CN110670010B - Method for reducing black spot defect of hot-dip galvanized plate - Google Patents
Method for reducing black spot defect of hot-dip galvanized plate Download PDFInfo
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- CN110670010B CN110670010B CN201911138923.2A CN201911138923A CN110670010B CN 110670010 B CN110670010 B CN 110670010B CN 201911138923 A CN201911138923 A CN 201911138923A CN 110670010 B CN110670010 B CN 110670010B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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Abstract
The invention discloses a method for reducing black spot defects of a hot-dip galvanized plate, which comprises the following operation steps: (1) adding erucic acid into n-hexane, continuously adding ammonia water while stirring, heating in water bath, and performing saponification reaction to obtain saponified solution; (2) adding neodymium chloride and samarium chloride into water, mixing and stirring uniformly, adding into the saponification liquid, stirring and extracting, collecting an organic phase, and performing rotary evaporation on the organic phase to remove n-hexane to obtain erucic acid mixed rare earth; (3) adding methacryloxypropyltriethoxysilane into water, hydrolyzing, adding polyethyleneimine and erucic acid mixed rare earth, and uniformly mixing and stirring to obtain a passivation solution; (4) and adding the hot-galvanized plate into the passivation solution, carrying out passivation treatment for 80-100s, taking out, and cooling to room temperature to obtain the passivated hot-galvanized plate. The hot-dip galvanized sheet prepared by the invention has excellent appearance quality, excellent corrosion resistance and excellent conductivity on the surface.
Description
Technical Field
The invention relates to the technical field of hot-galvanized plate preparation, in particular to a method for reducing black spot defects of a hot-galvanized plate.
Background
A hot-dip galvanized sheet is a sheet steel in which a zinc layer is adhered to the surface of a sheet steel immersed in a molten zinc bath. The hot dip galvanized steel sheet has excellent corrosion resistance and clean appearance and is widely applied to industries such as buildings, household appliances, automobiles and the like. In the process of transportation or storage, black spot defects are easily generated on hot-dip galvanized steel coils due to extrusion of steel coils and dislocation between steel strip layers, the black spot defects not only affect the appearance of the surfaces of the galvanized steel sheets, but also reduce the corrosion resistance of the galvanized steel sheets, and finally the hot-dip galvanized steel sheets are degraded and scrapped.
The surface galvanizing of the steel plate is an effective method for improving the atmospheric corrosion resistance of steel, the surface of a zinc layer is passivated by using a chromate solution, the technology is a method for improving the resistance performance of a hot galvanized plate, the technology appears in industrial production from the 20 th century and the 30 th century, and along with the enhancement of environmental awareness and the strict use of chromate and the restriction of wastewater discharge in the environmental protection regulations in recent years, the adoption of an environment-friendly grid-free passivation technology is more and more common. The currently applied chromium-free passivation processes include inorganic passivation, organic passivation, oxide passivation (silicate phosphating and the like), organic metal compound passivation and the like. However, the conventional methods cannot achieve an effective balance among the appearance, corrosion resistance, conductivity, blackening resistance, and coatability of the finished product.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for reducing the black spot defect of a hot-galvanized plate, which can effectively ensure the quality of the hot-galvanized plate.
The invention is realized by the following technical scheme:
a method for reducing black spot defects of hot galvanized plates comprises the following operation steps:
(1) adding 55-60 parts by weight of erucic acid into 70-80 parts by weight of normal hexane, continuously adding 25-30 parts by weight of 25% ammonia water under stirring, heating in water bath to 65-70 ℃, and performing saponification reaction for 45-50min to obtain saponification liquid;
(2) adding 8-15 parts by weight of neodymium chloride and 18-22 parts by weight of samarium chloride into 140 parts by weight of 120-140 parts by weight of water, uniformly mixing and stirring, adding into 170 parts by weight of 160-170 parts by weight of saponification liquid, stirring and extracting for 40-50min, collecting an organic phase, and performing rotary evaporation on the organic phase to remove n-hexane to obtain erucic acid mixed rare earth;
(3) adding 18-22 parts by weight of methacryloxypropyltriethoxysilane into 1000 parts by weight of 950-containing water, after hydrolysis treatment, adding 250 parts by weight of polyethyleneimine and 10-15 parts by weight of erucic acid mixed rare earth, and uniformly mixing and stirring to obtain passivation solution;
(4) and adding the hot-galvanized plate into the passivation solution, carrying out passivation treatment for 80-100s, taking out, and cooling to room temperature to obtain the passivated hot-galvanized plate.
Further, in the step (2), the temperature at the time of rotary evaporation was 70 ℃.
Further, in the step (3), the molecular weight of polyethyleneimine is 10000, and the purity is 98%.
Further, in the step (4), before the hot-dip galvanized sheet is added into the passivation solution, the surface stain of the hot-dip galvanized sheet is removed by using clean water, then the greasy dirt on the surface of the hot-dip galvanized sheet is removed by using an alkali liquor degreasing method, and finally the hot-dip galvanized sheet is dried after being cleaned by using clean water, wherein the alkali liquor is prepared from sodium hydroxide, trisodium phosphate, sodium silicate and sodium carbonate.
Further, in the step (4), the temperature of the passivation solution is 140-.
According to the technical scheme, the beneficial effects of the invention are as follows:
the method for reducing the black spot defect of the hot-dip galvanized plate, provided by the invention, has the advantages that the process is simple, excessive waste water is not generated in the reproduction process, the safety and the environmental protection are realized, and meanwhile, the surface of the prepared hot-dip galvanized plate has excellent appearance quality, excellent corrosion resistance and excellent conductivity. The erucic acid mixed rare earth prepared in the step (2) can effectively improve the film forming performance of methacryloxypropyltriethoxysilane and polyethyleneimine on the surface of a hot-dip galvanized plate, so that the hot-dip galvanized surface has excellent appearance quality and the corrosion resistance of the hot-dip galvanized plate can be effectively improved, and the rare earth elements in the erucic acid mixed rare earth can ensure that a formed passivation film has excellent conductivity; according to the invention, methacryloxypropyltriethoxysilane and polyethyleneimine are selected as organic film forming substances, and a crosslinking reaction can be generated between the methacryloxypropyltriethoxysilane and the polyethyleneimine, so that a net-shaped and compact organic film layer can be formed on the surface of the hot-dip galvanized plate, thereby effectively improving the corrosion resistance and wear resistance of the hot-dip galvanized plate and effectively avoiding the occurrence of black spot defects on the surface of the hot-dip galvanized plate.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
A method for reducing black spot defects of hot galvanized plates comprises the following operation steps:
(1) adding 55 parts by weight of erucic acid into 70 parts by weight of normal hexane, continuously adding 25 parts by weight of 25% ammonia water under stirring, heating in a water bath to 65 ℃, and performing saponification reaction for 45min to obtain a saponified solution;
(2) adding 8 parts by weight of neodymium chloride and 18 parts by weight of samarium chloride into 120 parts by weight of water, uniformly mixing and stirring, adding into 160 parts by weight of saponification liquid, stirring and extracting for 40min, collecting an organic phase, and carrying out rotary evaporation on the organic phase at the temperature of 70 ℃ to remove n-hexane so as to obtain the erucic acid mixed rare earth;
(3) adding 18 parts by weight of methacryloxypropyltriethoxysilane into 950 parts by weight of water, performing hydrolysis treatment, adding 220 parts of polyethyleneimine and 10 parts of erucic acid misch metal, and uniformly mixing and stirring to obtain a passivation solution, wherein the molecular weight of the polyethyleneimine is 10000, and the purity of the polyethyleneimine is 98%;
(4) adding the hot-galvanized plate into a passivation solution at 140 ℃, after passivation for 80s, taking out and cooling to room temperature to obtain a passivated hot-galvanized plate, wherein before the hot-galvanized plate is added into the passivation solution, surface stains are removed by adopting clear water, oil stains on the surface of the hot-galvanized plate are removed by adopting an alkali liquor degreasing method, and finally, after cleaning by adopting clear water, drying is carried out, wherein the alkali liquor comprises sodium hydroxide, trisodium phosphate, sodium silicate and sodium carbonate.
Example 2
A method for reducing black spot defects of hot galvanized plates comprises the following operation steps:
(1) adding 58 parts by weight of erucic acid into 75 parts by weight of normal hexane, continuously adding 28 parts by weight of 25% ammonia water while stirring, heating in a water bath to 68 ℃, and performing saponification reaction for 48min to obtain a saponified solution;
(2) adding 11 parts by weight of neodymium chloride and 20 parts by weight of samarium chloride into 130 parts by weight of water, uniformly mixing and stirring, adding into 165 parts by weight of saponification liquid, stirring and extracting for 45min, collecting an organic phase, and carrying out rotary evaporation on the organic phase at the temperature of 70 ℃ to remove n-hexane so as to obtain erucic acid mixed rare earth;
(3) adding 20 parts by weight of methacryloxypropyltriethoxysilane into 980 parts by weight of water, hydrolyzing, adding 230 parts of polyethyleneimine and 13 parts of erucic acid misch metal, and uniformly mixing and stirring to obtain a passivation solution, wherein the molecular weight of the polyethyleneimine is 10000, and the purity of the polyethyleneimine is 98%;
(4) adding the hot-galvanized plate into a passivation solution at 145 ℃, after passivation for 90s, taking out and cooling to room temperature to obtain a passivated hot-galvanized plate, wherein before the hot-galvanized plate is added into the passivation solution, surface stains are removed by adopting clear water, oil stains on the surface of the hot-galvanized plate are removed by adopting an alkali liquor degreasing method, and finally, after cleaning by adopting clear water, drying is carried out, wherein the alkali liquor comprises sodium hydroxide, trisodium phosphate, sodium silicate and sodium carbonate.
Example 3
A method for reducing black spot defects of hot galvanized plates comprises the following operation steps:
(1) adding 60 parts by weight of erucic acid into 80 parts by weight of normal hexane, continuously adding 30 parts by weight of 25% ammonia water while stirring, heating in water bath to 70 ℃, and performing saponification reaction for 50min to obtain saponification liquid;
(2) adding 15 parts by weight of neodymium chloride and 22 parts by weight of samarium chloride into 140 parts by weight of water, uniformly mixing and stirring, adding into 170 parts by weight of saponification liquid, stirring and extracting for 50min, collecting an organic phase, and carrying out rotary evaporation on the organic phase at the temperature of 70 ℃ to remove n-hexane so as to obtain the erucic acid mixed rare earth;
(3) adding 22 parts by weight of methacryloxypropyltriethoxysilane into 1000 parts by weight of water, performing hydrolysis treatment, adding 250 parts of polyethyleneimine and 15 parts of erucic acid misch metal, and uniformly mixing and stirring to obtain a passivation solution, wherein the molecular weight of the polyethyleneimine is 10000, and the purity of the polyethyleneimine is 98%;
(4) adding the hot-galvanized plate into a passivation solution at 150 ℃, after passivation for 100s, taking out and cooling to room temperature to obtain a passivated hot-galvanized plate, wherein before the hot-galvanized plate is added into the passivation solution, surface stains are removed by adopting clear water, oil stains on the surface of the hot-galvanized plate are removed by adopting an alkali liquor degreasing method, and finally, after cleaning by adopting clear water, drying is carried out, wherein the alkali liquor comprises sodium hydroxide, trisodium phosphate, sodium silicate and sodium carbonate.
Comparative example 1
Erucic acid misch metal is not added in the step (3), and the rest operation steps are completely the same as the example 1.
Comparative example 2
The methacryloxypropyltriethoxysilane in step (3) was replaced with the same amount of silane coupling agent KH-560, and the remaining procedure was identical to that in test 2.
Comparative example 3
The polyethyleneimine obtained in the step (3) was replaced with an equivalent amount of styrene-acrylic emulsion, and the remaining operation steps were completely the same as those in example 3.
The hot-dip galvanized sheet is prepared by the methods of each example and each comparative example respectively, and then the corrosion resistance and the surface conductivity of the passive film on the surface of the hot-dip galvanized sheet are tested, wherein the corrosion resistance is tested as follows: according to the national standard GB/T10125-:
TABLE 1 test of surface passivation film performance of hot-dip galvanized sheet
| Item | Corrosion area ratio of% | Resistance value omega |
| Example 1 | 1.3 | 958 |
| Comparative example 1 | 6.5 | ∞ |
| Example 2 | 1.1 | 902 |
| Comparative example 2 | 7.3 | 911 |
| Example 3 | 1.0 | 924 |
| Comparative example 3 | 7.9 | 920 |
As can be seen from the data of the example 1 and the comparative example 1 in the table 1, the film forming performance of methacryloxypropyltriethoxysilane and polyethyleneimine on the surface of a hot-dip galvanized plate can be effectively improved by mixing erucic acid with rare earth, so that the hot-dip galvanized surface has excellent appearance quality, the corrosion resistance of the surface of the hot-dip galvanized plate can be effectively improved, and the rare earth elements in the film can ensure that the formed passivation film has excellent conductivity; the data of the example 2 and the comparative example 2, and the data of the example 3 and the comparative example 3 show that methacryloxypropyltriethoxysilane and polyethyleneimine, as organic film forming substances, can generate a crosslinking reaction between the two, and can form a net-shaped and compact organic film layer on the surface of the hot-dip galvanized sheet, so that the corrosion resistance and the wear resistance of the hot-dip galvanized sheet are effectively improved, the occurrence of black spot defects on the surface of the hot-dip galvanized sheet is effectively avoided, and when the two substances are replaced by any components with similar properties, the beneficial effects cannot be achieved.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (5)
1. The method for reducing the black spot defects of the hot galvanized plate is characterized by comprising the following operation steps:
(1) adding 55-60 parts by weight of erucic acid into 70-80 parts by weight of normal hexane, continuously adding 25-30 parts by weight of 25% ammonia water under stirring, heating in water bath to 65-70 ℃, and performing saponification reaction for 45-50min to obtain saponification liquid;
(2) adding 8-15 parts by weight of neodymium chloride and 18-22 parts by weight of samarium chloride into 140 parts by weight of 120-140 parts by weight of water, uniformly mixing and stirring, adding into 170 parts by weight of 160-170 parts by weight of saponification liquid, stirring and extracting for 40-50min, collecting an organic phase, and performing rotary evaporation on the organic phase to remove n-hexane to obtain erucic acid mixed rare earth;
(3) adding 18-22 parts by weight of methacryloxypropyltriethoxysilane into 1000 parts by weight of 950-containing water, after hydrolysis treatment, adding 250 parts by weight of polyethyleneimine and 10-15 parts by weight of erucic acid mixed rare earth, and uniformly mixing and stirring to obtain passivation solution;
(4) and adding the hot-galvanized plate into the passivation solution, carrying out passivation treatment for 80-100s, taking out, and cooling to room temperature to obtain the passivated hot-galvanized plate.
2. The method for reducing black spot defects of hot-galvanized plates according to claim 1, wherein the temperature during the rotary evaporation in the step (2) is 70 ℃.
3. The method for reducing black spot defects of hot-galvanized plates according to claim 1, wherein in the step (3), the polyethyleneimine has a molecular weight of 10000 and a purity of 98%.
4. The method for reducing black spot defects of hot-galvanized plates according to claim 1, wherein in the step (4), the hot-galvanized plates are subjected to surface stain removal by using clean water before being added into the passivation solution, then are subjected to degreasing by using an alkali solution, and are dried after being washed by using clean water, wherein the alkali solution comprises sodium hydroxide, trisodium phosphate, sodium silicate and sodium carbonate.
5. The method for reducing black spot defects of hot-galvanized plates as claimed in claim 1, wherein in the step (4), the temperature of the passivation solution during the passivation treatment is 140 ℃ to 150 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911576A (en) * | 2015-07-02 | 2015-09-16 | 常熟风范电力设备股份有限公司 | Chrome-free passivant for hot-dip galvanized steel sheet and preparation method thereof |
| EP3059331A1 (en) * | 2013-10-18 | 2016-08-24 | Nihon Parkerizing Co., Ltd. | Surface treatment agent for metal material and production method for surface-treated metal material |
| CN108350578A (en) * | 2015-11-06 | 2018-07-31 | 新日铁住金株式会社 | Galvanized steel is used or plate golding zincio alloy steel water system surface conditioning agent, method for coating and cladding steel |
| CN108754480A (en) * | 2018-06-21 | 2018-11-06 | 上海优梓新材料科技有限公司 | A kind of environmental emission reduction Non-water washing type metal conditioner |
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- 2019-11-20 CN CN201911138923.2A patent/CN110670010B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3059331A1 (en) * | 2013-10-18 | 2016-08-24 | Nihon Parkerizing Co., Ltd. | Surface treatment agent for metal material and production method for surface-treated metal material |
| CN104911576A (en) * | 2015-07-02 | 2015-09-16 | 常熟风范电力设备股份有限公司 | Chrome-free passivant for hot-dip galvanized steel sheet and preparation method thereof |
| CN108350578A (en) * | 2015-11-06 | 2018-07-31 | 新日铁住金株式会社 | Galvanized steel is used or plate golding zincio alloy steel water system surface conditioning agent, method for coating and cladding steel |
| CN108754480A (en) * | 2018-06-21 | 2018-11-06 | 上海优梓新材料科技有限公司 | A kind of environmental emission reduction Non-water washing type metal conditioner |
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