CN1034682C - Chromating method of zinc-based plated steel sheet - Google Patents
Chromating method of zinc-based plated steel sheet Download PDFInfo
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- CN1034682C CN1034682C CN92101174A CN92101174A CN1034682C CN 1034682 C CN1034682 C CN 1034682C CN 92101174 A CN92101174 A CN 92101174A CN 92101174 A CN92101174 A CN 92101174A CN 1034682 C CN1034682 C CN 1034682C
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- Prior art keywords
- chromate
- steel plate
- zinc
- ion
- coating
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 39
- 239000010959 steel Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004532 chromating Methods 0.000 title claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 16
- 239000011701 zinc Substances 0.000 title description 16
- 229910052725 zinc Inorganic materials 0.000 title description 15
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 55
- 230000008021 deposition Effects 0.000 claims abstract description 15
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052745 lead Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract 2
- 239000011651 chromium Substances 0.000 claims description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- -1 nitrate ions Chemical class 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 229910001430 chromium ion Inorganic materials 0.000 claims description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 2
- 239000008397 galvanized steel Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 229940085991 phosphate ion Drugs 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 33
- 238000000576 coating method Methods 0.000 abstract description 33
- 238000001035 drying Methods 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 150000005837 radical ions Chemical class 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 30
- 238000000151 deposition Methods 0.000 description 13
- 238000010422 painting Methods 0.000 description 13
- 230000003628 erosive effect Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 229910007567 Zn-Ni Inorganic materials 0.000 description 3
- 229910007614 Zn—Ni Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- 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
- C23C22/24—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 hexavalent chromium compounds
- C23C22/33—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 hexavalent chromium compounds containing also phosphates
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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)
Abstract
本发明的络酸盐处理方法可以克服镀锌基钢板涂镀时产生陷穴和加工时发生粉化的缺点。该方法包括在镀锌基钢板上涂敷铬酸盐处理水溶液，然后不经水洗直接干燥，以形成Cr沉积量为20-160mg/m2铬酸盐膜。所述铬酸盐处理水溶液中含磷酸根离子、Cr+3和Cr+6，Cr+3/Cr+6的重量比为0.2-1.4。该溶液中还加入一种或多种选自SO4 ＝、No3 -和F-的酸根离子，以及选自Co、Ni、Sn、Cu、Fe和Pb中的一种或多种金属离子。The complex salt treatment method of the invention can overcome the defects of pits and pulverization during coating and processing of the galvanized base steel sheet. The method includes coating a chromate treatment aqueous solution on a galvanized base steel plate, and then drying directly without washing with water, so as to form a chromate film with a Cr deposition amount of 20-160mg/ m2 . The chromate treatment aqueous solution contains phosphate ions, Cr +3 and Cr +6 , and the weight ratio of Cr +3 /Cr +6 is 0.2-1.4. One or more acid radical ions selected from SO 4 = , No 3 − and F − , and one or more metal ions selected from Co, Ni, Sn, Cu, Fe and Pb are also added to the solution.
Description
The present invention relates to a kind of chromate treating method, this method can make the surface modification electrophoretic painting performance and the forming property of metallic surface, especially zinc-plated basic steel plate.
Zinc coating and zn alloy coating demonstrate good erosion resistance usually, but find that also this coating has many shortcomings.
One of its shortcoming is: electroplated metal is that zinc or zinc alloy are inhomogeneous at the surface deposition of steel plate, and especially the steel plate of zinc coating diffusion annealing processing is all the more so.This has caused the unfairness of surface of steel plate profile and steel plate electroconductibility inhomogeneous.This steel plate with the zinc-base metal-plated may produce cratering when carrying out electrophoretic painting.
Another shortcoming is that zinc-plated basic steel plate is in impact briquetting or similarly produce the powdery stores in the course of processing, so working (machining) efficiency is lower.
The Japanese Patent spy opens to have described among the clear 57-67195 on the surface at least simultaneously of the zinc-plated basic steel plate in two sides and electroplates the plating iron layer with specific thickness, and this plating iron layer is used for improving the phosphorization treatment performance of zinc coating and the sticking power of enamelled coating.
The special public clear 60-37880 of Japanese Patent has described plating iron on the surface of steel plate of having electroplated zinc, Zinc-base compounded material or zinc alloy, and then forms the thin chromate film of one deck.The secondary sticking power that has allegedly shown the cathodic electrophoretic paint that improves through such surface-treated steel plate.
The Japanese Patent spy opens and has described the paint film that forms the rich zinc of one deck on the chromate film that forms on the steel plate galvanized of regulation among the clear 59-171645, and this paint film contains the zinc powder or the zinc magnesium alloy powder of specified quantity, thereby improves the resistance to chalking energy.
In addition, the Japanese Patent spy opens and has announced a kind of method among the clear 60-105535, is to form the chromate coating of one deck specified amount and the rich zinc rete of one deck specific thickness on the steel plate of plating Zn-Ni alloy.It is said owing to rich zinc rete has reduced the powdery stores.
The special public clear 56-36868 of Japanese Patent has described the nickel layer that forms specified amount on steel plate galvanized, forms the chromate film of regulation deposition then.
The special public clear 60-18751 of Japanese Patent has described and applied the aqueous solution that contains chromic trioxide, siliceous colloid and tetra-sodium on galvanized steel plate, and the non-flushing then convection drying of washing is compared with the chromate treating of routine, and this method has improved enamelled coating sticking power.
The Japanese Patent spy opens clear 60-73900 and has described the pure zinc plated film that forms specified amount on the surface of steel plate of galvanized alloy, produces cratering to prevent the ability cathode electrophoresis doped envelope.
The purpose of above-mentioned prior art is to improve electrophoretic painting performance and forming property, for example impact briquetting performance.The method in order to obtain the performance that requires that is proposed is doped envelope, resin coating or other the similar coating that applies one deck plated film, chromate film, rich zinc on the surface of workpiece.But, adopt these methods to be difficult to accomplish not only improve the electrophoretic painting performance but also improve the impact briquetting performance.
In addition, aforesaid method also brings some shortcomings, makes treatment process become complicated and be difficult to and controls.
The inventor finds, adopts following method can overcome the shortcoming of these prior aries, makes the erosion resistance of paint film and sticking power all improve and improves.
Essence of the present invention is; On the surface of zinc-plated basic steel plate, apply the chromate treating liquid of the metal ion additive that contains regulation, so that at first form the displacement plating of the above-mentioned metallic additions of one deck; Without the water flushing, coated treatment solution is carried out drying then, form chromate coating.According to this new method, on the surface of zinc-plated basic steel plate, adopt the electroless method to form a coating, described electroless process is a direct coating processing liquid on the surface of zinc-plated basic steel plate, forms chromate coating by the coated treatment solution of convection drying.Therefore, processing method of the present invention is simple and easy to do, and can overcome the shortcoming of prior art.In addition, the sticking power of the erosion resistance of electroplating steel plate and doped envelope all improves.
So, the present invention relates to the chromate treating method of zinc-plated basic steel plate, its feature
Be: on the surface of zinc-plated basic steel plate, apply the aqueous solution that is used for chromate treating, make it dry then, contain 4.0-51.0g/l sexivalent chromium, the tervalent chromium of 6.0-38.0g/l and 0.5-97.0g/l phosphate anion in the described aqueous solution, trivalent chromium and chromic weight ratio are 0.2-1.4, have also added one or more and one or more metal ions of being selected from Co, Ni, Sn, Cu, Fe and Pb in sulfate ion, nitrate ion and the fluorion in the above-mentioned treatment solution.Forming the chromium deposition amount by aforesaid method on described surface is 20-160mg/m
2Chromate film.
Below the chromate treating aqueous solution of the present invention will be described at first.
The chromate treating aqueous solution of the present invention contains water and 4.0-51.0g/l hexavalent chromium and 6.0-38.0g/l trivalent chromic ion, and water is solvent, and chromium ion is as basal component.When the concentration of sexavalence and trivalent chromic ion during, be difficult to form chromate film with satisfied erosion resistance respectively less than 4.0g/l and 6.0/l; Otherwise when the concentration of hexavalent chromium and trivalent chromic ion surpassed 51.0g/l and 38.0g/l respectively, the viscosity of chromate treating liquid increased, and this treatment solution is stable weakened, thereby was difficult to control coating weight.During the content of chromium, the ratio of trivalent chromic ion and hexavalent chromium is very important in determining chromate treating liquid.The weight ratio of trivalent chromic ion/hexavalent chromium must be in the scope of 0.2-1.4.When the weight ratio of trivalent chromic ion/hexavalent chromium less than 0.2 the time, the concentration of hexavalent chromium increases along with the reduction of this ratio proportionally, consequently, when one or more metal ions are added in the chromate treating aqueous solution, hexavalent chromium is reduced by acid ion rather than phosphate anion easily, thereby causes the mis-behave of chromate treating liquid; Otherwise, if the weight ratio of trivalent chromic ion/hexavalent chromium is greater than 1.4, then often gelling easily of chromate treating liquid, the erosion resistance of formed chromate film is weakened.
By add known reductive agent for example ethanol, methyl alcohol, oxalic acid, starch, sucrose etc., can control the weight ratio of above-mentioned chromium ion.
Chromate treating liquid of the present invention also contains the 0.5-97.0g/l phosphate anion.Phosphate radical is preferably with ortho-phosphoric acid (H
3PO
4) form be added in the chromate treating aqueous solution.When the concentration of phosphate anion was lower than 0.5g/l, the erosion resistance and the alkaline resistance properties of chromate film were weakened; Otherwise when the concentration of phosphate anion was higher than 97.0g/l, chromate treating liquid was unsafty for forming replacement coating, and the chances are for its major cause, and hexavalent chromium makes the surface passivation of treated material.
When being applied to the chromate treating aqueous solution on the treated material, further add the surface of sulfate ion, nitrate ion and/or fluorion meeting corrosion treatment material in this treatment solution to.Metal ion such as Co, Ni has been replaced zinc, forms the coating of these metals.The material of handling with this chromate treating liquid has formed chromate film as the situation of common chromate treating without rinsing subsequently when carrying out drying without washing.
When adding resembles cupric nitrate, copper sulfate, single nickel salt like this during some oxysalts, above-mentioned acid ion and metal ion not necessarily will be added in the chromate treating aqueous solution respectively.If the concentration of at least a acid ion that is selected from vitriol, nitrate and fluorochemical is less than 0.01mol/l, then the corrosion on treated material surface is not enough to form replacement coating; Otherwise if the concentration of acid ion is greater than 2.9mol/l, the erosion on above-mentioned materials surface will be excessive, with
Cause in the Corrosion Protection of zinc-plated basic steel plate and weakened.Therefore, the concentration of acid ion 0.01-2.9mol/l preferably.
Be lower than 0.003mol/l if be selected from the concentration of one or more metal ions of Co, Ni, Sn, Cu, Fe and Pb, the weight of replacement coating will be smaller so; Otherwise if the concentration of one or more metal ions is higher than 0.85mol/l, the weight of replacement coating will be too big so, so that the bonding force of chromate coating film and metal is weakened.When acid ion not enough so that be added to whole deposits of metal ion in the chromate treating aqueous solution, that is to say deficiency so that the metal ion that is added is all replaced zinc, and when the concentration of one or more metal ions surpasses 0.85mol/l, that part of metal ion of deposit formation replacement coating just is not retained in the chromate coating, be transformed into metal oxide and metal hydroxides then gradually, thereby weakened the erosion resistance of chromate coating.
The chromate treating liquid that uses among the present invention for example can be by a roller coating machine coating
To the surface of zinc-plated basic steel plate, carry out drying then, the deposition that forms chromium metal is 20-160mg/m
2Chromate film.The deposition of chromium is lower than 20mg/m
2The time, the erosion resistance of chromate film and the erosion resistance of doped envelope are satisfactory inadequately; Otherwise, if the deposition of chromium surpasses 160mg/m
2, then be difficult to control deposition.In addition, improve erosion-resisting effect and reach capacity, promptly erosion resistance no longer improves with the increase of deposition.In addition, a large amount of so sedimentary chromate films are easy to come off when being subjected to external force, and the result makes that the sticking power of lacquer is weakened.
Do not make any regulation for drying conditions in the present invention.But preferred drying conditions be under 60-260 ℃ of temperature dry 3-60 second.
Owing to formed replacement coating in chromate coating, thereby it is inhomogeneous to have reduced the surface irregularity and the surface conductivity of zinc-plated basic steel plate, is not easy to produce cratering in the electrophoretic painting process.In addition, because displacement layer covers zinc-plated basic steel plate, so it is composed
The surface of giving zinc-plated basic steel plate is with lubricity.Machining tool slides on workpiece easily, thereby can prevent because the powdery stores that Zn base plating exfoliation produces the raising forming efficiency.
Below by embodiment the present invention is described in further detail.
Embodiment
Provided the composition of the chromate treating agent of embodiment 1-6 and Comparative Examples 1-6 in the table 1.Dilute above-mentioned chromate treating agent with an amount of water, with roller coating machine they are coated to then and give earlier with on the steel plate of the electroplating Zn-Ni of trieline oil removing and the surface of steel plate that zinc coating diffusion annealing is handled.Subsequently, clean, carry out drying at 180 ℃ without water.
Utilize the fluorescent X ray to measure the chromium deposition amount (mg/m of chromate coating
2), be about 70mg/m for each embodiment with the result that each Comparative Examples demonstrates
2
Also confirmed the deposition of replacement coating by the fluorescent X ray.
Behind chromate treating, above-mentioned steel plate electrophoretic painting (trade(brand)name of lacquer is Elecron9400, the product of Kansai Paint company) electrophoretic painting is carried out under following condition: deposition voltage 270V; 27 ℃ of electrolyte temperatures; 3 minutes cathode electrolytic deposition time.Water cleans then, places baking oven 175 ℃ of bakings 20 minutes again.
Press the doped envelope performance of the sample of above method preparation with following method evaluation:
(1) first adhesion test
1. grid test
With cutter the surface layer of said sample is cut into the square part of many 1mm.
On test surfaces, stick adhesive tape (cellophane tape), rapidly it is peeled off then.The ratio of the doped envelope that observation remains.
2. Du Pont's shock test
The weight of one heavy 500g, diameter 12.7mm is fallen on the sample by the 50cm eminence.Doped envelope destructive degree detects by an unaided eye.
3. Erichsen test
Hand over sample to extrude 6mm with Erichsen tester.The detect by an unaided eye vestige of doped envelope surface breakdown for example chaps, peels off or the like.
Evaluate the sticking power of doped envelope by following 4 kinds of discrimination standards according to the extent of exfoliation of doped envelope.
◎: doped envelope lost efficacy-0%
Zero: doped envelope lost efficacy less than 10%
△: doped envelope lost efficacy more than or equal to 10%, but less than 30%
*: doped envelope lost efficacy 30%, or more than 30
(2) salt-fog test
Carry out salt-fog test by the regulation among the Japanese industrial standards JIS-Z-2371.Stroke shade line that intersect on the sample top layer reach a certain degree of depth, and the cutting to doped envelope on this degree of depth reaches matrix.
Salt-fog test was carried out 1000 hours.
Evaluate erosion resistance according to the corrosion area with respect to the ratio of the sample total area.
◎: the area-0% that produces white
Zero: the area that produces white is less than 10%
△: the area that produces white more than or equal to 10%, but less than 30%
*: produce white area 30% or higher
(3) second adhesion tests
The salt-fog test of doped envelope was carried out 1000 hours, after the off-test, carried out the test identical with first adhesion test, promptly carried out grid test and evaluated according to first adhesion test.
(4) electrophoretic painting test
By mentioned above above-mentioned steel plate is carried out chromate treating, under 350V deposition voltage and 24 ℃ of paint temperatures, use electrocoating paint (EL-9400 that Kansai Paint company limited produces) to carry out electrophoretic painting then.After washing, above-mentioned japanning was toasted 20 minutes in 165 ℃ in baking oven.
Calculate the number of the cratering that forms on the painted surface, take this as a foundation and by the performance of following 4 standard rating electrophoretic paintings.
◎: 20 or less than 20 craterings
Zero: greater than 20, less than 40 craterings
△: greater than 40, less than 60 craterings
*: greater than 60 craterings
(5) forming property
Be bent 180 ℃ by the above thick steel plate of 1.4mm through chromate treating, its bending radius is about 1mm.
Adhesive tape is attached on the crooked position, then it is taken off, with the naked eye by its efflorescence degree of following standard rating.
◎: no powdery stores
Zero: a small amount of powdery stores
△: the powdery stores of moderate quatity
*: a large amount of powdery storess
The evaluation result of these performances is shown in table 2 (steel plate of electroplating Zn-Ni) and the table 3 (steel plate that zinc coating diffusion annealing is handled).
Table 1
Chromate treating liquid
Cr
3+Cr
6+Cr
3+PO
4 3-The acid ion metal ion
(g/l) (g/l)/Cr
6+(g/l) (mol/l) (mol/l) 1 25.0 25.0 1.0 50.0 nitrate ions of the present invention 0.5 Cu 0.45 embodiment fluorion 1.25
2 6.0 30.0 0.2 20.0 sulfate ions, 1.00 Sn 0.23
3 5.6 4.0 1.4 32.0 fluorions, 0.07 Pb 0.003
4 38.0 51.0 0.75 25.0 fluorions, 1.00 Ni 0.70
Nitrate ion 0.2
5 10.0 48.0 0.21 0.5 nitrate ions, 0.20 Co 0.30
6 35.0 25.0 1.4 97.0 sulfate ions, 2.90 Fe, 0.85 Comparative Examples
1?25.0 25.0 1.0 50.0
2 6.0 30.0 0.2 20.0
3 5.6 4.0 1.4 32.0
4?38.0 51.0 0.75 25.0
5?10.0 48.0 0.21 0.5
6 35.0 25.0 1.4 97.0Cr
6+Cr is provided by chromic trioxide
3+By providing with methyl alcohol reduction chromic anhydride.
Table 2
The embodiments of the invention Comparative Examples
123456123456 first adheres to the test of grid test ◎ 00 ◎ ◎ 0000 ◎ zero △ power: Du Pont's shock test zero ◎ zero ◎ ◎ 00 ◎ zero ◎ 00
Erichsen test zero ◎ zero ◎ 00 ◎ 0000 ◎ second adhere to the test of grid test 00 △ ◎ 0000 △ ◎ 00 power:
Salt-fog test 000 ◎ zero △ 000 ◎ zero △
Electrophoretic painting ◎ ◎ ◎ zero ◎ ◎ 00 * △ △ △
Forming property (efflorescence) ◎ ◎ ◎ ◎ zero ◎ zero △ △ * zero △
Table 3
The embodiments of the invention Comparative Examples
123456123456 first adheres to the test of grid test zero ◎ zero ◎ 00000 ◎ zero △ power: Du Pont's shock test 0000 △ zero △ ◎ 00 △ zero
Erichsen test ◎ ◎ zero ◎ 000 ◎ zero ◎ zero zero the second adheres to the test of grid test 00 △ zero △ 000 △ zero △ △ power:
Salt-fog test ◎ 00 ◎ 00 ◎ 00 ◎ 00
Electrophoretic painting ◎ ◎ 000 ◎ △ △ * △ zero *
Forming property (efflorescence) zero ◎ ◎ ◎ ◎ zero △ * * * * zero
Can clearly be seen that by table 2 and table 3 material that adopts chromate treating method of the present invention to handle has electrophoretic painting performance, forming property, corrosion resistance and the paint film adhesion of improvement.Especially, the performance that electrophoretic painting performance that employing the present invention obtains and forming property are better than Comparative Examples, the best situation of this binomial performance of the latter are with mark " zero " expression only.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92101174A CN1034682C (en) | 1992-02-27 | 1992-02-27 | Chromating method of zinc-based plated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92101174A CN1034682C (en) | 1992-02-27 | 1992-02-27 | Chromating method of zinc-based plated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1075756A CN1075756A (en) | 1993-09-01 |
| CN1034682C true CN1034682C (en) | 1997-04-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92101174A Expired - Fee Related CN1034682C (en) | 1992-02-27 | 1992-02-27 | Chromating method of zinc-based plated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1034682C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58224775A (en) * | 1982-06-24 | 1983-12-27 | Nippon Typewriter Kk | Controller for sending amount dividing gear in japanese character typewriter sideward feeder |
| JPH01123081A (en) * | 1987-11-04 | 1989-05-16 | Nippon Steel Corp | Manufacturing method of pre-coated metal plate with chemical conversion coating with excellent scratch resistance |
| CN1055775A (en) * | 1991-04-11 | 1991-10-30 | 上海市长城电镀厂 | Chromate composite used for passivation of zine plated layer on metal body and application thereof |
-
1992
- 1992-02-27 CN CN92101174A patent/CN1034682C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58224775A (en) * | 1982-06-24 | 1983-12-27 | Nippon Typewriter Kk | Controller for sending amount dividing gear in japanese character typewriter sideward feeder |
| JPH01123081A (en) * | 1987-11-04 | 1989-05-16 | Nippon Steel Corp | Manufacturing method of pre-coated metal plate with chemical conversion coating with excellent scratch resistance |
| CN1055775A (en) * | 1991-04-11 | 1991-10-30 | 上海市长城电镀厂 | Chromate composite used for passivation of zine plated layer on metal body and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1075756A (en) | 1993-09-01 |
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