CN114351130A - Army green passivation solution, preparation method thereof and passivation method - Google Patents
Army green passivation solution, preparation method thereof and passivation method Download PDFInfo
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- CN114351130A CN114351130A CN202111545616.3A CN202111545616A CN114351130A CN 114351130 A CN114351130 A CN 114351130A CN 202111545616 A CN202111545616 A CN 202111545616A CN 114351130 A CN114351130 A CN 114351130A
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Abstract
The embodiment of the invention discloses army green passivation solution, a preparation method thereof and a passivation method. Wherein, in the army green passivation solution, each liter of passivation solution comprises the following components: 3-21g of chromic anhydride; 2-6ml of phosphoric acid; 2-6ml of sulfuric acid; 3-5ml of nitric acid; 10-30g of acrylic resin; 0.1-0.4g of sulfur silane; 0.1-0.4ml of amino silane; 0.05-0.4ml of surfactant; the passivation solution also comprises distilled water. The embodiment of the invention adopts a four-acid system, which better meets the requirements of environmental protection; the content of chromic anhydride in each liter of passivation solution is controlled within the range of 3-21g, so that the color of the generated passivation film is green and the uniformity of the coating film is ensured; the additive adopts acrylic resin, sulfur silane and amino silane to jointly realize the function of stably mixing colors of the passivation solution, and the surfactant can enable the appearance of the generated passivation film to be uniform, bright and clean.
Description
Technical Field
The invention relates to the field of passivation, in particular to army green passivation solution, a preparation method thereof and a passivation method thereof.
Background
In order to reduce the chemical activity of zinc, passivation treatment is often used to form a chemical conversion coating on the surface of the galvanized layer to improve its corrosiveness.
The phosphoric acid in the solution can dissolve the alkaline oxide (ZnO) on the surface of the zinc layer, has the functions of activating the surface of the zinc layer and promoting the chromic acid passivation reaction, and can deposit the phosphoric acid crystal which is insoluble with zinc ions and trivalent chromium ion compounds in the solution on the surface of the zinc layer.
The prior art often uses a penta-acid system, which has the following disadvantages: (1) chromium pollution is great in a pentacid type system; (2) the pentaacid system is yellow and slightly colored in passivation color.
In view of the above problems in the prior art, there is currently no effective solution.
Disclosure of Invention
In order to solve the problems, the invention provides army green passivation solution and a preparation method and a passivation method thereof, and the army green passivation solution is used for solving the problems of large chromium pollution and slight color development in a pentacid type system in the prior art by converting the pentacid type system into a tetrabasic type system.
In order to achieve the aim, the invention provides army green passivation solution, and each liter of passivation solution comprises the following components:
the passivation solution also comprises distilled water.
Further optionally, the passivation solution has a pH ∈ [1,1.5 ].
Further alternatively, the temperature value t ∈ [20 ℃,30 ℃) of the solution.
On the other hand, the invention also provides a preparation method of the army green passivation solution, which comprises the following steps:
adding quantitative chromic anhydride, phosphoric acid, sulfuric acid and nitric acid into a plating tank, uniformly stirring, adding distilled water to completely dissolve solids, and adding distilled water until the volume of the distilled water reaches 80% of that of the plating tank;
adding a certain amount of acrylic resin, sulfur silane, amino silane and surfactant into the plating tank under stirring until all the acrylic resin, sulfur silane, amino silane and surfactant are dissolved to obtain army green passivation solution; the amount of each component added is as follows according to the amount of 1 liter of solution prepared:
further optionally, the adding the quantitative acrylic resin, the sulfur silane, the amino silane and the surfactant into the plating tank under stirring until all the acrylic resin, the sulfur silane, the amino silane and the surfactant are dissolved further comprises: and filtering the solution in the plating tank.
On the other hand, the invention also provides a passivation method which comprises the step of passivating the surface of the metal layer by adopting the army green passivation solution, wherein the passivation time T belongs to [30s,60s ].
The technical scheme has the following beneficial effects: the embodiment of the invention adopts a four-acid system, and the green hexavalent chromium conversion film has a penta-acid type and a tetra-acid type according to the components of the passivation solution; according to the content of chromic anhydride or potassium dichromate, the green hexavalent chromium conversion coating can be divided into a high chromium type, a medium chromium type and a low chromium type. The tetra-acid type is a low-chromium type, and the penta-acid type is a medium-chromium type. The tetra-acid type better meets the requirements of green environmental protection; the content of chromic anhydride in each liter of passivation solution is controlled within the range of 3-21g, so that the color of the generated passivation film is green and the uniformity of the coating film is ensured.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a preparation method of a military green passivation solution provided by the embodiment of the 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.
In the color passivation film, the content ratio of trivalent chromium and hexavalent chromium is changed with the change of various factors, and thus the color of the passivation film is changed. When the amount of the trivalent chromium compound is large, the film layer is relatively green; when the content of hexavalent chromium is high, the passive film is purple red. The color is within the range of rainbow color in actual production, and the requirement of production is that the corrosion resistance of the passive film is improved and the appearance consistency is good.
In order to solve the problems of large chromium pollution and slight color development in a pentacid type system in the prior art, the embodiment of the invention provides army green passivation solution, and each liter of passivation solution comprises the following components:
each liter of passivation solution also comprises distilled water.
Chromic anhydride (CrO)3) When the content is lower, the passive film is light yellow green; the green color of the passivation film deepens along with the increase of the content of chromic anhydride; when the content of the chromic anhydride is too high, the passive film is not uniform and even falls off, the self-corrosion current density is firstly reduced and then increased, and the corrosion resistance is firstly enhanced and then weakened along with the increase of the content of the chromic anhydride. The chromic anhydride in the solution has high mass concentration, fast film formation and dark color of the passive film, so the chromic anhydride turns greenThe film forming solution is a main film forming agent, but the mass concentration of chromic anhydride is too high, so that the dissolution of a zinc layer is accelerated, a passive film falling phenomenon appears at a thinner part of the zinc layer, and the chromium content of the wastewater is high, so that the wastewater is not beneficial to environmental protection. On the contrary, the chromic anhydride has low mass concentration and slow film forming, and the generated passivation film is thin, light in color and luster and not bright. Chromic anhydride (CrO) comprehensively considering the appearance and corrosion resistance of the film3) The optimal parameter is 3-21 g/L.
When phosphoric acid is not added into the army green conversion film solution, the conversion film is golden yellow; when the content of phosphoric acid is too high, the conversion film is yellow-green. In the aspect of corrosion resistance, the content of phosphoric acid in the solvent is increased, and the self-corrosion current density of the passive film tends to decrease and then increase. Phosphoric acid can generate insoluble phosphate with zinc ions and trivalent chromium ions, and a compact phosphating film layer is formed on the zinc coating. The phosphating film is thicker than the conversion film and can adsorb hexavalent chromium ions and trivalent chromium ions to form the conversion film formed by crosslinking chromate and phosphate, and the optimal content of phosphoric acid is 2-6 ml/L.
The sulfuric acid is a film forming promoter of the army green conversion film, and has great influence on the formation of the conversion film, the film layer binding force and the thickness. When the green conversion film solution does not contain sulfuric acid, the conversion film is grey and dull; gradually increasing the content of sulfuric acid, and converting the conversion film from army green to yellow green until the conversion film is gray green; when the content of sulfuric acid is too high, the uniformity, brightness and corrosion resistance of the conversion film are reduced, and the phenomena of film falling and whitening appear. The optimal content of sulfuric acid is 2-6 ml/L.
The acrylic resin, the sulfur silane and the amino silane jointly realize the function of stably mixing colors of the passivation solution, and the surfactant can enable the appearance of the generated passivation film to be uniform and bright. The four additives of acrylic resin, sulfur silane, amino silane and surfactant are easy to store, are not easy to volatilize and change color, and the performance of the passivation solution for generating a passivation film is improved; meanwhile, the additives are water-soluble additives, so that the environment is protected; in addition, the corrosion resistance of the formed passivation film can be improved.
Among them, the surfactant is preferably sodium lauryl sulfate.
As an alternative embodiment, the passivating solution has a pH e [1,1.5 ].
As an alternative embodiment, the temperature t e of the solution is 20 ℃,30 ℃.
The embodiment of the invention also provides a preparation method of the army green passivation solution, fig. 1 is a flow chart of the preparation method of the army green passivation solution provided by the embodiment of the invention, and as shown in fig. 1, the method comprises the following steps:
s1, adding quantitative chromic anhydride, phosphoric acid, sulfuric acid and nitric acid into the plating tank, uniformly stirring, adding distilled water to completely dissolve the solid, and adding distilled water until the volume of the solid reaches 80% of that of the plating tank;
s2, adding a certain amount of acrylic resin, sulfur silane, amino silane and surfactant into a plating bath under stirring until the components are completely dissolved to obtain army green passivation solution; the amount of each component added is as follows according to the amount of 1 liter of solution prepared:
as an alternative embodiment, adding the acrylic resin, the sulfur silane, the amino silane and the surfactant into the plating bath with stirring until all the components are dissolved further comprises: the solution in the plating tank is filtered.
The embodiment of the invention also provides a passivation method, which comprises the step of passivating the surface of the metal layer by adopting the army green passivation solution, wherein the passivation time T belongs to [30s,60s ].
The solution preparation process is as follows:
1. putting calculated amounts of chromic anhydride, phosphoric acid, sulfuric acid and nitric acid into a clean plating tank, stirring uniformly, adding 1/5 volume of distilled water to dissolve the solid completely, and adding water to 80% of the volume of the plating tank.
2. The calculated amounts of acrylic resin, sulfur silane, aminosilane and surfactant were added to the bath with agitation until completely dissolved.
3. And opening the filter to filter.
4. The bath solution was treated with a small current for 8 hours before plating. Specifically, the small current is 0.2A/dm2。
In the first embodiment, each liter of passivation solution in this embodiment comprises the following components:
12g of chromic anhydride;
4ml of phosphoric acid;
4ml of sulfuric acid;
4ml of nitric acid;
20g of acrylic resin;
0.25g of thiosilane;
0.25ml of aminosilane;
0.225ml of surfactant.
The balance of distilled water.
In this example, the volume of the plating bath is 2m3For illustration, the required amount of chromic anhydride, phosphoric acid, sulfuric acid and nitric acid are added according to the proportion of the components, and 0.4m is added after the components are evenly stirred2The solid was completely dissolved by distilled water of (1) and then water was added thereto to 1.6m2Adding the required amount of acrylic resin, sulfur silane, amino silane and surfactant according to the proportion of the components, and stirring the passivation solution until the additive is completely dissolved. And opening the filter to filter. The pH of the solution was adjusted to 1.2 and the temperature of the solution was adjusted to 25 ℃.
The passivation solution is adopted to passivate a galvanized workpiece, the passivation time is 45s, the passivated workpiece is placed in a salt spray box for performance test, and the experimental conditions are as shown in table 1:
TABLE 1
The test results are shown in table 2:
TABLE 2
As can be seen from Table 2, the corrosion resistance of the workpiece after passivation by using the passivation solution in the embodiment is obviously improved from the previous 96h to 130 h.
In the second embodiment, each liter of passivation solution in this embodiment includes the following components:
3g of chromic anhydride;
2ml of phosphoric acid;
2ml of sulfuric acid;
3ml of nitric acid;
10g of acrylic resin;
0.1g of thiosilane;
0.1ml of aminosilane;
0.05ml of surfactant.
The balance of distilled water.
In this example, the volume of the plating bath is 2m3For illustration, the required amount of chromic anhydride, phosphoric acid, sulfuric acid and nitric acid are added according to the proportion of the components, and 0.4m is added after the components are evenly stirred2The solid was completely dissolved by distilled water of (1) and then water was added thereto to 1.6m2Adding the required amount of acrylic resin, sulfur silane, amino silane and surfactant according to the proportion of the components, and stirring the passivation solution until the additive is completely dissolved. And opening the filter to filter. The pH of the solution was adjusted to 1 and the temperature of the solution was adjusted to 20 ℃.
The passivation solution is adopted to passivate a galvanized workpiece, and the passivation time is 30s
In a third specific embodiment, each liter of passivation solution in this embodiment comprises the following components:
21g of chromic anhydride;
6ml of phosphoric acid;
6ml of sulfuric acid;
5ml of nitric acid;
30g of acrylic resin;
0.4g of thiosilane;
0.4ml of aminosilane;
0.4ml of surfactant.
The balance of distilled water.
In this example, the volume of the plating bath is 2m3For illustration, the required amount of chromic anhydride, phosphoric acid, sulfuric acid and nitric acid are added according to the proportion of the components, and 0.4m is added after the components are evenly stirred2The solid was completely dissolved by distilled water of (1) and then water was added thereto to 1.6m2In the ratio of the above componentsThe required amounts of acrylic resin, thiosilane, aminosilane and surfactant are added and the passivation solution is stirred until the additive is completely dissolved. And opening the filter to filter. The pH of the solution was adjusted to 1.5 and the temperature of the solution was adjusted to 20 ℃.
And passivating the galvanized workpiece by adopting the passivation solution for 60 s.
In the fourth embodiment, the proportions of the components are the same as those in the first embodiment.
This example was prepared as follows, based on 2000L of passivating solution prepared: in a volume of 3m3Adding required amount of chromic anhydride, phosphoric acid, nitric acid and sulfuric acid into the passivation tank according to the proportion of the components, adding water, and fully stirring to dissolve the components;
then adding the required amount of acrylic resin, sulfur silane, amino silane and surfactant into the solution in proportion, supplementing deionized water into the plating bath to make the volume of the liquid reach 2000L, and uniformly stirring.
Other technical features are the same as those of the first embodiment.
In addition, the bath solution requires regular maintenance:
1. the main components of chromic anhydride, phosphoric acid, sulfuric acid and nitric acid are analyzed once every two weeks and adjusted according to the requirements.
2. The supplement amount of the additive acrylic resin is 400-500 ml/L per 1000A/h;
the supplementary amount of the sulfur silane, the amino silane and the surfactant is 200-300 ml/L per 1000A/h.
The technical scheme has the following beneficial effects: the embodiment of the invention adopts a four-acid system, and the green hexavalent chromium conversion film has a penta-acid type and a tetra-acid type according to the components of the passivation solution; according to the content of chromic anhydride or potassium dichromate, the green hexavalent chromium conversion coating can be divided into a high chromium type, a medium chromium type and a low chromium type. The tetra-acid type is a low-chromium type, and the penta-acid type is a medium-chromium type. The tetra-acid type better meets the requirements of green environmental protection; the content of chromic anhydride in each liter of passivation solution is controlled within the range of 3-21g, so that the color of the generated passivation film is green and the uniformity of the coating film is ensured; the additive adopts acrylic resin, sulfur silane and amino silane to jointly realize the function of stably mixing colors of the passivation solution, and the surfactant can enable the appearance of the generated passivation film to be uniform, bright and clean. The four additives of acrylic resin, sulfur silane, amino silane and surfactant are easy to store, are not easy to volatilize and change color, and the performance of the passivation solution for generating a passivation film is improved; meanwhile, the additives are water-soluble additives, so that the environment is protected; in addition, the corrosion resistance of the formed passivation film can be improved.
The above embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, it should be understood that the above embodiments are merely exemplary embodiments of the present invention and are not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. The army green passivation solution is characterized in that each liter of passivation solution comprises the following components:
the passivation solution also comprises distilled water.
2. The army green passivation solution of claim 1, characterized in that:
the PH epsilon of the passivation solution is [1,1.5 ].
3. The army green passivation solution of claim 1, characterized in that:
the temperature value t of the solution belongs to [20 ℃,30 ℃).
4. A preparation method of army green passivation solution is characterized by comprising the following steps:
adding quantitative chromic anhydride, phosphoric acid, sulfuric acid and nitric acid into a plating tank, uniformly stirring, adding distilled water to completely dissolve solids, and adding distilled water until the volume of the distilled water reaches 80% of that of the plating tank;
adding a certain amount of acrylic resin, sulfur silane, amino silane and surfactant into the plating tank under stirring until all the acrylic resin, sulfur silane, amino silane and surfactant are dissolved to obtain army green passivation solution; the amount of each component added is as follows according to the amount of 1 liter of solution prepared:
5. the method for preparing the army green passivation solution as claimed in claim 4, wherein the step of adding the acrylic resin, the sulfur silane, the amino silane and the surfactant into the plating tank under stirring until all the acrylic resin, the sulfur silane, the amino silane and the surfactant are dissolved further comprises the following steps:
and filtering the solution in the plating tank.
6. A passivation method, characterized in that it comprises passivating the surface of a metal layer with a army green passivation solution according to any of claims 1 to 3, with a passivation time T e [30s,60s ].
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| CN103069046A (en) * | 2010-09-29 | 2013-04-24 | 杰富意钢铁株式会社 | Production method for galvanized steel sheet and galvanized steel sheet |
| CN107250434A (en) * | 2015-02-26 | 2017-10-13 | 新日铁住金株式会社 | Galvanized steel with or plate golding zincio alloy steel metal conditioner, coating method and coated steel |
| CN107641802A (en) * | 2017-07-19 | 2018-01-30 | 合肥普庆新材料科技有限公司 | A kind for the treatment of fluid of resistance and fingerprint resistance containing chromium for hot-dip galvanizing sheet steel |
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- 2021-12-16 CN CN202111545616.3A patent/CN114351130A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103069046A (en) * | 2010-09-29 | 2013-04-24 | 杰富意钢铁株式会社 | Production method for galvanized steel sheet and galvanized steel sheet |
| CN107250434A (en) * | 2015-02-26 | 2017-10-13 | 新日铁住金株式会社 | Galvanized steel with or plate golding zincio alloy steel metal conditioner, coating method and coated steel |
| CN107641802A (en) * | 2017-07-19 | 2018-01-30 | 合肥普庆新材料科技有限公司 | A kind for the treatment of fluid of resistance and fingerprint resistance containing chromium for hot-dip galvanizing sheet steel |
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| 刘燕萍,段晓南: "镀锌层低铬军绿钝化膜性能的研究", 电镀与精饰, no. 03, pages 35 - 37 * |
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Application publication date: 20220415 |