CN111705295A - Zinc-magnesium-aluminum zincizing agent, anti-corrosion metal piece and zincizing method - Google Patents
Zinc-magnesium-aluminum zincizing agent, anti-corrosion metal piece and zincizing method Download PDFInfo
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- 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
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- C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step
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Abstract
The application provides a zinc-magnesium-aluminum zincizing agent, an anti-corrosion metal piece and a zincizing method. The zinc-magnesium-aluminum zincing agent comprises the following components in parts by mass: 20-100 parts of metal powder, 40-80 parts of dispersing agent and 0.2-5 parts of decomposing agent, wherein the metal powder comprises 60-95 parts of zinc powder, 5-40 parts of magnesium powder and 1-3 parts of aluminum powder. The application provides a zinc magnalium zinc penetrating agent both can realize the infiltration of magnesium and aluminium at the in-process of zinc penetrating, and zinc can form high corrosion resistant zinc magnesium alloy phase and almag phase with magnesium, aluminium and magnesium to can improve the corrosion resisting property on layer that oozes by a wide margin, can also guarantee the aesthetic property of metalwork, satisfy different user demands.
Description
Technical Field
The application relates to the technical field of chemical heat treatment of the surface of a metal material, in particular to a zinc-magnesium-aluminum zincizing agent, an anti-corrosion metal piece and a zincizing method.
Background
Zincing is a chemical heat treatment process for impregnating the surface of a metal material with zinc. The zinc impregnation treatment is carried out on the surface of the metal material, so that the atmospheric corrosion resistance of the metal material can be obviously improved. Among them, powder zincification is widely applied to the surface anticorrosion treatment of metal parts because of a series of advantages of no hydrogen embrittlement, high bonding strength, good corrosion resistance and the like. At present, most of global railway fasteners, high-strength fasteners and the like adopt a powder zinc impregnation anti-corrosion treatment method for surface protection.
However, the existing powder zinc impregnation technology still has the problem of low corrosion resistance. A cementation layer is formed on the metal piece after the metal piece is subjected to zinc cementation by the powder zincification agent, the cementation layer formed by the zinc cementation by the powder zincification agent on the market at present mainly comprises a zinc-iron alloy phase and a zinc phase, the crystal structure of zinc is an anisotropic close-packed hexagonal structure, and lattice constants are represented by a and c. During the zincizing process, the growth of zinc has orientation, the zinc preferentially grows along the c-axis direction, and the self-diffusion coefficient of the zinc is nearly 20 times of that of the zinc in the direction parallel to the c-axis and in the direction perpendicular to the c-axis. And because the existence of anisotropy, the grain boundary between the zinc crystals is a weak grain boundary structure in the growth process, and in the corrosion process, the weak grain boundary structure is transparent to corrosive substances such as chloride ions, and the corrosive substances can directly penetrate through the grain boundary of zinc to enter a steel matrix, so that red rusty spots can appear on the surface of a seeping layer quickly, and the time when the red rusty appears on the surface can be generally judged as the salt spray corrosion resistance life in a salt spray performance test. The service life of the common permeable layer salt mist resistance is only dozens of hours, and the requirement of the engineering salt mist resistance for hundreds of hours or even thousands of hours can not be met. This requires surface sealing, Dacromet coating, etc. after powder zincing to advance the overall corrosion resistance. However, most of the surface sealing and dacromet are organic or inorganic coatings, and under the conditions of wind sand, erosion and the like in the actual use environment, the sealing layer is easily worn away, so that premature corrosion often occurs, and the metal part is prematurely failed.
At present, the prior art mainly realizes the improvement of the corrosion resistance of a zincification layer by adding methods such as aluminum, nickel, rare earth and the like, but the methods are still limited to the improvement of the corrosion resistance of the zincification layer in practical application, and a patent named as a zinc-nickel cementation layer ferrous metal corrosion prevention process discloses a component of the zinc-nickel cementation layer and a powder cementation process, wherein the content of nickel powder is 0.5 wt% -1.4 wt%, but when the powder cementation treatment is carried out at the temperature of 500 ℃, nickel is difficult to infiltrate to form a cementation layer, so that a cementation layer with high corrosion resistance is difficult to form, the corrosion resistance of the cementation layer is basically equivalent to that of the traditional powder zincification, and the effect of improving the corrosion resistance of the cementation layer is not achieved.
The magnesium is very active chemically and can react with O2、N2、H2Many non-metallic substances such as O and the like react, and the dosage is very difficult to control. Because of the special chemical property of magnesium, magnesium powder is rarely added into the zincizing agent in the prior art, even if the zincizing agent contains magnesium powder components, the dosage of the magnesium powder components is very small, the main effect is not realized by the magnesium powder, and the magnesium powder components are usually required to be matched with various other components for use. For example, a patent entitled "a highly active, fast-penetrating powder zincating agent" discloses a highly active, fast-penetrating powder zincating agent in which aluminum and magnesium are added to improve the activity of the zincating agent to achieve fast penetration and also to fail to achieve the effect of improving the corrosion resistance of the infiltrated layer. In addition, the magnesium powder added into the existing powder zincizing agent generally has the particle size of below 10 μm, and the content of the magnesium powder in the metal powder is less than 5%. The purpose of adding magnesium powder into the existing powder zincizing agent is to clean the surface of a metal piece mostly through the high-temperature reaction of the magnesium powder, and the particle size and the content of the magnesium powder are enough to achieve the purpose. However, magnesium powder having a particle size of less than 10 μm, although it can clean surfaces, is easily exploded, has low safety, and reacts to form gaseous compounds under high temperature conditions. In addition, in the case where the content of magnesium powder in the metal powder is less than 5%, it reacts almost entirely with the metal surface under high temperature conditions, resulting in no or little penetration into the infiltrated layer.
In addition, when magnesium powder is added to the zincating agent, the zinc-magnesium alloy phase formed by the infiltration of magnesium is black, which results in a gray black appearance of the final zincated layer and poor aesthetics.
Therefore, whether magnesium can be used in the zincating agent, whether magnesium can play a positive role in the zincating agent, and whether the addition of magnesium can bring unexpected effects to the zincating agent are problems which are not solved.
Disclosure of Invention
In view of this, the embodiments of the present application provide a zinc-magnesium-aluminum zincating agent, an anti-corrosion metal member, and a zincating method, so as to solve the technical defects in the prior art.
The application provides a zinc-magnesium-aluminum zincizing agent, which comprises the following components in parts by mass: 20-100 parts of metal powder, 40-80 parts of dispersing agent and 0.2-5 parts of decomposing agent, wherein the metal powder comprises 60-95 parts of zinc powder, 5-40 parts of magnesium powder and 1-3 parts of aluminum powder.
Further, the zinc, magnesium and aluminum zincing agent also comprises 0.5-3 parts of a first active agent capable of promoting magnesium to permeate into a cementation layer and 0.1-2 parts of a second active agent capable of promoting aluminum to permeate into the cementation layer, wherein the mass part of the second active agent is less than that of the first active agent;
preferably, the first active agent is a magnesium halide and the second active agent is an aluminum halide.
Further, the magnesium powder is pure magnesium powder or magnesium alloy powder;
preferably, the magnesium powder is pure magnesium powder with the purity of more than 95% or magnesium alloy powder with the weight ratio of magnesium not less than 40%.
Further, the dispersing agent is ceramic powder, and the decomposing agent is ammonium halide.
Preferably, the ceramic powder comprises at least one of alumina, silica, magnesia, aluminum nitride, silicon carbide;
more preferably, the ammonium halide includes at least one of ammonium chloride, ammonium fluoride, ammonium iodide, ammonium bromide, ammonium hydrogen fluoride.
Furthermore, the particle size of the magnesium powder is 10-500 μm, the particle size of the zinc powder is 1-200 μm, and the particle size of the dispersing agent is 5-500 μm.
Further, the zinc, magnesium and aluminum zinc impregnation agent also comprises manganese dioxide, and the mass part of the manganese dioxide is not more than that of the decomposition agent.
The application also provides an anti-corrosion metal part, wherein the surface of the anti-corrosion metal part is penetrated with zinc, magnesium and aluminum through the zinc-magnesium-aluminum zincating agent to form a penetrating layer capable of preventing the metal part from being corroded.
Further, the average content of magnesium in the seeping layer is 0.5 wt% -20 wt%;
preferably, the thickness of the infiltrated layer is 5 μm to 200 μm.
The application also provides a zincizing method, which comprises the following steps:
s1, performing oil and rust removal treatment on the metal piece to be subjected to zinc impregnation, and putting the treated metal piece and the zinc-magnesium-aluminum-zinc impregnation agent into a closed impregnation tank together;
s2, driving the air in the closed infiltration tank, and closing a valve of the closed infiltration tank;
and S3, heating the sealed infiltration tank to a preset temperature, and then preserving heat for 1-10 hours to finish zinc infiltration.
Further, in step S2, the sealed infiltration tank is vacuumized, or a protective atmosphere is introduced into the sealed infiltration tank to drive air in the sealed infiltration tank, and a valve of the sealed infiltration tank is closed.
In step S3, the closed infiltration tank is heated up to 360-415 ℃ or 320-480 ℃ and then is kept for 1-10 hours, thus completing the zinc infiltration.
The application provides a zinc magnesium aluminium zinc penetrating agent, including metal powder, dispersant and decomposer, wherein, metal powder includes zinc powder, magnesium powder and aluminite powder, and it has following technological effect:
on one hand, because of the anisotropy of zinc, the grain boundary between zinc crystals in the growth process is a weak grain boundary structure which is transparent to corrosive substances such as chloride ions and the like, the corrosive substances can directly penetrate through the weak grain boundary structure to corrode, and magnesium can gather at the weak grain boundary structure of zinc to form MgZn through high-temperature reaction2、Mg2Zn11And the like, so that a weak grain boundary structure is converted into a strong grain boundary structure which can effectively block corrosive substances such as chloride ions, and the corrosion resistance of a permeable layer can be greatly improved.
On the other hand, although the corrosion resistance of a cementation layer can be improved by adding magnesium powder into a zincizing agent, a zinc-magnesium alloy phase formed by the magnesium powder and zinc is black and extremely unattractive, and the problem can be solved by adding aluminum. Under the condition that magnesium powder and aluminum powder are added into the zinc-magnesium-aluminum sherardizing agent, magnesium firstly reacts with aluminum in the sherardizing layer to form a white aluminum-magnesium alloy phase, so that the appearance of the sherardizing layer is changed from black to silver gray, the attractiveness is greatly improved, and different use requirements can be better met.
More importantly, the aluminum-magnesium alloy phase formed by the reaction of aluminum and magnesium also has extremely high corrosion resistance, and the aluminum-magnesium alloy phase formed by the reaction in the infiltration layer and the zinc-magnesium alloy are interwoven together to construct a compact corrosion-resistant protective barrier, so that the corrosion resistance of the infiltration layer is greatly improved.
The magnesium powder is 5-40 parts by mass, so that the average content of magnesium in the infiltrated layer can be ensured to be between 0.5 wt% and 20 wt%, and the corrosion resistance of the infiltrated layer can be improved to the maximum extent. A large number of experiments prove that when the magnesium content in the infiltration layer is less than 0.5 wt%, namely the mass fraction of the magnesium powder is less than 5 parts, magnesium mainly reacts with oxygen in oxygen-containing substances and cannot enter the infiltration layer, and when the magnesium content in the infiltration layer is more than 20 wt%, namely the mass fraction of the magnesium powder is more than 40 parts, the magnesium content in the infiltration layer is higher, so that the formed magnesium alloy has more phases, and the corrosion resistance of the infiltration layer is obviously reduced on the contrary because the magnesium alloy is extremely non-corrosion-resistant. Compared with the common permeable layer, the permeable layer containing 0.5-20 wt% of magnesium can prolong the service life of the neutral salt fog resistance by tens of times, and has extremely high engineering application value and application prospect.
In addition, the zinc-magnesium-aluminum zincizing agent provided by the application can also comprise a first active agent and a second active agent, the first active agent is preferably magnesium halide, the second active agent is preferably aluminum halide, the magnesium halide can promote the interaction between magnesium and zinc, can promote the aggregation of magnesium at a zinc grain boundary, and further improves the corrosion resistance of a cementation layer, and the aluminum halide can accelerate the penetration of aluminum, and further improves the cementation layer quality.
The application provides an anticorrosion metalwork, its surface forms through above-mentioned zinc magnalium zincizing agent infiltration zinc, magnesium, aluminium and can prevent that the metalwork from corroding and pleasing to the eye practical infiltration layer, and magnesium and zinc interact form MgZn2、Mg2Zn11Zinc-magnesium alloy phase with high corrosion resistance, magnesium and aluminum are interacted to formThe aluminum-magnesium alloy phase has the advantages of attractive appearance and high corrosion resistance, a solid protective barrier is constructed for the metal piece, corrosion of corrosive substances such as chloride ions and the like to the metal piece is prevented, the corrosion resistance of the metal piece is effectively improved, the service life of the metal piece is prolonged, the appearance of a seeping layer is beautified, the cost is low, and the aluminum-magnesium alloy phase is easy to popularize and use.
The application provides a zinc impregnation method, through driving airtight air that oozes in the jar, can effectively avoid magnesium and air reaction in the zinc magnalium zinc impregnation agent, through right airtight jar that oozes carries out the intensification processing, not only can further drive airtight air that oozes in the jar, has still created the suitable environmental condition who accomplishes the metalwork zinc impregnation simultaneously, heats up and keeps warm 1-10 hours after the preset temperature, accomplishes zinc impregnation, and zinc impregnation is effectual, and the layer quality height that oozes. The zinc impregnation method is simple to operate, convenient to use, low in cost, high in economic benefit and wide in application range.
Drawings
FIG. 1 is a comparison of the appearance of a metal part according to an embodiment of the present application;
FIG. 2 is a 1000 hour cross-sectional view of a metal part infiltrated salt spray in accordance with an embodiment of the present disclosure;
FIG. 3 is a 2000 hour cross-sectional view of a salt spray coating of a metallic article according to an embodiment of the present disclosure;
FIG. 4 is a 4000 hour cross-sectional view of a salt spray coating of a metal part according to an embodiment of the present application;
FIGS. 5a and 5b are graphs comparing salt spray test results for one embodiment of the present application;
FIG. 6 is an electronic image of a surface of a infiltrated layer of a metallic article according to an embodiment of the present application;
FIG. 7 is a chart of the elemental content of a infiltrated layer of a metal article according to an embodiment of the present disclosure;
FIG. 8 is a cross-sectional view of a infiltrated layer of a metal article in accordance with an embodiment of the present disclosure;
fig. 9 is a graph of spectral analysis of a infiltrated layer of a metallic article according to an embodiment of the present disclosure.
Detailed Description
The following description of specific embodiments of the present application refers to the accompanying drawings.
In the present invention, unless otherwise specified, scientific and technical terms used herein have the meanings that are commonly understood by those skilled in the art. Also, the reagents, materials and procedures used herein are those that are widely used in the corresponding fields.
Example 1
The embodiment provides a zinc-magnesium-aluminum zincizing agent, which comprises the following components in parts by mass: 20-100 parts of metal powder, 40-80 parts of dispersing agent and 0.2-5 parts of decomposing agent, wherein the metal powder comprises 60-95 parts of zinc powder, 5-40 parts of magnesium powder and 1-3 parts of aluminum powder.
On one hand, the atomic radius of zinc is 0.1332 nanometers, the atomic radius of magnesium is 0.1598 nanometers, the difference between the atomic radii of the zinc and the magnesium is less than 15 percent, and meanwhile, the magnesium and the zinc are in a close-packed hexagonal structure, so that the magnesium and the zinc can jointly act to form a permeation layer. Although magnesium is not corrosion resistant by itself, it can occupy some of the zinc atom sites in the zinc crystal structure, particularly at the grain boundaries, and some amount of magnesium can accumulate at the zinc weak grain boundaries and form MgZn by high temperature reaction2、Mg2Zn11Equal zinc-magnesium alloy phase, MgZn2、Mg2Zn11The alloy phase itself is a high corrosion resistant phase, and the original weak grain boundary structure can be promoted to be changed into a strong grain boundary structure formed at the grain boundary, particularly, the strong grain boundary structure is opaque to corrosive substances such as chloride ions, and the corrosive substances can be blocked outside. At the same time, MgZn2、Mg2Zn11In the corrosion process of the zinc-magnesium alloy phase, a corrosion product is changed from a loose structure of common powder zinc impregnation into a compact structure, so that the corrosion resistance of the metal piece is greatly improved, and the service life of the metal piece is greatly prolonged.
Although the corrosion resistance of the infiltrated layer can be improved by adding the magnesium, the zinc-magnesium alloy phase formed by the magnesium and the zinc is black and extremely unattractive, and the problem can be just solved by adding the aluminum. Zinc in the zinc-magnesium-aluminum zincizing agent firstly reacts with aluminum in the zincizing layer to form a white aluminum-magnesium alloy phase, so that the appearance of the zincizing layer is changed from black to silver gray, the aesthetic property is greatly improved, and different use requirements can be better met.
Referring to fig. 1, fig. 1 is an appearance comparison diagram of two metal parts, wherein the upper metal part is subjected to zincification treatment by using the zincating agent of zinc, magnesium and aluminum provided in this embodiment to form a zincification layer, and the lower metal part is subjected to zincification treatment by using the zincating agent containing only zinc and magnesium and containing no aluminum to form a zincification layer, so that the appearance of the metal part zincification layer can be remarkably improved by adding a proper amount of aluminum to the zincification agent, and the aesthetic property of the zincification layer can be improved.
More importantly, the aluminum-magnesium alloy phase formed by the reaction of aluminum and magnesium also has extremely high corrosion resistance, and the aluminum-magnesium alloy phase formed by the reaction in the infiltration layer and the zinc-magnesium alloy are interwoven together to construct a compact corrosion-resistant protective barrier, so that the corrosion resistance of the infiltration layer is greatly improved.
On the other hand, the mass part of the magnesium powder in the zinc-magnesium-aluminum zincizing agent is 5-40 parts, which can ensure that 0.5 wt% -20 wt% of magnesium can be dissolved in a cementation layer, thereby promoting the formation of high corrosion resistant MgZn2、Mg2Zn11The alloy phase with equal height and corrosion resistance, thereby greatly improving the corrosion resistance life of the metal piece. Since magnesium itself is very active, magnesium generally preferentially reacts with oxygen in oxygen-containing substances, such as oxygen in air, oxygen in iron oxides, oxygen in zinc oxides, and once oxides with a certain content are formed on the surface of magnesium, magnesium is difficult to re-diffuse into the metal body. Compared with the permeable layer formed by the common zinc-magnesium-aluminum zincing agent, the permeable layer containing 0.5-20 wt% of magnesium can prolong the service life of neutral salt fog resistance by tens of times, and has extremely high engineering application value and application prospect.
If the magnesium content is too low, it will react mainly with the oxygen in the oxygen-containing species and thus not enter the infiltrated layer. Since magnesium cannot react directly with metal (such as iron), only zinc diffuses into the metal member in the initial stage of the reaction, and magnesium diffuses into zinc when the concentration of zinc in the zincate layer reaches a certain level, thereby forming a zincate layer containing magnesium. Particularly, when the content of magnesium in the zinc-magnesium-aluminum zincizing agent is less than 2 wt%, the magnesium cannot directly permeate into the metal piece in the initial stage of reaction, and the magnesium reacts with an oxide film on the surface of the metal piece and an oxide film on the surface of zinc to improve the reactivity. When the zinc content in the carburized layer reaches a condition where magnesium can permeate, since the magnesium content is too small and has been almost consumed by the initial reaction, a sufficient amount of active magnesium atoms cannot be supplied and thus cannot permeate into the carburized layer. If the magnesium content is too high, the formed magnesium alloy is too much, the corrosion resistance of a seeping layer is reduced on the contrary because the magnesium alloy is not corrosion-resistant, and the magnesium content is too high, so that explosion is easily caused, and the safety is low.
In addition, the magnesium powder can be pure magnesium powder with the purity of more than 95 percent, and can also be magnesium alloy powder with the weight ratio of magnesium of not less than 40 percent so as to provide enough magnesium atoms to permeate into the infiltration layer.
In this embodiment, the metal powder may be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, preferably 40 to 80 parts, more preferably 50 to 70 parts, the metal powder may include 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, preferably 70 to 90 parts, more preferably 75 to 85 parts, the magnesium powder may include 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, preferably 8 to 38 parts, more preferably 10 to 35 parts, the aluminum powder may include 1 to 3 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, and the like, each of which may be determined specifically, this is not limited by the present application.
It should be noted that, in the existing zincizing agent containing a zinc-magnesium-aluminum component, the content of aluminum is often greater than the content of magnesium, so as to achieve the purposes of improving the activity of the zincizing agent, improving the permeation rate, and the like, but the present application is different from the present application in that the content of magnesium in the zinc-magnesium-aluminum zincizing agent provided by the present application is significantly greater than the content of aluminum, so that it can be ensured that after the reaction of magnesium with aluminum is completed, a sufficient amount of magnesium can still react with zinc to form a zinc-magnesium alloy phase with high corrosion resistance, so as to achieve the purposes of improving the corrosion resistance of a permeation layer and prolonging the service life.
The particle size of the zinc powder is preferably 1 μm to 200 μm, and may be 1 μm, 10 μm, 30 μm, 50 μm, 100 μm, 150 μm, 200 μm, etc., and the particle size of the magnesium powder is preferably 10 μm to 500 μm, and may be 1 μm, 10 μm, 30 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, etc. If the particle size of the magnesium powder is less than 10 μm, the magnesium powder is very easy to explode, the safety is very low, and if the particle size of the magnesium powder is more than 500 μm, the activity and the permeation speed are rapidly reduced, so the particle size of the magnesium powder in this embodiment is not limited at will, and the effect is most stably exerted only if the particle size is in the range of 10 μm to 500 μm.
Specifically, the dispersant is preferably a ceramic powder including at least one of alumina, silica, magnesia, aluminum nitride, silicon nitride, and silicon carbide. Ceramic powder is added into the zinc-magnesium-aluminum zincizing agent provided by the embodiment, so that the metal powder can be effectively prevented from being bonded.
In the present embodiment, the particle size of the dispersant is preferably 5 μm to 500 μm, specifically 5 μm, 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, etc., and the mass fraction of the dispersant may be 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, etc., as the case may be, and the present application is not limited thereto.
Specifically, the decomposing agent is preferably an ammonia halide including at least one of ammonium chloride, ammonium fluoride, ammonium iodide, ammonium bromide, ammonium hydrogen fluoride, and preferably ammonium chloride. Under the temperature condition of powder zinc impregnation, the ammonia halide can be decomposed to provide ammonia and hydrogen halide gas, so that the ammonia halide gas can play a role in cleaning the surface of the metal piece, and the hydrogen halide gas can play a role in activating other components to promote the zinc impregnation. Wherein, the mass portion of the decomposer can be 0.2 portion, 0.5 portion, 1 portion, 1.5 portion, 2 portions, 2.5 portions, 3 portions, 3.5 portions, 4 portions, 4.5 portions, 5 portions and the like.
We analyzed the metal article carburized layer obtained after the zincating treatment using the zincating agent for zinc, magnesium and aluminum provided in this example, see fig. 2-4. Fig. 2 is a sectional view of the metal member after 1000 hours of salt spray coating, fig. 3 is a sectional view of the metal member after 2000 hours of salt spray coating, and fig. 4 is a sectional view of the metal member after 4000 hours of salt spray coating, which clearly shows that the addition of magnesium powder and aluminum powder can effectively improve the salt spray resistance and corrosion resistance of the metal member coating and greatly prolong the salt spray resistance life of the metal member when the zincating agent for zinc, magnesium, aluminum and zinc is applied to the metal member.
In summary, the zinc, magnesium, aluminum and zincating agent provided by this embodiment includes metal powder, a dispersant and a decomposer, wherein the metal powder includes zinc powder, magnesium powder and aluminum powder, so that infiltration of magnesium and aluminum can be realized in the zincating process, zinc and magnesium can form a highly corrosion-resistant zinc-magnesium alloy phase, and aluminum and magnesium can form an aluminum-magnesium alloy phase with both aesthetic property and corrosion resistance, so as to greatly improve the corrosion resistance of the cementation layer, and also ensure the aesthetic property of the metal part, and meet different use requirements.
Example 2
On the basis of embodiment 1, this embodiment provides a zinc-magnesium-aluminum zincating agent, which further includes 0.5 to 3 parts, such as 0.5 part, 1 part, 1.5 part, 2 parts, 2.5 parts, 3 parts, etc., of a first active agent capable of promoting magnesium penetration into the cementation layer, and 0.1 to 2 parts, such as 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 1.2 part, 1.5 part, 1.8 part, etc., of a second active agent capable of promoting aluminum penetration into the body side, which is not limited in this application.
Specifically, the first active agent is preferably a magnesium halide, the magnesium halide comprises at least one of magnesium chloride, magnesium fluoride, magnesium iodide and magnesium bromide, the second active agent is preferably an aluminum halide, and the aluminum halide comprises at least one of aluminum chloride, aluminum fluoride, aluminum iodide and aluminum bromide, and more preferably is aluminum fluoride.
Because in the powder zinc impregnation process, the magnesium halide is solid all the time, can be abundant with the metalwork surface and oozing the layer contact reaction to the infiltration of easier realization magnesium, and then add the magnesium halide as the activator, can impel the quick effectual infiltration layer of magnesium ability, can promote the interact between magnesium and the zinc, can promote the gathering of magnesium in zinc grain boundary department, and then effectively improve the corrosion resisting property who oozes the layer. Although ammonium halides such as ammonium chloride and ammonium fluoride also have an activating effect on the magnesium, the activating effect on the magnesium is not strong. Taking ammonium chloride as an example, ammonium chloride is decomposed by heating to generate ammonia and hydrogen chloride gas, and most of active magnesium atoms generated by the reaction of magnesium and gaseous hydrogen chloride cannot be attached to the surface of the infiltrated layer to react with the infiltrated layer.
Similarly, the aluminum halide is solid and can fully contact and react with the surface of the metal part and the infiltrated layer, so that the infiltration of aluminum is easier to realize, the reaction of aluminum and magnesium can be promoted, the formation of an aluminum-magnesium alloy phase is accelerated, the corrosion resistance of the infiltrated layer is further improved, and the appearance of the infiltrated layer of the metal part is improved.
In summary, the zincate for zinc, magnesium, aluminum provided by this embodiment includes a metal powder, a dispersant, a decomposition agent, a first activator, and a second activator, where the metal powder includes zinc powder, magnesium powder, and aluminum powder, so as to achieve magnesium infiltration during zincate, the zinc and magnesium can form a highly corrosion-resistant zinc-magnesium alloy phase, so as to greatly improve the corrosion resistance of the cementation layer, the aluminum and magnesium can form a corrosion-resistant aluminum-magnesium alloy phase, which can beautify the appearance, and the addition of the first activator and the second activator can further promote the magnesium powder infiltration into the cementation layer, further accelerate the reaction between zinc, magnesium, and aluminum, and further improve the performance of the zincate for zinc, magnesium, aluminum, and magnesium.
Example 3
This embodiment provides a zinc-magnesium-aluminum zincate based on embodiment 1 or 2, which further includes manganese dioxide, wherein the mass part of the manganese dioxide is not greater than the mass part of the decomposer, specifically, the mass part of the manganese dioxide may be 0 to 3 parts, such as 0.01 part, 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 1 part, 1.5 part, 2 parts, 2.5 parts, 3 parts, and the like, as the case may be, and the present application is not limited thereto.
In practice, the addition of manganese dioxide to the zincating agent of zinc-magnesium-aluminum can act as a catalyst for the infiltration reaction of magnesium, which promotes the diffusion of magnesium into the infiltrated layer by reacting with the ammonium halide acting as a decomposition agent. Firstly, ammonia and hydrogen halide gas are obtained by pyrolysis of ammonium halide, then the hydrogen halide gas reacts with manganese dioxide to obtain gases such as manganese halide and chlorine, the gases such as chlorine can provide a large amount of active ions, the active ions react with magnesium to generate active anhydrous magnesium halide gas, finally the active anhydrous magnesium halide gas can exchange with zinc in a zincing layer, and further magnesium is diffused into the zincing layer.
Taking ammonium chloride as an example, at 350 ℃, ammonium chloride begins to decompose to generate ammonia and hydrogen chloride, the hydrogen chloride reacts with manganese dioxide to generate manganese chloride and chlorine gas, the chlorine gas can provide a large amount of active chloride ions on the surface of the infiltration layer, the active chloride ions react with magnesium to generate active anhydrous magnesium chloride gas, and the active anhydrous magnesium chloride gas can perform a displacement reaction with zinc in the infiltration layer to promote the diffusion of magnesium into the infiltration layer.
Particularly, under the condition that the zinc-magnesium-aluminum zincizing agent also comprises a magnesium halide active agent, solid magnesium halide and gaseous magnesium halide can generate double catalytic infiltration, so that a magnesium source is pushed to continuously infiltrate into a zincizing layer, the zincizing layer can contain sufficient magnesium and react with zinc to form a zinc-magnesium alloy phase with high corrosion resistance, and the corrosion resistance of the zincizing layer is improved.
Example 4
This example provides an anticorrosive metal material, the surface of which is permeated with zinc and magnesium by the zincating agent for zinc, magnesium and aluminum according to any one of examples 1 to 3 to form a permeated layer capable of preventing corrosion of the metal material.
The metal piece with the cleaned surface and the zinc-magnesium-aluminum zincizing agent are put into a sealed container, heated to the temperature below the melting point (419.4 ℃) of zinc, and then kept warm for a certain time, and then cooled to room temperature along with a furnace, and a cementation layer capable of preventing the metal piece from being corroded is formed on the surface of the metal piece.
The average content of magnesium in the infiltrated layer is between 0.5 wt% and 20 wt%, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, etc., to ensure that the corrosion resistance of the infiltrated layer can be maximally improved. A large number of experiments prove that under the condition that the magnesium content in the infiltration layer is less than 0.5 wt%, namely the mass fraction of the magnesium is less than 5 parts, the magnesium mainly reacts with oxygen in oxygen-containing substances and cannot enter the infiltration layer, and under the condition that the magnesium content in the infiltration layer is more than 12 wt%, namely the mass fraction of the magnesium is more than 40 parts, the magnesium content in the infiltration layer is higher, so that the formed magnesium alloy has more phases, and the corrosion resistance of the infiltration layer is obviously reduced on the contrary because the magnesium alloy is extremely non-corrosion-resistant. Compared with the common permeable layer, the permeable layer containing 0.5-20 wt% of magnesium can prolong the service life of the neutral salt fog resistance by tens of times, and has extremely high engineering application value and application prospect.
The thickness of the infiltrated layer is preferably 20 to 100 μm, and it may be 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, etc., as the case may be, and the present application is not limited thereto.
Wherein the content of magnesium in the infiltrated layer decreases with increasing depth of the infiltrated layer, the magnesium content is higher at shallower positions in the infiltrated layer, and the magnesium content is lower at deeper positions in the infiltrated layer.
In addition, it should be noted that the surface magnesium content of the infiltrated layer may be more than 20%, because the surface magnesium content of the infiltrated layer is high due to the adhesion of excessive magnesium powder on the surface of the infiltrated layer. But the part only appears on the surface layer of the infiltrated layer, the surface layer of the infiltrated layer with high magnesium content can be quickly corroded along with the corrosion, and then the infiltrated layer which has the magnesium content of 0.5-20 wt% and can prevent the metal piece from being corroded is exposed, and in the infiltrated layer, magnesium can be gathered at the weak grain boundary of zinc and MgZn is formed through high-temperature reaction2、Mg2Zn11Equal zinc-magnesium alloy phase, MgZn2、Mg2Zn11The alloy phase itself is a high corrosion resistant phase, and the original weak grain boundary structure can be promoted to be changed into a strong grain boundary structure formed at the grain boundary, particularly, the strong grain boundary structure is opaque to corrosive substances such as chloride ions, and the corrosive substances can be blocked outside. At the same time, MgZn2、Mg2Zn11In the corrosion process of the zinc-magnesium alloy phase, a corrosion product is changed from a loose structure of common powder zinc impregnation into a compact structure, so that the corrosion resistance of the metal piece is greatly improved, and the service life of the metal piece is greatly prolonged.
Example 5
The embodiment provides a zincating method, which comprises steps S1 to S3.
S1, performing oil and rust removal treatment on the metal piece to be subjected to zinc impregnation, and putting the treated metal piece and the zinc-magnesium-aluminum zinc impregnation agent in the embodiment 1 or 2 into a closed infiltration tank together.
And S2, driving the air in the closed infiltration tank, and closing a valve of the closed infiltration tank.
In practical application, the closed infiltration tank can be vacuumized, or protective atmosphere is introduced into the closed infiltration tank to drive air in the closed infiltration tank, and a valve of the closed infiltration tank is closed. Among them, the protective atmosphere is preferably an inert gas.
And S3, heating the sealed infiltration tank to a preset temperature, and then preserving heat for 1-10 hours to finish zinc infiltration.
In practical application, the closed infiltration tank can be subjected to heating treatment, and the temperature is kept for 1 to 10 hours, such as 2 hours, 4 hours, 6 hours, 8 hours and the like, under the condition that the temperature is raised to 360 to 415 ℃ or 320 to 480 ℃, so that the zinc infiltration can be completed. Wherein, when the zinc-magnesium-aluminum zincizing agent is static powder, the preset temperature is preferably 360-415 ℃, such as 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 415 ℃ and the like, and when the zinc-magnesium-aluminum zincizing agent is dynamic powder, the preset temperature is preferably 320-480 ℃, such as 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃ and the like.
According to the zinc impregnation method provided by the embodiment, magnesium in the zinc-magnesium-aluminum zinc impregnation agent can be effectively prevented from reacting with air by driving the air in the closed impregnation tank, the air in the closed impregnation tank can be further driven by heating the closed impregnation tank, meanwhile, a suitable environmental condition for completing zinc impregnation of a metal piece is created, the temperature is kept for 1-10 hours after the temperature is raised to the preset temperature, the zinc impregnation is completed, the zinc impregnation effect is good, and the impregnation layer quality is high. The zinc impregnation method is simple to operate, convenient to use, low in cost, high in economic benefit and wide in application range.
Example 6
The zinc, magnesium, aluminum and zinc impregnation agent and the zinc impregnation method provided by the application bring remarkable improvements to multiple aspects which can be applied, and are specifically described by taking lightning protection electricity, railway fasteners and high-strength fasteners as examples.
Firstly, in the aspect of lightning protection and power connection, the corrosion prevention mode adopted by the existing lightning protection and power connection is generally electrolytic copper plating, on one hand, the electrolytic copper plating cost is very high, the processing cost of electrolytic copper plating for one ton of grounding parts is more than twenty thousand, on the other hand, in the environment such as alkaline soil, copper is easy to corrode, the grounding parts are easy to corrode in advance to lose effectiveness, and heavy metal pollution can be caused to the environment such as soil, water source and the like. At present, the corrosion resistance of products such as pure electro-galvanizing, hot galvanizing and powder zinc impregnation can not meet the requirement of a grounding standard, and sealing and other treatment are needed to meet the requirement of corrosion resistance, but once the sealing and other treatment are carried out, the conductivity of a grounding part is obviously reduced, and the requirement of the conductivity of lightning protection grounding can not be met.
The zinc, magnesium, aluminum and zinc penetrating agent and the zinc penetrating method provided by the application can perfectly solve the problems. As the magnesium powder and the aluminum powder are added into the zinc-magnesium-aluminum zincizing agent, the corrosion resistance of the zincized zinc-magnesium-aluminum zincizing agent is greatly improved, the corrosion resistance can meet the standard requirement without sealing and other treatments, the service life can be prolonged, and the zinc and the magnesium can not cause any pollution to the ecological environment. Meanwhile, the zinc, magnesium, aluminum and zinc impregnation agent and the zinc impregnation method provided by the application have the total cost of less than five thousand yuan/ton, and the overall cost of the lightning protection and electricity connection industry can be greatly reduced.
In the aspect of railway fasteners, at present, the railway fasteners are subjected to zinc impregnation treatment by a powder zinc impregnation and sealing treatment method generally, but under the high-vibration service environment of the railway, the actual service life of the railway fasteners is far short of the design requirement, the actual service life of the railway fasteners does not reach half of the design life, and the railway fasteners are replaced integrally.
By adopting the zinc-magnesium-aluminum zincizing agent and the zincizing method provided by the application, the corrosion resistance of the railway fastener can be greatly improved by realizing the infiltration of a proper amount of magnesium and aluminum in the seeping layer of the railway fastener, the service life of the railway fastener is greatly prolonged, and the high-standard requirements of special scenes such as subways can be completely met.
The zinc, magnesium, aluminum and zinc impregnation agent and the zinc impregnation method can completely realize the preparation of a high-corrosion-resistant zinc impregnation layer of a metal piece used for a railway, the service life of the neutral salt fog resistance of the metal piece after zinc impregnation can reach more than 1500 hours, and meanwhile, the subsequent sealing, Dacromet and other coating treatments can be omitted, so that the process is simplified, and the performance of the metal piece is greatly improved.
In the aspect of high-strength fasteners, for example, the wind power industry, wind power bolts in the wind power industry are high-strength fasteners, most of the methods adopted at present are powder zinc impregnation and sealing or Dacromet, and subsequent maintenance basically depends on paint brushing. Wind-powered electricity generation bolt is in case difficult the change after the installation, in case because corrosion problem breaks off inefficacy, can cause very big loss of property even casualties.
The problems can not occur by adopting the zinc-magnesium-aluminum zincizing agent and the zincizing method provided by the application. Magnesium element and aluminum element are introduced into the infiltration layer, and a zinc-magnesium alloy phase and an aluminum-magnesium alloy phase which are equal to each other and have corrosion resistance are formed in the thermal diffusion process. In the corrosion process of the infiltration layer, the magnesium-zinc alloy phase and the aluminum-magnesium alloy phase can promote the generation of compact and insoluble corrosion products; at the same time, MgZn2The self structure of the isoalloy structure is compact, and the corrosion rate is effectively reduced. When the surface of the infiltrated layer is scratched, a compact compound layer can be quickly formed on the damaged part to prevent further corrosion, so that the infiltrated layer has a self-repairing function and can be perfectly suitable for high-strength fasteners.
Example 7
In this example, a test group and a control group were provided, and the composition of the zincating agent in each group is shown in Table 1.
TABLE 1 composition schematic table of zincizing agent for each group of Zn, Mg and Al
The results of subjecting the metal pieces to zincating treatment using the zincating agents of the test group and the control group and the zincating method described in example 5 and performing a salt spray test are shown in table 2, fig. 5a, and fig. 5 b.
TABLE 2 comparison table of salt spray test results of test group and control group
Under the condition of containing zinc powder and aluminum powder, the corrosion resistance of the infiltrated layer is the worst, and the corrosion resistance of the infiltrated layer is basically equivalent to that of pure infiltrated zinc. In the test group 2, under the condition that the zincizing agent contains zinc powder and magnesium powder, the corrosion resistance of the zincizing layer is obviously improved, and in the test group 3, a certain amount of aluminum is added on the basis of the test group 2, and the corrosion resistance is basically equivalent to that of the test group 2 without aluminum. Meanwhile, the neutral salt spray corrosion resistance time of the test group 2 and the test group 3 is 500 hours.
The test group 4 and the test group 5 were both added with magnesium fluoride energizer, and the test group 5 was also added with aluminum fluoride energizer. The neutral salt spray corrosion resistance time of the test group 4 and the test group 5 reaches 2000 hours, which shows that the magnesium halide is added to promote the penetration of magnesium, so that the corrosion resistance is improved. Meanwhile, aluminum halide is added into the test group 5 as an aluminum energizer, so that the appearance quality of the workpiece can be improved. In fig. 1, the 11-10-a sample is a sample corresponding to test group 5, and the 11-10-B sample is a sample corresponding to test group 4, although the neutral salt spray corrosion resistance time of the two samples is equivalent, the appearance of the sample 11-10-a added with aluminum is silver gray, which is obviously better than the gray black appearance of the sample 11-10-B without aluminum, and can better meet the aesthetic requirement.
In the test group 6, a manganese dioxide activator is added on the basis of the test group 5, as shown in fig. 6, fig. 6 is an electronic image of the surface of the infiltrated layer of the metal part of the test group 6 observed under a microscope, and a spectrogram analysis is performed on a part in a square frame, and as shown in fig. 7, it can be seen that in the infiltrated layer of the metal part of the test group 6, the content of zinc accounts for 36.8 wt%, the content of magnesium accounts for 19.4 wt%, and the content of aluminum accounts for 4.3 wt%. Immediately after the start of the test, the cross section of the metal infiltrated layer of test group 6 was as shown in fig. 8, and the portion in the box of fig. 8 was subjected to energy spectrum component analysis, and the results were as shown in fig. 9, and quantitative analysis was performed by the eZAF quantitative method, and the results are as shown in table 3.
Table 3 table of results of eZAF quantitative analysis of metal part infiltrated layer of test group 6
| Element(s) | By weight% | Atom% | Net strength | Net intensity error |
| MgK | 4.47 | 10.67 | 51.48 | 0.05 |
| AlK | 2.52 | 5.41 | 42.14 | 0.07 |
| FeK | 8.88 | 9.23 | 172.7 | 0.03 |
| ZnK | 84.13 | 74.69 | 667.39 | 0.01 |
The addition of manganese dioxide in test group 6 promoted the synergistic infiltration effect of magnesium and aluminum, further improving corrosion resistance. The neutral salt spray corrosion resistance time of the zinc alloy is rapidly increased from 2000 hours to 4000 hours, the existing zinc corrosion resistance can be increased to a new height, the problems of a large amount of economic loss, casualties and the like caused by corrosion problems are effectively reduced, and the zinc alloy has extremely high engineering application value for corrosion protection of steel parts.
Therefore, the zinc-magnesium-aluminum-zincizing agent provided by the application is characterized in that magnesium powder and aluminum powder are innovatively added into the zincizing agent, so that the corrosion resistance of a permeable layer can be obviously improved, the appearance of a permeable layer of a metal piece can be effectively improved, the components such as the metal powder, a decomposer, a dispersant and an activator interact and supplement with each other, an attractive and solid permeable layer protection barrier is constructed for the metal piece, and the service life of the metal piece is greatly prolonged.
In this document, "upper", "lower", "front", "rear", "left", "right", and the like are used only to indicate relative positional relationships between relevant portions, and do not limit absolute positions of the relevant portions.
In this document, "first", "second", and the like are used only for distinguishing one from another, and do not indicate the degree and order of importance, the premise that each other exists, and the like.
In this context, "equal", "same", etc. are not strictly mathematical and/or geometric limitations, but also include tolerances as would be understood by a person skilled in the art and allowed for manufacturing or use, etc.
Unless otherwise indicated, numerical ranges herein include not only the entire range within its two endpoints, but also several sub-ranges subsumed therein.
The preferred embodiments and examples of the present application have been described in detail with reference to the accompanying drawings, but the present application is not limited to the embodiments and examples described above, and various changes can be made within the knowledge of those skilled in the art without departing from the concept of the present application.
Claims (10)
1. The zinc-magnesium-aluminum zincizing agent is characterized by comprising the following components in parts by mass: 20-100 parts of metal powder, 40-80 parts of dispersing agent and 0.2-5 parts of decomposing agent, wherein the metal powder comprises 60-95 parts of zinc powder, 5-40 parts of magnesium powder and 1-3 parts of aluminum powder.
2. The zincate-magnesium-aluminum zincate as claimed in claim 1, further comprising 0.5 to 3 parts of a first active agent capable of promoting the penetration of magnesium into the cementation layer and 0.1 to 2 parts of a second active agent capable of promoting the penetration of aluminum into the cementation layer, wherein the mass part of the second active agent is less than that of the first active agent;
preferably, the first active agent is a magnesium halide and the second active agent is an aluminum halide.
3. The zincate-magnesium-aluminum zincating agent as set forth in claim 1, wherein the magnesium powder is pure magnesium powder or magnesium alloy powder;
preferably, the magnesium powder is pure magnesium powder with the purity of more than 95% or magnesium alloy powder with the weight ratio of magnesium not less than 40%.
4. The zincate-magnesium-aluminum zincating agent as set forth in claim 1, wherein the dispersant is ceramic powder and the decomposing agent is ammonium halide.
Preferably, the ceramic powder comprises at least one of alumina, silica, magnesia, aluminum nitride, silicon carbide;
more preferably, the ammonium halide includes at least one of ammonium chloride, ammonium fluoride, ammonium iodide, ammonium bromide, ammonium hydrogen fluoride.
5. The zincating agent for magnesium aluminum as claimed in claim 1, wherein the particle size of the magnesium powder is 10 μm to 500 μm, the particle size of the zinc powder is 1 μm to 200 μm, and the particle size of the dispersing agent is 5 μm to 500 μm.
6. The zincate of claim 1, further comprising manganese dioxide, wherein the mass fraction of manganese dioxide is not greater than the mass fraction of the decomposer.
7. An anti-corrosion metal article characterized in that the surface of the anti-corrosion metal article is permeated with zinc, magnesium and aluminum by the zincating agent for zinc, magnesium and aluminum according to any one of claims 1 to 6 to form a permeated layer capable of preventing corrosion of the metal article.
8. The anti-corrosion metal article of claim 7, wherein the average content of magnesium in the infiltrated layer is from 0.5 wt.% to 20 wt.%;
preferably, the thickness of the infiltrated layer is 5 μm to 200 μm.
9. A zincating method, comprising:
s1, performing oil and rust removal treatment on a metal piece to be subjected to zinc impregnation, and putting the treated metal piece and the zinc-magnesium-aluminum-zinc impregnation agent as claimed in any one of claims 1 to 6 into a closed impregnation tank;
s2, driving the air in the closed infiltration tank, and closing a valve of the closed infiltration tank;
and S3, heating the sealed infiltration tank to a preset temperature, and then preserving heat for 1-10 hours to finish zinc infiltration.
10. The zincizing method according to claim 9, wherein in step S2, the sealed infiltration tank is vacuumized, or a protective atmosphere is introduced into the sealed infiltration tank to drive air in the sealed infiltration tank, and a valve of the sealed infiltration tank is closed.
In step S3, the closed infiltration tank is heated up to 360-415 ℃ or 320-480 ℃ and then is kept for 1-10 hours, thus completing the zinc infiltration.
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