CN101519775B - Environmental-friendly chrome-free phosphating electrogalvanized sealed steel sheet and manufacturing method thereof - Google Patents
Environmental-friendly chrome-free phosphating electrogalvanized sealed steel sheet and manufacturing method thereof Download PDFInfo
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- CN101519775B CN101519775B CN200810033959XA CN200810033959A CN101519775B CN 101519775 B CN101519775 B CN 101519775B CN 200810033959X A CN200810033959X A CN 200810033959XA CN 200810033959 A CN200810033959 A CN 200810033959A CN 101519775 B CN101519775 B CN 101519775B
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Abstract
The invention provides an environmental-friendly chrome-free phosphating electrogalvanized sealed steel sheet and a manufacturing method thereof. The steel sheet comprises a base plate, a zinc coatingThe invention provides an environmental-friendly chrome-free phosphating electrogalvanized sealed steel sheet and a manufacturing method thereof. The steel sheet comprises a base plate, a zinc coating, a phosphating coating and a sealed coating. An electrogalvanized steel sheet is adopted as the base material, the phosphating coating which is taken as a low-layer coating is formed on the surface o, a phosphating coating and a sealed coating. An electrogalvanized steel sheet is adopted as the base material, the phosphating coating which is taken as a low-layer coating is formed on the surface of the base material, then a chrome-free sealing finishing agent is adopted to coat the surface of the phosphating coating so as to form an upper-layer coating, and finally the environmental-friendly cf the base material, then a chrome-free sealing finishing agent is adopted to coat the surface of the phosphating coating so as to form an upper-layer coating, and finally the environmental-friendly chrome-free phosphating electrogalvanized sealed steel sheet with excellent corrosion resistance and coating adhesive property is obtained after drying, thereby solving the problems in environmental frhrome-free phosphating electrogalvanized sealed steel sheet with excellent corrosion resistance and coating adhesive property is obtained after drying, thereby solving the problems in environmental friendliness and property caused by the traditional Cr <6+> sealing treatment.iendliness and property caused by the traditional Cr <6+> sealing treatment.
Description
Technical field
The present invention relates to the process for treating surface of cold-rolled steel sheet, specifically, the present invention relates to a kind of environment-friendly chromium-free sealing electro-galvanizing phosphatization steel plate and manufacture method thereof.
Background technology
The corrosion of ferrous materials is all taking place all the time, and annual have 10% steel to be wasted because of corrosion approximately.In order to prevent corrosion, prolong the work-ing life of ferrous materials, the modal measure of employing is overlay coating, phosphatization, passivation, japanning etc.
Electro-galvanizing is a kind of effective ways that improve the cold-rolled steel sheet corrosion resistance, but the coating of galvanizing surface non-processor, processibility are relatively poor.For improving coating, the processibility of electrogalvanizing steel plate, often implement to form the bonderizing of phosphate coating on the electrogalvanizing steel plate surface, phosphate coating is the crystalline film that one deck covers the zinc laminar surface, and a lot of spaces are arranged, its solidity to corrosion is relatively poor.For improving the solidity to corrosion of phosphate coating, must apply the sealer coat in one deck sealing phosphate coating space on the phosphate coating surface again, sealing treatment adopts usually and contains Cr
6+Confining liquid these spaces are filled up and are closed, this method is simple, cost is low, corrosion resisting property is good, but contains Cr
6+Objectionable impurities.
The open communique CN1399007 of Chinese patent discloses a kind of Martensite Stainless Steel passivation technology, this technology comprise to Martensite Stainless Steel clean, etch, passivation, sealing treatment, the composition of used confining liquid is Na
2Cr
2O
72H
2O, Na
2CO
3And GH～713; The open communique CN1063129 of Chinese patent discloses a kind of hot-dip galvanizing sheet steel surface passivation liquid, and this passivating solution is by CrO
3, SiO
2, emulsion stabilizer, dispersion agent, reductive agent form, and is applicable to the surface passivation of steel plate galvanized; The open communique CN1141354 of Chinese patent discloses the chemical treatment method of the low chromium surface film of a kind of electrolytic tinplate, and the main component of used passivating solution is Na
2Cr
2O
72H
2O, this passive film chrome content＜1.5mg/m
2, be suitable for using such as the packing of mushroom jar mouth.
In the surface treatment method of above-mentioned these steel plates of mentioning, all in treatment solution, added sexavalent chrome, as everyone knows, sexavalent chrome is the material of serious environment pollution, long-term contact will cause chrome ulcers, erosive rhinitis, perforation of nasal septum etc., and particularly it has high carcinogenic by a large amount of studies confirm that in recent years.Generally, the sealing of electro-galvanizing phosphatization is used and is contained Cr
6+Medicament carries out sealing treatment, has the harm of three aspects: the firstth, and workman and sexavalent chrome close contact have a strong impact on the healthy of workman in the production process; The secondth, have in the production process and contain chromic waste liquid discharge, serious harm environment in a large number; The 3rd is to contain a large amount of sexavalent chromes in the phosphatization closing membrane that forms, and user and environment are had disadvantageous effect.
In recent years, the problem pay attention to day by day of people's environmental pollution, the electronics and IT products prevention and cure of pollution management method that the ROHS of European Union instruction and China's Ministry of Information Industry issue all bans use of Cr
6+Etc. hazardous and noxious substances.Under this background, the environment-friendly chromium-free sealing electro-galvanizing phosphatization steel plate of exploitation excellent property is very necessary and urgent.
The open communique CN1043962 of Chinese patent discloses a kind of passivating solution of handling steel surface, be characterized in phosphoric acid, tartrate, N, N-dimethylformamide, benzotriazole, polyoxyethylene glycol, water form in the normal temperature and pressure reaction, this passivating solution does not contain chromic salts, heavy metal free salt and nitroso-group, be applicable to common iron and steel parts but only mention in the disclosure text, and its solidity to corrosion, coating do not had specify.The open communique CN1326012 of Chinese patent discloses a kind of passivation technique for filming on surface of stainless steel, adopts the acid solution HNO of strong oxidizing property
3And rare earth addition CeO
2The passivating solution of forming is with substitute chromium hydrochlorate passivating solution.Zinc layer weight 〉=the 30g/m of general similar electro-galvanizing phosphatization sealing steel plate
2, phosphate coating weight 0.5～1g/m
2, sealer coat weight 15～40mg/m
2It is the technology that the Chrome-free confining liquid of main component carries out sealing treatment with vinylformic acid that JP 5247668 discloses a kind of, and this technology is that the confining liquid of main component mechanically fills up the space in the phosphate coating and be closed to reach and replaces Cr in order to vinylformic acid mainly
6+The purpose of sealing treatment, and be not the employing film technique.
In order to address the above problem, the present inventor adopts a kind of Cr that do not contain
6+, Cr
3+The sealing treatment agent phosphate coating on electrogalvanizing steel plate surface is carried out sealing treatment, researched and developed out a kind of environment-friendly chromium-free sealing electro-galvanizing phosphatization steel plate, thereby finished the present invention.
One object of the present invention is to provide a kind of environment-friendly chromium-free sealing electro-galvanizing phosphatization steel plate.
Another object of the present invention is to provide the manufacture method of described steel plate.
Summary of the invention
First aspect of the present invention provides a kind of environment-friendly chromium-free sealing electro-galvanizing phosphatization steel plate, and this steel plate comprises substrate, zinc layer, phosphate coating and sealer coat, and wherein said sealer coat adopts sealing treatment agent coating, and described sealing treatment agent is made up of following compound::
(1) is selected from a kind of in the metallic compound of metal element Ti, V, Mo, W and Ce;
(2) water-dispersible silica;
(3) be selected from and contain a carboxyl in the molecule at least or contain a carboxyl at least and a hydroxyl, and satisfy a kind of in the organic acid of carbonatoms between 3～6;
And the weight ratio of metallic compound and water-dispersible silica is 0.01～0.1, and the weight ratio of organic acid and water-dispersible silica is 0.5～1.
In a preferred implementation: the zinc layer weight≤25g/m of described Chrome-free sealing electro-galvanizing phosphatization steel plate
2
In another preferred implementation: the phosphate coating weight of described steel plate is 0.5～3.0g/m
2
In another preferred implementation: the sealer coat weight of described steel plate is 50～400mg/m
2
In another preferred implementation: the form of described metallic compound is selected from a kind of in oxide compound, oxyhydroxide, coordination compound, inorganic acid salt and the organic acid salt.
In another preferred implementation: described water-dispersible silica is colloid silica or aerosil.
In another preferred implementation: described organic acid is selected from a kind of in citric acid, tartrate, hexanodioic acid, L-glutamic acid, propionic acid, phytic acid and the lactic acid.
Below, the moiety effect of the sealing treatment agent that environment-friendly chromium-free of the present invention sealing electro-galvanizing phosphatization steel plate is adopted elaborates.
Metallic compound can be a metal element Ti, V, Mo, the oxide compound of W and Ce, oxyhydroxide, coordination compound, mineral acid or organic acid salt, as long as it is well then applicable with the intermiscibility of other constituent in the surface treatment agent, titanium sulfate for example, diisopropoxy titanium diacetyl acetone, the reactant of lactic acid and titanium alkoxyl group, the titanium lauroleate, vanadium pentoxide, metavanadic acid, ammonium meta-vanadate, sodium metavanadate, vanadium oxytrichloride etc., three vanadium oxides, vanadium dioxide, vanadium trisulfide, the vanadium praseodynium, the vanadium methyl ethyl diketone, vanadium trichloride, phosphorus vanadium molybdenum heteropolyacid, molybdic acid, ammonium molybdate, Sodium orthomolybdate, the molybdenum oxygen compound, metatungstic acid, ammonium metawolframate, metatungstic acid sodium, para-tungstic acid, ammonium paratungstate, sodium paratungstate, cerous acetate, cerous nitrate, Cerium II Chloride etc., wherein about molybdenum (VI) compound, vanadium (V) compound, tungsten compounds such as (VI) is used alcohols, after reducing, also can use by reductive agents such as organic acid.
Water-dispersible silica can be colloid silica or aerosil, do not limit for both kinds are special, colloid silica can be Snowtex C, Snowtex O, Snowtex N, Snowtex S, Snowtex UP, Snowtex PS-M, Snowtex PS-L, Snowtex 20, Snowtex 30, Snowtex 40 grades (being daily output chemical industry product), aerosil can be AEROSIL50, AEROSIL 130, AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSIL TT600, AEROSIL MOX80, (being Japanese AEROSIL product) such as AEROSIL MOX170.
Organic acid can be to contain 1 carboxyl at least or contain a carboxyl at least and hydroxyl, the carbonatoms in the molecule is advisable with 3～6 simultaneously, for example citric acid, tartrate, hexanodioic acid, L-glutamic acid, propionic acid, phytic acid, lactic acid etc.If carbonatoms in the molecule is too much, and the constituent epithelium of formation can cause painting adhesion, solidity to corrosion and the processibility of steel plate to descend.If carbonatoms is very few, and the then feasible acid grow that contains the sealing treatment agent of above-mentioned constituent when being coated on surface of steel plate, causes the erosion to electro-galvanized layer to make the solidity to corrosion of steel plate, painting adhesion descend on the contrary.
The weight ratio of metallic compound and water-dispersible silica is advisable with 0.01～0.1.If weight ratio is low excessively, because the excessive existence of water-dispersible silica, the content of giving corrosion proof metallic compound tails off, and can reduce the solidity to corrosion of steel plate, and additive effect is poor.If weight ratio is too high, because the excessive existence of metallic compound, the feasible content of mainly giving the water-dispersible silica of painting adhesion descends, and can cause that the painting adhesion of steel plate descends.
The weight ratio of organic acid and water-dispersible silica is advisable with 0.5～1.If weight ratio is low excessively, because the excessive existence of water-dispersible silica, the feasible bad stability that contains the sealing treatment agent of above-mentioned composition possibly can't stably be synthesized above-mentioned sealing treatment agent.If weight ratio is too high because the excessive existence of organic acid remains in the epithelium excessive organic acid, hindered the bonding force with phosphate coating, thereby may cause the steel plate painting adhesion can decline.
In addition, can regard a cationoid as for above-mentioned excessive metallic compound with unoccupied orbital, has character equally to the metallic surface set, because it is fully overlapping with the shell track of the atoms metal of object being treated, by utilizing the feasible effect of corroding the electronics delocalization that is produced of φ track, guarantee the homogeneity of surface potential, thereby given the solidity to corrosion (planar portions, facial, the scratch portion of cut-out) of steel plate excellence.All there is good bonding force on paint and the electro-galvanizing surface of discovering water-dispersible silica and spraying, so the deducibility water-dispersible silica has improved the solidity to corrosion of steel plate.Organic acid is by the sequestering action to metallic compound in the sealing treatment agent, guaranteed the stable of metallic compound in the water system constituent, and it can also produce effect to oxidation and the corrosion that suppresses zinc simultaneously by the slight etching in steel sheet zinc coating surface being improved the painting adhesion of steel plate.
Second aspect of the present invention provides a kind of manufacture method of environment-friendly chromium-free sealing electro-galvanizing phosphatization steel plate, and this method may further comprise the steps:
(1) cleaning of electrogalvanizing steel plate: the aqueous solution with the grease-removing agent of neutral and alkali cleans surface of steel plate, washes with tap water again;
(2) bonderizing: the steel plate after the cleaning is adjusted in the treatment solution on the surface and was flooded 2～20 seconds, sprays in phosphating agent 3～20 seconds again, cleans oven dry then successively with tap water, pure water;
(3) sealing treatment: the sealing treatment agent is dissolved in water, is coated on the surface of steel plate phosphate coating again, with hot blast steel plate is heated to 60～100 ℃ of oven dry then.
In a preferred implementation: it is the colloidal titanium compound water solution that treatment solution is adjusted on the surface described in the step (2), and the composition of described phosphating agent comprises phosphate anion, zine ion, nickel ion, fluorion and nitrate ion.
In a preferred implementation: the concentration that treatment solution is adjusted on described surface is 0.25～2.5g/L.
Beneficial effect of the present invention is:
1, compared to containing Cr usually
6+Electro-galvanizing phosphatization sealing steel plate, steel plate of the present invention is environmentally friendly product, does not contain Cr
6+Etc. hazardous and noxious substances, avoided health damage in process of production to the producer, also in the finished product, prevented harm to user and environment.
2, environment-friendly chromium-free sealing electro-galvanizing phosphatization steel plate of the present invention has outstanding solidity to corrosion and coating, and solidity to corrosion is than containing Cr usually
6+Phosphatization sealing steel plate has improved more than 1 times.
Embodiment
Below for a more detailed description with embodiment to the present invention.These embodiment only are the descriptions to best mode for carrying out the invention, scope of the present invention are not had any restriction.
Embodiment 1
1, test piece
The product of market sale: thickness of slab 0.6mm, two-sided electrogalvanizing steel plate, wherein every zinc-plated amount is 20g/m
2
2, the cleaning of electrogalvanizing steel plate
Grease-removing agent (login trade mark: FC-364S with neutral and alkali, Nihon Parkerizing Co., Ltd.'s product) the aqueous solution (concentration is 20g/L) cleans the electrogalvanizing steel plate surface, 60 ℃ of treatment temps, 20 seconds treatment times, processing mode is spray, with the tap water washing, remove the remaining alkaline components in surface then.
3, bonderizing
(1) electrogalvanizing steel plate of earlier surface cleaning being crossed was adjusted in the treatment solution (PL-Z, Nihon Parkerizing Co., Ltd.'s product) dipping 20 seconds on the surface that is diluted with water to 0.6g/L, and wherein to adjust treatment solution be the colloidal titanium compound water solution on the surface.
(2) be that treatment solution (Nihon Parkerizing Co., Ltd.'s product) is diluted with water to 55g/L with bonderizing with the PB-3312M zinc phosphate, heat after 60 ℃, use NT-4055 (Nihon Parkerizing Co., Ltd.'s product) that free acid is adjusted to 1.4pt again.
(3) steel plate that the surface adjustment was handled sprayed 12 seconds in above-mentioned adjusted phosphating agent (this treatment agent main component is phosphate anion, zine ion, nickel ion, fluorion and nitrate ion), clean with tap water, pure water successively then, oven dry, phosphate coating weight sees Table 1.
4, sealing treatment
The sealing treatment agent of constituent shown in the table 1 is dissolved in water, it is coated on the phosphatization electrogalvanizing steel plate surface that cleans up again, sealer coat weight sees Table 1, with hot blast steel plate is heated to 80 ℃ of oven dry then.
Embodiment 2
1, test piece is with embodiment 1.
2, the cleaning of electrogalvanizing steel plate is with embodiment 1.
3, the concentration of surface adjustment treatment solution is 2.0g/L in the bonderizing, and steel plate sprayed in phosphating agent 20 seconds, and phosphate coating weight sees Table 1, and all the other embodiments are with embodiment 1.
4, the composition of sealing treatment agent and sealer coat weight see Table 1, and all the other embodiments see Table 1.
Embodiment 3
1, test piece is with embodiment 1.
2, the cleaning of electrogalvanizing steel plate is with embodiment 1.
3, the concentration of surface adjustment treatment solution is 0.8g/L in the bonderizing, and steel plate sprayed in phosphating agent 10 seconds, and phosphate coating weight sees Table 1, and all the other embodiments are with embodiment 1.
4, the composition of sealing treatment agent and sealer coat weight see Table 1, and all the other embodiments see Table 1.
Embodiment 4
1, test piece is with embodiment 1.
2, the cleaning of electrogalvanizing steel plate is with embodiment 1.
3, the concentration of surface adjustment treatment solution is 1.0g/L in the bonderizing, and steel plate sprayed in phosphating agent 16 seconds, and phosphate coating weight sees Table 1, and all the other embodiments are with embodiment 1.
4, the composition of sealing treatment agent and sealer coat weight see Table 1, and all the other embodiments see Table 1.
Embodiment 5
1, test piece is with embodiment 1.
2, the cleaning of electrogalvanizing steel plate is with embodiment 1.
3, the concentration of surface adjustment treatment solution is 0.8g/L in the bonderizing, and steel plate sprayed in phosphating agent 20 seconds, and phosphate coating weight sees Table 1, and all the other embodiments are with embodiment 1.
4, the composition of sealing treatment agent and sealer coat weight see Table 1, and all the other embodiments see Table 1.
Embodiment 6
1, test piece is with embodiment 1.
2, the cleaning of electrogalvanizing steel plate is with embodiment 1.
3, the concentration of surface adjustment treatment solution is 0.4g/L in the bonderizing, and steel plate sprayed in phosphating agent 7 seconds, and phosphate coating weight sees Table 1, and all the other embodiments are with embodiment 1.
4, the composition of sealing treatment agent and sealer coat weight see Table 1, and all the other embodiments see Table 1.
Comparative example 1-3
1, test piece is with embodiment 1.
2, the cleaning of electrogalvanizing steel plate is with embodiment 1.
3, the concentration of surface adjustment treatment solution is 0.8g/L in the bonderizing, and steel plate sprayed in phosphating agent 10 seconds, and phosphate coating weight sees Table 1, and all the other embodiments are with embodiment 1.
4, the composition of sealing treatment agent and sealer coat weight see Table 1, and all the other embodiments see Table 1.
Comparative example 4
1, test piece is with embodiment 1.
2, the cleaning of electrogalvanizing steel plate is with embodiment 1.
3, the concentration of surface adjustment treatment solution is 0.8g/L in the bonderizing, and steel plate sprayed in phosphating agent 10 seconds, and phosphate coating weight sees Table 1, and all the other embodiments are with embodiment 1.
4, do not adopt sealing treatment.
Comparative example 5-6
1, test piece is with embodiment 1.
2, the cleaning of electrogalvanizing steel plate is with embodiment 1.
3, the concentration of surface adjustment treatment solution is 0.8g/L in the bonderizing, and steel plate sprayed in phosphating agent 13 seconds, and phosphate coating weight sees Table 1, and all the other embodiments are with embodiment 1.
4, sealing treatment adopts traditional hexavalent chromium-treatments mode, and the medicament that uses is LN-62 (Nihon Parkerizing Co., Ltd.'s product), and sealer coat weight sees Table 1, with hot blast steel plate is heated to 60 ℃ (PMT) oven dry then.
The composition of the phosphate coating of table 1 embodiment 1-6, comparative example 1-6 electrogalvanizing steel plate, sealer coat weight and used sealing treatment agent
(
*1): colloid silica A:Snowtex C (daily output chemistry system), colloid silica B:Snowtex O (daily output chemistry system), colloid silica C:snowtex N (daily output chemistry system), silicon magnesium silicon A:AEROSIL 200 (Japanese AEROSIL system), silicon magnesium silicon B:AEROSIL 300 (Japanese AEROSIL system)
Test example 1
By the salt spray testing method and the condition of standard JIS-Z 2371 defineds, the steel plate of embodiment 1-6 and comparative example 1-6 gained is carried out corrosion resistant test, test period is 24 hours.
Judgment standard is for measuring the white rust area of steel plate planar portions: the white rust area be qualified less than 5%, the white rust area above 5% then be defective.Test-results sees Table 2.
Test example 2
The steel plate of embodiment 1-6 and comparative example 1-6 gained is carried out the painting adhesion test, and applying commercially available Melamine Alkyd at its surface of steel plate is coating, and coating thickness is 20 μ m, and baking condition is 140 ℃ of PMT, 30 minutes.
(1) steel plate after filming by 3312 couples of standard JIS-G carries out cross and draws the test of lattice tack, use NT to draw the lattice device marks checkerboard at each test surface of steel plate grid, the 1mm that is spaced apart of lattice drawn in cross, and 11 respectively is after horizontal, vertical decussate line is drawn, to use tape stripping again.
Determinating reference is no any the peeling off to qualified of filming, and is coated with membrane portions and is stripped from then for defective.Test-results sees Table 2.
(2) steel plate after filming by 3312 couples of standard JIS-G carries out shock test, its energy with 9J is fallen, again the state of peeling off of filming with judgement with tape stripping in impact site.
Judgment standard is no any the peeling off to qualified of filming, and is coated with membrane portions and is stripped from then for defective.Test-results sees Table 2.
The test-results of table 2 embodiment 1-6 and comparative example 1-6 steel plate
Associative list 1, table 2 as can be seen, the sealing treatment agent moisture-free that comparative example 1 the adopts property silicon-dioxide that looses, though the steel plate solidity to corrosion after the processing is good, the 9J shock test is defective, illustrates that water-dispersible silica is to obtaining the importance of abundant painting adhesion.In comparative example 2, having used carbonatoms in the composition of sealing treatment agent is 7 M-nitro benzoic acid, has caused the decline of painting adhesion.Comparative example 3 has shown that metallic compound specific in the sealing treatment agent of the present invention is to the corrosion proof importance of phosphatization electrogalvanizing steel plate.4 of comparative examples are the electrogalvanizing steel plates without the phosphatization sealing treatment, and its solidity to corrosion and painting adhesion are all defective, and the importance of the Chrome-free sealing treatment that the present invention describes has been described.Comparative example 5 and comparative example 6 all adopt traditional C r
6+The sealing treatment mode, find as Cr
6+Epithelium weight on the low side, the steel plate solidity to corrosion is defective, if the higher steel plate painting adhesion that then can cause descends the Cr but the both contains hazardous substance
6+
The test-results of embodiment 1-6 steel plate is all qualified, and therefore as can be seen, the Chrome-free sealing electro-galvanizing phosphatization steel plate after Chrome-free sealing treatment of the present invention agent is coated on electro-galvanizing phosphatization surface and oven dry has outstanding solidity to corrosion and painting adhesion, and does not contain Cr
6+Etc. hazardous and noxious substances.
Claims (10)
1. an environment-friendly chromium-free sealing electro-galvanizing phosphatization steel plate comprises substrate, zinc layer, phosphate coating and sealer coat, it is characterized in that described sealer coat adopts sealing treatment agent coating, and described sealing treatment agent is made up of following compound:
(1) is selected from a kind of in the metallic compound of metal element Ti, V, Mo, W and Ce;
(2) water-dispersible silica;
(3) be selected from and contain a carboxyl in the molecule at least or contain a carboxyl at least and a hydroxyl and satisfy a kind of in the organic acid of carbonatoms between 3～6;
And the weight ratio of metallic compound and water-dispersible silica is 0.01～0.1, and the weight ratio of organic acid and water-dispersible silica is 0.5～1.
2. environment-friendly chromium-free sealing electro-galvanizing phosphatization steel plate according to claim 1, wherein said zinc layer weight≤25g/m
2
3. environment-friendly chromium-free sealing electro-galvanizing phosphatization steel plate according to claim 1, wherein said phosphate coating weight is 0.5～3.0g/m
2
4. environment-friendly chromium-free sealing electro-galvanizing phosphatization steel plate according to claim 1, wherein said sealer coat weight is 50～400mg/m
2
5. environment-friendly chromium-free according to claim 1 sealing electro-galvanizing phosphatization steel plate, the form of wherein said metallic compound are selected from a kind of in oxide compound, oxyhydroxide, coordination compound, inorganic acid salt and the organic acid salt.
6. environment-friendly chromium-free sealing electro-galvanizing phosphatization steel plate according to claim 1, wherein said water-dispersible silica is colloid silica or aerosil.
7. environment-friendly chromium-free according to claim 1 sealing electro-galvanizing phosphatization steel plate, wherein said organic acid are selected from a kind of in citric acid, tartrate, hexanodioic acid, L-glutamic acid, propionic acid, phytic acid and the lactic acid.
8. the manufacture method of the described environment-friendly chromium-free sealing of claim 1 electro-galvanizing phosphatization steel plate is characterized in that, may further comprise the steps:
(1) cleaning of electrogalvanizing steel plate: the aqueous solution with the grease-removing agent of neutral and alkali cleans surface of steel plate, washes with tap water again;
(2) bonderizing: the electrogalvanizing steel plate after the cleaning is adjusted in the treatment solution on the surface and was flooded 2～20 seconds, sprays in phosphating agent 3～20 seconds again, cleans oven dry then successively with tap water, pure water;
(3) sealing treatment: the described sealing treatment agent of claim 1 is dissolved in water, is coated on the surface of steel plate phosphate coating again, with hot blast steel plate is heated to 60～100 ℃ of oven dry then.
9. manufacture method according to claim 8, wherein the adjustment of the surface described in the step (2) treatment solution is the colloidal titanium compound water solution, the composition of described phosphating agent comprises phosphate anion, zine ion, nickel ion, fluorion and nitrate ion.
10. according to Claim 8 or 9 described manufacture method, the wherein said surface concentration of adjusting treatment solution is 0.25～2.5g/L.
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| CN102061465B (en) * | 2010-12-31 | 2012-02-22 | 大连工业大学 | Chrome-free sealing agent |
| JP5853683B2 (en) * | 2011-01-25 | 2016-02-09 | Ｊｆｅスチール株式会社 | Method for producing cold-rolled steel sheet with excellent chemical conversion and post-coating corrosion resistance |
| CN103849866A (en) * | 2014-02-14 | 2014-06-11 | 浙江工业大学 | Grey protective layer for surface of titanium-zinc plate and preparation method |
| KR102450429B1 (en) * | 2016-08-12 | 2022-10-04 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Pretreatment composition |
| CN107541738A (en) * | 2017-07-17 | 2018-01-05 | 华意压缩机股份有限公司 | Cleaning before a kind of Dimensions Used in Shell of Refrigerator Compressor weldering |
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| CN1063129A (en) * | 1992-03-07 | 1992-07-29 | 冶金工业部钢铁研究总院 | The metallic surface treatment solution |
| CN1326012A (en) * | 2000-05-29 | 2001-12-12 | 北京科技大学 | Passivation technique for filming on surface of stainless steel |
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|---|---|---|---|---|
| CN1063129A (en) * | 1992-03-07 | 1992-07-29 | 冶金工业部钢铁研究总院 | The metallic surface treatment solution |
| CN1326012A (en) * | 2000-05-29 | 2001-12-12 | 北京科技大学 | Passivation technique for filming on surface of stainless steel |
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| Title |
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| JP特开平5-247668A 1993.09.24 |
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