CN111304611B - Preparation method of high-corrosion-resistance protective coating on surface of neodymium iron boron magnet - Google Patents
Preparation method of high-corrosion-resistance protective coating on surface of neodymium iron boron magnet Download PDFInfo
- Publication number
- CN111304611B CN111304611B CN202010228017.8A CN202010228017A CN111304611B CN 111304611 B CN111304611 B CN 111304611B CN 202010228017 A CN202010228017 A CN 202010228017A CN 111304611 B CN111304611 B CN 111304611B
- Authority
- CN
- China
- Prior art keywords
- target
- sputtering
- pulse
- frequency
- vacuum chamber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 69
- 239000011253 protective coating Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000011248 coating agent Substances 0.000 claims abstract description 43
- 238000000576 coating method Methods 0.000 claims abstract description 43
- 238000005260 corrosion Methods 0.000 claims abstract description 39
- 230000007797 corrosion Effects 0.000 claims abstract description 36
- 238000000151 deposition Methods 0.000 claims abstract description 30
- 238000005516 engineering process Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 19
- 230000008021 deposition Effects 0.000 claims abstract description 18
- 238000004544 sputter deposition Methods 0.000 claims description 72
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 66
- 238000004140 cleaning Methods 0.000 claims description 54
- 230000003595 spectral effect Effects 0.000 claims description 52
- 239000007789 gas Substances 0.000 claims description 44
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- 238000000295 emission spectrum Methods 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 22
- 150000002500 ions Chemical class 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 19
- 238000007872 degassing Methods 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 230000001360 synchronised effect Effects 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 7
- 238000012544 monitoring process Methods 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 6
- 239000007888 film coating Substances 0.000 claims description 5
- 238000009501 film coating Methods 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005488 sandblasting Methods 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000013077 target material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000000149 penetrating effect Effects 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 41
- 239000010408 film Substances 0.000 description 39
- 239000010410 layer Substances 0.000 description 20
- 238000007747 plating Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000696 magnetic material Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000005546 reactive sputtering Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- 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
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
-
- 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
- C23C14/58—After-treatment
-
- 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
- C23C14/58—After-treatment
- C23C14/5826—Treatment with charged particles
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The embodiment of the invention relates to a preparation method of a high-corrosion-resistance protective coating on the surface of a neodymium iron boron magnet, which is characterized in that Al/Al is formed by alternate deposition through detection and feedback control of plasma characteristic parameters2O3The multilayer film structure effectively reduces the micro defects of the coating, and the Al is uniform and compact2O3The layer blocks the crystal boundary penetrating through the coating, and the corrosion resistance of the neodymium iron boron magnet is obviously improved; meanwhile, the surface hardness of the Al coating is improved, and the coating failure caused by surface scratch can be effectively prevented. In addition, the method also solves the problems of low deposition rate, difficult structure control, limited coating thickness and the like in the prior preparation technology, and ensures the process stability and repeatability in the industrial production process. Meanwhile, the super-strong corrosion resistance can be used for a long time in high salinity climate, and the neodymium iron boron permanent magnet material is particularly suitable for neodymium iron boron permanent magnet materials in offshore wind energy motors, and can bring great economic and social benefits.
Description
Technical Field
The invention relates to the technical field of coating preparation, in particular to a preparation method of a high-corrosion-resistance protective coating on the surface of a neodymium iron boron magnet.
Background
Neodymium iron boron (NdFeB) is used as a third-generation rare earth permanent magnet material, and is widely applied to the sunrise industry such as wind power generation, new energy automobiles, energy-saving household appliances and the like due to excellent magnetic performance and high cost performance. However, since the sintered nd-fe-b permanent magnet material is a powder metallurgy material with strong chemical activity, the surface of the magnet is easily corroded and oxidized, which seriously hinders the large-scale application in the industrial field. At present, in order to improve the corrosion resistance of the NdFeB magnet, the most commonly adopted methods mainly include an alloying method and a surface coating protective layer method, but the former method usually sacrifices the magnetic performance of the magnet and has no obvious effect, so that the surface coating treatment of the permanent magnet material becomes the main means for improving the corrosion resistance of the magnet in the NdFeB industry at present.
Because metallic aluminum and alloy and compound thereof are nonmagnetic and do not influence the magnetic performance of the material, the related technology of aluminum plating, aluminum alloy and compound thereof has gained wide attention in the field of the anti-corrosion protective coating of the NdFeB magnet. Among them, the Al film has excellent ductility and good adhesion, and can withstand large tensile or impact deformation. However, the Al film prepared by sputtering deposition has microscopic defects such as holes, cracks and the like, and the application of the Al film in the field of high-corrosion-resistance protection is limited. Al (Al)2O3The film has excellent performances of high hardness, wear resistance, corrosion resistance, good high-temperature stability and the like; but due to Al2O3Belongs to intrinsic brittle materials, and is easy to be damaged and fail. Thus, it can be seen that the Al film is in contact with Al2O3The film has obvious performance complementarity and is alternately deposited to form Al/Al2O3The corrosion-resistant protective coating with the multilayer film structure not only has high hardness, but also can improve toughness and friction resistance and corrosion resistance, and is an ideal structural material with excellent comprehensive performance in the fields of wear resistance and corrosion resistance.
As a physical vapor deposition method which is low in cost, green and pollution-free and is suitable for large-area large-scale production, the magnetron sputtering technology is widely applied to improving the surface protection performance of various substrates. Preparing Al/Al by magnetron sputtering technology2O3The corrosion-resistant protective coating has already made a good progress, but has not been widely applied to the field of high corrosion-resistant protective coatings on the surface of neodymium iron boron magnets. The reason for this is mainly due to Al2O3The preparation of thin films still has the following problems and disadvantages, in particular: 1. reactive sputtering of Al2O3The film has a typical target poisoning phenomenon, and as the deposition time is prolonged, the gradually deepened target poisoning state can obviously reduce the energy of film forming particles, thereby leading to loose and porous film structure and having adverse effects on corrosion resistance. 2. The reactive sputtering process is difficult to control, and in order to ensure the stoichiometric ratio of the aluminum oxide, the deposition process is mostly in a target poisoning mode of the reactive sputtering, the deposition rate is very low, and the industrialized requirement cannot be met. 3. Al (Al)2O3Film(s)Belongs to intrinsic brittle materials, the stress of the film is continuously increased due to the growth difference of the thermal expansion coefficient and the structure, the phenomenon of brittle damage or falling is very easy to occur, and the thick film (a) which is beneficial to improving the corrosion resistance can not be realized>5 μm). Therefore, the method for rapidly preparing Al/Al with high density, binding force and excellent corrosion resistance is explored2O3The multilayer film method breaks through the technical bottleneck and promotes the high corrosion resistance Al/Al of the surface of the neodymium iron boron magnet2O3The protective coating is applied in a large scale, and has important scientific and engineering significance.
Disclosure of Invention
The embodiment of the invention provides a preparation method of a high-corrosion-resistance protective coating on the surface of a neodymium iron boron magnet. The method comprises the following steps:
step 100, pretreatment: cleaning the neodymium iron boron magnet and a vacuum chamber of the coating equipment;
step 200: setting plasma parameters: cleaning a Ti target by adopting a high-frequency magnetron sputtering technology, cleaning an Al target by adopting a medium-frequency magnetron sputtering technology, acquiring an emission spectrum of a target surface plasma through a plasma emission spectrum feedback system, selecting Al-396nm as a monitoring spectral line, and setting the spectral line intensity of the Al-396 nm;
step 300, preparing the composite corrosion-resistant coating: adopt high frequency magnetron sputtering technique right the Ti target carries out once sputtering, through once sputter to the neodymium iron boron magnet applys negative high bias voltage, carries out the ion to the sculpture on deposition surface, after once sputtering the neodymium iron boron magnet loading forward pulse bias voltage carries out the degasification, then adopts high frequency magnetron sputtering technique right the Ti target carries out the secondary sputtering, obtains the Ti anchor coat, and based on plasma emission spectrum at last, it is right to adopt intermediate frequency magnetron sputtering technique the Al target sputters, simultaneously to vacuum chamber lets in oxygen, and alternate deposition obtains multilayer structure's alumina coating.
In one possible embodiment, the plasma parameters are set: cleaning a Ti target by adopting a high-frequency magnetron sputtering technology, cleaning an Al target by adopting a medium-frequency magnetron sputtering technology, acquiring an emission spectrum of a target surface plasma through a plasma emission spectrum feedback system, selecting Al-396nm as a monitoring spectral line, and setting the spectral line intensity of the Al-396nm, wherein the method comprises the following steps:
step 201, cleaning a Ti target: introducing high-purity argon, setting the flow of the Ar to be 60-250 sccm, and increasing the air pressure in the vacuum chamber to 0.5-3 Pa; using a high-energy pulse magnetron sputtering power supply, starting a Ti target, and sputtering and cleaning a cathode target material for 5-20 min; wherein, the peak power density is set to be 1-2 kW/cm2The frequency is 10-100 Hz, and the pulse length is 10-200 mus; the pulse bias voltage of the matrix is-600V to-900V, the frequency is 10 Hz to 100Hz, and the sputtering power supply is closed;
step 202, cleaning of the Al target: introducing high-purity argon, setting the flow of the Ar to be 60-250 sccm, and increasing the air pressure in the vacuum chamber to 0.5-3 Pa; starting an Al target by using a medium-frequency magnetron sputtering power supply, and sputtering and cleaning the cathode target for 15-40 min; wherein, the target current is set to be 3-8A, and the duty ratio is 10-80%; the pulse bias of the matrix is-600V to-900V, and the frequency is 10 Hz to 100 Hz;
step 203, calibrating spectral line intensity: starting a plasma emission spectrum feedback control system, obtaining a target surface plasma emission spectrum of the Al target, and selecting a 396nm position of an Al atomic spectral line; wherein, the flow rate of Ar gas is set to be 60-200 sccm, and the air pressure in the vacuum chamber is set to be 0.5-2 Pa; setting the target current to be 3-8A and the duty ratio to be 10-80%; the pulse bias of the matrix is-40 to-150V, and the frequency is 10 to 100 Hz; calibrating the spectral line intensity of Al-396nm to be maximum; and (4) turning off a sputtering power supply, and calibrating the spectral line intensity of Al-396nm to be extremely small.
In one possible embodiment, the composite corrosion resistant coating is prepared by: adopt high frequency magnetron sputtering technique right the Ti target carries out once sputtering, through once sputter to neodymium iron boron magnet applys negative high bias voltage, carries out the ion to the sculpture on deposition surface, after once sputtering the neodymium iron boron magnet loading forward pulse bias voltage carries out the degasification, then adopts high frequency magnetron sputtering technique right the Ti target carries out the secondary sputtering, obtains the Ti anchor coat, and based on plasma emission spectrum at last, adopt intermediate frequency magnetron sputtering technique right the Al target sputters, simultaneously to vacuum chamber lets in oxygen, and alternate deposition obtains multilayer structure's alumina coating, includes:
step 301, etching: opening a front baffle of the Ti target, using a high-power pulse magnetron sputtering power supply, opening the Ti target, and continuously sputtering for 2-10 min; wherein, the flow rate of Ar gas is set to be 40-150 sccm, so that the air pressure in the vacuum chamber is 0.3-0.8 Pa; setting the peak power density to be 1-2 kW/cm2The frequency is 10-100 Hz, and the pulse length is 10-200 mus; the pulse bias voltage of the matrix is-800V to-1000V, the pulse frequency is synchronous with the high-power pulse magnetron sputtering power supply, and the pulse length is 10-200 mu s;
step 302, degassing: turning off a sputtering power supply, loading forward pulse bias on the substrate, and performing electron bombardment degassing treatment for 1-10 min; repeating the steps 301 and 302 until the circulation process reaches 2 to 10 times; wherein, the flow rate of Ar gas is set to be 40-150 sccm, so that the air pressure in the vacuum chamber is 0.3-0.8 Pa; the positive bias voltage is set to 200-800V, and the pulse frequency is 10-100 Hz;
step 303, depositing a bonding layer Ti: starting a Ti target by using a high-power pulse magnetron sputtering power supply, and continuously sputtering for 1-8 min; setting the flow rate of Ar gas to be 40-150 sccm, and making the air pressure in the vacuum chamber to be 0.3-0.8 Pa; wherein, the peak power density is set to be 1-2 kW/cm2The frequency is 10-100 Hz, and the pulse length is 10-200 mus; the pulse bias of the substrate is-150 to-250V, the pulse frequency is synchronous with the high-power pulse magnetron sputtering power supply, and the pulse length is 10 to 200 mu s. The thickness of the plating layer is 0.06-0.2 μm;
step 304, depositing multi-layer Al/Al film2O3：
Step 3041, using the medium frequency magnetron sputtering power supply to turn on the Al target. Setting the flow rate of Ar gas to be 60-200 sccm, and making the air pressure in the vacuum chamber to be 0.5-2 Pa;
wherein, the target current is set to be 3-8A, and the duty ratio is 10-80%; the pulse bias of the matrix is-40 to-150V, and the frequency is 10 to 100 Hz;
3042 closing the front baffle of the Al target, and sputtering and cleaning the cathode target for 5-10 min; opening the baffle, and continuously sputtering for 1-20 min, wherein the thickness of the Al coating is 0.06-2 μm;
3043 setting the spectral line intensity at Al-396nm to 5-95% of any value in the feedback control system; opening an oxygen passage, and dynamically adjusting the introduction amount by a gas flowmeter according to real-time plasma parameters until the spectral line intensity is stabilized at a parameter set value; the whole adjusting process is approximately 1-10 min, and the introduction amount of oxygen is 0-20 sccm;
3044, fixing the Al spectral line intensity value, and continuously sputtering for 2-80 min to obtain Al2O3The thickness of the plating layer is 0.2-6 μm, and an oxygen passage is closed;
repeat step 3042 and 3044 until the sub-cycle reaches 2-10 times.
In one possible embodiment, the method further comprises:
step 400, cooling and discharging: and after the film coating is finished, closing the target power supply, the bias power supply and the feedback control system power supply, closing the gas circuit, cooling the coated neodymium-iron-boron magnet along with the furnace for 30min, and discharging the neodymium-iron-boron magnet out of the furnace.
The preparation method of the high-corrosion-resistance protective coating on the surface of the neodymium iron boron magnet has the following advantages that on the one hand, the target poisoning phenomenon in the reactive sputtering process of the insulating film is eliminated and Al is realized by the plasma emission spectrum feedback control method based on the monitoring of the characteristic peak of the sputtered particles2O3The film grows fast, stably and uniformly. On the second aspect, a metal Ti bonding layer with a central thermal expansion coefficient is added on the surface of the NdFeB magnetic material, so that a thermal matching effect is achieved, and the method has great benefit for improving the bonding force; meanwhile, the Ti film prevents the outward diffusion of Fe element in the magnetic material in the Al film plating process, thereby effectively improving the corrosion resistance of the magnetic material; in the third aspect, a high-energy pulse magnetron sputtering technology is introduced, and through the matching of sputtering pulses and positive and negative matrix bias pulses, high-corrosion-resistant Al/Al with high hardness (20GPa), low friction coefficient (0.2), good adhesive force (more than 50N) and excellent corrosion resistance (more than 800h of neutral salt spray experiment) is obtained2O3And (4) protective coating.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is a flowchart of a method for preparing a high corrosion-resistant protective coating on a surface of a neodymium-iron-boron magnet according to an embodiment of the present disclosure;
FIG. 2 is a cross-sectional view of an alumina monolayer film when the Al content setting value in the plasma emission spectrum is 60%;
FIG. 3 shows Al/Al ratios at a set Al content of 60% in example 2 of the present application2O3A cross-sectional profile of the protective coating;
FIG. 4 shows the results of the salt spray resistance test of example 2 with Al/Al after 800h2O3A neodymium iron boron magnet object picture of the protective coating.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, technical methods in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without any creative effort, shall fall within the scope of the present invention.
It should be noted that, if directional indications (such as up, down, left, right, front, back, etc.) are involved in the embodiment of the present invention, the directional indications are only used for explaining the relative positional relationship between the components in a certain posture, the motion situation, etc., and if the certain posture is changed, the directional indications are changed accordingly.
The embodiment of the application aims at the crystalline alumina filmHas the problems of low deposition rate, difficult structure control, limited coating thickness and the like in the preparation technology, provides a method for preparing high corrosion resistance Al/Al on the surface of a neodymium iron boron magnet2O3A method of protective coating. The obtained coating has high surface hardness, density, binding force and excellent corrosion resistance, and is used for meeting the protection requirement of the neodymium iron boron magnet on the surface when applied in various severe environments.
Fig. 1 is a flowchart of a method for preparing a high corrosion-resistant protective coating on a surface of a neodymium iron boron magnet according to an embodiment of the present disclosure, and as shown in fig. 1, the embodiment of the present disclosure provides a method for preparing a high corrosion-resistant protective coating on a surface of a neodymium iron boron magnet, including:
step 100, pretreatment: the vacuum chamber of the neodymium iron boron magnet and the coating equipment is cleaned, and the steps specifically comprise:
step 101, magnet pretreatment: chamfering the neodymium iron boron magnet, putting the neodymium iron boron magnet into a vibration type grinding machine to obtain an NdFeB magnet with the corner arc not less than 0.5mm, then carrying out sand blasting and ultrasonic cleaning of an acid-base solution, drying the surface of the magnet by using an air pump, and putting the surface of the magnet into a vacuum chamber of coating equipment;
102, gas path cleaning: the vacuum chamber is pumped to 1.0X 10-3Introducing argon and oxygen into a vacuum chamber below Pa, and cleaning a gas path;
103, ion source bombardment cleaning: and closing the front baffle of the cathode target and opening the ion source baffle. Introducing high-purity argon into the vacuum chamber, and cleaning for 15-60 min by adopting ion source gas glow discharge; setting power of a power supply to be 5-6 kW and current to be 3-8A; setting the flow rate of Ar gas to be 200-350 sccm, and increasing the pressure in the vacuum chamber to 3-10 Pa; the substrate pulse bias voltage is-700V to-1000V, the frequency is 10 Hz to 100Hz, and the ion source baffle is closed.
Step 200: setting plasma parameters: the method comprises the following steps of cleaning a Ti target by adopting a high-frequency magnetron sputtering technology, cleaning an Al target by adopting a medium-frequency magnetron sputtering technology, obtaining an emission spectrum of a target surface plasma through a plasma emission spectrum feedback system, selecting Al-396nm as a monitoring spectral line, and setting the spectral line intensity of the Al-396nm, wherein the method specifically comprises the following steps:
step 201, cleaning a Ti target: introducing high-purity argon, setting the flow of the Ar to be 60-250 sccm, and increasing the air pressure in the vacuum chamber to 0.5-3 Pa; using a high-energy pulse magnetron sputtering power supply, starting a Ti target, and sputtering and cleaning a cathode target material for 5-20 min;
wherein, the peak power density is set to be 1-2 kW/cm2The frequency is 10-100 Hz, and the pulse length is 10-200 mus; the pulse bias voltage of the matrix is-600V to-900V, the frequency is 10 Hz to 100Hz, and the sputtering power supply is closed;
step 202, cleaning of the Al target: introducing high-purity argon, setting the flow of the Ar to be 60-250 sccm, and increasing the air pressure in the vacuum chamber to 0.5-3 Pa; starting an Al target by using a medium-frequency magnetron sputtering power supply, and sputtering and cleaning the cathode target for 15-40 min;
wherein, the target current is set to be 3-8A, and the duty ratio is 10-80%; the pulse bias of the matrix is-600V to-900V, and the frequency is 10 Hz to 100 Hz;
step 203, calibrating spectral line intensity: starting a plasma emission spectrum feedback control system, obtaining a target surface plasma emission spectrum of the Al target, and selecting a 396nm position of an Al atomic spectral line;
wherein, the flow rate of Ar gas is set to be 60-200 sccm, and the air pressure in the vacuum chamber is set to be 0.5-2 Pa; setting the target current to be 3-8A and the duty ratio to be 10-80%; the pulse bias of the matrix is-40 to-150V, and the frequency is 10 to 100 Hz; calibrating the spectral line intensity of Al-396nm to be maximum; and (4) turning off a sputtering power supply, and calibrating the spectral line intensity of Al-396nm to be extremely small.
It should be noted that: in this embodiment, a feedback control system of plasma emission spectrum is introduced, a method combining high energy pulse magnetron sputtering (HiPIMS) and medium frequency pulse (40kHz) magnetron sputtering is adopted, and positive bias pulses are applied to bombard the substrate in the process. A flat rectangular pure titanium, pure aluminum target (650 × 130mm, > 99.99%) was used; argon and oxygen are used as working gases, and the purity of the working gases is 99.999 percent. The sample stage can perform revolution and rotation, and is applied with pulse bias.
The plasma emission spectrum feedback control system mainly comprises a plasma full spectrum analyzer (OES), a feedback controller and a gas flowmeter. The detection optical fiber is inserted into the surface of the sputtering target, so that the emission spectrum of the plasma on the target surface can be obtained in real time, and the wavelength range is 200-1100 nm. Selecting a typical characteristic spectral line of the particles to be monitored according to requirements, calibrating a maximum (100%) value and a minimum (0%) value of intensity under experimental conditions, setting the relative intensity (0% -100%) of the spectral line to deposit the film, and feeding back and adjusting the gas introduction amount of the flowmeter by using the characteristic peak intensity as a calibration object by using a controller, thereby ensuring the stability of the particle content in the film deposition process.
Step 300, preparing the composite corrosion-resistant coating: adopt high frequency magnetron sputtering technique to carry out once sputtering to the Ti target, apply the high bias voltage of negative-going to the neodymium iron boron magnet through once sputtering, carry out the ion to the sculpture on deposition surface, load forward pulse bias to the neodymium iron boron magnet and carry out the degasification after once sputtering, then adopt high frequency magnetron sputtering technique to carry out the secondary sputtering to the Ti target, obtain the Ti anchor coat, finally based on plasma emission spectrum, adopt intermediate frequency magnetron sputtering technique to sputter the Al target, let in oxygen to vacuum chamber simultaneously, alternate deposition obtains multilayer structure's alumina coating, this step specifically includes:
step 301, etching: opening a front baffle of the Ti target, using a high-power pulse magnetron sputtering power supply, opening the Ti target, and continuously sputtering for 2-10 min;
wherein, the flow rate of Ar gas is set to be 40-150 sccm, so that the air pressure in the vacuum chamber is 0.3-0.8 Pa; setting the peak power density to be 1-2 kW/cm2The frequency is 10-100 Hz, and the pulse length is 10-200 mus; the pulse bias voltage of the matrix is-800V to-1000V, the pulse frequency is synchronous with the high-power pulse magnetron sputtering power supply, and the pulse length is 10-200 mu s;
step 302, degassing: turning off a sputtering power supply, loading forward pulse bias on the base body, carrying out electron bombardment degassing treatment for 1-10 min, and repeating the steps 301 and 302 until the cycle process reaches 2-10 times;
wherein, the flow rate of Ar gas is set to be 40-150 sccm, so that the air pressure in the vacuum chamber is 0.3-0.8 Pa; the positive bias voltage is set to 200-800V, and the pulse frequency is 10-100 Hz;
step 303, depositing a bonding layer Ti: starting a Ti target by using a high-power pulse magnetron sputtering power supply, and continuously sputtering for 1-8 min; setting the flow rate of Ar gas to be 40-150 sccm, and making the air pressure in the vacuum chamber to be 0.3-0.8 Pa;
wherein, the peak power density is set to be 1-2 kW/cm2The frequency is 10-100 Hz, and the pulse length is 10-200 mus; the pulse bias of the substrate is-150 to-250V, the pulse frequency is synchronous with the high-power pulse magnetron sputtering power supply, and the pulse length is 10 to 200 mu s. The thickness of the plating layer is 0.06-0.2 μm;
it is noted that the metal Ti bonding layer with the thermal expansion coefficient centered is added on the surface of the NdFeB magnetic material, so that the thermal matching effect is achieved, and the bonding force is improved; meanwhile, the Ti film prevents the outward diffusion of Fe element in the magnetic material in the Al film plating process, and effectively improves the corrosion resistance of the magnetic material.
Step 304, depositing multi-layer Al/Al film2O3：
Step 3041, using the medium frequency magnetron sputtering power supply to turn on the Al target. Setting the flow rate of Ar gas to be 60-200 sccm, and making the air pressure in the vacuum chamber to be 0.5-2 Pa;
wherein, the target current is set to be 3-8A, and the duty ratio is 10-80%; the pulse bias of the matrix is-40 to-150V, and the frequency is 10 to 100 Hz;
3042 closing the front baffle of the Al target, and sputtering and cleaning the cathode target for 5-10 min; opening the baffle, and continuously sputtering for 1-20 min, wherein the thickness of the Al coating is 0.06-2 μm;
3043 setting the spectral line intensity at Al-396nm to 5-95% of any value in the feedback control system; opening an oxygen passage, and dynamically adjusting the introduction amount by a gas flowmeter according to real-time plasma parameters until the spectral line intensity is stabilized at a parameter set value; the whole adjusting process is approximately 1-10 min, and the introduction amount of oxygen is 0-20 sccm;
it should be noted that: in the preparation of the aluminum oxide film, sputtering Al atoms of a cathode target are taken as monitoring objects, a spectral line position of 396nm is selected, the spectral line intensity when a sputtering power supply is not started is marked as minimum (0%), the power supply is started but oxygen is not introduced, the spectral line intensity when pure aluminum is sputtered is marked as maximum (100%), and then any relative intensity (such as 10%, 20%, 30% and 40% … …) in the interval is set for deposition of the film. The whole preparation process is a dynamic balance for continuously feeding back and adjusting the oxygen input, and realizes the design and control of the components of the film forming particles.
3044, fixing the Al spectral line intensity value, and continuously sputtering for 2-80 min to obtain Al2O3The thickness of the plating layer is 0.2-6 μm, and an oxygen passage is closed;
repeat the steps 3042 and 3044 until the cycle reaches 2-10 times.
As can be understood, the embodiment is based on the detection and feedback control of the characteristic parameters of the plasma, and Al/Al formed by alternate deposition2O3The multilayer film structure effectively reduces the micro defects of the coating, and the Al is uniform and compact2O3The layer blocks a crystal boundary penetrating through the coating, and the corrosion resistance of the neodymium iron boron (NdFeB) magnet is remarkably improved; meanwhile, the surface hardness of the Al coating is improved, and the coating failure caused by surface scratch can be effectively prevented.
The preparation method in this embodiment further includes: step 400, cooling and discharging: and after the film coating is finished, closing the target power supply, the bias power supply and the feedback control system power supply, closing the gas circuit, cooling the coated neodymium-iron-boron magnet along with the furnace for 30min, and discharging the neodymium-iron-boron magnet out of the furnace.
As shown in fig. 2, the cross-sectional morphology of the single-layer film of aluminum oxide was found when the Al content in the plasma emission spectrum was set to 60%. It can be seen that the film layer has uniform and compact structure, fine crystal grains and no obvious defects; the deposition rate of the film is 110nm/min, and the film is not obviously reduced compared with a pure Al film, so that the rapid preparation of a large-area alumina coating is realized, and the possibility of being applied to industrial production is greatly increased.
The preparation method disclosed by the embodiment is based on detection and feedback of the content of film forming particles in a vacuum environment, provides a feedback control method of plasma emission spectrum, eliminates the hysteresis effect caused by target poisoning in the preparation process, transfers the aluminum oxy-chemical reaction from a target surface to a substrate, is assisted by technologies such as high-energy pulse magnetron sputtering and the like, and successfully prepares the high-corrosion-resistant Al/Al on the surface of the neodymium iron boron magnet at room temperature by controlling and optimizing the components and energy of the film forming particles2O3The protective coating lays a good foundation for engineering application of the protective coating, and has very important industrial value. Al/Al obtained2O3The nano multilayer film has high hardness (20GPa), low friction coefficient (0.2), good adhesive force (more than 50N) and excellent corrosion resistance (the neutral salt spray test is more than 800 h).
Example 2
The embodiment is a preparation method of a high corrosion-resistant protective coating on the surface of a neodymium iron boron magnet, and the embodiment prepares the high corrosion-resistant protective coating on the surface of the neodymium iron boron magnet by using the spectral line intensity of Al-396nm as 60%, and the method comprises the following steps:
pretreatment:
(1) magnet pretreatment: chamfering, putting the magnet into a vibration type grinder to obtain an NdFeB magnet with the corner arc not less than 0.5mm, then carrying out sand blasting and ultrasonic cleaning of an acid-base solution, drying the surface of the magnet by using an air pump, and putting the magnet into a vacuum chamber of coating equipment;
in this embodiment, the size of the ndfeb magnet is 60 × 10 mm.
(2) Cleaning a gas path: the vacuum chamber is pumped to 1.0X 10-3And introducing argon and oxygen into the vacuum chamber below Pa to perform gas path cleaning.
(3) Ion source bombardment cleaning: and closing the front baffle of the cathode target and opening the ion source baffle. Introducing high-purity argon into the vacuum chamber, and cleaning for 30min by adopting ion source gas glow discharge; setting the power of a power supply to be 5kW and the current to be 4A;
wherein, the flow rate of Ar is set to be 250sccm, so that the air pressure in the vacuum chamber is increased to 5 Pa; the substrate was pulsed at-800V and 50Hz, and the ion source shutter was closed.
(II) plasma parameter calibration:
(1) cleaning a Ti target: introducing high-purity argon, setting the flow rate of the Ar to be 180sccm, and increasing the air pressure in the vacuum chamber to 1.5 Pa; using a high-energy pulse magnetron sputtering power supply, starting a Ti target, and sputtering and cleaning a cathode target for 10 min;
wherein the peak power density is set to be 1.5kW/cm2The frequency is 50Hz, and the pulse length is 10 mus;the substrate was pulsed at-900V bias and 50Hz frequency. The sputtering power supply is turned off.
(2) Cleaning an Al target: introducing high-purity argon, setting the flow rate of the Ar to be 180sccm, and increasing the air pressure in the vacuum chamber to 1.5 Pa; starting an Al target by using a medium-frequency magnetron sputtering power supply, and sputtering and cleaning the cathode target for 15 min;
wherein, the target current is set to be 4A, and the duty ratio is 80 percent; the substrate was pulsed at-900V bias and 50Hz frequency.
(3) Calibrating spectral line intensity: starting a plasma emission spectrum feedback control system, obtaining a target surface plasma emission spectrum of the Al target, and selecting a 396nm position of an Al atomic spectral line; setting the flow rate of Ar to be 80sccm, and enabling the air pressure in the vacuum chamber to be 0.8 Pa;
wherein, the target current is set to be 4A, and the duty ratio is 80 percent; the pulse bias voltage of the matrix is-50V, and the frequency is 50 Hz; calibrating the spectral line intensity of Al-396nm to be maximum (100%); and (3) turning off a sputtering power supply, and calibrating the spectral line intensity of Al-396nm to be extremely small (0%).
(III) preparing the composite corrosion-resistant coating:
(1) etching: opening a front baffle of the Ti target, using a high-power pulse magnetron sputtering power supply, opening the Ti target, and continuously sputtering for 2 min; setting the flow rate of Ar to be 60sccm, and enabling the air pressure in the vacuum chamber to be 0.4 Pa;
wherein the peak power density is set to be 1.5kW/cm2The frequency is 50Hz, and the pulse length is 10 mus; the pulse bias voltage of the matrix is-800V, the pulse frequency is synchronous with the high-power pulse magnetron sputtering power supply, and the pulse length is 10 mus.
(2) Degassing: turning off the sputtering power supply, loading forward pulse bias on the substrate, and performing electron bombardment degassing treatment for 2 min;
wherein, the flow rate of Ar gas is set to be 60sccm, and the air pressure in the vacuum chamber is 0.4 Pa; the positive bias voltage was set at 400V and the pulse frequency was 50 Hz.
Repeat step 1 and step 2 until this cycle reaches 3 times.
(3) Depositing a bonding layer Ti: using a high-power pulse magnetron sputtering power supply, starting a Ti target, and continuously sputtering for 2 min; setting the flow rate of Ar to be 60sccm, and enabling the air pressure in the vacuum chamber to be 0.4 Pa;
wherein,setting the peak power density to be 1.2kW/cm2The frequency is 50Hz, and the pulse length is 10 mus; the pulse bias voltage of the matrix is-200V, the pulse frequency is synchronous with the high-power pulse magnetron sputtering power supply, and the pulse length is 10 mus. The thickness of the plating layer was 0.1. mu.m.
(4) Depositing multi-layer film Al/Al2O3：
a. And (4) starting the Al target by using a medium-frequency magnetron sputtering power supply. Setting the flow rate of Ar to be 80sccm, and enabling the air pressure in the vacuum chamber to be 0.8 Pa; setting the target current to be 4A and the duty ratio to be 80 percent; the substrate was pulsed at-50V bias and 50Hz frequency.
b. Closing the front baffle of the Al target, and sputtering and cleaning the cathode target for 5 min; the baffle is opened, sputtering is continued for 5min, and the thickness of the Al coating is 0.5 mu m.
c. Setting the spectral line intensity at the position of Al-396nm to be 60% in a feedback control system according to research and preparation requirements; opening an oxygen passage, and dynamically adjusting the introduction amount by a gas flowmeter according to real-time plasma parameters until the spectral line intensity is stabilized at a parameter set value; the whole adjusting process needs 2min approximately, and the introduction amount of oxygen is 0-20 sccm.
d. Fixing the Al spectral line intensity value unchanged, continuously sputtering for 3min, wherein Al2O3The thickness of the plating layer was 0.3. mu.m.
The oxygen passage is closed.
e. Repeating the steps b-d until the circulation process reaches 5 times.
Cooling and discharging: and after the film coating is finished, closing the target power supply, the bias power supply and the feedback control system power supply, closing the gas circuit, cooling the coated neodymium-iron-boron magnet along with the furnace for 30min, and discharging the neodymium-iron-boron magnet out of the furnace.
FIG. 3 is a graph showing Al/Al ratios at a set value of Al content of 60% in example 22O3And (4) a cross-sectional profile of the protective coating. The surface of the neodymium iron boron magnet plated by the process is bright black, smooth and flat. The surface showed no significant change after 800h of neutral salt spray test as shown in FIG. 4.
Example 3
The embodiment is a preparation method of a high corrosion-resistant protective coating on the surface of a neodymium iron boron magnet, and the embodiment prepares the high corrosion-resistant protective coating on the surface of the neodymium iron boron magnet by using the spectral line intensity of Al-396nm as 65%, and the method comprises the following steps:
(I) pretreatment
(1) Magnet pretreatment: and (3) chamfering the neodymium iron boron magnet (with the size of 30 x 10 x 5mm), putting the neodymium iron boron magnet into a vibration type grinding machine to obtain an NdFeB magnet with the corner circular arc not less than 0.5mm, then carrying out sand blasting and ultrasonic cleaning of an acid-base solution, blowing dry the surface of the magnet by using an air pump, and putting the magnet into a vacuum chamber of coating equipment.
(2) Cleaning a gas path: the vacuum chamber is pumped to 1.0X 10-3And introducing argon and oxygen into the vacuum chamber below Pa to perform gas path cleaning.
(3) Ion source bombardment cleaning: and closing the front baffle of the cathode target and opening the ion source baffle. Introducing high-purity argon into the vacuum chamber, and cleaning for 15min by adopting ion source gas glow discharge;
wherein, the power of the power supply is set to be 5kW, and the current is set to be 5A; setting the flow rate of Ar to be 300sccm, and increasing the air pressure in the vacuum chamber to 6 Pa; the substrate was pulsed at-700V bias and 50Hz frequency. The ion source shutter is closed.
(II) plasma parameter calibration
(1) Cleaning a Ti target: introducing high-purity argon, setting the flow rate of the Ar to be 150sccm, and increasing the air pressure in the vacuum chamber to 1.2 Pa; using a high-energy pulse magnetron sputtering power supply, starting a Ti target, and sputtering and cleaning a cathode target for 10 min;
wherein the peak power density is set to be 1.5kW/cm2The frequency is 50Hz, and the pulse length is 10 mus; the substrate was pulsed at-700V bias and 50Hz frequency. The sputtering power supply is turned off.
(2) Cleaning an Al target: introducing high-purity argon, setting the flow rate of the Ar to be 150sccm, and increasing the air pressure in the vacuum chamber to 1.2 Pa; starting an Al target by using a medium-frequency magnetron sputtering power supply, and sputtering and cleaning the cathode target for 20 min;
wherein, the target current is set to be 5A, and the duty ratio is 80 percent; the substrate was pulsed at-800V bias and 50Hz frequency.
(3) Calibrating spectral line intensity: starting a plasma emission spectrum feedback control system, obtaining a target surface plasma emission spectrum of the Al target, and selecting a 396nm position of an Al atomic spectral line; setting the flow rate of Ar to be 100sccm, and enabling the air pressure in the vacuum chamber to be 1 Pa;
wherein, the target current is set to be 5A, and the duty ratio is 80 percent; the pulse bias voltage of the matrix is-70V, and the frequency is 50 Hz; calibrating the spectral line intensity of Al-396nm to be maximum (100%); and (3) turning off a sputtering power supply, and calibrating the spectral line intensity of Al-396nm to be extremely small (0%).
(III) preparation of composite corrosion-resistant coating
(1) Etching: opening a front baffle of the Ti target, using a high-power pulse magnetron sputtering power supply, opening the Ti target, and continuously sputtering for 3 min; setting the flow rate of Ar to be 80sccm, and enabling the air pressure in the vacuum chamber to be 0.6 Pa;
wherein the peak power density is set to be 1.5kW/cm2The frequency is 50Hz, and the pulse length is 10 mus; the pulse bias voltage of the matrix is-800V, the pulse frequency is synchronous with the high-power pulse magnetron sputtering power supply, and the pulse length is 10 mus.
(2) Degassing: turning off the sputtering power supply, loading forward pulse bias on the substrate, and performing electron bombardment degassing treatment for 2 min;
wherein, the flow rate of Ar is set to be 80sccm, and the air pressure in the vacuum chamber is 0.6 Pa; the positive bias voltage was set at 500V and the pulse frequency was 50 Hz.
Repeating the step 1) and the step 2) until the circulation process reaches 2 times.
(3) Depositing a bonding layer Ti: using a high-power pulse magnetron sputtering power supply, starting a Ti target, and continuously sputtering for 6 min; setting the flow rate of Ar to be 80sccm, and enabling the air pressure in the vacuum chamber to be 0.6 Pa;
wherein the peak power density is set to be 1.5kW/cm2The frequency is 50Hz, and the pulse length is 10 mus; the pulse bias voltage of the matrix is-200V, the pulse frequency is synchronous with the high-power pulse magnetron sputtering power supply, and the pulse length is 10 mus. The thickness of the plating layer was 0.15. mu.m.
(4) Depositing multi-layer film Al/Al2O3：
a. Starting an Al target by using a medium-frequency magnetron sputtering power supply;
wherein, the flow rate of Ar is set to be 100sccm, and the air pressure in the vacuum chamber is made to be 1 Pa; setting the target current to be 5A and the duty ratio to be 80 percent; the substrate was pulsed at-70V bias and 50Hz frequency.
b. Closing the front baffle of the Al target, and sputtering and cleaning the cathode target for 5 min; the baffle plate is opened, sputtering is continued for 10min, and the thickness of the Al coating is 1 mu m.
c. According to research and preparation requirements, setting the spectral line intensity at the Al-396nm position to be 65% in a feedback control system; opening an oxygen passage, and dynamically adjusting the introduction amount by a gas flowmeter according to real-time plasma parameters until the spectral line intensity is stabilized at a parameter set value; the whole adjusting process needs 1min approximately, and the introduction amount of oxygen is 0-20 sccm.
d. Fixing the Al spectral line intensity value unchanged, continuously sputtering for 10min, wherein Al2O3The thickness of the plating layer was 0.8. mu.m.
The oxygen passage is closed.
e. Repeating the steps b-d until the circulation process reaches 3 times.
(IV) cooling and tapping
And after the film coating is finished, closing the target power supply, the bias power supply and the feedback control system power supply, closing the gas circuit, cooling the coated neodymium-iron-boron magnet along with the furnace for 30min, and discharging the neodymium-iron-boron magnet out of the furnace.
In conclusion, the preparation method of the high-corrosion-resistance protective coating on the surface of the neodymium iron boron magnet solves the problems of low deposition rate, difficult structure control, limited coating thickness and the like in the prior art, and guarantees the process stability and repeatability in the industrial production process. Meanwhile, the super-strong corrosion resistance can be used for a long time in high salinity climate, and the neodymium iron boron permanent magnet material is particularly suitable for neodymium iron boron permanent magnet materials in offshore wind energy motors, and can bring great economic and social benefits.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments described above as examples. It will be appreciated by those skilled in the art that various equivalent changes and modifications can be made without departing from the spirit and scope of the invention, and it is intended to cover all such modifications and alterations as fall within the true spirit and scope of the invention.
Claims (4)
1. A preparation method of a high-corrosion-resistance protective coating on the surface of a neodymium iron boron magnet is characterized by comprising the following steps:
step 100, pretreatment: cleaning the neodymium iron boron magnet and a vacuum chamber of the coating equipment;
step 200: setting plasma parameters: cleaning a Ti target by adopting a high-frequency magnetron sputtering technology, cleaning an Al target by adopting a medium-frequency magnetron sputtering technology, acquiring an emission spectrum of a target surface plasma through a plasma emission spectrum feedback system, selecting Al396nm as a monitoring spectral line, and setting the spectral line intensity of Al-396 nm;
step 300, preparing the composite corrosion-resistant coating: carrying out primary sputtering on the Ti target by adopting a high-frequency magnetron sputtering technology, applying negative high bias voltage to the neodymium iron boron magnet by the primary sputtering, etching the deposition surface by ions, loading positive pulse bias voltage to the neodymium iron boron magnet for degassing after the primary sputtering, carrying out secondary sputtering on the Ti target by adopting the high-frequency magnetron sputtering technology to obtain a Ti bonding layer, sputtering the Al target by adopting a medium-frequency magnetron sputtering technology based on a plasma emission spectrum, simultaneously introducing oxygen into the vacuum chamber, and alternately depositing to obtain an aluminum oxide coating with a multilayer structure;
wherein, the preparation of the composite corrosion resistant coating comprises the following steps: adopt high frequency magnetron sputtering technique right the Ti target carries out once sputtering, through once sputter to neodymium iron boron magnet applys negative high bias voltage, carries out the ion to the sculpture on deposition surface, after once sputtering the neodymium iron boron magnet loading forward pulse bias voltage carries out the degasification, then adopts high frequency magnetron sputtering technique right the Ti target carries out the secondary sputtering, obtains the Ti anchor coat, and based on plasma emission spectrum at last, adopt intermediate frequency magnetron sputtering technique right the Al target sputters, simultaneously to vacuum chamber lets in oxygen, and alternate deposition obtains multilayer structure's alumina coating, includes:
step 301, etching: opening a front baffle of the Ti target, using a high-power pulse magnetron sputtering power supply, opening the Ti target, and continuously sputtering for 2-10 min; wherein, the flow rate of Ar gas is set to be 40-150 sccm, so that the air pressure in the vacuum chamber is 0.3-0.8 Pa; set peak power density 1E2kW/cm2The frequency is 10-100 Hz, and the pulse length is 10-200 mus; the pulse bias voltage of the matrix is-800V to-1000V, the pulse frequency is synchronous with the high-power pulse magnetron sputtering power supply, and the pulse length is 10-200 mu s;
step 302, degassing: turning off a sputtering power supply, loading forward pulse bias on the base body, carrying out electron bombardment degassing treatment for 1-10 min, and repeating 301 and 302 until the cycle process reaches 2-10 times; wherein, the flow rate of Ar gas is set to be 40-150 sccm, so that the air pressure in the vacuum chamber is 0.3-0.8 Pa; the positive bias voltage is set to 200-800V, and the pulse frequency is 10-100 Hz;
step 303, depositing a bonding layer Ti: starting a Ti target by using a high-power pulse magnetron sputtering power supply, and continuously sputtering for 1-8 min; setting the flow rate of Ar gas to be 40-150 sccm, and making the air pressure in the vacuum chamber to be 0.3-0.8 Pa; wherein, the peak power density is set to be 1-2 kW/cm2, the frequency is 10-100 Hz, and the pulse length is 10-200 mus; the pulse bias voltage of the substrate is-150 to-250V, the pulse frequency is synchronous with a high-power pulse magnetron sputtering power supply, the pulse length is 10 to 200 mu s, and the coating thickness is 0.06 to 0.2 mu m;
step 304, depositing multi-layer Al/Al film2O3: 3041, starting an Al target by using a medium-frequency magnetron sputtering power supply, setting the flow of Ar gas to be 60-200 sccm, and making the air pressure in the vacuum chamber to be 0.5-2 Pa; wherein, the target current is set to be 3-8A, and the duty ratio is 10-80%; the pulse bias of the matrix is-40 to-150V, and the frequency is 10 to 100 Hz;
3042 closing the front baffle of the Al target, and sputtering and cleaning the cathode target for 5-10 min; opening the baffle, and continuously sputtering for 1-20 min, wherein the thickness of the Al coating is 0.06-2 μm;
3043 setting the spectral line intensity at Al-396nm to 5-95% of any value in the feedback control system; opening an oxygen passage, and dynamically adjusting the introduction amount by a gas flowmeter according to real-time plasma parameters until the spectral line intensity is stabilized at a parameter set value; the whole adjusting process needs 1-10 min, and the introduction amount of oxygen is 0-20 sccm;
3044, fixing the Al spectral line intensity value, and continuously sputtering for 2-80 min to obtain Al2O3The thickness of the coating is 0.2-6 μm, and the oxygen is turned offA way; repeat the steps 3042 and 3044 until the cycle reaches 2-10 times.
2. The method for preparing according to claim 1, wherein the pretreatment: cleaning a magnet and a vacuum chamber of a coating device, comprising:
step 101, magnet pretreatment: chamfering the neodymium iron boron magnet, putting the neodymium iron boron magnet into a vibration type grinding machine to obtain the neodymium iron boron magnet with the corner arc not less than 0.5mm, then carrying out sand blasting and ultrasonic cleaning of an acid-base solution, drying the surface of the magnet by using an air pump, and putting the magnet into a vacuum chamber of coating equipment;
102, gas path cleaning: the vacuum chamber is pumped to 1.0X 10-3Introducing argon and oxygen into a vacuum chamber below Pa, and cleaning a gas path;
103, ion source bombardment cleaning: closing a front baffle of the cathode target, opening an ion source baffle, introducing high-purity argon into the vacuum chamber, and cleaning for 15-60 min by adopting ion source gas glow discharge; setting power of a power supply to be 5-6 kW and current to be 3-8A; setting the flow rate of Ar gas to be 200-350 sccm, and increasing the pressure in the vacuum chamber to 3-10 Pa; the substrate pulse bias voltage is-700V to-1000V, the frequency is 10 Hz to 100Hz, and the ion source baffle is closed.
3. The method according to claim 2, wherein the plasma parameter setting: cleaning a Ti target by adopting a high-frequency magnetron sputtering technology, cleaning an Al target by adopting a medium-frequency magnetron sputtering technology, acquiring an emission spectrum of a target surface plasma through a plasma emission spectrum feedback system, selecting Al-396nm as a monitoring spectral line, and setting the spectral line intensity of the Al-396nm, wherein the method comprises the following steps:
step 201, cleaning a Ti target: introducing high-purity argon, setting the flow of the Ar to be 60-250 sccm, and increasing the air pressure in the vacuum chamber to 0.5-3 Pa; using a high-energy pulse magnetron sputtering power supply, starting a Ti target, and sputtering and cleaning a cathode target material for 5-20 min; wherein, the peak power density is set to be 1-2 kW/cm2The frequency is 10-100 Hz, and the pulse length is 10-200 mus; the pulse bias of the matrix is-600V to-900V, and the frequency is 1Turning off a sputtering power supply at 0-100 Hz;
step 202, cleaning of the Al target: introducing high-purity argon, setting the flow of the Ar to be 60-250 sccm, and increasing the air pressure in the vacuum chamber to 0.5-3 Pa; starting an Al target by using a medium-frequency magnetron sputtering power supply, and sputtering and cleaning the cathode target for 15-40 min; wherein, the target current is set to be 3-8A, and the duty ratio is 10-80%; the pulse bias of the matrix is-600V to-900V, and the frequency is 10 Hz to 100 Hz;
step 203, calibrating spectral line intensity: starting a plasma emission spectrum feedback control system, obtaining a target surface plasma emission spectrum of the Al target, and selecting a 396nm position of an Al atomic spectral line; wherein, the flow rate of Ar gas is set to be 60-200 sccm, and the air pressure in the vacuum chamber is set to be 0.5-2 Pa; setting the target current to be 3-8A and the duty ratio to be 10-80%; the pulse bias of the matrix is-40 to-150V, and the frequency is 10 to 100 Hz; calibrating the spectral line intensity of Al-396nm to be maximum, turning off a sputtering power supply, and calibrating the spectral line intensity of Al-396nm to be minimum.
4. The method of manufacturing according to claim 1, further comprising:
step 400, cooling and discharging: and after the film coating is finished, closing the target power supply, the bias power supply and the feedback control system power supply, closing the gas circuit, cooling the coated neodymium-iron-boron magnet along with the furnace for 30min, and discharging the neodymium-iron-boron magnet out of the furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010228017.8A CN111304611B (en) | 2020-03-27 | 2020-03-27 | Preparation method of high-corrosion-resistance protective coating on surface of neodymium iron boron magnet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010228017.8A CN111304611B (en) | 2020-03-27 | 2020-03-27 | Preparation method of high-corrosion-resistance protective coating on surface of neodymium iron boron magnet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111304611A CN111304611A (en) | 2020-06-19 |
| CN111304611B true CN111304611B (en) | 2021-08-24 |
Family
ID=71145972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010228017.8A Active CN111304611B (en) | 2020-03-27 | 2020-03-27 | Preparation method of high-corrosion-resistance protective coating on surface of neodymium iron boron magnet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111304611B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0794268A1 (en) * | 1996-03-06 | 1997-09-10 | Vacuumschmelze GmbH | Process for improving corrosion protection of aluminium coated surfaces |
| CN104018133A (en) * | 2014-06-04 | 2014-09-03 | 北京汇磁粉体材料有限公司 | Multilayer composite protective coating on surface of sintered NdFeB magnet by multi-arc ion plating and process thereof |
| CN104630726A (en) * | 2015-01-28 | 2015-05-20 | 四川亚力超膜科技有限公司 | Nano ceramic heat-insulating film and preparation method thereof |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19827587A1 (en) * | 1998-06-20 | 1999-12-23 | Ardenne Anlagentech Gmbh | Double-magnetron sputtering unit for large area reactive plasma-enhanced deposition of e.g. light absorbing layers on metal strips for solar absorbers or heat reflective layers on window glass |
-
2020
- 2020-03-27 CN CN202010228017.8A patent/CN111304611B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0794268A1 (en) * | 1996-03-06 | 1997-09-10 | Vacuumschmelze GmbH | Process for improving corrosion protection of aluminium coated surfaces |
| CN104018133A (en) * | 2014-06-04 | 2014-09-03 | 北京汇磁粉体材料有限公司 | Multilayer composite protective coating on surface of sintered NdFeB magnet by multi-arc ion plating and process thereof |
| CN104630726A (en) * | 2015-01-28 | 2015-05-20 | 四川亚力超膜科技有限公司 | Nano ceramic heat-insulating film and preparation method thereof |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| corrosion behavior of sintered NdFeB coated with Al/Al2O3 multilayers by magnetron sputtering;Shoudong Mao et.al;《applied surface science》;20101202;第257卷;第3980-3984页 * |
| NdFeB表面磁控溅射沉积Al-Mn薄膜的耐蚀性;白巍栋等;《金属热处理》;20170831;第42卷(第8期);第15-19页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111304611A (en) | 2020-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107620033B (en) | Preparation method of high-purity strong dense MAX phase coating | |
| CN111349901B (en) | Preparation method of high-temperature-resistant alumina thick film coating for cutting tool | |
| CN103668095A (en) | High-power pulse plasma reinforced composite magnetron sputtering deposition device and application method thereof | |
| CN110098044B (en) | Composite modification method for surface protection of neodymium iron boron magnet | |
| JP2022520091A (en) | How to improve the coercive force, wear resistance and corrosion resistance of neodymium iron boron magnets | |
| CN114717516B (en) | Strongly-combined high corrosion-resistant TiAl/Ti2Preparation method of AlC coating | |
| CN109082647B (en) | Preparation method of DLC protective film on aluminum alloy surface | |
| CN107858684B (en) | Metal-diamond-like composite coating, preparation method and application thereof and coated tool | |
| CN112359319B (en) | Preparation method of double-period wear-resistant antibacterial and high-toughness composite film | |
| CN112080724B (en) | Preparation method of anticorrosive wear-resistant multi-component hard composite coating | |
| CN112662939B (en) | Ultrathin permanent magnet with surface deposited coating | |
| CN111304611B (en) | Preparation method of high-corrosion-resistance protective coating on surface of neodymium iron boron magnet | |
| CN102905495A (en) | Shell and producing method thereof | |
| CN111304596A (en) | Preparation method of anticorrosive coating on surface of neodymium-iron-boron magnet | |
| CN111850484A (en) | Device and method for preparing tough amorphous carbon-based multiphase hybrid film | |
| CN101570851B (en) | Method for applying magnetic field to sputtering coated cathode | |
| CN113174571B (en) | Ultra-microcrystalline titanium diboride composite coating and preparation method and application thereof | |
| CN113061859B (en) | Metal coating for X-ray tube anode target and preparation method thereof | |
| CN114959613A (en) | Method for enhancing corrosion resistance of medium-entropy alloy CoCrNi film | |
| CN112553580B (en) | Diboride composite coating and preparation method and application thereof | |
| CN114807845B (en) | Titanium copper nitride coating with gradient increasing nitrogen content | |
| CN109957757B (en) | Method for preparing ultra-thick Ti-Al-C ternary coating by two-step PVD (physical vapor deposition) technology | |
| CN117089810A (en) | Corrosion-resistant aluminum-based multilayer coating on surface of sintered NdFeB magnet and preparation method thereof | |
| CN108251810A (en) | A kind of preparation method of corrosion-resistant Sintered NdFeB magnet | |
| CN113088904B (en) | Metal Cr coating with nano multilevel structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |