the unit surface of DIN53204 foam degrees data.
The size of bubble is 0～5 feature numeral with characteristic symbol g and scope.Characteristic symbol and feature numeral g0 represent not steep formation, and g5 represents that the size of steeping is corresponding with the foam degrees data by DIN53209.
By with coating comparative measurement foam degrees, foam degrees is the data the most close with coatingsurface.
Carrying out spray test according to DIN53167 is by measuring institute's spray sodium chloride solution to painting, paint and the effect of other coatings, if coating has little trachoma, aperture or scar, salt solution will be with these places to the infiltration of coating lower floor so, and this causes the bounding force of coating and the corrosion resistance of metallic matrix to reduce.
Utilize salt mist experiment to find the defects detection infiltration.
The meaning of the infiltration in the standard (sapping) is, sodium chloride solution is in infiltration between coating and matrix or the infiltration in a certain way between each crackle (crack) that each produced, or has soaking between trachoma (for example ommatidium, edge).The reduction degree of bounding force is weighed the anti-sodium-chlor spraying ability of substrate surface coating with fork-like farm tool used in ancient China.
The variation test that VW standard P-VW1210 is made up of various standardized test method comprises 4 hours salt-fog tests according to DIN50021 in 15 and 30 days test loop process,
At room temperature placed 4 hours,
Carry out 16 hours water concentration by the DIN50017 condition.
During the test beginning, sample hits with the steel bomb of a certain size quantity, through experiment after a while, represent its extent of corrosion with a feature numeral fork-like farm tool used in ancient China, the scope of feature numeral is 1～10, wherein 1 expression of feature numeral does not have obvious corrosion, and feature numeral 10 then all is corroded on the whole surface of expression.
Test panel becomes with differently curved radius bend in 1～2 second and rolls parallel 180 ℃ of direction in the bent test of T.Coating is positioned at outside surface, and the crooked and minimum bending radius that coating shedding do not occur of sample shows that sample is 180 ° of viscosity intensity when crooked.In the experimental implementation process, do not have the steel plate bending in middle layer after, observe with the magnifying glass that amplifies ten times immediately, very Yan Ge testing method is, securely adhesive coating is attached to an edge, rapidly it is torn the coating quantity that calculating is torn then.

Claims (14)

  1. With the acid phosphatase salts solution to electroplating and/or the fused solution dipping Galvanized Steel Strip short period of time handles and carries out phosphated method, wherein the treatment time is 2～30 seconds, phosphatization is carried out in the temperature range of 40～70C, and bonderize liquid meets the following conditions:
    Positively charged ion Zn 2+Content 0.02～0.75g/l
    Positively charged ion Mn 2+Content 0.2～2.0g/l
    Positively charged ion Ni 2+Content 0.1～2.0g/l
    Negatively charged ion PO 4 3-Content 10～20g/l
    Anion N O 3 -Content 0.5～30g/l
    " free acid " content is in 1.6～3.0 point ranges;
    " total acid " content in 12～40 point ranges,
    Positively charged ion Ni 2+With anion N O 3 -Weight ratio in 1: 10～1: 60 scope.
    Positively charged ion Mn 2+With anion N O 3 -Weight ratio in 1: 1～1: 40 scope, the weight per unit area of the phosphate layer that obtains thus is less than 2g/m 2
  2. 2. in accordance with the method for claim 1, it is characterized in that phosphatizing liquid meets the following conditions:
    Positively charged ion Zn 2+Content 0.4～0.6g/l
    Positively charged ion Mn 2+Content 0.9～1.1g/l
    Positively charged ion Ni 2+Content 0.6～0.9g/l
    Negatively charged ion PO 4 3-Content 12～16g/l
    Anion N O 3 -Content 10～30g/l
  3. 3. according to claim 1 and 2 at least one described methods, it is characterized in that the treatment time is 3～20 seconds.
  4. 4. according at least one described method of claim 1 to 3, it is characterized in that positively charged ion Ni 2+With anion N O 3 -Weight ratio in 1: 20 to 1: 60 scope.
  5. 5. according at least one described method of claim 1 to 4, it is characterized in that positively charged ion Mn 2+With anion N O 3 -Weight ratio in 1: 6 to 1: 20 scope.
  6. 6. according at least one described method of claim 1 to 5, it is characterized in that phosphatizing liquid comprises that content is the negatively charged ion F-of 0.1～1.0g/l.
  7. 7. according at least one described method of claim 1 to 6, it is characterized in that phosphatizing liquid comprises that content is the negatively charged ion F of 0.4～0.6g/l -
  8. 8. according at least one described method of claim 1 to 7, it is characterized in that phosphatization operates in 55～65 ℃ the temperature range carries out.
  9. 9. according at least one described method of claim 1～7, it is characterized in that then the weight per unit area of zinc phosphate layer is at 0.7～1.6g/m if adopt the plating steel band 2Scope.
  10. 10. according at least one described method of claim 1～7, it is characterized in that then the weight per unit area of zinc phosphate layer is at 0.8～1.6g/m if adopt by the galvanized steel band of melt impregnation 2Scope.
  11. 11. according at least one described method of claim 1～10, it is characterized in that adopting electroplating/or the melt impregnation Galvanized Steel Strip, this steel band is handled through known pre-activated in advance, specifically uses the pre-treatment of titaniferous activation solution.
  12. 12. according at least one described method of claim 1～11, it is characterized in that using when electroplating steel band, the ratio of total acid content and free acid is adjusted in 25: 1～10: 1 scope.
  13. 13. according at least one described method of claim 1～11, it is characterized in that using when electroplating steel band, the ratio of total acid content and free acid is adjusted in 15: 1～10: 1 scope in.
  14. 14., it is characterized in that NO according at least one described method of claim 1～13 3 -Ion content is 1.0～30g/l.
CN90106684A 1989-08-17 1990-08-15 Method for making manganese-containing zinc phosphate layer on surface of zinc-plated steel Expired - Fee Related CN1034681C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3927131A DE3927131A1 (en) 1989-08-17 1989-08-17 METHOD FOR THE PRODUCTION OF MANGANIZED ZINC PHOSPHATE LAYERS ON GALVANIZED STEEL
DEP3927131.5 1989-08-17

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CN1049531A CN1049531A (en) 1991-02-27
CN1034681C true CN1034681C (en) 1997-04-23

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CA (1) CA2065004A1 (en)
DE (2) DE3927131A1 (en)
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DE4326388A1 (en) * 1993-08-06 1995-02-09 Metallgesellschaft Ag Process for the phosphating treatment of one-sided galvanized steel strip
DE4443882A1 (en) * 1994-12-09 1996-06-13 Metallgesellschaft Ag Process for applying phosphate coatings on metal surfaces
DE19808755A1 (en) 1998-03-02 1999-09-09 Henkel Kgaa Layer weight control for strip phosphating
DE10010355A1 (en) * 2000-03-07 2001-09-13 Chemetall Gmbh Applying phosphate coatings to metallic surfaces comprises wetting with an aqueous acidic phosphatizing solution containing zinc ions, manganese ions and phosphate ions, and drying the solution
EP1291453A1 (en) * 2000-05-30 2003-03-12 Nkk Corporation Organic coating covered steel sheet
JP4603502B2 (en) * 2006-03-30 2010-12-22 新日本製鐵株式会社 Coated steel
CN101660164B (en) * 2008-08-26 2011-12-28 宝山钢铁股份有限公司 Lubricating electro-galvanized steel plate and production method thereof
CN102677034A (en) * 2012-05-25 2012-09-19 衡阳市金化科技有限公司 Medium-temperature low-sediment zinc phosphorizing solution
AT516956B1 (en) * 2015-06-29 2016-10-15 Andritz Ag Maschf DEVICE AND METHOD FOR PRODUCING A ZINCED STEEL STRIP
CN112195429B (en) * 2020-09-25 2022-08-23 河钢股份有限公司承德分公司 Zinc-free flower 900g/m 2 Production method of galvanized sheet with double-sided ultra-thick zinc layer
CN112410768B (en) * 2020-10-30 2023-06-23 马鞍山钢铁股份有限公司 Galvanized steel sheet surface treating agent, preparation method of surface treating agent, self-lubricating galvanized steel sheet and preparation method of steel sheet

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JPS57152472A (en) * 1981-03-16 1982-09-20 Nippon Paint Co Ltd Phosphating method for metallic surface for cation type electrodeposition painting
JPS5935681A (en) * 1982-08-24 1984-02-27 Nippon Paint Co Ltd Method for phosphating metallic surface for coating by cationic electrodeposition
DE3245411A1 (en) * 1982-12-08 1984-07-05 Gerhard Collardin GmbH, 5000 Köln METHOD FOR PHOSPHATING ELECTROLYTICALLY GALVANIZED METAL GOODS
ATE160592T1 (en) * 1985-08-27 1997-12-15 Henkel Corp METHOD FOR PHOSPHATING METAL SURFACES
DE3537108A1 (en) * 1985-10-18 1987-04-23 Collardin Gmbh Gerhard METHOD FOR PHOSPHATING ELECTROLYTICALLY GALVANIZED METALWARE
DE3631759A1 (en) * 1986-09-18 1988-03-31 Metallgesellschaft Ag METHOD FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES
JPS63227786A (en) * 1987-03-16 1988-09-22 Nippon Parkerizing Co Ltd Phosphating method for pretreating steel sheet before coating by electrodeposition

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ATE121803T1 (en) 1995-05-15
ES2071110T3 (en) 1995-06-16
CA2065004A1 (en) 1991-02-18
WO1991002829A2 (en) 1991-03-07
EP0486576A1 (en) 1992-05-27
AU633135B2 (en) 1993-01-21
JPH04507436A (en) 1992-12-24
AU6167590A (en) 1991-04-03
CN1049531A (en) 1991-02-27
WO1991002829A3 (en) 1991-04-04
EP0486576B1 (en) 1995-04-26
DE3927131A1 (en) 1991-02-21
ZA906507B (en) 1991-04-24
DE59008978D1 (en) 1995-06-01

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