CN112267115A - Corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron and preparation method thereof - Google Patents
Corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron and preparation method thereof Download PDFInfo
- Publication number
- CN112267115A CN112267115A CN202011060444.6A CN202011060444A CN112267115A CN 112267115 A CN112267115 A CN 112267115A CN 202011060444 A CN202011060444 A CN 202011060444A CN 112267115 A CN112267115 A CN 112267115A
- Authority
- CN
- China
- Prior art keywords
- coating
- resistant
- metal
- plating
- corrosion
- 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.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 86
- 239000011248 coating agent Substances 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 32
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000005260 corrosion Methods 0.000 title claims abstract description 29
- 230000007797 corrosion Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000007747 plating Methods 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 34
- 238000009713 electroplating Methods 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000002161 passivation Methods 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 4
- 150000004767 nitrides Chemical class 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 15
- 238000001994 activation Methods 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 230000033001 locomotion Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001096 P alloy Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000861 blow drying Methods 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000007733 ion plating Methods 0.000 claims description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 claims description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000005406 washing Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000001771 vacuum deposition Methods 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000003746 surface roughness Effects 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
-
- 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
- C23C14/0617—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
-
- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/50—Substrate holders
- C23C14/505—Substrate holders for rotation of the substrates
-
- 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
- C23C14/5846—Reactive treatment
- C23C14/5853—Oxidation
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
Abstract
The invention discloses a corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron and a preparation method thereof, belonging to the technical field of metal magnet treatment. Plating a metal coating on the surface of a metal magnet by electroplating, and plating a secondary coating on the surface of the metal coating by vacuum plating; the secondary plating layer is a nonmetal alloy layer and/or a metal oxide layer and/or a metal nitride layer; and/or oxidizing gas is introduced to react with the secondary coating to obtain a compact passivation layer. The coating prepared by the invention can improve the surface structure and the wear resistance of the coating on one hand, and can prevent corrosive liquid from permeating and improve the corrosion resistance of the coating on the other hand. The preparation method is simple and economic, has reasonable design and wide application prospect.
Description
Technical Field
The invention relates to the technical field of metal magnet treatment, in particular to a corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron and a preparation method thereof.
Background
The neodymium iron boron permanent magnet material is a rare earth permanent magnet material with the largest usage amount at present, is widely applied to various industries such as computers, motors, wind driven generators, electric automobiles, instruments and meters, magnetic transmission bearings, high-fidelity speakers, nuclear magnetic resonance imagers, aerospace navigators and the like, and has great potential application prospects in the emerging technical fields of maglev trains and the like. China vigorously develops the industry of the neodymium iron boron magnet by virtue of the advantages of rare earth resources and production cost, and has become the first producing and consuming countries in the world.
The surface treatment of the neodymium iron boron permanent magnet material has important influence on the performance of the neodymium iron boron permanent magnet material, the existing surface treatment comprises electroplating, chemical plating, electrophoresis, vacuum deposition, coating and the like, the wear resistance of a metallic coating obtained by the traditional electroplating process is poor, the vacuum coating technology can be used for preparing metal-nonmetal alloy (such as TiN), nonmetal alloy (such as SiC) and other films besides the metallic coating, but the cost of the real-fast coating equipment is high, and the efficiency is low. Taking NiCuNi + TiN as an example, if a vacuum plating mode is adopted in the whole process, independent vacuum Ni plating equipment, Cu plating equipment and TiN plating equipment are needed, the equipment needs to wait for vacuum degree and temperature rise and fall during switching, the efficiency is low, and the cost is high. These conventional single surface treatment methods all result in limited corrosion resistance and wear resistance of the prepared surface coating, and therefore, it is an urgent need to develop a novel composite coating for the surface of a metal magnet to improve the corrosion resistance and wear resistance.
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide a corrosion-resistant and wear-resistant composite plating layer applicable to neodymium iron boron and a preparation method thereof, aiming at the technical problem that the wear resistance and corrosion resistance of the surface treated metal magnet materials such as neodymium iron boron in the prior art are poor.
Technical scheme
The invention provides a preparation method of a corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron, which comprises the steps of firstly plating a metal coating on the surface of a metal magnet through electroplating, and then plating a secondary coating on the surface of the metal coating through vacuum plating; the secondary plating layer is a non-metal alloy layer and/or a metal oxide layer and/or a metal nitride layer.
Preferably, the metal plating layer is a single layer or multiple layers;
and/or the metal coating is one or more of zinc, nickel, copper, tin, zinc-nickel alloy, zinc-iron alloy and nickel-phosphorus alloy;
and/or the thickness of the metal plating layer is 5-20 μm.
Preferably, the metal element in the secondary coating is Al and/or Zn and/or Ti and/or Zr;
and/or the thickness of the secondary plating layer is 2-20 μm.
Preferably, the secondary coating is oxidized to obtain a composite coating with a dense passivation layer on the surface.
Preferably, the method comprises the following specific steps:
(1) plating a metal coating on the neodymium iron boron workpiece in a mode of oil removal, rust removal, activation, electroplating and blow drying;
(2) loading a metal magnet workpiece plated with a metal coating and a buffer material by a stainless steel mesh cage, carrying out vacuum nano composite coating, allowing the mesh cage to rotate and revolve simultaneously in the coating process, and carrying out multi-arc ion plating and/or magnetron sputtering coating to obtain a secondary coating.
(3) And introducing oxidizing gas into the vacuum chamber to react with the secondary coating to obtain a compact passivation layer.
Preferably, the electroplating mode in the step (1) is barrel plating and/or rack plating; the barrel plating adopts a unidirectional rotation mode or a forward and reverse alternate rotation mode, and the rack plating adopts a cathode linear movement mode or a rotary movement mode.
Preferably, one or more of sulfuric acid, nitric acid, hydrochloric acid and organic carboxylic acid is/are used as the activation solution in the step (1), the concentration of the activation solution is 0.05-4%, and the activation time is 5-120 s.
Preferably, the net cage in the step (2) is a cylindrical cage-shaped hanger, the diameter of which is 80-180mm, and the height of which is 800-1200 mm;
and/or the revolution rotating speed in the step (2) is 2-10r/min, the rotation rotating speed is 10-20r/min, and the coating current is 20-80A.
Preferably, the oxidizing gas in step (3) is one or more of nitrogen, oxygen, ozone and nitrogen oxide,
or a mixture of one or more of nitrogen, oxygen, ozone, nitrogen oxides and an inert gas.
The invention also provides a composite coating prepared by any one of the preparation methods.
Technical effects
Compared with the prior art, the invention has the beneficial effects that:
1. according to the corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron, the metal coating is plated on the surface of the metal magnet through electroplating, and then the secondary coating is plated on the surface of the metal coating through vacuum plating, wherein the secondary coating is a metal layer and/or a metal oxide layer and/or a metal nitride layer, and the prepared composite coating can effectively improve the wear resistance and the corrosion resistance.
2. According to the preparation method of the corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron, the secondary coating is oxidized to obtain the composite coating with the surface containing the compact passivation layer, and the surface of the composite coating is passivated after the preparation of the composite coating is completed, so that the surface roughness of the composite coating can be improved, the wear-resistant performance of the composite coating is improved, the corrosion-resistant performance of the composite coating is improved, and the penetration of corrosive liquid is prevented.
3. The corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron and the preparation method thereof have the advantages of simple preparation process, economic materials and wide application prospect.
Drawings
FIG. 1 is a schematic representation of a 200 hour neutral salt spray test conducted on the composite deposit of example 1 of the present invention;
FIG. 2 is an SEM image of the surface of the composite coating layer of example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions 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 some embodiments of the present invention, but not all embodiments; moreover, the embodiments are not relatively independent, and can be combined with each other according to needs, so that a better effect is achieved. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of a corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron, which comprises the following specific steps:
step (1): loading 3kg of 20mm by 5mm neodymium iron boron magnet and 3kg of steel balls into a roller together, and removing oil at the temperature of 55 ℃ for 10 min;
step (2): performing acid cleaning and rust removal on the product obtained in the step (1) after twice water cleaning, wherein the acid cleaning time is 3min, and the acid cleaning conductivity is 100 mS/cm;
and (3): performing two-time washing on the product obtained in the step (2), then performing ultrasonic cleaning, and immediately activating after the cleaning is finished, wherein the activation time is 1 min; wherein, the activation adopts sulphuric acid as the activation liquid, and the concentration of the activation liquid is 0.05 percent;
and (4): performing two times of water washing on the product obtained in the step (3), then putting the product into a nickel tank for electroplating, controlling the film thickness to be 3 microns, wherein the current is 40A, and the time is 60 min;
and (5): and (5) washing the product obtained in the step (4) with three times of water, and activating for 1 min. Then copper plating is carried out after two times of water washing, the current is 30A, the time is 90min, and the film thickness is controlled to be 5 microns;
and (6): drying the product obtained in the step (5) by blanking and drying, loading the product in a stainless steel net cage, then placing the product in vacuum coating equipment, heating the product to 100 ℃, and vacuumizing the vacuum coating equipment to 9 x 10-3pa；
And (7): performing vacuum coating by adopting magnetron sputtering AlN plating, wherein revolution and rotation are performed simultaneously in the coating process, and the film layer is controlled to be 2 microns; wherein the net cage is a cylindrical cage-shaped hanger, the diameter of the net cage is 80mm, the height of the net cage is 800mm, the revolution speed is 5r/min, the rotation speed is 10r/min, and the coating current is 20A;
and (8): and (4) closing the target power supply after the film coating is finished, continuously filling oxygen until the vacuum degree is 2 x 10pa, and oxidizing for 20min to obtain a compact passivation layer.
The embodiment also provides the corrosion-resistant and wear-resistant composite coating which is prepared by the method and can be applied to the neodymium iron boron.
The composite coating obtained in the embodiment has high appearance consistency, high binding force grade 0 in a Baige test (GB/T9286-1998 paint and varnish paint film lattice test), high Vickers hardness 3301HV and excellent wear resistance;
as can be seen from figure 1, the composite plating layer subjected to the neutral salt spray test has a perfect surface and effectively prevents the invasion of corrosive liquid, and the neutral salt spray test is more than 200 hours; as can be seen from the SEM of fig. 2, the composite plating layer has a dense surface, small and few pores, can effectively prevent corrosive substances from entering, and has excellent corrosion resistance.
Comparative example 1
The comparative example provides a preparation method of a coating applicable to neodymium iron boron, which is different from the preparation method of example 1 in that only nickel and copper electroplating is carried out, subsequent magnetron sputtering coating is not carried out, and the rest steps are substantially the same, and the specific preparation method comprises the following steps:
step (1): loading 3kg of 20mm by 5mm neodymium iron boron magnetic steel and 3kg of steel balls into a roller together, and performing ultrasonic oil removal at the oil removal temperature of 55 ℃, for 10min and at the roller rotation speed of 4 r/min;
step (2): performing acid washing and rust removal on the product obtained in the step (1) after twice water washing, wherein the acid washing time is 3min, the acid washing conductivity is 100mS/cm, and the roller rotating speed is 4 r/min;
and (3): performing two-time washing on the product obtained in the step (2), then performing ultrasonic cleaning, and immediately activating after the cleaning is finished, wherein the activation time is 1min, and the rotating speed of a roller is 4 r/min;
and (4): performing two times of water washing on the product obtained in the step (3), then putting the product into a nickel tank for electroplating, controlling the current to be 40A, the time to be 60min, the rotating speed of a roller to be 4r/min, and controlling the film thickness to be 3 microns;
and (5): and (5) washing the product obtained in the step (4) with three times of water, and activating for 1 min. Then copper plating is carried out after two times of water washing, the current is 30A, the time is 90min, the film thickness is controlled to be 5 microns, and the rotating speed of a roller is 4 r/min;
and (6): and (5) washing the product obtained in the step (5) with three times of water, and activating for 1 min. Then, after two times of water washing, nickel plating is carried out, the current is 30A, the time is 90min, the film thickness is controlled to be 2 microns, and the rotating speed of a roller is 4 r/min;
and (7): and (4) drying the product obtained in the step (6) at a temperature of 80 ℃ for 1 h.
This comparative example also provides a coating prepared as described above.
The composite coating obtained by the comparative example has high appearance consistency, and the binding force is in the grade of 0 in the Baige test (GB/T9286-1998 paint and varnish test), the neutral salt spray test is carried out for 72h, the rust is generated, and the Vickers hardness is 550 HV.
Comparing comparative example 1 with example 1, it can be seen that the corrosion resistance and wear resistance of the plating layer obtained by the single electroplating method are reduced, which shows the excellent performance of the composite plating layer of example 1 of the present invention.
Comparative example 2
The comparative example provides a preparation method of a coating applicable to neodymium iron boron, which is different from the preparation method of example 1 in that only magnetron sputtering coating is carried out, electroplating is not carried out, and the rest steps are approximately the same, and the specific preparation method comprises the following steps:
step (1): loading 3kg of 20mm by 5mm neodymium iron boron magnetic steel and 3kg of steel balls into a roller together, and performing ultrasonic oil removal at the oil removal temperature of 55 ℃, for 10min and at the roller rotation speed of 4 r/min;
step (2): performing acid washing and rust removal on the product obtained in the step (1) after twice water washing, wherein the acid washing time is 3min, the acid washing conductivity is 100mS/cm, and the roller rotating speed is 4 r/min;
and (3): washing the product obtained in the step (2) twice, blanking and drying;
and (4): putting the product obtained in the step (3) and 3kg of steel balls into a stainless steel mesh cage, heating the stainless steel mesh cage to 100 ℃ in vacuum coating equipment, and vacuumizing the vacuum coating equipment to 9 x 10-3pa；
And (5): performing vacuum coating by adopting magnetron sputtering AlN plating, and controlling the film layer to be 5 microns;
and (6): and (3) closing the target power supply after the film coating is finished, continuously filling oxygen to the vacuum degree of 2 x 10pa, oxidizing for 20min, cooling to the temperature below 80 ℃, and discharging.
This comparative example also provides a coating prepared as described above.
The composite plating layer obtained by the comparative example has high appearance consistency and binding force of grade 0 (GB/T9286-1998 paint and varnish test), and the composite plating layer rusts in 48h of neutral salt spray test and has Vickers hardness of 2905 HV.
It can be seen that the vacuum-coated layer exhibited poor corrosion resistance and wear resistance in the absence of the electroplated layer in this comparative example.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined (e.g., between various embodiments), adapted and/or substituted as would be recognized by those skilled in the art from the foregoing detailed description, and which may be combined as desired. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Claims (10)
1. A preparation method of a corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron is characterized in that a metal coating is plated on the surface of a metal magnet through electroplating, and then a secondary coating is plated on the surface of the metal coating through vacuum plating; the secondary plating layer is a non-metal alloy layer and/or a metal oxide layer and/or a metal nitride layer.
2. The method for preparing a corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron according to claim 1, wherein the metal coating is a single layer or multiple layers;
and/or the metal coating is one or more of zinc, nickel, copper, tin, zinc-nickel alloy, zinc-iron alloy and nickel-phosphorus alloy;
and/or the thickness of the metal plating layer is 5-20 μm.
3. The method for preparing a corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron according to claim 1, wherein the metal elements in the secondary coating comprise Al and/or Zn and/or Ti and/or Zr;
and/or the thickness of the secondary plating layer is 2-20 μm.
4. The method for preparing the corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron according to claim 1, wherein the secondary coating is oxidized to obtain a coating with a dense passivation layer on the surface.
5. The preparation method of the corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron according to claim 1, which is characterized by comprising the following specific steps:
(1) plating a metal coating on the neodymium iron boron workpiece in a mode of oil removal, rust removal, activation, electroplating and blow drying;
(2) loading a metal magnet workpiece plated with a metal coating and a buffer material by a stainless steel mesh cage, carrying out vacuum nano composite coating, allowing the mesh cage to rotate and revolve simultaneously in the coating process, and carrying out multi-arc ion plating and/or magnetron sputtering coating to obtain a secondary coating.
(3) And introducing oxidizing gas into the vacuum chamber to react with the secondary coating to obtain a compact passivation layer.
6. The method for preparing the corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron according to claim 5, wherein the electroplating mode in the step (1) is barrel plating and/or rack plating; wherein the barrel plating adopts a unidirectional rotation mode or a forward and reverse alternate rotation mode; and/or the rack plating adopts a cathode linear movement or rotary movement mode.
7. The method for preparing a corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron according to claim 5, wherein one or more of sulfuric acid, nitric acid, hydrochloric acid and organic carboxylic acid is/are used as an activation solution for the activation in the step (1), the concentration of the activation solution is 0.05-4%, and the activation time is 5-120 s.
8. The method as claimed in claim 5, wherein the cylinder cage in step (2) is a cylindrical cage-shaped hanger with a diameter of 80-180mm and a height of 800-;
and/or the revolution rotating speed in the step (2) is 2-10r/min, the rotation rotating speed is 10-20r/min, and the coating current is 20-80A.
9. The method for preparing a corrosion-resistant and wear-resistant composite coating applied to NdFeB according to claim 5, wherein the oxidizing gas in the step (3) is one or more of nitrogen, oxygen, ozone and nitrogen oxide,
or a mixture of one or more of nitrogen, oxygen, ozone, nitrogen oxides and an inert gas.
10. A corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron, which is characterized in that the composite coating prepared by the preparation method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011060444.6A CN112267115B (en) | 2020-09-30 | 2020-09-30 | Corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011060444.6A CN112267115B (en) | 2020-09-30 | 2020-09-30 | Corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112267115A true CN112267115A (en) | 2021-01-26 |
| CN112267115B CN112267115B (en) | 2022-07-12 |
Family
ID=74337022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011060444.6A Active CN112267115B (en) | 2020-09-30 | 2020-09-30 | Corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112267115B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010057967A (en) * | 1999-12-23 | 2001-07-05 | 신현준 | Multilayer coated Nd-Fe-B magnet and its manufacturing method |
| CN101457357A (en) * | 2007-12-14 | 2009-06-17 | 比亚迪股份有限公司 | Film coating material and preparation method thereof |
| CN101724845A (en) * | 2008-10-31 | 2010-06-09 | 中国科学院金属研究所 | Method for electroplating zinc-nickel alloy on sintered neodymium-iron-boron material |
| CN106756794A (en) * | 2017-01-18 | 2017-05-31 | 安徽大地熊新材料股份有限公司 | A kind of preparation method of high temperature resistant Sintered NdFeB magnet |
-
2020
- 2020-09-30 CN CN202011060444.6A patent/CN112267115B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010057967A (en) * | 1999-12-23 | 2001-07-05 | 신현준 | Multilayer coated Nd-Fe-B magnet and its manufacturing method |
| CN101457357A (en) * | 2007-12-14 | 2009-06-17 | 比亚迪股份有限公司 | Film coating material and preparation method thereof |
| CN101724845A (en) * | 2008-10-31 | 2010-06-09 | 中国科学院金属研究所 | Method for electroplating zinc-nickel alloy on sintered neodymium-iron-boron material |
| CN106756794A (en) * | 2017-01-18 | 2017-05-31 | 安徽大地熊新材料股份有限公司 | A kind of preparation method of high temperature resistant Sintered NdFeB magnet |
Non-Patent Citations (1)
| Title |
|---|
| 邓文宇等: "钕铁硼永磁材料腐蚀机理及防护研究进展", 《真空》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112267115B (en) | 2022-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102808210B (en) | Micro-arc oxidation surface treatment method and product prepared by same | |
| CN100464007C (en) | Process for preparing neodymium-iron-boron permanent magnetic material surface gradient function coating layer | |
| EP3486925B1 (en) | Ndfeb magnet with composite coating and preparation process thereof | |
| US11242612B2 (en) | Composite electroplating method for sintered Nd—Fe-B magnet | |
| CN101226800B (en) | Surface treating method for sintering type Nd iron boron permanent magnetic material | |
| CN102021629A (en) | Method for preparing titanium-alloy surface micro-arc oxidation antifriction compound film layer | |
| CN111005050B (en) | Preparation method of double coating for improving corrosion resistance of sintered neodymium-iron-boron magnet | |
| CN103173763A (en) | Electroplating and vapor deposition composite protection method for neodymium-iron-boron magnet | |
| CN106756794A (en) | A kind of preparation method of high temperature resistant Sintered NdFeB magnet | |
| CN102586829A (en) | Process method for reducing magnetic loss of neodymium-iron-boron permanent magnet under high-temperature and high-humidity conditions | |
| CN102828218B (en) | Electrolyte used for magnesium alloy anode oxidation treatment and treatment method | |
| JP2009099853A (en) | Highly corrosion-resistant r-t-b based rare earth magnet | |
| CN101845653A (en) | Preparation method of micro-arc oxidation film layer under effect of magnetic field | |
| CN112267115B (en) | Corrosion-resistant and wear-resistant composite coating applicable to neodymium iron boron and preparation method thereof | |
| CN103668190A (en) | Magnesium alloy surface treatment method and product thereof | |
| CN109609899B (en) | Surface modification method of magnesium alloy | |
| JP2005310975A (en) | Sintered neodymium magnet, its manufacturing method and rotary machine | |
| CN110993231A (en) | Surface-alloyed high-corrosion-resistance sintered NdFeB magnet and preparation method thereof | |
| CN111020482A (en) | Sintered NdFeB magnet surface densification Al coating and preparation method thereof | |
| CN112176286B (en) | Coating, metal magnet with coating and preparation method of coating | |
| CN114875353A (en) | Preparation method of high-corrosion-resistance sintered neodymium-iron-boron magnet | |
| CN111020484B (en) | Neodymium-iron-boron magnet containing nano composite film and preparation method thereof | |
| CN114686799A (en) | Surface treatment method for metal nitridation, oxidation and reduction | |
| CN101451263B (en) | Method for electrophoretic deposition of rare-earth lanthanum oxide film on aluminium alloy surface | |
| CN112522749B (en) | Preparation method of rare earth permanent magnet material surface corrosion-resistant coating and product |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220609 Address after: 366300 new industrial zone, Changting Economic Development Zone, Longyan City, Fujian Province Applicant after: FUJIAN CHANGTING GOLDEN DRAGON RARE-EARTH Co.,Ltd. Address before: 366300 new industrial zone, Changting Economic Development Zone, Longyan City, Fujian Province Applicant before: FUJIAN CHANGTING GOLDEN DRAGON RARE-EARTH Co.,Ltd. Applicant before: XIAMEN TUNGSTEN Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 366300 new industrial zone, Changting Economic Development Zone, Longyan City, Fujian Province Patentee after: Fujian Jinlong Rare Earth Co.,Ltd. Address before: 366300 new industrial zone, Changting Economic Development Zone, Longyan City, Fujian Province Patentee before: FUJIAN CHANGTING GOLDEN DRAGON RARE-EARTH Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |