CN112226754A - Non-washing acrylic acid chromium-free passivator suitable for aluminum profile - Google Patents
Non-washing acrylic acid chromium-free passivator suitable for aluminum profile Download PDFInfo
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- CN112226754A CN112226754A CN202011117641.7A CN202011117641A CN112226754A CN 112226754 A CN112226754 A CN 112226754A CN 202011117641 A CN202011117641 A CN 202011117641A CN 112226754 A CN112226754 A CN 112226754A
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- 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
- C23C22/68—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 solutions with pH between 6 and 8
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- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
- C09D191/06—Waxes
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- C09D5/08—Anti-corrosive paints
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/61—Additives non-macromolecular inorganic
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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 washing-free acrylic acid chromium-free passivator suitable for aluminum profiles, which comprises silane coupling agent, aluminum polysilicate, disodium ethylene diamine tetraacetate, water-soluble phenolic resin, cerium nitrate, dispersible nanoparticles, sodium dodecyl benzene sulfonate, preservative, complexing agent and deionized water, wherein the preservative is prepared by mixing paraffin, peppermint oil, acrylic acid emulsion and zirconium potassium carbonate. The invention relates to the technical field of passivators, in particular to a water-washing-free acrylic acid chromium-free passivator suitable for aluminum profiles.
Description
Technical Field
The invention relates to the technical field of passivators, in particular to a water-washing-free acrylic acid chromium-free passivator suitable for aluminum profiles.
Background
With the continuous development of the industry, the demand for aluminum alloy is more and more, the aluminum alloy is frequently used in daily life, the aluminum alloy is a non-ferrous metal structural material which is most widely applied in the industry, and is widely applied in the aviation, aerospace, automobile, mechanical manufacturing, ship and chemical industries, and in order to protect the surface of the aluminum alloy, a layer of passivating agent needs to be sprayed on the surface of the aluminum alloy when the aluminum alloy is produced.
However, although the current aluminum alloy chromium-free passivation treating agent products also meet the environmental protection requirements, the products can not achieve the traditional passivation performance on the coating matching performance of subsequent coatings, and the aluminum alloy still generates oxidation corrosion after a long time, thereby further influencing the service life of the aluminum alloy.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a washing-free acrylic acid chromium-free passivator suitable for aluminum profiles, which solves the problems that although the existing aluminum alloy chromium-free passivation treating agent products also meet the environmental protection requirement, the products can not reach the traditional passivation performance on the coating matching performance of subsequent coatings, and the aluminum alloy still generates oxidation corrosion after a long time, thereby further influencing the service life of the aluminum alloy.
In order to achieve the purpose, the invention is realized by the following technical scheme: the acrylic acid chromium-free passivator suitable for washing-free aluminum profiles comprises silane coupling agent, aluminum polysilicate, disodium ethylene diamine tetraacetate, water-soluble phenolic resin, cerium nitrate, dispersible nanoparticles, sodium dodecyl benzene sulfonate, preservative, complexing agent and deionized water, and is prepared from the following components in parts by weight: 140-180 g of silane coupling agent, 146-230 g of aluminum polysilicate, 18-84 g of ethylene diamine tetraacetic acid, 55-130 g of water-soluble phenolic resin, 12-14 g of cerium nitrate, 8-14 g of dispersible nanoparticles, 24-55 g of sodium dodecyl benzene sulfonate, 260-430 g of preservative, 115-259 g of complexing agent and 280-380 g of deionized water.
Preferably, the formula is prepared from the following components in parts by weight: 140g of silane coupling agent, 146g of aluminum polysilicate, 18g of ethylene diamine tetraacetic acid, 55g of water-soluble phenolic resin, 12g of cerium nitrate, 8g of dispersible nanoparticles, 24g of sodium dodecyl benzene sulfonate, 260g of preservative, 115g of complexing agent and 280g of deionized water.
Preferably, the formula is prepared from the following components in parts by weight: 180g of silane coupling agent, 230g of aluminum polysilicate, 84g of ethylene diamine tetraacetic acid, 130g of water-soluble phenolic resin, 14g of cerium nitrate, 14g of dispersible nanoparticles, 55g of sodium dodecyl benzene sulfonate, 430g of preservative, 259g of complexing agent and 380g of deionized water.
Preferably, the formula is prepared from the following components in parts by weight: 160g of silane coupling agent, 188g of aluminum polysilicate, 52g of ethylene diamine tetraacetic acid, 93g of water-soluble phenolic resin, 13g of cerium nitrate, 11g of dispersible nanoparticles, 32g of sodium dodecyl benzene sulfonate, 350g of preservative, 214g of complexing agent and 345g of deionized water.
Preferably, the preservative is prepared by mixing paraffin, peppermint oil, acrylic emulsion and zirconium potassium carbonate, wherein the weight ratio of the components of the paraffin, the peppermint oil, the acrylic emulsion and the zirconium potassium carbonate is 1: 1.2-1.4: 0.8-0.96: 0.42 to 0.49.
Preferably, the complexing agent is prepared by mixing ethylene diamine tetra methylene phosphonic acid sodium and sodium hydroxide, wherein the weight ratio of the components of the ethylene diamine tetra methylene phosphonic acid sodium to the sodium hydroxide is 1: 1.08 to 2.24.
Preferably, the preparation method of the water-free acrylic acid chromium-free passivator suitable for the aluminum profile comprises the following steps:
s1: sequentially putting a silane coupling agent, aluminum polysilicate, disodium ethylene diamine tetraacetate, water-soluble phenolic resin, cerium nitrate, dispersible nanoparticles, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, and stirring for 20-35 min to fully mix the components;
s2: and S1, adding the preservative and the complexing agent into the reaction kettle after stirring, continuously stirring and mixing for 10-23 min, taking out the solution after stirring and mixing are finished, and naturally cooling the solution to room temperature to obtain the acrylic acid chromium-free passivator.
Preferably, in the step S1, the stirring speed is 120-140 r/min, the stirring temperature is set to be 30-44 ℃, and in the step S2, the stirring speed is 160-190 r/min, and the stirring temperature is set to be 42-54 ℃.
Advantageous effects
The invention provides a washing-free acrylic acid chromium-free passivator suitable for aluminum profiles, which has the following beneficial effects compared with the prior art:
(1) the acrylic acid chromium-free passivator applicable to washing of aluminum profiles is a preservative prepared by mixing paraffin, peppermint oil, acrylic emulsion and zirconium potassium carbonate, when the passivator is sprayed on the surface of an aluminum alloy, a layer of film can be formed on the surface of the aluminum alloy, so that the aluminum alloy and the outside air can be well isolated, and under the double water-resistant effects of the acrylic emulsion and the zirconium potassium carbonate, when the passivator is sprayed on the surface of the aluminum alloy, the corrosion-resistant effect of the aluminum alloy can be improved, and the service life of the aluminum alloy is prolonged.
(2) The acrylic acid chromium-free passivator suitable for washing-free aluminum profiles is characterized in that a complexing agent is added into the passivator, and the passivator is sprayed on the surface of an aluminum alloy, so that the brilliance of the aluminum alloy can be ensured, the chemical stability of the passivator is improved, and meanwhile, the aluminum alloy can have a good high-temperature resistant effect.
Drawings
FIG. 1 is a comparative experiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Referring to fig. 1, the present invention provides three technical solutions:
example one
The chromium-free acrylic acid passivator suitable for washing aluminum profiles comprises silane coupling agent, aluminum polysilicate, disodium ethylene diamine tetraacetate, water-soluble phenolic resin, cerium nitrate, dispersible nanoparticles, sodium dodecyl benzene sulfonate, preservative, complexing agent and deionized water.
Further, the formula is prepared from the following components in parts by weight: 140g of silane coupling agent, 146g of aluminum polysilicate, 18g of ethylene diamine tetraacetic acid, 55g of water-soluble phenolic resin, 12g of cerium nitrate, 8g of dispersible nanoparticles, 24g of sodium dodecyl benzene sulfonate, 260g of preservative, 115g of complexing agent and 280g of deionized water.
Further, the preservative is prepared by mixing paraffin, peppermint oil, acrylic emulsion and zirconium potassium carbonate, wherein the weight ratio of the components of the paraffin, the peppermint oil, the acrylic emulsion and the zirconium potassium carbonate is 1: 1.2: 0.8: 0.42.
further, the complexing agent is formed by mixing ethylene diamine tetra methylene phosphonic acid sodium and sodium hydroxide, wherein the weight ratio of the components of the ethylene diamine tetra methylene phosphonic acid sodium to the sodium hydroxide is 1: 1.08.
further, the preparation method of the water-washing-free acrylic acid chromium-free passivator suitable for the aluminum profile comprises the following steps:
s1: sequentially putting a silane coupling agent, aluminum polysilicate, disodium ethylene diamine tetraacetate, water-soluble phenolic resin, cerium nitrate, dispersible nanoparticles, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, and stirring for 20min to fully mix the components;
s2: and step S1, adding the preservative and the complexing agent into the reaction kettle after stirring, continuously stirring and mixing for 10min, taking out the solution after stirring and mixing, and naturally cooling the solution to room temperature to obtain the acrylic acid chromium-free passivator.
Further, in step S1, the stirring speed was 120r/min and the stirring temperature was set to 30 ℃, and in step S2, the stirring speed was 160r/min and the stirring temperature was set to 42 ℃.
Example two
The chromium-free acrylic acid passivator suitable for washing aluminum profiles comprises silane coupling agent, aluminum polysilicate, disodium ethylene diamine tetraacetate, water-soluble phenolic resin, cerium nitrate, dispersible nanoparticles, sodium dodecyl benzene sulfonate, preservative, complexing agent and deionized water.
Further, the formula is prepared from the following components in parts by weight: the formula is prepared from the following components in parts by weight: 180g of silane coupling agent, 230g of aluminum polysilicate, 84g of ethylene diamine tetraacetic acid, 130g of water-soluble phenolic resin, 14g of cerium nitrate, 14g of dispersible nanoparticles, 55g of sodium dodecyl benzene sulfonate, 430g of preservative, 259g of complexing agent and 380g of deionized water.
Further, the preservative is prepared by mixing paraffin, peppermint oil, acrylic emulsion and zirconium potassium carbonate, wherein the weight ratio of the components of the paraffin, the peppermint oil, the acrylic emulsion and the zirconium potassium carbonate is 1: 1.4: 0.96: 0.49.
further, the complexing agent is formed by mixing ethylene diamine tetra methylene phosphonic acid sodium and sodium hydroxide, wherein the weight ratio of the components of the ethylene diamine tetra methylene phosphonic acid sodium to the sodium hydroxide is 1: 2.24.
further, the preparation method of the water-washing-free acrylic acid chromium-free passivator suitable for the aluminum profile comprises the following steps:
s1: sequentially putting a silane coupling agent, aluminum polysilicate, disodium ethylene diamine tetraacetate, water-soluble phenolic resin, cerium nitrate, dispersible nanoparticles, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, and stirring for 35min to fully mix;
s2: and step S1, adding the preservative and the complexing agent into the reaction kettle after stirring, continuously stirring and mixing for 23min, taking out the solution after stirring and mixing, and naturally cooling the solution to room temperature to obtain the acrylic acid chromium-free passivator.
Further, in step S1, the stirring speed was 140r/min and the stirring temperature was 44 ℃, and in step S2, the stirring speed was 190r/min and the stirring temperature was 54 DEG C
EXAMPLE III
The chromium-free acrylic acid passivator suitable for washing aluminum profiles comprises silane coupling agent, aluminum polysilicate, disodium ethylene diamine tetraacetate, water-soluble phenolic resin, cerium nitrate, dispersible nanoparticles, sodium dodecyl benzene sulfonate, preservative, complexing agent and deionized water.
Further, the formula is prepared from the following components in parts by weight: the formula is prepared from the following components in parts by weight: 160g of silane coupling agent, 188g of aluminum polysilicate, 52g of ethylene diamine tetraacetic acid, 93g of water-soluble phenolic resin, 13g of cerium nitrate, 11g of dispersible nanoparticles, 32g of sodium dodecyl benzene sulfonate, 350g of preservative, 214g of complexing agent and 345g of deionized water.
Further, the preservative is prepared by mixing paraffin, peppermint oil, acrylic emulsion and zirconium potassium carbonate, wherein the weight ratio of the components of the paraffin, the peppermint oil, the acrylic emulsion and the zirconium potassium carbonate is 1: 1.3: 0.91: 0.45.
further, the complexing agent is formed by mixing ethylene diamine tetra methylene phosphonic acid sodium and sodium hydroxide, wherein the weight ratio of the components of the ethylene diamine tetra methylene phosphonic acid sodium to the sodium hydroxide is 1: 1.96.
further, the preparation method of the water-washing-free acrylic acid chromium-free passivator suitable for the aluminum profile comprises the following steps:
s1: sequentially putting a silane coupling agent, aluminum polysilicate, disodium ethylene diamine tetraacetate, water-soluble phenolic resin, cerium nitrate, dispersible nanoparticles, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, and stirring for 28min to fully mix the components;
s2: and step S1, adding the preservative and the complexing agent into the reaction kettle after stirring, continuously stirring and mixing for 18min, taking out the solution after stirring and mixing, and naturally cooling the solution to room temperature to obtain the acrylic acid chromium-free passivator.
Further, in step S1, the stirring speed was 130r/min and the stirring temperature was 37 ℃, and in step S2, the stirring speed was 172r/min and the stirring temperature was 48 ℃.
Further, the passivator prepared by the method is sprayed on the surface of the aluminum alloy, and the spraying method comprises the following steps:
s1, removing grease, impurities, pollutants and the like attached to the surface of the aluminum alloy, and ensuring that the passivator can be smoothly sprayed on the surface of metal;
s2, before the aluminum alloy is placed into the passivation tank, the passivation tank is clean, free of slag residue, free of pollutants and other chemical residues, whether a nozzle is blocked or not and whether the angle is correct or not are checked, then the aluminum alloy is placed into the passivation tank, and ionized water is added to the 3/4 position of the passivation tank;
s3, adding the passivator prepared in the invention into the passivation tank, stirring and mixing, and determining the pH value to be in the process range during stirring.
Further, in the spraying step, the pH value and the total acid point number are controlled, the optimal supplement proportion can be determined according to the actual conditions of the production line, the MD-22 grooving water quality standard and the electric conductivity are below 10us/cm, a polypropylene precision filter is adopted for the working solution to be less than 0.5 mu m for circular filtration, the groove solution is kept clear, the aluminum content of the solution can continuously rise in the production process, and the content can be analyzed by acid-base titration; when the aluminum content is higher than 0.5 g/L, 25% of working solution needs to be removed, a new passivating agent solution is supplemented, and when chemical products are added, a pump is adopted for slow addition.
And those not described in detail in this specification are well within the skill of those in the art.
Taking six groups of aluminum alloys, setting each group as three, then spraying the passivators prepared by the three embodiments of the invention on the surfaces of three groups of aluminum alloys in turn, then spraying the passivators of the prior art on the surfaces of the other three groups of aluminum alloys, after the spraying is finished, putting the three groups of aluminum alloys sprayed with the passivators of the invention into 5% nitric acid solution, 5% sodium chloride solution and common water solution in turn, then putting the three groups of aluminum alloys sprayed with the passivators of the prior art into 5% nitric acid solution, 5% sodium chloride solution and common water solution in turn, setting the test temperature and humidity of the six groups as the same, comparing the six groups of tests, comparing the corrosion time of each group of tests, and the test result is shown in figure 1, and after the test comparison, adopting the passivators of the three embodiments of the invention in 5% nitric acid solution for 220h respectively, 225h and 198h later, the aluminum alloy begins to corrode after 85h by adopting the traditional passivator, in a 5% sodium chloride solution, the aluminum alloy begins to corrode after 165h, 163h and 168h by adopting the passivator of the three embodiments of the invention respectively, and the aluminum alloy begins to corrode after 67h by adopting the traditional passivator, in a common aqueous solution, the aluminum alloy adopting the passivator of the three embodiments of the invention has no change within two months, but the aluminum alloy adopting the traditional passivator has no change within one month, therefore, the corrosion resistance of the aluminum alloy adopting the passivator of the invention is superior to that of the aluminum alloy adopting the traditional passivator.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The non-washing acrylic acid chromium-free passivator suitable for aluminum profiles is characterized by comprising silane coupling agent, aluminum polysilicate, disodium ethylene diamine tetraacetate, water-soluble phenolic resin, cerium nitrate, dispersible nanoparticles, sodium dodecyl benzene sulfonate, preservative, complexing agent and deionized water, and is prepared from the following components in parts by weight: 140-180 g of silane coupling agent, 146-230 g of aluminum polysilicate, 18-84 g of ethylene diamine tetraacetic acid, 55-130 g of water-soluble phenolic resin, 12-14 g of cerium nitrate, 8-14 g of dispersible nanoparticles, 24-55 g of sodium dodecyl benzene sulfonate, 260-430 g of preservative, 115-259 g of complexing agent and 280-380 g of deionized water.
2. The water-free acrylic chromium-free passivator for aluminum profiles according to claim 1, wherein the formula is prepared from the following components by weight: 140g of silane coupling agent, 146g of aluminum polysilicate, 18g of ethylene diamine tetraacetic acid, 55g of water-soluble phenolic resin, 12g of cerium nitrate, 8g of dispersible nanoparticles, 24g of sodium dodecyl benzene sulfonate, 260g of preservative, 115g of complexing agent and 280g of deionized water.
3. The water-free acrylic chromium-free passivator for aluminum profiles according to claim 1, wherein the formula is prepared from the following components by weight: 180g of silane coupling agent, 230g of aluminum polysilicate, 84g of ethylene diamine tetraacetic acid, 130g of water-soluble phenolic resin, 14g of cerium nitrate, 14g of dispersible nanoparticles, 55g of sodium dodecyl benzene sulfonate, 430g of preservative, 259g of complexing agent and 380g of deionized water.
4. The water-free acrylic chromium-free passivator for aluminum profiles according to claim 1, wherein the formula is prepared from the following components by weight: 160g of silane coupling agent, 188g of aluminum polysilicate, 52g of ethylene diamine tetraacetic acid, 93g of water-soluble phenolic resin, 13g of cerium nitrate, 11g of dispersible nanoparticles, 32g of sodium dodecyl benzene sulfonate, 350g of preservative, 214g of complexing agent and 345g of deionized water.
5. The water-washing-free acrylic acid chromium-free passivator suitable for aluminum profiles as claimed in claim 1, wherein: the preservative is prepared by mixing paraffin, peppermint oil, acrylic emulsion and zirconium potassium carbonate, wherein the weight ratio of the components of the paraffin, the peppermint oil, the acrylic emulsion and the zirconium potassium carbonate is 1: 1.2-1.4: 0.8-0.96: 0.42 to 0.49.
6. The water-washing-free acrylic acid chromium-free passivator suitable for aluminum profiles as claimed in claim 1, wherein: the complexing agent is prepared by mixing ethylene diamine tetra (methylene phosphonic acid) sodium and sodium hydroxide, wherein the weight ratio of the components of the ethylene diamine tetra (methylene phosphonic acid) sodium to the sodium hydroxide is 1: 1.08 to 2.24.
7. The water-washing-free acrylic acid chromium-free passivator for aluminum profiles as claimed in any one of claims 1-6, wherein the preparation method comprises the following steps:
s1: sequentially putting a silane coupling agent, aluminum polysilicate, disodium ethylene diamine tetraacetate, water-soluble phenolic resin, cerium nitrate, dispersible nanoparticles, sodium dodecyl benzene sulfonate and deionized water into a reaction kettle, and stirring for 20-35 min to fully mix the components;
s2: and S1, adding the preservative and the complexing agent into the reaction kettle after stirring, continuously stirring and mixing for 10-23 min, taking out the solution after stirring and mixing are finished, and naturally cooling the solution to room temperature to obtain the acrylic acid chromium-free passivator.
8. The preparation method of the water-washing-free acrylic acid chromium-free passivator suitable for aluminum profiles as claimed in claim 7, wherein: in the step S1, the stirring speed is 120-140 r/min, the stirring temperature is set to be 30-44 ℃, in the step S2, the stirring speed is 160-190 r/min, and the stirring temperature is set to be 42-54 ℃.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN104213114A (en) * | 2014-09-22 | 2014-12-17 | 徐震霖 | Black film coating agent for metal surface treatment and application thereof |
| CN107002246A (en) * | 2014-12-10 | 2017-08-01 | 新日铁住金株式会社 | Surface treating agent for galvanized steel sheet |
| CN107532304A (en) * | 2015-04-24 | 2018-01-02 | 日本帕卡濑精株式会社 | surface treating agent for metallic materials and metal material |
| CN106756967A (en) * | 2016-12-02 | 2017-05-31 | 兰州理工大学 | A kind of chrome-free tanning agent and the method being passivated to aluminum or aluminum alloy surface |
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| CN110776827A (en) * | 2019-10-31 | 2020-02-11 | 张继 | Metal preservative |
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Application publication date: 20210115 |