阅读说明：本技术 一种热镀锌高效防漏镀耐高铝助镀液添加剂及其制备方法 (High-efficiency, leak-proof and high-aluminum-resistant additive for plating assistant solution for hot galvanizing and preparation method thereof ) 是由 崔小进 韩辉升 于 2021-06-08 设计创作，主要内容包括：本发明提供一种热镀锌高效防漏镀耐高铝助镀液添加剂及其制备方法,所述的热镀锌高效防漏镀耐高铝助镀液添加剂包括以下重量份数的组分：铝盐10～20％；氯化镍2～5％；乙酸钴0.5～2％；氯化锡2～5％；表面活性剂1～5％；催干剂1～5％；氧化剂1～2％；络合剂1～3％,其余组分为去离子水。本发明提供的一种高铝助镀液添加剂,既能提高锌锅中的铝添加量,控制镀锌层厚度,又能防止出现漏镀现象,同时,又能降低爆锌的几率、减少烟雾,提高镀锌层的附着力,可避免镀锌过程中产生斑点、小黑点等缺陷。(The invention provides a hot galvanizing efficient anti-plating leakage high-aluminum-resistant plating assistant additive and a preparation method thereof, wherein the hot galvanizing efficient anti-plating leakage high-aluminum-resistant plating assistant additive comprises the following components in parts by weight: 10-20% of aluminum salt; 2-5% of nickel chloride; 0.5-2% of cobalt acetate; 2-5% of stannic chloride; 1-5% of a surfactant; 1-5% of a drier; 1-2% of an oxidant; 1-3% of complexing agent and the balance of deionized water. The high-aluminum plating assistant solution additive provided by the invention can improve the aluminum addition amount in a zinc pot, control the thickness of a galvanized layer, prevent the occurrence of a plating leakage phenomenon, reduce the zinc explosion probability, reduce smoke, improve the adhesive force of the galvanized layer and avoid the defects of spots, small black spots and the like in the galvanizing process.)

1. A hot galvanizing efficient leak-proof plating high-aluminum-resistant plating assistant liquid additive and a preparation method thereof are characterized in that: the high-efficiency, leak-proof and high-aluminum-resistant additive for the hot galvanizing plating assistant comprises the following components in parts by weight:

the rest components are deionized water.

2. The additive for the high-efficiency, leak-proof and high-aluminum-resistant plating assistant for hot galvanizing and galvanizing of the claim 1 and the preparation method thereof are characterized in that: the aluminum salt is one or more of aluminum fluoride, cryolite, aluminum sulfate, aluminum chloride and aluminum nitrate.

3. The additive for the high-efficiency, leak-proof and high-aluminum-resistant plating assistant for hot galvanizing and galvanizing of the claim 1 and the preparation method thereof are characterized in that: the surfactant is a cationic surfactant and mainly comprises one or more of behenamide propyl dimethylamine, cetyl trimethyl ammonium chloride, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, stearamide propyl dimethylamine, dodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride and didecyl dimethyl ammonium.

4. The additive for the high-efficiency, leak-proof and high-aluminum-resistant plating assistant for hot galvanizing and galvanizing of the claim 1 and the preparation method thereof are characterized in that: the drier is one or more of dibutyltin dilaurate, fatty alcohol EO-PO block polyether copolymer, cobalt 2-ethylhexanoate, zinc naphthenate, alkyl glycoside, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether and isomeric alcohol TO-40.

5. The additive for the high-efficiency, leak-proof and high-aluminum-resistant plating assistant for hot galvanizing and galvanizing of the claim 1 and the preparation method thereof are characterized in that: the oxidant is one or more of persulfate, permanganate, hypochlorous acid, organic bromine and chromic acid.

6. The additive for the high-efficiency, leak-proof and high-aluminum-resistant plating assistant for hot galvanizing and galvanizing of the claim 1 and the preparation method thereof are characterized in that: the complexing agent is one or more of lactic acid, acetic acid, soluble lactate, soluble acetate, disodium ethylene diamine tetraacetate, citric acid and sodium aminotriacetate.

7. The additive for the high-efficiency leak-proof plating high-aluminum-resistant plating assistant solution for hot galvanizing according to the claims 1 to 5 and the preparation method thereof are characterized in that: the process route is as follows

(1) Under the condition of stirring, sequentially dissolving aluminum salt, nickel chloride, cobalt acetate, stannic chloride and a complexing agent in deionized water according to a certain proportion, and uniformly stirring to obtain a mixed liquid;

(2) under the condition of stirring, dissolving a drier, an oxidant and a surfactant in the mixed liquid obtained in the step (1) in sequence according to a proportion, uniformly stirring, standing and packaging;

8. the plating aid additive according to claims 1 to 6, wherein: after the addition, the pH value of the plating assistant solution is controlled to be 2-5, and the temperature of the plating assistant solution tank is controlled to be 40-65 ℃.

9. The plating aid additive according to claims 1 to 6, wherein:

(1) the hot galvanizing plating assistant additive is used for improving the surface state of a hot-dip galvanized steel part, improving the corrosion resistance after plating, simultaneously improving the adhesive force between zinc-aluminum alloy (especially aluminum) with higher aluminum content and the surface of a workpiece and avoiding plating leakage when the aluminum content in a zinc pot is too high through aluminum salt, nickel chloride, cobalt acetate and tin chloride in the additive;

(2) the oxidant is used for oxidizing and reducing ferrous ions in the plating assistant solution, and meanwhile, the added complexing agent is matched to generate a bidirectional complexing effect on the base metal and the coating metal, so that the binding capacity of the base metal and the coating is improved, the condition of plating leakage is avoided, and the brightness of the coating is improved;

(3) the surfactant and the drier are added to improve the drying speed of the workpiece before hot galvanizing, and the workpiece can be quickly dried without heating, so that the zinc explosion probability is reduced, smoke is reduced, the method is safer and more environment-friendly, the zinc consumption is reduced, and the cost is saved;

(4) the comprehensive performance of the hot galvanizing plating assistant liquid additive can effectively improve the aluminum content added in a zinc pot, a layer of high-adhesion plating assistant film is formed on the surface of a workpiece, the adhesion of a zinc coating layer is improved, and the defects of spots, small black spots and the like generated in the galvanizing process are avoided; the thickness and uniformity of the zinc coating can be controlled by adding different aluminum contents, and the purposes of controlling the hot galvanizing process and saving the cost are achieved.

Technical Field

The invention belongs to the technical field of metal surface corrosion protection treatment, and particularly relates to a high-efficiency, leak-proof and high-aluminum-resistant additive for a hot-dip galvanizing plating aid and a preparation method thereof. The invention achieves excellent plating-assistant effect under the coordination of various components of the plating-assistant liquid additive; in the using process, before galvanization, the workpiece does not need to be heated, the drying speed is high, the galvanization smoke is less, the zinc explosion is avoided, the brightness of the galvanized workpiece is good, and the corrosion resistance is improved; in the zinc pot, the content of the added aluminum is obviously improved, aluminum with different contents can be added, the thickness of a zinc coating is controlled, the defects in the galvanizing process are reduced, the plating missing phenomenon can not occur, and the cost is saved.

Background

The steel is the basis of almost all industries, the steel products are used everywhere, including the industries such as household appliances, automobiles, railways, trains, bridges, aerospace, ships, capital constructions, real estate and respective mechanical manufacturing industries, and the like, and the quantity of the used steel is increasing day by day; in addition, the method is widely used in the aspects of chemical industry, ocean development and the like.

The steel has the advantages of being recyclable for unlimited times, and being a conveniently regenerated material which does not pollute the environment. The rust-proof coating has the defects of rust, and the most main means in modern industry are coating, adding an anti-rust layer, hot galvanizing and the like on steel in order to prevent the steel from rusting;

hot galvanizing, which adopts a solvent method, a workpiece to be galvanized is immersed into a liquid zinc bath in a molten state, the workpiece is taken out to be cooled, and a zinc coating is formed on the surface of the workpiece. Before a workpiece is immersed into a zinc pot, the most important process in the hot galvanizing pretreatment process is needed to avoid the occurrence of defects of a zinc coating and improve the galvanizing quality. The process is called plating assistant, and the quality of the plating assistant solution directly determines the quality of the zinc plating and has great influence on the cost.

The traditional plating-assistant process is a process of immersing steel parts into zinc chloride and ammonium chloride plating-assistant solution with certain components to form a layer of thin zinc chloride ammonium salt film. The plating assistant principle is as follows: at room temperature, the plating assistant film isolates air, greatly reduces the diffusion of oxygen molecules to the steel substrate, and prevents iron oxide from generating and attaching on the steel surface. The zinc ammonium chloride salt film covered on the surface of the workpiece after plating assistant plays a role in activation, and a complex salt film of coordination acid H2[ Zn (OH)2Cl2] is formed on the surface of the workpiece, and is strong acid, so that the surface of the workpiece cannot quickly form an oxide film in the drying process, and the activation state is kept. However, when the surface temperature of the plated part rises to over 200 ℃, ammonium chloride in the salt film of the plating assistant agent can be decomposed to form HCl and NH3, and the HCl and NH3 are recombined to form NH4Cl particles when meeting the air at normal temperature, so that a large amount of smoke is generated, and the quality of the workpiece is seriously influenced.

With the progress of society and science and technology, the product quality requirements of automobile, high-speed rail and household appliance industries on galvanized parts are higher and higher, and particularly, the outer plates cannot have any defects. The aluminum content of the zinc pot is one of key process parameters for producing galvanized parts, and the large fluctuation of the aluminum content directly causes the instability of the surface quality of a galvanized layer, thereby becoming a bottleneck influencing the product quality. If the aluminum content is higher, the plating leakage is easy to cause; the lower aluminum content results in too thick a zinc coating. How to control the thickness of the galvanized layer can prevent the galvanized layer from being leaked and the surface of the galvanized layer from being defective, reduce the generation of smoke and prevent the occurrence of zinc explosion in the galvanizing process, which becomes a difficult problem which troubles the hot galvanizing industry.

In order to solve the problems in the prior art, the additive is developed, which can improve the aluminum addition amount in a zinc pot, control the thickness of a galvanized layer, prevent the phenomenon of plating leakage, reduce the zinc explosion probability, reduce smoke, improve the adhesive force of the galvanized layer, and avoid the defects of spots, small black spots and the like in the galvanizing process. Has extremely high industrial value and social benefit for the hot galvanizing industry.

Disclosure of Invention

The invention aims to develop a hot galvanizing plating assistant liquid additive which can control the adding amount of aluminum in a zinc pot, prevent plating leakage, reduce zinc explosion and reduce smoke.

A high-efficiency, leak-proof and high-aluminum-resistant additive for a plating assistant for hot galvanizing comprises the following components in parts by weight:

the rest components are deionized water

Furthermore, the hot galvanizing efficient leak-proof plating high-aluminum-resistant plating assistant liquid additive is prepared by adding one or more of aluminum fluoride, cryolite, aluminum sulfate, aluminum chloride and aluminum nitrate into aluminum salt.

Furthermore, the surface active agent is a cationic surface active agent, and mainly comprises one or more of behenamide propyl dimethylamine, cetyl trimethyl ammonium chloride, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, stearamide propyl dimethylamine, dodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride and didecyl dimethyl ammonium.

Further, the hot galvanizing efficient anti-plating-leakage high-aluminum-resistant plating assistant additive is characterized in that the drier is one or more of dibutyltin dilaurate, fatty alcohol EO-PO block polyether copolymer, cobalt 2-ethylhexanoate, zinc naphthenate, alkyl glycoside, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether and isomeric alcohol TO-40.

Furthermore, the hot galvanizing efficient anti-plating leakage high-aluminum-resistant plating assistant liquid additive is prepared by using one or more of persulfate, permanganate, hypochlorous acid, organic bromine and chromic acid as an oxidant.

Further, the hot galvanizing efficient anti-plating leakage high-aluminum-resistant plating assistant solution additive is characterized in that the complexing agent is one or more of lactic acid, acetic acid, soluble lactate, soluble acetate, disodium ethylene diamine tetraacetate, citric acid and sodium aminotriacetate.

Further, the hot galvanizing efficient anti-plating leakage high-aluminum-resistant plating assistant liquid additive comprises the following using process: after the addition, the pH value of the plating assistant solution is controlled to be 2-5, and the temperature of the plating assistant solution tank is controlled to be 40-65 ℃.

Further, the production process of the hot galvanizing efficient anti-leakage plating high-aluminum-resistant plating assistant liquid additive comprises the following steps:

(1) under the condition of stirring, sequentially dissolving aluminum salt, nickel chloride, cobalt acetate, stannic chloride and a complexing agent in deionized water according to a certain proportion, and uniformly stirring to obtain a mixed liquid;

(2) under the condition of stirring, dissolving a drier, an oxidant and a surfactant in the mixed liquid obtained in the step (1) in sequence according to a proportion, uniformly stirring, standing and packaging;

advantageous effects

The high-aluminum plating assistant solution additive provided by the invention can improve the aluminum addition amount in a zinc pot, control the thickness of a galvanized layer and prevent the phenomenon of plating leakage; meanwhile, the zinc explosion probability can be reduced, smoke can be reduced, the adhesive force of a zinc coating can be improved, and the defects of spots, small black spots and the like generated in the galvanizing process can be avoided.

Detailed Description

The invention will be further illustrated with reference to specific examples.

Reference will now be made in detail to embodiments of the invention, examples of which, methods of use and advantages of the invention will be apparent from the following description. In the description, some principles of the present invention are illustrated, and specific embodiments among the embodiments of the present invention are specifically disclosed, but the present invention is not limited in any form, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention fall within the scope of the technical solution of the present invention.

The additive of the high-efficiency, leak-proof and high-aluminum-resistant plating assistant agent for hot galvanizing perfectly overcomes the defect caused by overhigh aluminum content of hot galvanizing, and can control the added aluminum content according to the galvanizing requirement, thereby controlling the thickness of a galvanizing coat, ensuring the uniformity of the galvanizing coat and preventing the phenomenon of leak galvanizing; meanwhile, the additive of the high-efficiency, leak-proof and high-aluminum-resistant plating assistant agent for hot galvanizing can also play a role in reducing the zinc explosion rate and inhibiting smoke.

The following specific examples and comparative experiments illustrate the effects of the additive of the high-efficiency, leak-proof and high-aluminum-resistant plating assistant solution for hot galvanizing in the actual hot galvanizing process, and the hot galvanizing workpiece is evaluated according to the following three technical indexes: (1) evaluating the galvanizing effect of adding different aluminum contents into the zinc pot, judging whether the appearance of the plating layer has the problems of plating leakage, zinc deficiency, pockmarks, zinc nodules and the like, and whether the thickness of the zinc layer meets the requirement; (2) whether the generation amount of smoke is reduced or not in the process of immersing the workpiece into the zinc bath; (3) and (3) whether the zinc explosion phenomenon exists or not in the process of immersing the workpiece into the zinc bath.

The specific embodiment comprises the following components in percentage by weight:

example 1

The invention relates to a hot galvanizing efficient leak-proof plating high-aluminum-resistant plating assistant additive which comprises the following components in parts by weight:

120g/L of aluminum chloride and 20g/L of nickel chloride

Cobalt acetate 5g/L stannic chloride 25g/L

Fatty alcohol EO-PO block polyether copolymer 10g/L

30g/L of dodecyl dimethyl benzyl ammonium chloride, and the balance of deionized water.

After 5 percent of additive is added, the effect of the plating assistant solution is obviously improved, the plating assistant solution is slightly green and smoky during zinc plating, the phenomenon of zinc explosion is avoided, a plated piece has no plating leakage, the surface is smooth, no pockmark or black spot is generated, and the brightness is good.

Example 2

The invention relates to a hot galvanizing efficient leak-proof plating high-aluminum-resistant plating assistant additive which comprises the following components in parts by weight:

after 5 percent of the additive is added, the effect of the plating assistant solution is obviously improved, the plating assistant solution is slightly green and smokeless during zinc plating, the zinc explosion phenomenon is avoided, a plated piece has no plating leakage, the surface is smooth, no pockmark or black spot is generated, and the brightness is good.

Example 3

The invention relates to a hot galvanizing efficient leak-proof plating high-aluminum-resistant plating assistant additive which comprises the following components in parts by weight:

after 5 percent of the additive is added, the effect of the plating assistant solution is improved, a small amount of green smoke exists during zinc plating, the phenomenon of slight zinc explosion exists, a plated part has no plating leakage, the surface is smooth, no pockmark or black spot exists, and the brightness is good.

Example 4

The invention relates to a hot galvanizing efficient leak-proof plating high-aluminum-resistant plating assistant additive which comprises the following components in parts by weight:

after 5 percent of the additive is added, the effect of the plating assistant solution is obviously improved, basically no smoke and zinc explosion phenomenon exist during galvanizing, a galvanized part has no plating leakage, the surface is smooth, no pockmark or black spot exists, and the brightness is good.

Example 5

The invention relates to a hot galvanizing efficient leak-proof plating high-aluminum-resistant plating assistant additive which comprises the following components in parts by weight:

after 5 percent of the additive is added, the effect of the plating assistant solution is obviously improved, basically no smoke and zinc explosion phenomenon exist during galvanizing, a galvanized part has no plating leakage, the surface is smooth, no pockmark or black spot exists, and the brightness is good.

The following table shows the specific effects of the plating assistant solutions prepared in examples 1 to 5:

the following are comparisons of the present invention with conventional additives on the market, comparative example 1 is a plating assistant solution without additives, comparative example 2 is a plating assistant solution with 0.8% of additive TSD on the market, and comparative example 3 is a plating assistant solution with 0.8% of additive described in example 3, and the effects are shown as follows:

the results show that the plating assistant solution of the additive provided by the invention has better plating assistant capability and adhesion effect than the plating assistant solution provided on the market.

Although the present invention has been described in detail with reference to the foregoing examples, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.