CN115770719A - Zinc-aluminum-magnesium material surface coating treatment process capable of preventing coating from being stamped and falling off - Google Patents
Zinc-aluminum-magnesium material surface coating treatment process capable of preventing coating from being stamped and falling off Download PDFInfo
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Abstract
The invention relates to the technical field of material surface treatment, in particular to a zinc-aluminum-magnesium material surface coating treatment process capable of preventing a coating from being stamped and falling off, wherein the zinc-aluminum-magnesium material surface is treated by utilizing a screening (polishing) -nicking-acid leaching soaking washing process, so that the surface treatment effect is improved, and the subsequent surface coating adhesion effect is favorably improved; meanwhile, the coating slurry dipping-oscillating-standing-vacuum drying treatment process is introduced, so that the coating is prevented from being formed uniformly, the coating is prevented from being oxidized due to contact with air in the hardening process, the coating forming effect is improved, the flexibility and the adhesiveness of the coating are improved, the coating is effectively prevented from falling off when being stamped, and the protection effect on the zinc-aluminum-magnesium material is enhanced.
Description
Technical Field
The invention relates to the technical field of material surface treatment, in particular to a zinc-aluminum-magnesium material surface coating treatment process capable of preventing a coating from being stamped and falling off.
Background
The zinc-aluminum-magnesium material is an alloy material containing zinc, aluminum and magnesium, has the characteristics of light weight and the like, and is also called as light metal. However, different contents of zinc, aluminum, magnesium and other components in the zinc-aluminum-magnesium material affect various performances of the zinc-aluminum-magnesium material, such as: the aluminum component is too much, which can cause the poor wear resistance of the surface of the metal material; the magnesium component is too much, which results in poor corrosion resistance. The traditional zinc-aluminum-magnesium alloy is formed by adding a proper amount of zinc in an aluminum-magnesium alloy process, and the zinc is generally high in cost and extremely low in addition amount, so that the main components in the zinc-aluminum-magnesium material are aluminum and magnesium components. Because the zinc-aluminum-magnesium material contains all metals with the highest chemical activity in industrial alloys, the magnesium-containing alloy is easier to be oxidized compared with other aluminum alloys, especially in a humid environment, the oxidation corrosion effect is more obvious, a large amount of white spots are formed on the surface, the attractiveness and even the mechanical property of the zinc-aluminum-magnesium alloy are influenced, the abrasion resistance and corrosion resistance of the zinc-aluminum-magnesium material are poor, and the application of the zinc-aluminum-magnesium material is severely limited.
The surface modification treatment can overcome the defects of poor wear resistance and corrosion resistance of the zinc-aluminum-magnesium material on the basis of keeping the overall performance of light metals such as the zinc-aluminum-magnesium material and the like, and the surface modification treatment is widely concerned and researched at home and abroad, so that a great amount of technologies related to metal surface modification treatment are formed. For example: patent No. 200410009189.7 discloses that placing medium ball, composite powder and the part to be treated in a closed container, heating and mechanical vibration modes in a furnace are adopted, so that under the combination of heat energy, mechanical impact and the like, a plurality of physical and chemical processes such as diffusion, reaction, sintering and the like are carried out simultaneously, the purpose of forming an alloy coating on the surface of the part to be treated is met, the defects of high heating temperature, long heat preservation time and high energy consumption of the traditional metal infiltration process are overcome, and meanwhile, the defects of weak impact effect, limited action effect and the like of small particles are overcome. However, this method is processed in a closed space, resulting in failure to process large-area parts.
For another example: the preparation method of the light metal surface compound coating disclosed in the patent number 201310701052.7 comprises the steps of treating the surface of light metal by a laser fusing method, presetting metal powder for alloying on the surface of the light metal subjected to the laser fusing treatment, treating the surface of the light metal with the preset powder by laser shot blasting under the condition of medium temperature, accelerating the diffusion reaction of the preset powder and a metal matrix to prepare the surface compound coating, reducing the formation temperature of the compound coating, increasing the thickness of the surface compound coating, refining the microstructure of the expressed compound coating, and improving the surface performance of the light metal. However, the laser treatment cost is high, the depth of action on the surface of the light metal is deep, and the laser treatment method is used for treating the zinc-aluminum-magnesium light metal and easily causes the structural performance of a zinc-aluminum-magnesium matrix to change.
For another example: the technology for the high-oxidation-resistance nano coating on the surface of the magnesium aluminum part disclosed by the patent application No. 202121762204.9 comprises the steps of carrying out appearance inspection and screening on the appearance surface of the magnesium aluminum part, removing the aluminum magnesium part which is deformed and has the appearance surface with deep scratches of more than 0.1mm, polishing the appearance surface of the aluminum magnesium part with white spots and rusts, and removing an oxide layer on the surface of the aluminum magnesium part; and cleaning the surface of the polished and derusted magnesium aluminum part, removing residual metal powder on the surface of the magnesium aluminum part, and then putting the magnesium aluminum part into pickling equipment for pickling. The magnesium aluminum part is treated by adopting an acid washing activation process, a chemical nickel plating layer can be directly obtained through deposition, and then the nano coating is sprayed, so that a plurality of layers of protection are formed on the surface of the magnesium aluminum part, and the nano coating can be attached to the nickel plating layer, so that the adhesion is enhanced; the nano coating is formed by a spraying process, so that the nano coating is easy to fall off when being impacted.
In view of the technical defects, in order to form a better surface coating on the surface of the zinc-aluminum-magnesium material, the enhanced coating and the surface of the zinc-aluminum-magnesium material are attached into a whole, meanwhile, the influence on the internal crystal phase structure of the zinc-aluminum-magnesium material is avoided, and the zinc-aluminum-magnesium material processing method can be suitable for processing zinc-aluminum-magnesium materials of various sizes.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a zinc-aluminum-magnesium material surface coating treatment process capable of preventing a coating from being stamped and falling off.
The method is realized by the following technical scheme:
the zinc-aluminum-magnesium material surface coating treatment process capable of preventing the coating from being stamped and falling comprises the following steps:
(1) Screening a zinc-aluminum-magnesium material without white spots or polishing the zinc-aluminum-magnesium material with white spots until no white spots exist to obtain a qualified zinc-aluminum-magnesium material;
(2) Etching a plurality of notches with the depth of 0.01-0.07mm on the surface of the qualified zinc-aluminum-magnesium material, then cleaning the surface, removing metal powder on the surface of the zinc-aluminum-magnesium material, soaking and pickling with a pickling agent, washing with deionized water, and drying in a vacuum environment to obtain a pickled zinc-aluminum-magnesium material;
(3) And (3) putting the acid-washed zinc-aluminum-magnesium material into the coating slurry for dipping, vibrating the acid-washed zinc-aluminum-magnesium material for 50-80 times/min for 10min, standing for 3min, taking out, placing in a vacuum environment for drying at constant temperature, detecting that the surface has no cracks, and coating and packaging.
The surface of the zinc-aluminum-magnesium material is treated by using a screening (polishing) -nicking-acid leaching-soaking process, so that the surface treatment effect is improved, and the subsequent surface coating adhesion effect is improved; meanwhile, the coating slurry dipping-oscillating-standing-vacuum drying treatment process is introduced, so that the coating is prevented from being formed uniformly, the coating is prevented from being oxidized due to contact with air in the hardening process, the coating forming effect is improved, the flexibility and the adhesiveness of the coating are improved, the coating is effectively prevented from falling off when being stamped, and the protection effect on the zinc-aluminum-magnesium material is enhanced.
In order to ensure the pickling effect and improve the subsequent coating forming effect, preferably, the pickling agent contains Zn 2+ 80-100mg/L of Al 3+ 5-10mg/L, 10-20g/L oxalic acid, and the temperature is 30-50 ℃. More preferably, the pickling agent is Zn-containing 2+ 90mg/L of Al 3+ 8mg/L, 15g/L oxalic acid and water are prepared into 1L, and the temperature is 40 ℃.
To avoid strong acid formsThe corrosion is enhanced, the acid washing process influences the surface crystal phase structure of the zinc-aluminum-magnesium material, preferably, the Zn 2+ Is provided by adding zinc sulfate, and the Al 3+ Provided using aluminum ammonium sulfate.
In order to guarantee the drying effect and prevent the preformed film layer and the coating from cracking and affecting the protection effect, preferably, in the step (2), the vacuum environment is 60-80kPa, the drying temperature is 40-60 ℃, and the drying treatment time is 10-20min. More preferably, in the step (3), the vacuum degree is 60-80kPa, the constant-temperature drying temperature is 40-60 ℃, and the drying treatment time is 10-20min.
In order to ensure that deposition and film formation can occur on the surface of the zinc-aluminum-magnesium material in the soaking process and the formation of a coating structure is realized, the coating slurry is preferably 5-7 parts by mass of sodium sulfate, 10-15 parts by mass of alumina sol, 8-12 parts by mass of cobalt oxide, 0.1-0.5 part by mass of zinc oxide and 100-150 parts by mass of absolute ethyl alcohol. More preferably, the coating slurry comprises 6 parts by mass of sodium sulfate, 12 parts by mass of alumina sol, 9 parts by mass of cobalt oxide, 0.4 part by mass of zinc oxide and 130 parts by mass of absolute ethyl alcohol. More preferably, the solid content of the alumina sol is more than or equal to 15%, the particle size of the cobalt oxide is less than or equal to 50 mu m, and the particle size of the zinc oxide is less than or equal to 50 mu m.
In order to improve the flexibility of the coating and improve the anti-impact pressure-drop effect, the coating slurry preferably contains 3-10% of ammonium bicarbonate powder by mass of sodium sulfate.
Compared with the prior art, the technical effects created by the invention are as follows:
according to the invention, in the pickling process of the pickling agent, the effects of particle deposition adhesion and filling are introduced, the activation layer is formed on the surface of the zinc-aluminum-magnesium material by adopting a shallow mark carving mode, meanwhile, the combination of gel film forming and particle deposition performance in the coating slurry dipping process is introduced, the stable forming of the coating structure and the activation layer structure is realized, the adhesion on the surface of the zinc-aluminum-magnesium material is enhanced, and then the effect of resisting impact pressure and falling is improved.
The invention has simple process flow and low manufacturing cost, and the adopted pickling agent and the coating slurry can be recycled, thereby being beneficial to reducing environmental pollution, reducing the surface protection treatment cost of the zinc-aluminum-magnesium material and ensuring the surface protection effect of the zinc-aluminum-magnesium material.
Drawings
FIG. 1 is the overall process flow diagram created by the present invention.
Detailed Description
The technical solution of the present invention is further defined in the following description with reference to the accompanying drawings and the specific embodiments, but the scope of the claimed invention is not limited to the description.
As shown in fig. 1, in some embodiments, the process for treating a surface coating of a zinc-aluminum-magnesium material to prevent the coating from being removed by stamping includes the following steps:
(1) Screening a zinc-aluminum-magnesium material without white spots or polishing the zinc-aluminum-magnesium material with white spots until no white spots exist to obtain a qualified zinc-aluminum-magnesium material; the surface of the zinc-aluminum-magnesium material to be treated is not oxidized, and the adhesion stability of a subsequent coating is ensured;
(2) Etching a plurality of nicks with the depth of 0.01-0.07mm on the surface of the qualified zinc-aluminum-magnesium material, and then cleaning the surface to remove metal powder on the surface of the zinc-aluminum-magnesium material; the method is favorable for depositing and attaching particle components in the pickling agent to corresponding notches in the pickling process of the pickling agent, and simultaneously avoids the phenomenon that the overall performance of the zinc-aluminum-magnesium material is influenced due to the fact that the crystal phase structure of the zinc-aluminum-magnesium material is damaged due to the over-deep notches; soaking and pickling with a pickling agent, washing with deionized water, and drying in a vacuum environment to obtain a pickled zinc-aluminum-magnesium material; the adhesion force of the preformed particle components in the pickling agent adhered to the surface of the zinc-aluminum-magnesium material is facilitated to enhance the coating effect formed by the subsequent process, the coating preparation procedure is simplified, and the coating preparation difficulty is reduced;
(3) And (3) putting the acid-washed zinc-aluminum-magnesium material into the coating slurry for dipping, vibrating the acid-washed zinc-aluminum-magnesium material for 50-80 times/min for 10min, standing for 3min, taking out, placing in a vacuum environment for drying at constant temperature, detecting that the surface has no cracks, and coating and packaging. The forming uniformity of the coating and the flexibility in the forming and hardening process are improved, the strength attached to the surface of the zinc-aluminum-magnesium material is enhanced, and the impact pressure and falling resistant effect is improved.
The invention eliminates the surface oxide layer of the zinc-aluminum-magnesium material, strictly limits the notch depth by utilizing the notch, combines the pickling agent pickling-vacuum drying process to improve the forming effect of the surface coating of the zinc-aluminum-magnesium material in the subsequent process, and combines the coating slurry to dip and pickle the zinc-aluminum-magnesium material, oscillate, stand and form the coating by the vacuum environment constant temperature drying process, thereby enhancing the anti-impact pressure falling-off capability of the surface coating of the zinc-aluminum-magnesium material and improving the anti-oxidation protection effect of the zinc-aluminum-magnesium material.
In some research examples of the invention, the pickling agent is Zn-containing 2+ 80-100mg/L of Al 3+ 5-10mg/L, 10-20g/L oxalic acid and 30-50 ℃. For example: according to the Zn content in the pickling agent 2+ 80mg/L of Al 3+ 5mg/L, 10g/L oxalic acid and water are added to prepare 1L, and the temperature is adjusted to 30 ℃. For another example: according to the Zn content in the pickling agent 2+ 100mg/L of Al 3+ 10mg/L, 20g/L oxalic acid and water are added to prepare 1L, and the temperature is adjusted to be 50 ℃. For another example: according to the Zn content in the pickling agent 2+ 90mg/L of Al 3+ 8mg/L, 15g/L oxalic acid and water are added to prepare 1L, and the temperature is adjusted to 40 ℃. For another example: according to the Zn content in the pickling agent 2+ 80mg/L, containing Al 3+ 10mg/L, 15g/L oxalic acid and water are added to prepare 1L, and the temperature is adjusted to 40 ℃. For another example: according to the Zn content in the pickling agent 2+ 90mg/L of Al 3+ 10mg/L, 10g/L oxalic acid and water are added to prepare 1L, and the temperature is adjusted to be 50 ℃. For another example: according to the Zn content in the pickling agent 2+ 100mg/L of Al 3+ 8mg/L, 15g/L oxalic acid and water are added to prepare 1L, and the temperature is adjusted to 30 ℃. Fully ensured can not lead to the fact excessive corrosion to zinc-aluminium magnesium material surface in the pickling agent pickling process, prevent to zinc-aluminium magnesium material surface crystalline phase structure destruction, ensured zinc-aluminium magnesium material comprehensive properties, simultaneously, introduce zinc, aluminium plasma for deposit in the pickling process in zinc-aluminium magnesium material surface formed shallow nick, the adhesive force that reinforcing zinc-aluminium magnesium material surface coating formed. Said Zn 2+ Is provided by adding zinc sulfate, and the Al 3+ Provided using aluminum ammonium sulfate. The principle of strong acid to weak acid is fully utilized to prevent the formation of strong corrosive acid.
In some research embodiments of the invention, in the step (2), the vacuum degree is 60-80kPa, the drying temperature is 40-60 ℃, and the drying treatment time is 10-20min. Fully ensures that an activated layer (particle deposition pre-formed film) formed on the surface of the zinc-aluminum-magnesium material in the acid washing process is hardened and adhered to the surface of the zinc-aluminum-magnesium material.
In some research embodiments of the invention, in the step (3), the vacuum degree is 60-80kPa, the constant-temperature drying temperature is 40-60 ℃, and the drying treatment time is 10-20min. The adhesion strength between the coating slurry component and the activation layer formed by acid cleaning is enhanced, the stability of the zinc-aluminum-magnesium material surface coating structure is improved, the stamping falling rate is reduced, and the surface protection effect on the zinc-aluminum-magnesium material is improved.
The coating slurry introduced by the researchers in the research process utilizes the sol film-forming property and the microparticle deposition property, and further in the research embodiment created by the invention, the coating slurry comprises 5-7 parts by mass of sodium sulfate, 10-15 parts by mass of alumina sol, 8-12 parts by mass of cobalt oxide, 0.1-0.5 part by mass of zinc oxide and 100-150 parts by mass of absolute ethyl alcohol. For example: the coating slurry comprises, by mass, 5 parts of sodium sulfate, 10 parts of alumina sol, 8 parts of cobalt oxide, 0.1 part of zinc oxide and 100 parts of absolute ethyl alcohol. For another example: the coating slurry comprises 7 parts by mass of sodium sulfate, 15 parts by mass of alumina sol, 12 parts by mass of cobalt oxide, 0.5 part by mass of zinc oxide and 150 parts by mass of absolute ethyl alcohol. For another example: the coating slurry comprises, by mass, 6 parts of sodium sulfate, 12 parts of alumina sol, 9 parts of cobalt oxide, 0.4 part of zinc oxide and 130 parts of absolute ethyl alcohol. For another example: the coating slurry comprises, by mass, 5 parts of sodium sulfate, 15 parts of alumina sol, 8 parts of cobalt oxide, 0.5 part of zinc oxide and 100 parts of absolute ethyl alcohol. For another example: the coating slurry comprises 7 parts by mass of sodium sulfate, 15 parts by mass of alumina sol, 8 parts by mass of cobalt oxide, 0.1 part by mass of zinc oxide and 100 parts by mass of absolute ethyl alcohol. Can interact with the pickling agent and the pickling process, a coating structure with better toughness is formed on the surface of the zinc-aluminum-magnesium material, the coating is prevented from falling off due to stamping, and the protection effect on the surface of the zinc-aluminum-magnesium material is enhanced.
In the related research created by the invention, the solid content of the alumina sol is more than or equal to 15%, the particle size of the cobalt oxide is less than or equal to 50 μm, and the particle size of the zinc oxide is less than or equal to 50 μm.
In a more preferred embodiment, the coating slurry contains 3-10% by mass sodium sulfate of ammonium bicarbonate powder. The stamping resistance effect of the coating is enhanced.
In order to better explain the technical effects of the technical solutions of the present invention, the following descriptions and explanations will be made by the relevant experiments conducted during the research of researchers so as to enable those skilled in the art to fully understand and understand the technical solutions of the present invention.
Test 1: research on surface protection effect of zinc-aluminum-magnesium material by coating preparation process
Example 1
(1) Screening the zinc-aluminum-magnesium material without white spots to obtain a qualified zinc-aluminum-magnesium material;
(2) Scratching the surface of the qualified zinc-aluminum-magnesium material with a plurality of nicks with the depth of 0.01-0.07mm, cleaning the surface, removing metal powder on the surface of the zinc-aluminum-magnesium material, soaking and pickling the zinc-aluminum-magnesium material by using a pickling agent, washing the zinc-aluminum-magnesium material by using deionized water, and drying the zinc-aluminum-magnesium material for 10min at 40 ℃ in a vacuum environment with the vacuum degree of 60kPa to obtain a pickled zinc-aluminum-magnesium material; the pickling agent is prepared by adding zinc sulfate, ammonium aluminum sulfate and oxalic acid into water to prepare Zn-containing pickling agent 2+ 80mg/L of Al 3+ 5mg/L and 10g/L oxalic acid, and in the acid washing process, the temperature of the mixed solution is adjusted to be 30 ℃.
(3) Soaking the acid-washed zinc-aluminum-magnesium material in the coating slurry, vibrating the acid-washed zinc-aluminum-magnesium material for 50 times/min for 10min, standing for 3min, taking out, drying at a constant temperature of 40 ℃ for 10min in a vacuum environment with a vacuum degree of 60kPa, detecting that no crack exists on the surface, and coating and packaging. The coating slurry is prepared by mixing 5g of sodium sulfate, 10g of alumina sol, 8g of cobalt oxide, 0.1g of zinc oxide and 100g of absolute ethyl alcohol by mass, and stirring at 1000r/min for 30min, wherein the solid content of the alumina sol is 15%, the particle size of the cobalt oxide is 10-50 mu m, and the particle size of the zinc oxide is 10-50 mu m.
Example 2
(1) Polishing the zinc-aluminum-magnesium material with the white spots until no white spots exist to obtain a qualified zinc-aluminum-magnesium material;
(2) Scratching the surface of the qualified zinc-aluminum-magnesium material to form a plurality of scratches with the depth of 0.01-0.07mm, cleaning the surface, removing metal powder on the surface of the zinc-aluminum-magnesium material, soaking and pickling the zinc-aluminum-magnesium material by using a pickling agent, washing the zinc-aluminum-magnesium material by using deionized water, and drying the zinc-aluminum-magnesium material for 20min at the temperature of 60 ℃ in a vacuum environment with the vacuum degree of 80kPa to obtain a pickled zinc-aluminum-magnesium material; the pickling agent is prepared by adding zinc sulfate, ammonium aluminum sulfate and oxalic acid into water to prepare Zn-containing pickling agent 2+ 100mg/L of Al 3+ 10mg/L and 20g/L of oxalic acid, and in the acid washing process, the temperature of the mixed solution is adjusted to be 50 ℃.
(3) Soaking the acid-washed zinc-aluminum-magnesium material in the coating slurry, vibrating the acid-washed zinc-aluminum-magnesium material for 10min for 80 times/min, standing for 3min, taking out, drying at a constant temperature of 60 ℃ for 20min in a vacuum environment with a vacuum degree of 80kPa, detecting that no crack exists on the surface, and coating and packaging. The coating slurry is prepared by mixing 7g of sodium sulfate, 15g of alumina sol, 12g of cobalt oxide, 0.5g of zinc oxide and 150g of absolute ethyl alcohol by mass, and stirring at 1000r/min for 30min, wherein the solid content of the alumina sol is 18%, the particle size of the cobalt oxide is 20-40 μm, and the particle size of the zinc oxide is 10-30 μm.
Example 3
(1) Screening a zinc-aluminum-magnesium material without white spots to obtain a qualified zinc-aluminum-magnesium material;
(2) Scratching the surface of the qualified zinc-aluminum-magnesium material with a plurality of nicks with the depth of 0.01-0.07mm, cleaning the surface, removing metal powder on the surface of the zinc-aluminum-magnesium material, soaking and pickling the zinc-aluminum-magnesium material by using a pickling agent, washing the zinc-aluminum-magnesium material by using deionized water, and drying the zinc-aluminum-magnesium material for 15min at 50 ℃ in a vacuum environment with the vacuum degree of 70kPa to obtain a pickled zinc-aluminum-magnesium material; the pickling agent is prepared by adding zinc sulfate, aluminum ammonium sulfate and oxalic acid into water to prepare Zn-containing pickling agent 2+ 90mg/L of Al 3+ 9mg/L and 15g/L of oxalic acid, and in the acid washing process, the temperature of the mixed solution is adjusted to 40 ℃.
(3) And (3) soaking the acid-washed zinc-aluminum-magnesium material in the coating slurry, vibrating the acid-washed zinc-aluminum-magnesium material for 60 times/min for 10min, standing for 3min, taking out, drying at the constant temperature of 50 ℃ for 15min in a vacuum environment with the vacuum degree of 70kPa, detecting that the surface has no crack, and coating and packaging. The coating slurry is prepared by mixing 6g of sodium sulfate, 13g of alumina sol, 9g of cobalt oxide, 0.4g of zinc oxide and 130g of absolute ethyl alcohol by mass, and stirring at 1000r/min for 30min, wherein the solid content of the alumina sol is 16%, the particle size of the cobalt oxide is 5-20 μm, and the particle size of the zinc oxide is 10-30 μm.
Example 4
(1) Screening a zinc-aluminum-magnesium material without white spots to obtain a qualified zinc-aluminum-magnesium material;
(2) Scratching the surface of the qualified zinc-aluminum-magnesium material to form a plurality of notches with the depth of 0.01-0.07mm, cleaning the surface, removing metal powder on the surface of the zinc-aluminum-magnesium material, soaking and pickling the zinc-aluminum-magnesium material by using a pickling agent, washing the zinc-aluminum-magnesium material by using deionized water, and drying the zinc-aluminum-magnesium material for 10min at 40 ℃ in a vacuum environment with the vacuum degree of 80kPa to obtain a pickled zinc-aluminum-magnesium material; the pickling agent is prepared by adding zinc sulfate, aluminum ammonium sulfate and oxalic acid into water to prepare Zn-containing pickling agent 2+ 100mg/L of Al 3+ 5mg/L and 10g/L oxalic acid, and in the acid washing process, the temperature of the mixed solution is adjusted to 40 ℃.
(3) And (3) soaking the acid-washed zinc-aluminum-magnesium material in the coating slurry, vibrating the acid-washed zinc-aluminum-magnesium material for 70 times/min for 10min, standing for 3min, taking out, drying at the constant temperature of 40 ℃ for 20min in a vacuum environment with the vacuum degree of 70kPa, detecting that the surface has no crack, and coating and packaging. The coating slurry is prepared by mixing 5g of sodium sulfate, 15g of alumina sol, 12g of cobalt oxide, 0.1g of zinc oxide and 100g of absolute ethyl alcohol by mass, and stirring at 1000r/min for 30min, wherein the solid content of the alumina sol is 17%, the particle size of the cobalt oxide is 5-15 μm, and the particle size of the zinc oxide is 20-40 μm.
Example 5
The same procedure as in example 1 was repeated except that the pickled zinc-aluminum-magnesium material was immersed in the coating slurry while the coating slurry was still immersed in the pickled zinc-aluminum-magnesium material in example 1.
Example 6
The method is the same as the method in the embodiment 1 except that the qualified zinc-aluminum-magnesium material is directly put into the pickling agent for pickling without shallow etching treatment on the material.
Example 7
The pickling agent is acid-washed on the basis of the acid-washed acid of the embodiment 1, and is directly put into the coating slurry for dipping after being washed by deionized water, and the rest is the same as the embodiment 1.
The zinc-aluminum-magnesium material containing the coating obtained in the embodiment 1 to the embodiment 7 is subjected to an impact test and a thermal shock test, and the weight loss rate is measured; meanwhile, the weight gain of the zinc-aluminum-magnesium material prepared in examples 1 to 7 was measured by a section weighing method, each section being 50cm, and the test results are shown in table 1 below.
TABLE 1 protective effect of coating preparation process on surface of zinc-aluminum-magnesium material
Remarking: (1) In the cold impact, the zinc-aluminum-magnesium material is stamped by a stamping machine under the normal temperature environment, so that the zinc-aluminum-magnesium material is weighed after 5% of bending, and the weight loss rate of the zinc-aluminum-magnesium material before and after impact is measured; (2) The thermal shock is a stamping test treatment by a stamping machine in a cold shock mode under the environment of 120 ℃.
As can be seen from table 1: different treatment processes can lead to the formation uniformity and the thickness of the coating on the surface of the zinc-aluminum-magnesium material and can also influence the stamping resistance of the zinc-aluminum-magnesium material; the process of nicking and vibration-standing treatment is adopted, so that the formation of the coating is promoted, the thickness of the coating is improved, and the uniformity of the formed coating is ensured; and the vacuum drying treatment after the deionized water washing is adopted, so that the subsequent coating slurry dipping and adhering effect is facilitated, and the coating weight increasing effect is improved.
Test 2: research on surface protection effect of pickling agent on zinc-aluminum-magnesium material
Example 8
Based on the embodiment 1, the acid washing agent is prepared by adding ammonium aluminum sulfate and oxalic acid into water to prepare Al-containing acid 3+ 5mg/L and 10g/L oxalic acid, and the temperature of the mixed solution is adjusted to 30 ℃ in the acid washing process, and the rest is the same as that of the embodiment 1.
Example 9
On the basis of the embodiment 1, the pickling agent is prepared by adding zinc sulfate and oxalic acid into water to prepare Zn-containing pickling agent 2+ 80mg/L of oxalic acid and 10g/L of oxalic acid, and the temperature of the mixed solution is adjusted to 30 ℃ in the acid washing process, and the rest is the same as that of the mixed solution in the embodiment 1.
Example 10
On the basis of example 1, the pickling agent is prepared by adding zinc sulfate and aluminum ammonium sulfate into water to prepare Zn-containing pickling agent 2+ 80mg/L, containing Al 3+ 5mg/L of the mixed solution, and the temperature of the mixed solution was adjusted to 30 ℃ in the acid washing process, all other things being equal to example 1.
The coated zinc-aluminum-magnesium materials obtained in examples 8 to 10 were subjected to a cold impact test, a thermal impact test and a weight increase test according to the treatment manner of test 1, and the test results are shown in table 2 below.
TABLE 2 surface protection effect of pickling agent components on zinc-aluminum-magnesium material
As can be seen from tables 1 and 2: the change of the components of the pickling agent can seriously affect the impact resistance of the surface coating of the zinc-aluminum-magnesium material, so that the stamping falling effect is obvious, the coating formed on the surface of the zinc-aluminum-magnesium material is extremely uneven, and then a large amount of falling and weight loss occur when stamping deformation is caused due to different thicknesses.
Test 3: research on surface protection effect of coating slurry components on zinc-aluminum-magnesium material
Example 11
The coating slurry was prepared in the same manner as in example 1 except that the coating slurry was prepared by mixing 5g of sodium sulfate, 8g of cobalt oxide, 0.1g of zinc oxide and 100g of absolute ethyl alcohol by mass and then stirring at 1000r/min for 30 min.
Example 12
The coating slurry was prepared by mixing 5g of sodium sulfate, 10g of alumina sol, 8g of cobalt oxide and 100g of absolute ethanol in mass in example 1, and then stirring at 1000r/min for 30min, as in example 1, except that the coating slurry was prepared.
Example 13
The coating slurry was prepared by mixing 5g of sodium sulfate, 10g of alumina sol, 0.1g of zinc oxide and 100g of absolute ethanol in mass in example 1, and then stirring at 1000r/min for 30min, and the same procedure was followed as in example 1.
Example 14
The coating slurry was prepared in the same manner as in example 1 except that 10g of alumina sol, 8g of cobalt oxide, 0.1g of zinc oxide and 100g of absolute ethanol were mixed and stirred at 1000r/min for 30min in mass, based on the mass of example 1.
Example 15
The coating slurry was added with ammonium hydrogen carbonate powder accounting for 1% of the mass of sodium sulfate based on the coating slurry in example 1, and the coating slurry was otherwise the same as in example 1.
Example 16
The coating slurry was added with 3% by mass of ammonium bicarbonate powder based on the mass of sodium sulfate in example 1, and the rest was the same as in example 1.
Example 17
The coating slurry was added with 5% by mass of ammonium bicarbonate powder based on the mass of sodium sulfate in example 1, and the rest was the same as in example 1.
Example 18
The coating slurry was added with ammonium bicarbonate powder in an amount of 7% by mass based on the mass of sodium sulfate in example 1, and the other examples were the same as example 1.
Example 19
The coating slurry was added with ammonium bicarbonate powder in an amount of 10% by mass based on the mass of sodium sulfate in example 1, and the other examples were the same as example 1.
Example 20
The coating slurry was added with ammonium bicarbonate powder in an amount of 13% by mass based on the mass of sodium sulfate in example 1, and the other examples were the same as example 1.
Example 21
The coating slurry was added with ammonium bicarbonate powder 15% by mass of sodium sulfate based on example 1, and the rest was the same as example 1.
Example 22
The coating slurry was added with ammonium bicarbonate powder in an amount of 20% by mass based on the mass of sodium sulfate in example 1, and the other examples were the same as example 1.
The zinc-aluminum-magnesium materials obtained in examples 11 to 22 were subjected to a cold impact test, a thermal impact test and a weight increase test according to the method of test 1, and the test results are shown in table 3 below.
TABLE 3 protective effect of coating slurry composition on surface of zinc-aluminum-magnesium material
As can be seen from tables 1 and 3, the change of the components of the coating slurry will also affect the coating forming effect on the surface of the zinc-aluminum-magnesium material, so that the coating is formed, the weight gain rate is greatly reduced, the coating thickness is not good, and the weight loss is easily caused by the punching fracture during impact resistance, but the influence on the uniform distribution effect of the whole coating is little; to the volume change that adds ammonium bicarbonate powder, will greatly influence and form thickness at zinc-aluminium magnesium material surface coating, suitable addition will help the guarantee coating to form the thickness preferred, and the homogeneity of distribution preferred, and the shock-resistant effect of droing is showing, and the addition is unsuitable, will lead to the whole ammonium ion relative content of coating thick liquid to change, influences the formation of coating structure then, more can influence the distribution of coating thickness homogeneity, leads to resistant punching press effect to reduce.
The invention creates substantial research contents in consideration of the performance of increasing the thickness, uniformly distributing and the like when forming the coating on the surface of the zinc-aluminum-magnesium material, so as to improve the effect of stamping resistance and falling prevention of the coating on the surface of the zinc-aluminum-magnesium material and achieve the effect of enhancing the protection effect of the zinc-aluminum-magnesium material. The invention may be practiced in other ways without departing from the spirit and scope of the claims, which are defined by the claims.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (10)
1. A zinc-aluminum-magnesium material surface coating treatment process capable of preventing a coating from being stamped and falling off is characterized by comprising the following steps of:
(1) Screening a zinc-aluminum-magnesium material without white spots or polishing the zinc-aluminum-magnesium material with white spots until no white spots exist to obtain a qualified zinc-aluminum-magnesium material;
(2) Etching a plurality of nicks with the depth of 0.01-0.07mm on the surface of the qualified zinc-aluminum-magnesium material, cleaning the surface, removing metal powder on the surface of the zinc-aluminum-magnesium material, soaking and pickling the zinc-aluminum-magnesium material by using a pickling agent, washing the zinc-aluminum-magnesium material by using deionized water, and drying the zinc-aluminum-magnesium material in a vacuum environment to obtain a pickled zinc-aluminum-magnesium material;
(3) And (3) putting the acid-washed zinc-aluminum-magnesium material into the coating slurry for dipping, vibrating the acid-washed zinc-aluminum-magnesium material for 50-80 times/min for 10min, standing for 3min, taking out, placing in a vacuum environment for drying at constant temperature, detecting that the surface has no cracks, and coating and packaging.
2. The process for treating a Zn-Al-Mg material surface coating capable of preventing the coating from being removed by stamping as claimed in claim 1, wherein said pickling agent comprises Zn 2+ 80-100mg/L of Al 3+ 5-10mg/L, 10-20g/L oxalic acid and water are prepared into 1L, and the temperature is 30-50 ℃.
3. The process for treating a surface coating of a zinc-aluminum-magnesium material as claimed in claim 1 or 2, wherein the pickling agent is Zn-containing 2+ 90mg/L of Al 3+ 8mg/L, 15g/L oxalic acid and water are prepared into 1L, and the temperature is 40 ℃.
4. The process for treating Zn-Al-Mg surface coating capable of preventing the coating from being removed by punching as claimed in claim 2, wherein said Zn 2+ Is provided by adding zinc sulfate, and the Al 3+ Provided using aluminum ammonium sulfate.
5. The process for treating the surface coating of the zinc-aluminum-magnesium material, which can prevent the coating from being stamped and shed, according to claim 1, wherein in the step (2), the vacuum degree is 60 to 80kPa, the drying temperature is 40 to 60 ℃, and the drying treatment time is 10 to 20min.
6. The process for treating the surface coating of the zinc-aluminum-magnesium material capable of preventing the coating from being stamped and shed as claimed in claim 1, wherein in the step (3), the vacuum degree is 60 to 80kPa, the constant-temperature drying temperature is 40 to 60 ℃, and the drying treatment time is 10 to 20min.
7. The process for treating the surface coating of the zinc-aluminum-magnesium material capable of preventing the coating from being stamped and shed as claimed in claim 1, wherein the coating slurry comprises, by mass, 5 to 7 parts of sodium sulfate, 10 to 15 parts of alumina sol, 8 to 12 parts of cobalt oxide, 0.1 to 0.5 part of zinc oxide and 100 to 150 parts of absolute ethyl alcohol.
8. The process for treating the zinc-aluminum-magnesium surface coating capable of preventing the coating from being stamped and shed according to claim 1 or 7, wherein the coating slurry comprises 6 parts by mass of sodium sulfate, 12 parts by mass of alumina sol, 9 parts by mass of cobalt oxide, 0.4 part by mass of zinc oxide and 130 parts by mass of absolute ethyl alcohol.
9. The process for treating the zinc-aluminum-magnesium material surface coating capable of preventing the coating from being stamped and shed as claimed in claim 7, wherein the solid content of the alumina sol is not less than 15%, the particle size of the cobalt oxide is not more than 50 μm, and the particle size of the zinc oxide is not more than 50 μm.
10. The process of claim 7, wherein the coating slurry contains 3-10 wt% ammonium bicarbonate powder based on sodium sulfate.
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