CN114574801A - Novel multi-element alloy co-permeation agent and preparation method thereof - Google Patents

Abstract

A novel multi-element alloy co-permeation agent and a preparation method thereof are disclosed, wherein the multi-element alloy co-permeation agent comprises the following components in parts by weight: 42-52 parts of composite zinc-aluminum alloy powder, 28-36 parts of composite zinc-magnesium alloy powder, 4-5 parts of aluminum powder, 4-5 parts of chromium powder, 2-3 parts of rare earth element compound powder, 25-35 parts of a dispersing agent and 3-5 parts of a permeation promoter. Uniformly mixing the composite zinc-aluminum alloy powder, the composite zinc-magnesium alloy powder, the aluminum powder, the chromium powder and the rare earth element compound powder, adding the permeation aid agent after ball milling, uniformly mixing, adding the dispersing agent after ball milling again, uniformly mixing, and finally drying at 80-120 ℃ under the protection of inert atmosphere to obtain the zinc-aluminum alloy powder. The multi-element alloy co-permeation agent has the advantages of wide raw materials, high activity of the permeation agent, high permeation speed, high utilization rate of the raw materials, larger thickness and microhardness of a permeation layer, stronger bonding force with a metal member, excellent surface performance of the obtained permeation layer and capability of effectively retarding the corrosion of a casting.

Description

Novel multi-element alloy co-permeation agent and preparation method thereof

Technical Field

The invention relates to the technical field of metal rust prevention, in particular to a novel multi-element alloy co-permeation agent and a preparation method thereof.

Background

Today, metals have a wide range of applications in people's lives. Accordingly, corrosion prevention of metals is becoming a considerable problem. The corrosion of metal not only consumes the indispensable natural resources in human life, but also seriously damages the normal operation of many activities such as natural environment, industrial production, human life and the like, and the huge economic loss and serious environmental pollution caused by the corrosion become one of the important factors influencing the modern society and the economic sustainable development. In order to deal with the corrosion of metal, especially to delay the corrosion of metal in a severe working environment, a plurality of methods are adopted to deal with the problem, and the traditional methods comprise oil coating, electroplating, single coating and the like. At present, the method of coating the surface with the anti-rust oil is difficult to maintain the anti-rust performance of the metal component for a long time under severe outdoor conditions, and the traditional processes of electroplating, single zinc-chromium coating and the like are difficult to meet the use requirements of metal parts. This has prompted people to explore new anticorrosion technologies.

The powder zincizing technology is to form a zinc-iron alloy layer on the surface of a substrate by utilizing mutual diffusion of zinc and iron atoms, plays a good role in protection and is widely applied to the field of corrosion prevention of steel parts. The multicomponent alloy co-cementation technology is the latest anticorrosion treatment technology developed and innovated on the basis of powder zincification, and is the hot technology for the corrosion prevention of the metal components at present. The technical principle of the multi-element alloy co-infiltration is as follows: under the vacuum condition, the multi-element metal powder forms a coating on the surface of the workpiece by physical and chemical adsorption deposition and mechanical collision. Besides zinc powder, accelerant and anti-adhesive agent, the penetrant is added with metal elements such as aluminum, magnesium and rare earth, so that the permeated layer is made of similar multiple alloys, thereby improving the antirust performance of the permeated layer. Compared with other zinc coatings, the coating has the advantages of high bonding strength, high coating hardness, no hydrogen embrittlement hazard, good coating thickness uniformity, simple process, raw material saving and the like.

Although the multi-component alloy co-permeation corrosion prevention technology has many advantages, the following bottlenecks and technical problems to be solved still exist: the thickness of the infiltrated layer on the surface of the metal component after the co-infiltration treatment is not uniform; the existing permeating agent has low absorptivity, large zinc powder consumption and high cost; the salt spray resistance test time of the metal member after the surface passivation sealing treatment is not long enough, and the corrosion resistance can not meet the requirement.

Disclosure of Invention

The invention aims to solve the problems of low absorptivity, large zinc powder consumption and uneven thickness of a permeation layer in the multi-element alloy co-permeation process in the prior art, and provides a novel multi-element alloy co-permeation agent and a preparation method thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

a novel multi-element alloy co-permeation agent comprises the following components in parts by weight: 42-52 parts of composite zinc-aluminum alloy powder, 28-36 parts of composite zinc-magnesium alloy powder, 4-5 parts of aluminum powder, 4-5 parts of chromium powder, 2-3 parts of rare earth element compound powder, 25-35 parts of a dispersing agent and 3-5 parts of a permeation promoter.

The composite zinc-aluminum alloy powder comprises, by mass, not less than 80% of zinc element, not less than 10% of aluminum element, and has a particle diameter of 2-18 μm.

By taking the mass percentage as a unit, in the composite zinc-magnesium alloy powder, the content of zinc element is not less than 80%, the content of magnesium element is not less than 10%, and the particle diameter of the composite zinc-magnesium alloy powder is 4-20 μm.

In the added aluminum powder, the content of aluminum element is not less than 95% by mass percentage, and the particle size of the aluminum powder is 12-20 μm.

In the added chromium powder, the content of chromium element is not less than 90% by mass percent, and the particle size of the chromium powder is 10-16 μm.

The adopted rare earth element compound is at least one of yttrium oxide and cerium oxide, and the content of yttrium oxide in yttrium oxide powder is not lower than 88 percent by mass percent; in the cerium oxide powder, the content of cerium oxide is not less than 85%.

The adopted dispersant is at least one of white corundum, bauxite and silicon dioxide, wherein the particle diameter of the dispersant is 0.25-1 mm.

The penetration assistant agent can be one or more of ammonium fluoroaluminate, aluminum chloride and ammonium chloride.

The purity of ammonium fluoroaluminate, aluminum chloride and ammonium chloride in the adopted permeation assistant agent is not lower than 80%.

The preparation method of the novel multi-element alloy co-permeation agent comprises the following steps:

1) weighing 42-52 parts of composite zinc-aluminum alloy powder, 28-36 parts of composite zinc-magnesium alloy powder, 4-5 parts of aluminum powder, 4-5 parts of chromium powder, 2-3 parts of rare earth element compound powder, 25-35 parts of a dispersing agent and 3-5 parts of a permeation aid according to parts by mass;

2) uniformly mixing composite zinc-aluminum alloy powder, composite zinc-magnesium alloy powder, aluminum powder, chromium powder and rare earth element compound powder, performing ball milling, adding a permeation assistant, uniformly mixing, performing ball milling again to obtain mixture powder, and adding a dispersing agent, and uniformly mixing;

3) and drying the mixture powder at 80-120 ℃ under the protection of inert atmosphere to obtain the multi-element alloy co-permeation agent.

Compared with the prior art, the technical scheme of the invention has the following beneficial effects:

1. the multicomponent alloy co-permeation agent mainly contains various metals such as zinc, magnesium, aluminum and the like, and can permeate into a casting to form a co-permeation layer on the surface of the casting so as to enhance the surface performance of the metal of the casting, delay the corrosion of the casting and further prolong the service life of the casting. The multi-element alloy co-infiltration formula of the invention has considerable infiltration layer thickness and high bonding strength with castings.

2. The invention adopts a large amount of alloy powder to replace most pure metal powder in the existing formula, and compared with the existing formula, the mixing of different metal powder is more uniform, the particle size difference of the powder is smaller, and the infiltration layer is uniform.

3. The dispersant provided by the invention can slow down the mutual impact among products and reduce the damage of threads in the co-cementation process, can clear away a secondary oxidation layer on the surface of the product, and plays roles in diluting and filling in the co-cementation process. Furthermore, the bauxite and the white corundum can simultaneously provide additional active aluminum to participate in the metal infiltration process, improve the quality of an infiltration layer and increase the thickness of the infiltration layer. Wherein, the bauxite has the advantage of price, the white corundum has the advantage of performance, and the proportion of the bauxite and the white corundum is adjustable within the range of the formula provided by the invention according to the production condition. Further, silica provides active silicon, has a favorable effect on co-permeation, and has a price advantage, and the proportion thereof is adjustable within the range of the formulation provided by the present invention depending on actual production conditions. The dispersant provided by the invention can be recycled in the production process, and the dispersant obtained after recycling can be put into use again under the condition that the particle size is not less than 0.25 mm.

4. The penetration assistant agent provided by the invention is at least one of ammonium fluoroaluminate, aluminum chloride and ammonium chloride. The three have the functions of removing impurities on the surface of the casting, activating the surface and catalyzing the co-permeation process to generate active metal, and can be used as an activating agent and a catalyst in the co-permeation process. Furthermore, gas generated by decomposing ammonium fluoroaluminate and ammonium chloride in the reaction process has the functions of removing oxygen in the device and guaranteeing the surface performance of the casting, and can serve as an oxygen scavenger in the co-permeation process. Further, the ammonium fluoroaluminate and the aluminum chloride have the function of providing an intermediate product of the cementation reaction, thereby improving the thickness and microhardness of the cementation layer. Further, ammonium chloride and aluminum chloride have safety performance advantages, and ammonium fluoroaluminate has performance advantages. The proportion can be adjusted within the range of the formula provided by the invention according to specific production requirements.

5. In the metal penetrant provided by the invention, yttrium oxide can reduce the corrosion rate of a permeated layer, cerium oxide can increase the thickness of the permeated layer within the adding parts of the formula, the two can improve the quality of the permeated layer, and the proportion is adjustable according to the actual production requirement.

6. In the metal penetrating agent provided by the invention, the chromium element can improve the coating structure and slow down the oxygen diffusion on the surface of a penetrating layer in the use process of a product so as to prolong the service life of the penetrating layer and slow down corrosion.

7. The formula provided by the invention is simple to prepare and easy to operate.

Drawings

FIG. 1 is a schematic diagram of the method of using the multi-element alloy co-permeation agent of the present invention.

Detailed Description

To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to a novel and efficient multi-component alloy co-permeation agent and a preparation method thereof according to the preferred embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope 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. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

It is to be noted that those who do not specify the specific conditions are carried out under the conventional conditions or conditions recommended by the manufacturer, and those who do not specify the manufacturer of the reagent or apparatus used are commercially available as conventional products.

The composite zinc-aluminum alloy powder and the composite zinc-magnesium alloy powder are used as zinc supplying agents, and the diameter of the metal powder is not more than 30 mu m. The rare earth element compound powder is at least one of yttrium oxide or cerium oxide. The dispersant is one or a mixture of more of bauxite, white corundum and quartz sand. The penetration assistant agent is one or a mixture of more of ammonium fluoroaluminate, aluminum chloride and ammonium chloride.

The preparation method of the multi-element alloy co-permeation agent comprises the following specific steps:

step 1: weighing 42-52 parts of composite zinc-aluminum alloy powder, 28-36 parts of composite zinc-magnesium alloy powder, 4-5 parts of aluminum powder, 4-5 parts of chromium powder, 2-3 parts of rare earth element compound powder, 25-35 parts of a dispersing agent and 3-5 parts of a permeation aid according to parts by mass;

and 2, step: uniformly mixing composite zinc-aluminum alloy powder, composite zinc-magnesium alloy powder, aluminum powder, chromium powder and rare earth element compound powder, performing ball milling, adding a permeation aid, uniformly mixing, performing ball milling again to obtain mixture powder, and adding a dispersing agent, and uniformly mixing;

and step 3: and drying the mixture powder at 80-120 ℃ under the protection of inert atmosphere to obtain the multi-element alloy co-permeation agent.

Examples 1 to 5: a novel high-efficiency multi-element alloy co-permeation agent and a preparation method thereof are disclosed, wherein the components and the corresponding parts by weight are shown in Table 1. Wherein, the penetration enhancer is ammonium chloride and aluminum chloride, and the ratio of the ammonium chloride to the aluminum chloride is 80: 20.

TABLE 1

Components	Example 1	Example 2	Example 3	Example 4	Example 5
						Zinc-aluminum alloy powder	40 portions of	35 portions of	25 portions of	40 portions of	40 portions of
Zinc-magnesium alloy powder	25 portions of	23 portions of	20 portions of	25 portions of	25 portions of
						Aluminum powder	10 portions of	9 portions of	8 portions of	10 portions of	10 portions of
Chromium powder	3 portions of	2 portions of	2 portions of	3 portions of	3 portions of
						Oxidation by oxygenCerium (Ce)	1.5 parts of	1.5 parts of	1.5 parts of	3 portions of	0 portion of
Yttria	1.5 parts of	1.5 parts of	1.5 parts of	0 portion of	3 portions of
						Silicon dioxide	75 portions of	55 portions of	60 portions of	75 portions of	75 portions of
Permeation aid	5 portions of	4 portions of	3 portions of	5 portions of	5 portions of

Weighing the components according to the table 1, uniformly mixing the composite zinc-aluminum alloy powder, the composite zinc-magnesium alloy powder, the aluminum powder, the chromium powder and the rare earth element compound powder, adding the permeation aid after ball milling, uniformly mixing, performing ball milling again, adding the dispersing agent, uniformly mixing, and finally drying for 1.5 hours at 100 ℃ under the protection of inert atmosphere to obtain the zinc-aluminum alloy powder.

Examples 5 to 10: and (3) putting the multi-element alloy co-permeation agent obtained in the embodiment 1-5 and 306 steel into a sealed crucible, heating the crucible along with the furnace to 450 ℃, standing, heating and zinc permeation for 4 hours, cooling the crucible along with the furnace to below 200 ℃, taking out the crucible, and cooling the crucible to room temperature.

The zincized members obtained in examples 5 to 10 were examined for the thickness of the zincized layer, which was uniform and dense, and had a thickness of 60 to 100 μm, a hardness of 450HV or more, and high bonding strength.

As shown in figure 1, the application of the multi-element alloy co-permeation agent in the steel product comprises the following steps:

step 1, adding the steel casting to be subjected to the multi-element alloy co-infiltration into a gas zinc-infiltrating furnace, adding the multi-element alloy co-infiltration agent obtained according to the method, and sealing.

And 2, setting the temperature of the gas furnace to be 500 ℃, setting the temperature rise time to be 1.2h, setting the heat preservation time in a heating state to be 5h, and setting the air rotation time in the furnace chamber to be 3 h.

And 3, starting the rotating motor and starting the fan.

And 4, after heating and heat preservation are finished, closing the fan, opening the heating body door, driving the furnace pipe trolley to a waiting station for idling, stopping idling when the temperature of the idling furnace pipe of the co-infiltration furnace is about 250 ℃, and then cooling in a natural state or air cooling.

And 5, lifting the furnace pipe out, moving the furnace pipe to a designated area, opening a furnace cover, taking out the workpiece, and recovering part of the dispersing agent.

The novel efficient multi-element alloy co-permeation agent provided by the invention has the advantages of high activity, high permeation speed, wide raw material, high utilization rate, smaller powder particle size difference, uniform permeation layer, considerable thickness, high bonding strength with a casting, high hardness, wear resistance and strong corrosion resistance; and the preparation process is simple and easy to operate.

Claims (10)

1. The novel multi-element alloy co-permeation agent is characterized by comprising the following components in parts by weight: 42-52 parts of composite zinc-aluminum alloy powder, 28-36 parts of composite zinc-magnesium alloy powder, 4-5 parts of aluminum powder, 4-5 parts of chromium powder, 2-3 parts of rare earth element compound powder, 25-35 parts of a dispersing agent and 3-5 parts of a permeation promoter.

2. The novel multicomponent alloy co-permeation agent of claim 1, wherein: the composite zinc-aluminum alloy powder comprises, by mass, not less than 80% of zinc element, not less than 10% of aluminum element, and has a particle diameter of 2-18 μm.

3. The novel multicomponent alloy co-permeation agent of claim 1, wherein: by taking the mass percentage as a unit, in the composite zinc-magnesium alloy powder, the content of zinc element is not less than 80%, the content of magnesium element is not less than 10%, and the particle diameter of the composite zinc-magnesium alloy powder is 4-20 μm.

4. The novel multicomponent alloy co-permeation agent of claim 1, wherein: in the added aluminum powder, the content of aluminum element is not less than 95% by mass percentage, and the particle size of the aluminum powder is 12-20 μm.

5. The novel multicomponent alloy co-permeation agent of claim 1, wherein: in the added chromium powder, the content of chromium element is not less than 90% by mass percent, and the particle size of the chromium powder is 10-16 μm.

6. The novel multicomponent alloy co-permeation agent of claim 1, wherein: the adopted rare earth element compound is at least one of yttrium oxide and cerium oxide, and the content of yttrium oxide in yttrium oxide powder is not lower than 88 percent by mass percentage; in the cerium oxide powder, the content of cerium oxide is not less than 85%.

7. The novel multi-element alloy co-permeation agent of claim 1, wherein: the adopted dispersing agent is at least one of white corundum, bauxite and silicon dioxide, wherein the particle diameter of the dispersing agent is 0.25-1 mm.

8. The novel multi-element alloy co-permeation agent of claim 1, wherein: the penetration assistant agent can be one or more of ammonium fluoroaluminate, aluminum chloride and ammonium chloride.

9. The novel multi-element alloy co-permeation agent of claim 8, wherein: the purity of ammonium fluoroaluminate, aluminum chloride and ammonium chloride in the adopted permeation assistant agent is not lower than 80%.

10. The preparation method of the novel multicomponent alloy co-permeation agent as claimed in any one of claims 1 to 9, characterized by comprising the following steps:

1) weighing 42-52 parts of composite zinc-aluminum alloy powder, 28-36 parts of composite zinc-magnesium alloy powder, 4-5 parts of aluminum powder, 4-5 parts of chromium powder, 2-3 parts of rare earth element compound powder, 25-35 parts of a dispersing agent and 3-5 parts of a permeation assistant according to parts by mass;

2) uniformly mixing composite zinc-aluminum alloy powder, composite zinc-magnesium alloy powder, aluminum powder, chromium powder and rare earth element compound powder, performing ball milling, adding a permeation aid, uniformly mixing, performing ball milling again to obtain mixture powder, and adding a dispersing agent, and uniformly mixing;

3) and drying the mixture powder at 80-120 ℃ under the protection of inert atmosphere to obtain the multi-element alloy co-permeation agent.

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