CN103088335B - A kind of metal surface modification silane finish and preparation method thereof - Google Patents
A kind of metal surface modification silane finish and preparation method thereof Download PDFInfo
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- CN103088335B CN103088335B CN201210550944.7A CN201210550944A CN103088335B CN 103088335 B CN103088335 B CN 103088335B CN 201210550944 A CN201210550944 A CN 201210550944A CN 103088335 B CN103088335 B CN 103088335B
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- gram
- silane
- metal surface
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- maleic anhydride
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 238000012986 modification Methods 0.000 title claims abstract description 7
- 230000004048 modification Effects 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 12
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 9
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 trihydroxyethyl isocyanuric ester Chemical class 0.000 claims abstract description 8
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 7
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 7
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 7
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 7
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004202 carbamide Substances 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000006884 silylation reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 11
- 229910001335 Galvanized steel Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000008397 galvanized steel Substances 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229940098458 powder spray Drugs 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000002444 silanisation Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GZCWLCBFPRFLKL-UHFFFAOYSA-N 1-prop-2-ynoxypropan-2-ol Chemical compound CC(O)COCC#C GZCWLCBFPRFLKL-UHFFFAOYSA-N 0.000 description 1
- 102000013563 Acid Phosphatase Human genes 0.000 description 1
- 108010051457 Acid Phosphatase Proteins 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000737 Duralumin Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a kind of metal surface modification silane finish, made by following component, the weight of each component in every 500 grams of mixed liquors (gram) being: sodium dihydrogen phosphate 1-2, ammonium molybdate 1-2, neopelex 1-2, rosin 3-5, trihydroxyethyl isocyanuric ester 1-2, maleic anhydride 5-8, diethylene glycol butyl ether 4-6, isobutanol 5-8, oxalic acid 3-5, urea 1-2, vinyl three ('beta '-methoxy ethyoxyl) silane 7-10, surplus are deionized water. The present invention adopts rosin as reaction raw materials, with the polymerizable raw material such as maleic anhydride, silane, can form in metal surface stronger diaphragm; Strengthen the decay resistance of metallic matrix.
Description
Technical field
The present invention relates to a kind of metallic surface silanization treating agent and with it technique in metallic surface silanization processing.
Background technology
Phosphatization is processed in coated metal pre-treatment, the industry such as lubricated, antirust and is widely applied. Particularly, in Coating Pretreatment industry, phosphatization processing is one of the most frequently used preprocess method. Phosphatization processing is the process that forms biphosphate ammonium salt diaphragm after metal reacts in acid phosphatase ammonium dihydrogen salting liquid on its surface. Phosphating coat also has good lubricity, insulating properties and corrosion resistance, thereby be widely used in the manufacture field of the products such as automobile, machine-building, Aero-Space and household electrical appliance. Phosphorization treatment process is taking ammonium dihydrogen phosphate (ADP), zinc, manganese, nickel as primary raw material, cause the serious environmental pollution such as heavy metal, phosphorus, nitrite, and in processing procedure, all more or less can produce sediment and pernicious gas, what impact was produced normally carries out, and the waste water COD of discharge and heavy metal will endanger environment if do not carried out environmental protection treatment; In addition, phosphatization processing major part need be carried out under the condition of heating, and energy consumption is larger, complex process, and operation is also inconvenient. Existingly occurred silane surface treatment technology, but silane surface treatment agent is unstable in metal surface film forming, antiseptic property is unstable, poor effect.
Summary of the invention
The object of this invention is to provide a kind of metal surface modification silane finish and preparation method thereof; this solution does not need to heat; not phosphorous, without sediment produce, containing heavy metal, energy-conservation, simple and convenient management, can form stronger diaphragm on duralumin, hard alumin ium alloy surface, anticorrosion ability is good.
Technical scheme of the present invention is as follows:
A kind of metal surface modification silane finish, is characterized in that, made by following component, the weight of each component in every 500 grams of mixed liquors (gram) be:
Sodium dihydrogen phosphate 1-2, ammonium molybdate 1-2, neopelex 1-2, rosin 3-5, trihydroxyethyl isocyanuric ester 1-2, maleic anhydride 5-8, diethylene glycol butyl ether 4-6, isobutanol 5-8, oxalic acid 3-5, urea 1-2, vinyl three ('beta '-methoxy ethyoxyl) silane 7-10, surplus are deionized water.
The preparation method of described metal surface silylation protection treating agent, is characterized in that comprising the following steps:
(1), by rosin heating fusing, to 110-115 DEG C, add diethylene glycol butyl ether, vinyl three ('beta '-methoxy ethyoxyl) silane, stirring reaction 35-50 minute;
(2), be warming up to 145-160 DEG C, add trihydroxyethyl isocyanuric ester, maleic anhydride, stirring reaction 40-50 minute;
(3), continue to be warming up to 190-205 DEG C, add sodium dihydrogen phosphate, ammonium molybdate, neopelex, stirring reaction 40-50 minute;
(4), be cooled to 80-90 DEG C, add other material, stir, insulation reaction 1-2 hour, cooling after, adjust PH be neutrality.
Silane surface treatment agent of the present invention, first metallic matrix can directly be entered in inorganic agent of the present invention and be processed after degreasing, washing, after processing, metal base surface can obtain one deck coating, then can wash or not wash lower one technique-oven dry according to process requirements, after oven dry, can carry out the operations such as powder spray, technological parameter in processing procedure is: operating temperature: 25 DEG C of room temperatures, pure water is washed electrical conductivity < 20 μ s/cm, the processing time: 90-250 second.
Compared to the prior art the present invention, has the following advantages:
(1) the present invention adopts rosin as reaction raw materials, with the polymerizable raw material such as maleic anhydride, silane, can form in metal surface stronger diaphragm; Strengthen the decay resistance of metallic matrix.
(2) in raw material, contain corrosion inhibiter, increase the anticorrosion ability of diaphragm.
(3), the protective film that forms is fine and close evenly, polarized current density is less.
(4) (10 ~ 15 μ m) to protect thickness (< 150nm) to be significantly less than traditional phosphating solutions film.
Detailed description of the invention
A kind of metal surface modification silane finish, is made up of following component, the weight of each raw material components in every 500 grams of mixed liquors (gram) be:
Sodium dihydrogen phosphate 2, ammonium molybdate 2, neopelex 2, rosin 5, trihydroxyethyl isocyanuric ester 2, maleic anhydride 8, diethylene glycol butyl ether 6, isobutanol 5, oxalic acid 3, urea 2, vinyl three ('beta '-methoxy ethyoxyl) silane 10, surplus are deionized water.
The preparation method of described metal surface silylation protection treating agent, is characterized in that comprising the following steps:
(1), by rosin heating fusing, to 110-115 DEG C, add diethylene glycol butyl ether, vinyl three ('beta '-methoxy ethyoxyl) silane, stirring reaction 35-50 minute;
(2), be warming up to 145-160 DEG C, add trihydroxyethyl isocyanuric ester, maleic anhydride, stirring reaction 40-50 minute;
(3), continue to be warming up to 190-205 DEG C, add sodium dihydrogen phosphate, ammonium molybdate, neopelex, stirring reaction 40-50 minute;
(4), be cooled to 80-90 DEG C, add other material, stir, insulation reaction 1-2 hour, cooling after, adjust PH be neutrality.
First galvanized steel plain sheet can directly be entered in inorganic agent of the present invention and be processed after degreasing, washing, after processing, matrix surface can obtain one deck coating, then can wash or not wash lower one technique-oven dry according to process requirements, after oven dry, can carry out the operations such as powder spray, technological parameter in processing procedure is: operating temperature: 25 DEG C of room temperatures, pure water is washed electrical conductivity < 20 μ s/cm, the processing time: 90-250 second.
Galvanized steel plain sheet first adopts alkali-free degreasing fluid to wash and removes oil stain, then puts into silane surface treatment agent of the present invention and process, and after oven dry, carries out immersion test, adopts the NaCl aqueous solution of 0.1M, observes sample surfaces situation; Testing impedance carries out in 3.5 (wt) %NaCl aqueous solution. There is not red rust for 9 days in galvanized steel plain sheet, detecting coating and galvanized steel plain sheet adhesion strength is 9.1Mpa, and ︱ Z ︳ 10mHz value is 6.7E7.
Claims (1)
1. a metal surface modification silane finish, it is characterized in that, be made up of following component, in every 500 grams of mixed liquors, the weight of each component is: sodium dihydrogen phosphate 1-2 gram, ammonium molybdate 1-2 gram, neopelex 1-2 gram, rosin 3-5 gram, trihydroxyethyl isocyanuric ester 1-2 gram, maleic anhydride 5-8 gram, 4-6 gram of diethylene glycol butyl ether, isobutanol 5-8 gram, oxalic acid 3-5 gram, urea 1-2 gram, silane 7-10 gram of vinyl three ('beta '-methoxy ethyoxyl), surplus are deionized water;
The preparation method of described metal surface silylation protection treating agent, comprises the following steps:
(1), by rosin heating fusing, to 110-115 DEG C, add diethylene glycol butyl ether, vinyl three ('beta '-methoxy ethyoxyl) silane, stirring reaction 35-50 minute;
(2), be warming up to 145-160 DEG C, add trihydroxyethyl isocyanuric ester, maleic anhydride, stirring reaction 40-50 minute;
(3), continue to be warming up to 190-205 DEG C, add sodium dihydrogen phosphate, ammonium molybdate, neopelex, stirring reaction 40-50 minute;
(4), be cooled to 80-90 DEG C, add other material, stir, insulation reaction 1-2 hour, cooling after, adjust pH be neutrality.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210550944.7A CN103088335B (en) | 2012-12-18 | 2012-12-18 | A kind of metal surface modification silane finish and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210550944.7A CN103088335B (en) | 2012-12-18 | 2012-12-18 | A kind of metal surface modification silane finish and preparation method thereof |
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| CN103088335A CN103088335A (en) | 2013-05-08 |
| CN103088335B true CN103088335B (en) | 2016-05-18 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104099003A (en) * | 2014-06-17 | 2014-10-15 | 安徽省六安市朝晖机械制造有限公司 | Environment-friendly aluminum alloy surface treatment agent |
| CN104099012B (en) * | 2014-06-19 | 2016-08-24 | 锐展(铜陵)科技有限公司 | A kind of whisker type Aluminum alloy surface treatment agent |
| CN104109466A (en) * | 2014-06-19 | 2014-10-22 | 锐展(铜陵)科技有限公司 | Long-lasting type aluminum alloy surface treating agent |
| CN104109854A (en) * | 2014-06-19 | 2014-10-22 | 锐展(铜陵)科技有限公司 | Long-lasting aluminum alloy surface treating agent with long shelf life |
| CN104087166A (en) * | 2014-07-15 | 2014-10-08 | 杨美 | Water-sensitive discoloring paint |
| CN104498924A (en) * | 2014-11-28 | 2015-04-08 | 安徽华灿彩钢薄板科技有限公司 | Steel plate surface phosphatization treatment agent |
| CN104498946A (en) * | 2014-11-28 | 2015-04-08 | 安徽华灿彩钢薄板科技有限公司 | Steel plate surface phosphatization method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381532A (en) * | 2001-04-19 | 2002-11-27 | 日本油漆株式会社 | Nonchromate metal surface finishing agent, surface handling and method and processed steel products |
| CN102409325A (en) * | 2011-12-06 | 2012-04-11 | 中国科学院金属研究所 | Preparation method of environment-friendly corrosion-resistant chromium-free chemical conversion solution and chemical conversion film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3898302B2 (en) * | 1997-10-03 | 2007-03-28 | 日本パーカライジング株式会社 | Surface treatment agent composition for metal material and treatment method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381532A (en) * | 2001-04-19 | 2002-11-27 | 日本油漆株式会社 | Nonchromate metal surface finishing agent, surface handling and method and processed steel products |
| CN102409325A (en) * | 2011-12-06 | 2012-04-11 | 中国科学院金属研究所 | Preparation method of environment-friendly corrosion-resistant chromium-free chemical conversion solution and chemical conversion film |
Non-Patent Citations (1)
| Title |
|---|
| 三羟基乙基异氰尿酸酯的研究与应用;韩虹;《新乡学院学报》;20080331;第25卷(第1期);全文 * |
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