CN105316672A - Chromium-containing passivation liquid used for surface treatment of galvanized plate and use method thereof - Google Patents
Chromium-containing passivation liquid used for surface treatment of galvanized plate and use method thereof Download PDFInfo
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- CN105316672A CN105316672A CN201410298518.8A CN201410298518A CN105316672A CN 105316672 A CN105316672 A CN 105316672A CN 201410298518 A CN201410298518 A CN 201410298518A CN 105316672 A CN105316672 A CN 105316672A
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- chromium
- sheet surface
- galvanized sheet
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- passivating liquid
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 69
- 239000011651 chromium Substances 0.000 title claims abstract description 69
- 239000007788 liquid Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002161 passivation Methods 0.000 title abstract description 29
- 238000004381 surface treatment Methods 0.000 title abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000077 silane Inorganic materials 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 150000001282 organosilanes Chemical class 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- GTXWPZRNXZAPGM-UHFFFAOYSA-N NCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCC[SiH](OC(OCC)(OCC)OCC)OC GTXWPZRNXZAPGM-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 150000002148 esters Chemical group 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- LAIOKZCTQAIQDM-UHFFFAOYSA-H chromium(3+);diphosphate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cr+3].[Cr+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LAIOKZCTQAIQDM-UHFFFAOYSA-H 0.000 claims description 3
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 3
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 23
- 238000005260 corrosion Methods 0.000 abstract description 23
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 20
- 238000001556 precipitation Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 229910000831 Steel Inorganic materials 0.000 description 14
- 239000010959 steel Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 230000003628 erosive effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000009849 deactivation Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a chromium-containing passivation liquid used for surface treatment of a galvanized plate. The passivation liquid includes, by weight, 0.1-1.0% of trivalent chromium, 0.1-10.0% of organic silane, 0.1-2.0% of a complex agent, and the balanced being deionized water and unavoidable impurities. The invention also discloses a use method of the chromium-containing passivation liquid in surface treatment of the galvanized plate, wherein the method includes the steps of coating a surface of the galvanized plate by the passivation liquid containing chromium and roast-drying the passivation liquid. The passivation liquid only contains the trivalent chromium and does not contain hexavalent chromium, so that toxicity of subsequent waste water of the process is reduced greatly and waste water treatment cost caused by hexavalent chromium is reduced. The passivation liquid greatly reduces adverse influence on environment and human body due to the production process and is increased in corrosion resistance and processing coating property of a film layer formed by the passivation liquid by means of combination effect between the trivalent chromium and the organic silane, thereby improving the corrosion resistance and processability of the galvanized plate.
Description
Technical field
The present invention relates to a kind of composition, particularly relate to a kind of passivating solution.
Background technology
Zinc-plated at surface of steel plate is one of effective ways improving its corrosion resistance nature.But in the Working environment of humidity, the surface of steel plate galvanized is also easily corroded, the corrosion product of white loose is formed at coating surface, not only affect the outward appearance of steel plate, and also can corrode steel plate further and cause the corrosion of iron matrix, and then produce red embroidery; Therefore, in order to improve the erosion resistance of zinc coating, usually adopt most effective means to be adopt sexavalent chrome deactivation method, i.e. chromating method.The method technique is simple, with low cost, good corrosion resistance, but the chromic salt in sexavalent chrome passivating solution belongs to toxicity more greatly and easily carcinogenic material, and in passivating process, the volatilization of aerosol and the discharge of factory effluent all can cause serious harm to human body and environment.
Along with since two thousand three " objectionable impurities restriction instruction ", the promulgation successively of relevant environmental protection instructions such as " scrapping electronic and electrical equipment instruction ", people also more and more pay attention to the environmental hazard caused by sexavalent chrome, and reducing and limiting chromic use is the trend solving the environmental problem caused by it.In this context, the research based on the non-hexavalent chromium passivation technology on steel plate galvanized mainly concentrates on chromium-free deactivation and these two aspects of trivalent chromium passivation.
Chromium-free deactivation method mainly adopts the materials such as titanate, molybdate, tungstate, rare earth, silicate and silane coupling agent.This chromium-free passivation liquid adopts the formula of pure inorganic salt, because of its outward appearance and erosion resistance bad, can not industrial production be widely used for.
In addition, the passivation of employing organic resin is again another trend of chromium-free deactivation method, the barrier property had after utilizing organic resin film forming, it can prevent extraneous corrosive deposit, such as, steam, oxygen etc. and the contact of steel panel substrate base material, meanwhile, can also introduce inorganic inhibitor and improve its corrosion resistance nature further in organic resin.Publication number is CN101250699A, and publication date is on August 27th, 2008, and the Chinese patent literature that name is called " a kind of chromium-free passivation liquid for galvanized sheet and preparation method thereof " discloses a kind of organic resin chromium-free passivation liquid and preparation method thereof.The step of this preparation method is: add in stirring tank after being dissolved by inorganic salt inhibiter, add dispersion agent, organic acid, encapsulant, organosilicon crylic acid latex while stirring, all the other are for water, regulate pH value to 2.0 ~ 5.0 with mineral acid or alkali again, then under 20 ~ 30 DEG C of conditions, stir 1 ~ 2hr.Often liter of content of each component in this organic resin chromium-free passivation liquid is: inorganic salt inhibiter is 10 ~ 55g, additive is 4 ~ 10g, organic acid is 5 ~ 20g, encapsulant is 5 ~ 30g, organosilicon crylic acid latex is 150 ~ 300ml, and surplus is water.The technical scheme of this invention forms one deck organic resin barrier layer again on the basis forming inorganic metal compound precipitation membrane.But use organic resin passivation also to there is shortcoming, because organic resin film forming needs the longer time, whole passivating process lasts length, be unfavorable for working continuously on zinc-plated panel production line, and cost is relatively high.
Except chromium-free deactivation method, trivalent chromium deactivating liquid also can be used for carrying out passivation anti-corrosive treatment to steel plate galvanizing surface, but trivalent chromium deactivating liquid also exists the problem of some; Such as, the erosion resistance of the coating that its coating is formed can not completely and the sexavalent chrome passivation erosion resistance that applies the coating formed afterwards compare favourably, the passivation layer also having its coating to be formed and bonding force of coating poor, thus the field making it be confined to some to need to carry out painting operation.
Summary of the invention
The object of this invention is to provide one for galvanized sheet surface-treated containing chromium passivating liquid, this passivating solution is not containing sexavalent chrome, adopt the steel plate galvanized after this passivating solution process to have excellent corrosion resistance nature, Paint Adhesion energy and processing characteristics simultaneously, multiple painting operation field can be widely used in.In addition, owing to not containing sexavalent chrome, this passivating solution toxicity is little, and the cost of wastewater treatment is low, few to the harm of HUMAN HEALTH and external environment.
According to above-mentioned purpose of the present invention, the present invention proposes one for galvanized sheet surface-treated containing chromium passivating liquid, its component is:
Trivalent chromium 0.1 ~ 1.0wt%;
Organosilane 0.1 ~ 10.0wt%;
Complexing agent 0.1 ~ 2.0wt%;
Surplus is deionized water and inevitable impurity.
In the inventive solutions, in passivating solution, trivalent chromium can form one deck containing chromium passivation film at galvanized steel sheet surface, organosilane is then main filmogen, they are cross-linked with each other reaction, the silane adsorption film of one deck densification can be formed in metallic surface, this is just equivalent on trivalent chromium passivation film, define again the three-dimensional fine and close closed barrier layer of one deck, thus further increasing the corrosion resistance nature of whole substrate.The erosion resistance of coating formed after the coating of this passivating solution can match in excellence or beauty the erosion resistance of the coating formed after sexavalent chrome passivation coating completely.Meanwhile, the substrate after the passivating solution process containing organosilane component, the coating bonding force of the rete formed in its surface and subsequent coated is good, thus substantially improves coating performance and the processing characteristics of substrate.
Further, of the present invention for galvanized sheet surface-treated containing in chromium passivating liquid, above-mentioned trivalent chromium comprise chromium chloride, chromium sulphate, chromium nitrate and Plessy's green at least one of them.Preferably chromium chloride.
Further, contain in chromium passivating liquid of the present invention for galvanized sheet surface-treated, above-mentioned organosilane is the silane containing tri-alkoxy ester functional group.
Further, contain in chromium passivating liquid of the present invention for galvanized sheet surface-treated, the above-mentioned silane containing tri-alkoxy ester functional group comprises: two-(triethoxysilyl) ethane (BTSE), 1,2-is two-(trimethoxysilyl) ethane (TMSE), in γ-glycidyl ether oxygen propyl trimethoxy silicane and γ-aminopropyltriethoxy dimethoxysilane (γ-APS) at least one of them.Further preferably, the above-mentioned silane containing tri-alkoxy ester functional group comprises: two-(triethoxysilyl) ethane (BTSE) and/or γ-aminopropyltriethoxy dimethoxysilane (γ-APS).
Further, of the present invention for galvanized sheet surface-treated containing in chromium passivating liquid, above-mentioned complexing agent comprise fluorochemical and organic carboxyl acid at least one of them.
Further, of the present invention for galvanized sheet surface-treated containing in chromium passivating liquid, above-mentioned fluorochemical comprises ammonium bifluoride, Sodium Fluoride and Potassium monofluoride at least one of them.Further preferably, above-mentioned fluorochemical comprises Sodium Fluoride.
Further, of the present invention for galvanized sheet surface-treated containing in chromium passivating liquid, above-mentioned organic carboxyl acid comprise propanedioic acid, citric acid and tartaric at least one of them.Further preferably, above-mentioned organic carboxyl acid comprises tartrate.
Because mentioned above can be used in galvanized sheet surface treatment containing chromium passivating liquid, the non-corrosibility of the steel plate galvanized after passivating solution surface treatment mentioned above is close to the non-corrosibility of the steel plate galvanized with coating sexavalent chrome passivating solution, the passivation layer formed at surface of steel plate and the fitness of various coating good, improve application and the processing characteristics on galvanized sheet surface, for this reason, present invention also offers and be a kind ofly used in using method in actual production for galvanized sheet surface-treated containing chromium passivating liquid by above-mentioned.
In order to realize above-mentioned purpose of the present invention, it is a kind of for the using method of galvanized sheet surface-treated containing chromium passivating liquid that the present invention proposes, and it comprises: mentioned above is coated in galvanized sheet surface containing chromium passivating liquid, then carries out baking dry.
Further, of the present invention for galvanized sheet surface-treated containing in the using method of chromium passivating liquid, baking drying temperature is 80-200 DEG C, and baking time of drying is 10-100s.
In the inventive solutions, air cooking or the mode of Infrared Heating can be adopted to carry out baking drying to being coated with containing the galvanized sheet surface of chromium passivating liquid.
Further, contain in the using method of chromium passivating liquid for galvanized sheet surface-treated of the present invention, mentioned above is 0.2-2.0g/m containing the coating thickness of chromium passivating liquid on galvanized sheet surface
2.
Further, contain for galvanized sheet surface-treated in the using method of chromium passivating liquid of the present invention, above-mentioned coating method comprises roller coat, dip-coating, brushing or spray etc.
It should be noted that, the equipment of whole enforcement passivation process can continue to use the equipment of sexavalent chrome Passivation Treatment substantially, without the need to adjusting on a large scale the device on production line or production line.
Of the present invention for galvanized sheet surface-treated containing chromium passivating liquid, only do not contain sexavalent chrome containing trivalent chromium, greatly reduce the toxicity of technique postorder waste water and consequent cost for wastewater treatment, reduce the disadvantageous effect that production technique causes environment and human body significantly.
Of the present invention for galvanized sheet surface-treated containing chromium passivating liquid, make full use of trivalent chromium and organosilane in conjunction with effect, improve non-corrosibility and the processing coating of the rete formed containing chromic passivating solution, thus promote Corrosion Protection and the processing characteristics of steel plate galvanized.
Of the present invention for galvanized sheet surface-treated, containing the using method of chromium passivating liquid, operation is simple, can continue to use the equipment on existing sexavalent chrome passivation technology production line, is convenient to manufacturing enterprise and implements to utilize.Excellent and the steel plate galvanized product that processibility is good of erosion resistance can be obtained by this using method.
Embodiment
To be described further containing chromium passivating liquid and using method thereof for galvanized sheet surface-treated of the present invention according to specific embodiment below, but following specific embodiment and related description do not form the improper restriction for technical scheme of the present invention.
Embodiment A 1-A12 and comparative example B1-B2 is respectively the embodiment and the comparative example that contain chromium passivating liquid for galvanized sheet surface-treated.
Embodiment A 1-A12
According to the following step prepare in above-described embodiment A1-A12 for galvanized sheet surface-treated containing chromium passivating liquid:
1) configure organosilane solution: at room temperature, join in Enough Dl water by part silicone alkane, fully stir and treat that it dissolves completely, and then add another part organosilane wherein, after fully stirring, obtain mixture A;
2) configure trivalent chromium solutions: will join in deionized water containing chromium cpd, and after stirring and dissolving, then add a certain amount of complexing agent, after stirring and dissolving, add remainder complexing agent again, after fully stirring, obtain mixture B;
3) mix: the mixture B configured is poured in mixture A, supplement amount of deionized water and reach 1000g to the gross weight to mixed solution, after fully stirring, obtain the trivalent chromium deactivating liquid in embodiment A 1-A12.
Comparative example B1
Comparative example B1 is pure trivalent chromium deactivating liquid, not containing organosilane, prepares the trivalent chromium deactivating liquid in comparative example B1 according to the following step:
1) by CrCl
36H
2o joins in deionized water, abundant stirring and dissolving;
2) then Sodium Fluoride is added, abundant stirring and dissolving;
3) finally add tartrate, supplement and add deionized water to gross weight to 1000g.
Comparative example B2
Comparative example B2 is pure silane passivating solution, not containing trivalent chromium and complexing agent, prepares the pure silane passivating solution in comparative example B2 according to the following step:
1) by content for two-(triethoxysilyl) ethane (BTSE) joins in deionized water, fully stir;
2) after it dissolves completely, then add γ-aminopropyltriethoxy dimethoxysilane (γ-APS), fully stir;
3) after it dissolves, supplement and add deionized water to gross weight 1000g.
In embodiment A 1-A12, the preparation-obtained massfraction containing each constituent in chromium passivating liquid is specifically as shown in table 1, and the massfraction of each constituent in the pure trivalent chromium deactivating liquid for preparing respectively of comparative example B1 and B2 and pure silane passivating solution is concrete also as shown in table 1.
Table 1. (surplus is deionized water)
1) BTSE is 92% pair-(triethoxysilyl) ethane.2) γ-APS is γ-aminopropyltriethoxy dimethoxysilane.
Trivalent chromium in above-described embodiment A1-A12 can be come from chromium sulphate, chromium nitrate and Plessy's green at least one of them; Organosilane can also be 1,2-pair-(trimethoxysilyl) ethane and/or γ-glycidyl ether oxygen propyl trimethoxy silicane.
Complexing agent in above-described embodiment A1-A12 can be ammonium bifluoride, Potassium monofluoride, propanedioic acid and citric acid at least one of them.
Passivating solution in above-described embodiment A1-A12 and comparative example B1-B2 is coated on galvanized sheet surface, and then carry out baking dry, baking drying temperature is 80-150 DEG C, and baking time of drying is 10-50s, and the coating thickness of passivating solution on galvanized sheet surface is 0.2-2.0g/m
2.
In addition, by coating methods such as roller coat, dip-coating, brushing or sprays, the passivating solution in embodiment and comparative example can be coated on galvanized sheet surface.
In addition, can first dry up galvanized sheet degreasing 30s after washing under temperature 60 C with alkaline defatting agent before coating passivating solution.
Above-mentioned specifically as shown in table 2 containing the correlation parameter in the step of the using method of chromium passivating liquid for galvanized sheet surface-treated.
Table 2.
| Sequence number | Baking drying temperature (DEG C) | Baking time of drying (s) | Coating thickness (g/m 2) |
| Embodiment A 1 | 80 | 20 | 0.33 |
| Embodiment A 2 | 100 | 15 | 0.51 |
| Embodiment A 3 | 120 | 15 | 0.66 |
| Embodiment A 4 | 120 | 15 | 0.78 |
| Embodiment A 5 | 120 | 20 | 1.10 |
| Embodiment A 6 | 120 | 20 | 0.72 |
| Embodiment A 7 | 100 | 20 | 0.58 |
| Embodiment A 8 | 120 | 15 | 0.74 |
| Embodiment A 9 | 100 | 20 | 0.61 |
| Embodiment A 10 | 120 | 15 | 0.81 |
| Embodiment A 11 | 100 | 20 | 0.63 |
| Embodiment A 12 | 120 | 15 | 0.79 |
| Comparative example B1 | 100 | 10 | 0.28 |
| Comparative example B2 | 120 | 20 | 0.68 |
Galvanized sheet surface area after the passivating solution coating in above-described embodiment A1-A12 and comparative example B1-B2 is cut into normal size and tests as follows, thus obtain respectively and evaluate the testing data of its properties, concrete test event and testing method as follows:
I) solidity to corrosion test
With reference to the standard of GB/T/10125-1997, adopt spraying continuously to sample, spraying reagent adopts concentration to be the NaCl of 50 ± 5g/L, and salt fog cabinet temperature is 35 ± 2 DEG C, and pH is 6.5 ~ 7.2, and spray pressure is 70 ~ 170Kpa, and salt fog settling velocity is 1 ~ 2ml/80cm
2.Test period is 72 hours and 96 hours.The corrosion rate percentage ratio that coating white rust area accounts for the coating total area represents.
II) sticking power test
With reference to the standard of GB GB/T9286-1998, utilize QFH Checker marking knife according to draw lattice plate on passive film surface each stroke of direction 11 cuttves in length and breadth, form 100 sub-boxes, then 100 Box Section to be adhered completely compacting with scotch tape, after waiting for 5min, torn fast by scotch tape, observing and adding up in 100 grid has the passivation layer at how many grid place to come off.
III) stability test
By the passivating solution in embodiment A 1-A6 and comparative example B1-B2 as in thermostat container, in constant temperature 40 DEG C of environment, seal preservation 3 months, observe passivating solution and whether produce muddiness or whether have precipitation.
Table 3 illustratively show coating above-described embodiment A1-A12 and comparative example B1-B2 in each passivating solution after galvanized sheet sample after tested after correlation test data.
Table 3.
| Sequence number | 72hr corrosion rate | 96hr corrosion rate * | Sticking power | Stability |
| A1 | 2％ | 10％ | 5％ | Without precipitation |
| A2 | 0％ | 5％ | 5％ | Without precipitation |
| A3 | 0％ | 0％ | 0％ | Without precipitation |
| A4 | 2％ | 5％ | 0％ | Without precipitation |
| A5 | 0％ | 2％ | 0％ | Without precipitation |
| A6 | 2％ | 10 | 0％ | Without precipitation |
| A7 | 1.5％ | 7％ | 0％ | Without precipitation |
| A8 | 1.0％ | 5％ | 0％ | Without precipitation |
| A9 | 1.5％ | 6％ | 3％ | Without precipitation |
| A10 | 1.0％ | 8％ | 3％ | Without precipitation |
| A11 | 1.5％ | 8％ | 5％ | Without precipitation |
| A12 | 1.5％ | 10％ | 5％ | Without precipitation |
| B1 | 5％ | 15％ | 15％ | Without precipitation |
| B2 | 5％ | 20％ | 0％ | Without precipitation |
As can be seen from Table 3, passivating solution in comparative example B1 and B2 carry out the test period be 72 hours solidity to corrosion test after, its corrosion rate just reaches 5%, have passed through after the test period is the solidity to corrosion test of 96 hours, the corrosion rate of sample of the pure silane passivating solution of coating comparative example B2 is up to 20%.Compared to comparative example B1 and B2, coating embodiment A 1-A12 containing chromium passivating liquid sample go through the test period be 72 hours solidity to corrosion test after corrosion rate≤2.0%, and have passed through the test period be 96 hours solidity to corrosion test after the most serious corrosion rate be also only 10%.Meanwhile, compare to comparative example B1-B2, through embodiment A 1-A6 containing chromium passivating liquid coating after the passivation film amount of coming off few.Therefore, through of the present invention coated containing chromium passivating liquid for galvanized sheet surface-treated after steel plate galvanized have good corrosion resistance and excellent sticking power concurrently.
Associative list 1 and table 3 can be learnt, of the present invention for galvanized sheet surface-treated containing chromium passivating liquid take full advantage of between trivalent chromium and organosilane in conjunction with effect, both are indispensable.
In addition, of the present invention also have excellent stability for galvanized sheet surface-treated containing chromium passivating liquid.
That enumerates it should be noted that above is only specific embodiments of the invention, obviously the invention is not restricted to above embodiment, has many similar changes thereupon.If all distortion that those skilled in the art directly derives from content disclosed by the invention or associates, protection scope of the present invention all should be belonged to.
Claims (11)
1. contain a chromium passivating liquid for galvanized sheet surface-treated, it is characterized in that, its component is:
Trivalent chromium 0.1 ~ 1.0wt%;
Organosilane 0.1 ~ 10.0wt%;
Complexing agent 0.1 ~ 2.0wt%;
Surplus is deionized water and inevitable impurity.
2. as claimed in claim 1 for galvanized sheet surface-treated containing chromium passivating liquid, it is characterized in that, described trivalent chromium comprise chromium chloride, chromium sulphate, chromium nitrate and Plessy's green at least one of them.
3. contain chromium passivating liquid for galvanized sheet surface-treated as claimed in claim 1, it is characterized in that, described organosilane is the silane containing tri-alkoxy ester functional group.
4. contain chromium passivating liquid for galvanized sheet surface-treated as claimed in claim 3, it is characterized in that, the described silane containing tri-alkoxy ester functional group comprises two-(triethoxysilyl) ethane, 1,2-is two-(trimethoxysilyl) ethane, in γ-glycidyl ether oxygen propyl trimethoxy silicane and γ-aminopropyltriethoxy dimethoxysilane at least one of them.
5. as claimed in claim 1 for galvanized sheet surface-treated containing chromium passivating liquid, it is characterized in that, described complexing agent comprise fluorochemical and organic carboxyl acid at least one of them.
6. as claimed in claim 5 for galvanized sheet surface-treated containing chromium passivating liquid, it is characterized in that, described fluorochemical comprises ammonium bifluoride, Sodium Fluoride and Potassium monofluoride at least one of them.
7. as claimed in claim 5 for galvanized sheet surface-treated containing chromium passivating liquid, it is characterized in that, described organic carboxyl acid comprise propanedioic acid, citric acid and tartaric at least one of them.
8. as the using method containing chromium passivating liquid for galvanized sheet surface-treated in claim 1-7 as described in any one, it is characterized in that, be coated in galvanized sheet surface by described containing chromium passivating liquid, then carry out baking dry.
9. using method as claimed in claim 8, it is characterized in that, baking drying temperature is 80-200 DEG C, and baking time of drying is 10-100s.
10. using method as claimed in claim 8, is characterized in that, described is 0.2-2.0g/m containing the coating thickness of chromium passivating liquid on galvanized sheet surface
2.
11. using method as claimed in claim 8, it is characterized in that, coating method is roller coat, dip-coating, brushing or spray.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017214777A1 (en) * | 2016-06-12 | 2017-12-21 | 深圳市恒兆智科技有限公司 | Passivator for zinc plating and passivation treatment method for zinc-plated workpiece surface |
| CN112301338A (en) * | 2020-07-02 | 2021-02-02 | 上海兴赛尔表面材料有限公司 | Medium-low temperature fast curing trivalent chromium passivation solution and manufacturing and using method thereof |
| CN112481575A (en) * | 2020-11-27 | 2021-03-12 | 广东达志化学科技有限公司 | Hot galvanizing passivation solution and preparation method thereof |
| CN112538306A (en) * | 2020-12-04 | 2021-03-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Zinc-aluminum-magnesium coating surface treating agent and preparation method and use method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255559A (en) * | 2008-02-25 | 2008-09-03 | 合肥华清金属表面处理有限责任公司 | Metal finishing agent using silane coupling agent as main component for metal surface pretreatment |
| CN101492816A (en) * | 2009-02-27 | 2009-07-29 | 张国良 | Passivation liquid for zincing tube and passivation process thereof |
| CN102330082A (en) * | 2010-07-13 | 2012-01-25 | 伟业重工(安徽)有限公司 | Trivalent chromium passivation concentrated solution |
-
2014
- 2014-06-26 CN CN201410298518.8A patent/CN105316672A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255559A (en) * | 2008-02-25 | 2008-09-03 | 合肥华清金属表面处理有限责任公司 | Metal finishing agent using silane coupling agent as main component for metal surface pretreatment |
| CN101492816A (en) * | 2009-02-27 | 2009-07-29 | 张国良 | Passivation liquid for zincing tube and passivation process thereof |
| CN102330082A (en) * | 2010-07-13 | 2012-01-25 | 伟业重工(安徽)有限公司 | Trivalent chromium passivation concentrated solution |
Non-Patent Citations (1)
| Title |
|---|
| 于元春 等: "无铬钝化与三价铬钝化的研究进展", 《表面技术》 * |
Cited By (8)
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| WO2017214777A1 (en) * | 2016-06-12 | 2017-12-21 | 深圳市恒兆智科技有限公司 | Passivator for zinc plating and passivation treatment method for zinc-plated workpiece surface |
| CN112301338A (en) * | 2020-07-02 | 2021-02-02 | 上海兴赛尔表面材料有限公司 | Medium-low temperature fast curing trivalent chromium passivation solution and manufacturing and using method thereof |
| CN112481575A (en) * | 2020-11-27 | 2021-03-12 | 广东达志化学科技有限公司 | Hot galvanizing passivation solution and preparation method thereof |
| CN112538306A (en) * | 2020-12-04 | 2021-03-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Zinc-aluminum-magnesium coating surface treating agent and preparation method and use method thereof |
| CN112538306B (en) * | 2020-12-04 | 2022-07-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Zinc-aluminum-magnesium coating surface treating agent and preparation method and use method thereof |
| CN113403615A (en) * | 2021-06-23 | 2021-09-17 | 上海兴赛尔表面材料有限公司 | Trivalent chromium passivation solution capable of providing deep processing performance and preparation method thereof |
| CN115786896A (en) * | 2022-09-07 | 2023-03-14 | 上海兴赛尔表面材料有限公司 | A kind of environment-friendly passivation solution for galvanized aluminum-magnesium board and preparation method thereof |
| CN116288304A (en) * | 2023-02-28 | 2023-06-23 | 马鞍山钢铁股份有限公司 | Trivalent chromium passivation solution and method for coating steel plate |
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