CN111560589A - HIPIMS preparation method of low-manganese-content amorphous aluminum-manganese coating applied to neodymium iron boron - Google Patents

HIPIMS preparation method of low-manganese-content amorphous aluminum-manganese coating applied to neodymium iron boron Download PDF

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CN111560589A
CN111560589A CN202010418357.7A CN202010418357A CN111560589A CN 111560589 A CN111560589 A CN 111560589A CN 202010418357 A CN202010418357 A CN 202010418357A CN 111560589 A CN111560589 A CN 111560589A
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magnetic material
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manganese
aluminum
cleaning
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CN111560589B (en
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夏原
李光
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Institute of Mechanics of CAS
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3485—Sputtering using pulsed power to the target

Abstract

The invention provides a HIPIMS preparation method of a low-manganese-content amorphous aluminum-manganese coating applied to neodymium iron boron, which is used for preparing aluminum manganese-rare earth serving as a composite target; firstly, grinding and cleaning neodymium iron boron magnetic materials and carrying out vacuum ion bombardment cleaning; the temperature of the magnetic material is reduced to 120-150 ℃, the argon flow in the vacuum chamber is adjusted to the working vacuum degree of 0.3-0.8Pa, the pulse power supply is started, the base distance between the pulse power supply and the target material is 60-100mm, the negative bias is 50-150V, and the peak power density is 500-800W/cm2Then, pulse magnetron sputtering coating is started, the temperature of the magnetic material is controlled not to exceed 200 ℃, and the coating is stopped after the coating is continuously carried out for 30-60 min; and (5) after the magnetic material is cooled, inflating the vacuum chamber, taking out the coated magnetic material, and finishing the coating process. The invention obtains the magnetron sputtering technological parameters most suitable for preparing the amorphous aluminum-manganese coating by adjusting the parameters such as the target base distance, the bias voltage, the substrate temperature, the power and the like, and reduces the manganese content required by forming the aluminum-manganese amorphous structure。

Description

HIPIMS preparation method of low-manganese-content amorphous aluminum-manganese coating applied to neodymium iron boron
Technical Field
The invention relates to the technical field of material surface modification in low-temperature plasma physics and chemistry, in particular to a preparation process for preparing an aluminum-manganese amorphous coating with low manganese content on the surface of a neodymium-iron-boron magnetic material by using a high-power pulse HIPIMS technology.
Background
Neodymium iron boron (NdFeB) is used as a third-generation rare earth permanent magnet material, has excellent magnetic property and high cost performance, and is widely applied to the fields of electronic communication, aerospace, traffic energy, computers and the like. However, the neodymium iron boron magnet is manufactured by adopting a powder sintering technology, and due to the characteristics of looseness and porosity, an oxide protective layer is difficult to form on the surface of the magnet material and is extremely easy to corrode, so that a protective coating must be prepared on the surface of the neodymium iron boron magnet in the using process.
At present, the anticorrosive coating on the surface of the magnetic material is mainly a nickel, zinc or aluminum layer, but the pure metal coating has limited protective capability due to the unicity of the anticorrosive mechanism. The aluminum-manganese alloy coating has a corrosion potential lower than that of the neodymium-iron-boron matrix, and is used as an anode in an electrochemical corrosion environment to form sacrificial anode protection for the neodymium-iron-boron matrix; meanwhile, the surface of the aluminum-manganese alloy film can also be subjected to oxidation reaction to form a compact and stable passivation film, so that the corrosion process of the neodymium-iron-boron substrate in a corrosive environment is further delayed.
The main treatment method for the surface protection of the NdFeB magnetic material in China is electroplating and chemical plating, and the patent CN 107923003 a forms an aluminum-manganese coating on the surface of the magnetic material by using the electroplating method, but the coating prepared by the electroplating and chemical plating technology generally has the phenomena of low adhesive force, fast magnetic energy attenuation and the like, and the waste liquid can cause serious environmental pollution and does not accord with the development direction of green environmental protection. The vacuum coating technology has the advantages of low cost, no waste, no pollution and the like when the surface of the NdFeB magnet is protected, so that the vacuum coating technology has strong practical significance as a new generation of green manufacturing technology for protecting the surface of the NdFeB magnet.
In vacuum coating, the magnetron sputtering technology (HIPIMS) is to prepare a coating by sputtering target atoms through particle bombardment, is a dry coating in a vacuum cavity, is not easy to pollute and is beneficial to forming an amorphous structure, and has the advantages of high compactness, few pinholes in the coating, high binding force and the like, and the corrosion resistance service life of the aluminum-manganese coating prepared by magnetron sputtering is 5-10 times that of electroplating. In addition, the corrosion resistance of the aluminum-manganese amorphous coating is greatly influenced by the crystal structure type of the corrosion-resistant coating, and the corrosion resistance service life of the aluminum-manganese amorphous coating is more than ten times that of the aluminum-manganese crystal coating.
When the amorphous aluminum-manganese coating is prepared by electroplating, the amorphous structure can be formed only by the manganese content of more than 24 percent, although the magnetron sputtering technology is more favorable for forming the amorphous coating, the amorphous structure can be formed only by the manganese content of more than 20 percentForming an amorphous structure, but when the manganese content of the aluminum-manganese alloy exceeds 14 percent, Al is precipitated6The Mn brittle compound becomes a crack production source, so that the brittleness of the alloy is increased, the cracks are increased, and the forging and shearing processing of the smelting alloy to become the magnetron sputtering target material are difficult.
Although the coating can be prepared by using the aluminum-manganese spliced target material, the accuracy and the smoothness of the components of the coating prepared by using the spliced target material are lower than those of a smelting target material, and the quality of the coating is poor. In order to prepare the aluminum-manganese amorphous coating on the surface of the neodymium iron boron by using a magnetron sputtering method, the manganese content in the target coating must be reduced, but the reduction of the manganese content can cause the conversion of the amorphous structure of the coating, so a new preparation process is needed, and the requirement of the aluminum-manganese alloy on the manganese content when the amorphous structure is formed is reduced.
Disclosure of Invention
The invention aims to provide a preparation method for preparing an aluminum-manganese amorphous coating with low manganese content on the surface of a neodymium-iron-boron magnetic material by a high-power pulse magnetron sputtering technology.
Specifically, the invention provides a HIPIMS preparation method of a low-manganese amorphous aluminum-manganese coating applied to neodymium iron boron, which comprises the following steps:
step 100, preparing aluminum manganese-rare earth as a composite target material; preparing an aluminum-manganese-rare earth composite target material with low manganese content, which can be used for depositing an amorphous AlMn coating;
step 200, grinding and cleaning the neodymium iron boron magnetic material, and then putting the neodymium iron boron magnetic material into a vacuum chamber for vacuum ion bombardment cleaning;
step 300, after the magnetic material is cleaned and the temperature is reduced to 120-150 ℃, adjusting the argon flow in the vacuum chamber to the working vacuum degree of 0.3-0.8Pa, starting the pulse power supply with the target base distance of 60-100mm, the negative bias of the magnetic material of 50-150V, the peak power density of the pulse power supply of 500-800W/cm2Then, pulse magnetron sputtering coating is started, the temperature of the magnetic material is controlled not to exceed 200 ℃, and the coating is stopped after the coating is continuously carried out for 30-60 min;
and step 400, inflating the vacuum chamber after the magnetic material is cooled, opening the vacuum chamber, and taking out the coated magnetic material to finish the coating process.
In one embodiment of the present invention, the preparation process of the composite target material is as follows:
101, preparing Mn 10-12%, Pr0.8-1.5% and the balance of Al according to the percentage;
step 102, firstly heating and melting Al, then sequentially adding Mn and Pr, and after all additives are melted, adding a slagging medium for standing and deslagging for 10 min;
103, pouring the slag-removed melt into a water-cooled mold for cooling to obtain an alloy ingot;
and step 104, carrying out hot forging, rolling, shearing and surface treatment on the obtained alloy ingot to obtain the composite target formed by the aluminum manganese and the rare earth.
In one embodiment of the present invention, in the step 200, the process of performing the polishing and cleaning process on the magnetic material is as follows:
step 201, firstly, placing the magnetic material in a vibration type grinder, and chamfering and grinding the magnetic material by using a mixture of silicon carbide and brown corundum until the edge angle circular arc of the magnetic material is not less than 0.5 mm;
step 202, performing sand blasting on the magnetic material for 20min, and then performing polishing treatment;
step 203, placing the polished magnetic material in an ultrasonic cleaner, performing ultrasonic cleaning for 30min by using a metal cleaning agent, performing ultrasonic cleaning for 10min by using deionized water, performing ultrasonic cleaning for 5min by using absolute ethyl alcohol, and finally drying by using hot air to finish the cleaning process.
In one embodiment of the present invention, the step 200 of placing the wafer into a vacuum chamber for vacuum ion bombardment cleaning comprises the following steps:
step 211, assembling the cleaned magnetic material on a clamp of a vacuum chamber, adjusting the target base distance to be 60-100mm, and closing a furnace door;
step 212, respectively starting the mechanical pump and the molecular pump to perform vacuum pumping operation, wherein the vacuum degree in the vacuum chamber is 3 × 10-3When Pa, introducing argon into the vacuum chamber;
and 213, keeping the working gas pressure at 1.5-2 Pa, applying 900V negative bias, and performing vacuum glow cleaning on the magnetic material for 15min to finish the cleaning process.
In an embodiment of the present invention, in the step 300, before the magnetic material is coated, the temperature of the magnetic material needs to be decreased to 120 to 150 ℃.
In one embodiment of the present invention, in the step 300, the time for plating the magnetic material is preferably 30 to 60 min.
In one embodiment of the invention, in the step 300, the peak power density of the pulse power supply is preferably 500-800W/cm2。
In one embodiment of the present invention, the final thickness of the plated film of the magnetic material in the step 300 is 4 to 6 μm.
In one embodiment of the present invention, the cooling time for the magnetic material in the step 400 is 10 min.
In one embodiment of the invention, the method further comprises a corrosion resistance experiment step, wherein the magnetic material after coating is put into neutral salt fog and taken out after 1000 hours, and no corrosion trace on the surface of the magnetic material indicates that the coating is successful.
According to the invention, the rare earth element Pr is added into the aluminum-manganese target material, so that the manganese content required for forming the aluminum-manganese amorphous structure coating is reduced, the situation that alloy cast ingots are too brittle is avoided, the alloy cast ingots can be forged and processed into the target material, and the preparation of the amorphous aluminum-manganese coating by the magnetron sputtering technology is realized.
Parameters such as target power, target base distance, bias voltage, substrate temperature and the like are adjusted to obtain magnetron sputtering technological parameters which are most suitable for preparing the amorphous aluminum-manganese coating, and the manganese content required by forming the aluminum-manganese amorphous structure is further reduced.
Drawings
FIG. 1 is a schematic flow diagram of a HIPIMS preparation process according to one embodiment of the present invention;
fig. 2 is a schematic flow diagram of a composite target material preparation process according to an embodiment of the present invention;
FIG. 3 is a schematic view of a process flow for cleaning and polishing a magnetic material according to one embodiment of the present invention;
FIG. 4 is a schematic view of a vacuum cleaning process for magnetic material according to one embodiment of the present invention;
FIG. 5 is a schematic view of a magnetic material coating process according to an embodiment of the present invention.
Detailed Description
The magnetron sputtering cold plating is a dry coating in a vacuum cavity, the coating is not easy to be polluted, and an amorphous structure is easier to form (the AlMn electroplating coating can form amorphous only when the Mn content exceeds 24 percent, and the magnetron sputtering can form amorphous only by 20 percent of Mn); and magnetron sputtering does not discharge waste liquid and has no environmental pollution, and the method has the characteristics of environmental protection.
Because the energy of sputtering particles can be improved by increasing the power, the sputtering particles can more easily fill in the gaps of the crystal lattices to form an amorphous structure coating, a high-power impulse magnetron sputtering (HIPIMS) technology is selected and used on the basis of magnetron sputtering.
As shown in fig. 1, in one embodiment of the present invention, a HIPIMS preparation method of an amorphous aluminum-manganese coating with low manganese content is disclosed, which is characterized by comprising the following steps:
100, preparing an aluminum-manganese-rare earth composite target material with low manganese content, which can be used for depositing an amorphous AlMn coating;
in order to reduce the manganese content required for forming the aluminum-manganese amorphous coating, the preparation process parameters need to be adjusted to promote the amorphization process of the coating. According to the scheme, the aluminum manganese target material is doped with the trace rare earth element Pr, and the Pr has the function of refining grains, so that the tissue structure of the coating can be improved, the compactness of the coating is improved, and the non-crystallization of the coating is promoted. The addition of Pr greatly reduces the manganese content required for forming an amorphous state, so that an amorphous aluminum-manganese alloy can be formed under the condition that the addition amount of Mn is lower than 14%, and the problems of overlarge alloy brittleness, incapability of processing and the like caused by precipitation of brittle compounds are avoided.
As shown in fig. 2, the following steps for manufacturing the composite target material are given through multiple sets of orthogonal experiments:
101, preparing Mn 10-12%, Pr0.8-1.5% and the balance of Al according to the percentage;
the corrosion resistance of the magnetic material after being plated with the amorphous aluminum-manganese coating is more than ten times that of the crystalline aluminum-manganese coating, but if the amorphous aluminum-manganese coating is directly prepared by adopting magnetron sputtering, the required manganese addition amount exceeds 20 percent, and when the manganese content exceeds 14 percent, a brittle compound is separated out from the interior of the coating, so that the alloy brittleness is increased, and the alloy is difficult to process and forge into a target material to be used in the magnetron sputtering technology. Therefore, at present, no scheme for directly preparing the amorphous aluminum-manganese coating by using a melting alloy target material through a magnetron sputtering technology exists, only aluminum blocks and manganese blocks can be spliced into the target material to prepare the coating in the prior art, but the accuracy and the smoothness of the components of the coating prepared by splicing the target material are lower than those of the melting target material, the compactness is poor, and the high-quality amorphous aluminum-manganese coating is difficult to prepare on the surface of a magnetic material. Therefore, in order to prepare high-quality amorphous aluminum-manganese coating by using magnetron sputtering technology, the manganese content required for forming the aluminum-manganese amorphous coating must be reduced.
After the rare earth element Pr is added, an intermetallic compound is formed between Al and Pr to hinder the growth of crystal grains, so that the effect of refining the crystal grains is achieved, the non-crystallization of the coating is promoted, and the manganese content required by preparing the amorphous aluminum-manganese coating is reduced. The Pr content is 0.8-1.5% because the refined grains are not obvious when the Pr addition amount is low, but the grains are aggregated when the Pr addition amount is too high, which is not beneficial to the amorphization of the coating.
The non-crystallization degree of the coating can be promoted to the maximum extent by carrying out magnetron sputtering according to the parameters in the design range under the content, so that the amorphous aluminum-manganese coating is prepared under the condition of small manganese addition amount. Step 102, firstly heating and melting Al, then sequentially adding Mn and Pr, and after all additives are melted, adding a slagging medium for standing and deslagging for 10 min;
103, pouring the slag-removed melt into a water-cooled mold for cooling to obtain an alloy ingot;
and step 104, carrying out hot forging, rolling, shearing and surface treatment on the obtained alloy ingot to obtain the composite target formed by the aluminum manganese and the rare earth.
The hot forging, rolling and surface method are realized by the related treatment schemes in the prior art.
The amorphous degree of the aluminum-manganese coating generated by the aluminum-manganese-rare earth target material obtained through the steps and the content is most obvious.
Step 200, grinding and cleaning the neodymium iron boron magnetic material, and then putting the neodymium iron boron magnetic material into a vacuum chamber for vacuum ion bombardment cleaning;
the treated magnetic material can reduce the influence of the surface shape, oil stain and impurities on etching, and improve the final coating effect. As shown in fig. 3, the process of polishing and cleaning the magnetic material made of neodymium iron boron is as follows:
step 201, firstly, placing the magnetic material in a vibration type grinder, and chamfering and grinding the magnetic material by using a mixture of silicon carbide and brown corundum until the edge angle circular arc of the magnetic material is not less than 0.5 mm;
step 202, performing sand blasting on the magnetic material for 20min, and then performing polishing treatment;
step 203, placing the polished magnetic material in an ultrasonic cleaner, performing ultrasonic cleaning for 30min by using a metal cleaning agent, performing ultrasonic cleaning for 10min by using deionized water, performing ultrasonic cleaning for 5min by using absolute ethyl alcohol, and finally drying by using hot air to finish the cleaning process.
The impurities on the surface of the magnetic material can be completely eliminated through the steps, and meanwhile, the phenomenon that the thickness of the coating is uneven at the corners can be avoided.
As shown in FIG. 4, the process of vacuum ion bombardment cleaning in the vacuum chamber is as follows:
step 211, assembling the cleaned magnetic material on a clamp of a vacuum chamber, adjusting the target base distance to be 60-100mm, and closing a furnace door;
step 212, respectively starting the mechanical pump and the molecular pump to perform vacuum pumping operation, wherein the vacuum degree in the vacuum chamber is 3 × 10-3When Pa, introducing argon into the vacuum chamber;
and 213, keeping the working gas pressure at 1.5-2 Pa, applying 900V negative bias, and performing vacuum glow cleaning on the magnetic material for 15min to finish the cleaning process.
The surface of the magnetic material cleaned by the steps is uniform and consistent in performance, and can provide a good foundation for later-stage coating, so that the formed film layer is combined with the magnetic material substrate more strongly.
Step 300, when the magnetic material is cleanedAfter washing, the temperature is reduced to 120-150 ℃, the argon flow in the vacuum chamber is adjusted to the working vacuum degree of 0.3-0.8Pa, the pulse power supply is started, the base distance between the pulse power supply and the target material is 60-100mm, the negative bias voltage of the magnetic material is 50-150V, and the peak power density of the pulse power supply is 500-2Then, pulse magnetron sputtering coating is started, the temperature of the magnetic material is controlled not to exceed 200 ℃, and the coating is stopped after the coating is continuously carried out for 30-60 min;
because the temperature can rise by more than 200 ℃ when the magnetic material is glow cleaned, and the coating film is not beneficial to the formation of an amorphous phase, the temperature of the magnetic material needs to be reduced to 120-150 ℃ before the magnetic material is coated.
The main effects of the target distance, bias voltage and power are the particle energy to promote the formation of the amorphous structure of the coating. When the energy of the particles is small, columnar crystals are not sufficiently eliminated to form an amorphous structure; when the particle energy is too large, the temperature of the matrix increases, and the formation of a coarse columnar crystal structure is promoted. The present scheme determines experimentally the appropriate range of target base distance, bias voltage and power parameters.
In addition to the sputtering power of the target material, parameters such as substrate bias, substrate temperature and target base distance have certain influence on the crystal structure and corrosion resistance of the coating, for example, high temperature can promote the crystallization tendency of the coating, and when the substrate temperature is higher than 300 ℃, the anisotropy degree of the coating can be increased, which is not beneficial to the amorphization of the coating. Therefore, in order to reduce the addition amount of the manganese element in the aluminum-manganese amorphous coating, the process parameters most suitable for growing the amorphous structure need to be selected. We obtained by multiple sets of orthogonal experiments, when the peak power density of magnetron sputtering is 500-2When the target base distance is 60-100mm and the negative bias of the substrate is 50-150V, the temperature of the substrate is controlled not to exceed 200 ℃, so that the coating with higher non-crystallization degree can be obtained and has the best corrosion resistance.
And step 400, inflating the vacuum chamber after the magnetic material is cooled, opening the vacuum chamber, and taking out the coated magnetic material to finish the coating process.
In the step, the cooling time of the magnetic material can be set to be 10-30 min, so that the temperature of the magnetic material is reduced to be below 100 ℃.
The thickness of the coating film on the surface of the magnetic material after the treatment of the steps is about 4-6 mu m. Too thick a coating may have limited corrosion resistance enhancement, which may affect magnetic properties, and too long a deposition time may affect production efficiency.
According to the embodiment, parameters such as target power, target base distance, bias voltage and substrate temperature are adjusted to obtain magnetron sputtering technological parameters most suitable for preparing the amorphous aluminum-manganese coating, so that the manganese content required for forming an aluminum-manganese amorphous structure is reduced, and the problem of overlarge brittleness is avoided.
By adding the rare earth element Pr into the aluminum-manganese target material, the manganese content required for forming an aluminum-manganese amorphous structure is further reduced, so that the situation that alloy cast ingots are too brittle is avoided, the alloy cast ingots can be forged and processed into the target material, the preparation of high-quality amorphous aluminum-manganese coatings by the magnetron sputtering technology is realized, the corrosion resistance of neodymium-iron-boron magnetic materials is improved, and the problems of corrosion and pollution caused by wet plating on the magnetic materials are avoided.
The coating is doped with trace rare earth element Pr, so that the tissue structure can be improved and the amorphization of the coating is promoted. After Pr is added, Al and Pr can form an intermetallic compound to prevent the crystal grains from growing, thereby playing a role in refining the crystal grains, promoting the non-crystallization of the coating and reducing the manganese content required by preparing the amorphous aluminum-manganese coating. In addition, Pr can also play a role in dispersion strengthening of the aluminum-manganese alloy, so that the mechanical property of the coating can be improved.
In order to reduce the manganese content required for forming the aluminum-manganese amorphous coating, the preparation process parameters are adjusted, so that the non-crystallization process of the coating is promoted. For the magnetron sputtering technology, the sputtering power is increased to improve the energy of sputtering particles, and the particles with larger energy are easier to diffuse and fill crystal lattice vacancies when being deposited on a substrate, so that an amorphous structure is easier to form. We therefore prepared the al-mn coating by using high power impulse magnetron sputtering technique (HIPIMS) to obtain stronger working power and ionization rate. The coating prepared by the high-power pulse magnetron sputtering technology has higher compactness, smoothness and bonding strength due to the increase of the ionization rate.
Furthermore, the magnetic material after the coating is finished also comprises a corrosion resistance experiment, the magnetic material after the coating is finished is placed into neutral salt fog and taken out after 1000 hours, and no corrosion trace on the surface of the magnetic material indicates that the coating is successful.
Through experiments, the amorphous-structure aluminum-manganese coating prepared on the surface of the neodymium iron boron by using the high-power pulse magnetron sputtering technology does not have obvious pitting phenomenon within 1000h of a neutral salt spray experiment, the service life of the coating is more than ten times that of a crystal aluminum-manganese coating, and the service life of the neodymium iron boron magnetic material is greatly prolonged.
As shown in fig. 5, the following describes a manufacturing process of the present solution by using a specific embodiment:
1. firstly, preparing the low-manganese-content aluminum-manganese-rare earth composite target material.
Preparing ingredients of Mn 12%, Pr1.2% and the balance of Al according to the percentage; firstly, heating and melting Al, and then sequentially adding Mn and Pr for smelting; after the additives are completely melted, adding a slagging agent, standing for 10min, and taking out the slagging material; pouring the residual molten alloy into a water-cooling mold to form an alloy ingot; the obtained alloy ingot is subjected to hot forging, rolling, shearing and surface treatment to obtain the aluminum-manganese-rare earth alloy composite target material for subsequent magnetron sputtering coating.
2. And then the magnetic material is pretreated.
Firstly, placing a blocky NdFeB magnet in a vibration type grinding machine, chamfering and grinding the magnet to make the corner arc of the magnet not less than 0.5mm, performing sand blasting for 20min after chamfering, and then performing polishing treatment on the magnet; placing the magnetic material with the surface treated in an ultrasonic cleaner, and ultrasonically cleaning for 30min by using a metal cleaning agent; finally, ultrasonically cleaning the mixture for 10min by using deionized water, and then ultrasonically cleaning the mixture for 5min by using absolute ethyl alcohol for dehydration; and drying for later use.
3. And (4) carrying out vacuum ion bombardment cleaning on the processed magnetic material.
Assembling the processed magnetic material on a vacuum chamber clamp, adjusting the target base distance to 80mm, closing the furnace door, respectively starting a mechanical pump and a molecular pump to vacuumize until the working vacuum degree is 3 × 10-3When Pa, argon is introducedAnd gas, keeping the working gas pressure at 1.8Pa, applying 900V negative bias, and performing glow cleaning on the target material for 15 min.
4. Then the high-power pulse magnetron technology is utilized to sputter and coat the magnetic material.
After the ion cleaning is finished, film coating is started after the magnetic material is cooled, the argon flow is adjusted to the working vacuum degree of 0.5Pa, the HIPIMS power supply is started, the negative bias is reduced to 80V, and the power supply peak power density is set to be 600W/cm2And controlling the temperature of the substrate to be 180 ℃ during film coating, and continuously coating for 30min after stabilization, wherein the thickness of the coated film is 4.7 mu m.
5. And taking out the magnetic material finished product after film coating after cooling.
After the film coating is finished, maintaining the film coating chamber to be cooled for 10min under vacuum, inflating and opening the furnace, and taking out the coated neodymium iron boron magnetic material.
6. And (5) carrying out corrosion resistance detection.
And after the preparation is finished, opening the furnace to take out the magnetic material sample, performing neutral salt spray test on ten magnetic materials randomly selected from the block magnetic materials, observing for 1000 hours, wherein the magnet is intact, and the surface of the magnet does not have any corrosion rust points.
Thus, it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been illustrated and described in detail herein, many other variations or modifications consistent with the principles of the invention may be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.

Claims (10)

1. The HIPIMS preparation method of the low-manganese amorphous aluminum-manganese coating applied to neodymium iron boron is characterized by comprising the following steps:
100, preparing an aluminum-manganese-rare earth composite target material with low manganese content, which can be used for depositing an amorphous AlMn coating;
step 200, grinding and cleaning the neodymium iron boron magnetic material, and then putting the neodymium iron boron magnetic material into a vacuum chamber for vacuum ion bombardment cleaning;
step 300, after the magnetic material is cleaned and at the temperatureReducing the temperature to 120-150 ℃, adjusting the argon flow in the vacuum chamber to the working vacuum degree of 0.3-0.8Pa, starting the pulse power supply, wherein the target base distance is 60-100mm, the negative bias voltage of the magnetic material is 50-150V, and the peak power density of the pulse power supply is 500-2Then, pulse magnetron sputtering coating is started, the temperature of the magnetic material is controlled not to exceed 200 ℃, and the coating is stopped after the coating is continuously carried out for 30-60 min;
and step 400, inflating the vacuum chamber after the magnetic material is cooled, opening the vacuum chamber, and taking out the coated magnetic material to finish the coating process.
2. The plating method according to claim 1,
the preparation process of the composite target material is as follows:
101, preparing 10-12% of Mn, 0.8-1.5% of Pr and the balance of Al according to percentage;
step 102, firstly heating and melting Al, then sequentially adding Mn and Pr, and after all additives are melted, adding a slagging medium for standing and deslagging for 10 min;
103, pouring the slag-removed melt into a water-cooled mold for cooling to obtain an alloy ingot;
and step 104, carrying out hot forging, rolling, shearing and surface treatment on the obtained alloy ingot to obtain the composite target formed by the aluminum manganese and the rare earth.
3. The plating method according to claim 1,
in the step 200, the magnetic material is ground and cleaned as follows:
step 201, firstly, placing the magnetic material in a vibration type grinder, and chamfering and grinding the magnetic material by using a mixture of silicon carbide and brown corundum until the edge angle circular arc of the magnetic material is not less than 0.5 mm;
step 202, performing sand blasting on the magnetic material for 20min, and then performing polishing treatment;
step 203, placing the polished magnetic material in an ultrasonic cleaner, performing ultrasonic cleaning for 30min by using a metal cleaning agent, performing ultrasonic cleaning for 10min by using deionized water, performing ultrasonic cleaning for 5min by using absolute ethyl alcohol, and finally drying by using hot air to finish the cleaning process.
4. The plating method according to claim 1,
in the step 200, the process of placing the glass substrate into a vacuum chamber for vacuum ion bombardment cleaning is as follows:
step 211, assembling the cleaned magnetic material on a clamp of a vacuum chamber, adjusting the target base distance to be 60-100mm, and closing a furnace door;
step 212, respectively starting the mechanical pump and the molecular pump to perform vacuum pumping operation, wherein the vacuum degree in the vacuum chamber is 3 × 10-3When Pa, introducing argon into the vacuum chamber;
and 213, keeping the working gas pressure at 1.5-2 Pa, applying 900V negative bias, and performing vacuum glow cleaning on the magnetic material for 15min to finish the cleaning process.
5. The plating method according to claim 1,
in the step 300, before the magnetic material is coated, the temperature of the magnetic material needs to be reduced to 120-150 ℃.
6. The plating method according to claim 1,
in the step 300, the time for coating the magnetic material is preferably 30 to 60 min.
7. The plating method according to claim 1,
in the step 300, the peak power density of the pulse power supply is preferably 500-800W/cm2。
8. The plating method according to claim 1,
the final coating thickness of the magnetic material in the step 300 is 4-6 μm.
9. The plating method according to claim 1,
the cooling time for the magnetic material in step 400 is 10 min.
10. The plating method according to claim 1,
and the method also comprises a corrosion resistance experiment step, wherein the magnetic material after the film coating is finished is placed in neutral salt fog and taken out after 1000 hours, and no corrosion trace on the surface of the magnetic material indicates that the film coating is successful.
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US20110005920A1 (en) * 2009-07-13 2011-01-13 Seagate Technology Llc Low Temperature Deposition of Amorphous Thin Films
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CN110098044A (en) * 2019-04-18 2019-08-06 中国科学院力学研究所 A kind of composite modifying method of neodymium iron boron magnetic body surfacecti proteon

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2454743A (en) * 2007-11-19 2009-05-20 Hauzer Techno Coating Bv TiCr binary coating
US20110005920A1 (en) * 2009-07-13 2011-01-13 Seagate Technology Llc Low Temperature Deposition of Amorphous Thin Films
DE102011080898A1 (en) * 2011-08-12 2013-02-14 Robert Bosch Gmbh Inlaid layer for metallic workpieces
CN110098044A (en) * 2019-04-18 2019-08-06 中国科学院力学研究所 A kind of composite modifying method of neodymium iron boron magnetic body surfacecti proteon

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