CN116497325A - Surface protection modification method for neodymium-iron-boron magnet for magnetic squeezing - Google Patents
Surface protection modification method for neodymium-iron-boron magnet for magnetic squeezing Download PDFInfo
- Publication number
- CN116497325A CN116497325A CN202310322019.7A CN202310322019A CN116497325A CN 116497325 A CN116497325 A CN 116497325A CN 202310322019 A CN202310322019 A CN 202310322019A CN 116497325 A CN116497325 A CN 116497325A
- Authority
- CN
- China
- Prior art keywords
- magnetic
- magnet
- magnetron sputtering
- transition layer
- prepared
- 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.)
- Pending
Links
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 28
- 238000002715 modification method Methods 0.000 title description 2
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 31
- 230000007704 transition Effects 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 26
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910004353 Ti-Cu Inorganic materials 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 19
- 238000004544 sputter deposition Methods 0.000 claims description 14
- 238000007747 plating Methods 0.000 abstract description 31
- 230000003872 anastomosis Effects 0.000 abstract description 10
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 41
- 239000010949 copper Substances 0.000 description 34
- 238000012360 testing method Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000013077 target material Substances 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 5
- 241000590002 Helicobacter pylori Species 0.000 description 5
- 241000191940 Staphylococcus Species 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229940037467 helicobacter pylori Drugs 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000003678 scratch resistant effect Effects 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000001035 gastrointestinal tract Anatomy 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018484 Ni—Cu—Ni Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 neodymium-iron-boron rare earth Chemical class 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
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
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- 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
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/345—Applying energy to the substrate during sputtering using substrate bias
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/026—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets protecting methods against environmental influences, e.g. oxygen, by surface treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/70—Wind energy
- Y02E10/72—Wind turbines with rotation axis in wind direction
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physical Vapour Deposition (AREA)
- Manufacturing Cores, Coils, And Magnets (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention discloses a method for protecting and modifying the surface of a neodymium-iron-boron magnet for magnetic pressing, which comprises the following steps: ti metal and Ti-Cu alloy are used as targets, a Ti metal transition layer is firstly prepared on the surface of a sintered NdFeB magnet matrix by magnetron sputtering, and then a TiN-Cu composite coating is prepared on the Ti metal transition layer, so that the NdFeB magnet for magnetic squeezing is prepared. Thicker coatings can be deposited on the magnet surface in a shorter period of time. The method is environment-friendly, accords with the environment-friendly development concept, and has good mechanical property, higher hardness, better toughness and good scratch resistance of the coating; the binding force between the plating layer and the magnet is good, and the plating layer is not easy to fall off. The plating layer has good chemical stability and good antibacterial property. Solves the problems of poor corrosion resistance and poor antibacterial property of the magnetic device for magnetic anastomosis in the prior art.
Description
Technical field:
the invention relates to the technical field of surface protection of neodymium-iron-boron permanent magnets for magnetic squeezing, in particular to a method for surface protection modification of a neodymium-iron-boron permanent magnet for magnetic squeezing.
The background technology is as follows:
magnetic squeezing techniques utilize the special properties of magnetic forces to accomplish certain specific operations in the clinic, such as connecting and recanalizing viscera, squeezing and closing tissues, restricting the contents of a lumen, etc. Magnetic anastomosis is an important branch of magnetic squeezing technology, and is essentially a technology for completing anastomosis or recanalization of tissue lumen by using magnetic force instead of pulling force of suture and titanium nails. At present, magnetic anastomosis is mainly applied to digestive tract cavity anastomosis, digestive tract occlusion or narrow recanalization and vascular anastomosis in clinic.
The neodymium-iron-boron rare earth permanent magnet material is an ideal material for magnetic pressing technology because of having excellent magnetic performance. However, since commercial sintered neodymium-iron-boron magnets have a multiphase structure and many voids exist on the surface, the commercial sintered neodymium-iron-boron magnets are easy to react with external media and corrode. In addition, if the magnetic device is not subjected to any surface treatment, it may disintegrate when implanted in the body, resulting in the attenuation of the magnetic force and failure to complete the corresponding anastomosis; in addition, the disintegration of the magnet may release harmful metal ions, jeopardizing the body. Therefore, the in vivo implantation harmless surface treatment of the magnetic device for magnetic anastomosis is a primary consideration for animal experiments and clinical application. Aiming at the problem of poor corrosion resistance of the NdFeB magnet, a common effective method is to deposit a corrosion-resistant metal coating on the surface of the magnet by a chemical or physical method, thereby improving the corrosion resistance of the magnet. Traditional nickel/copper/nickel (Ni-Cu-Ni), zinc (Zn) plating and nickel (Ni) plating processes are mature, but the biocompatibility is poor, and rejection reaction is easy to generate. In addition, the electroplating process is not friendly to the environment and does not accord with the green environment protection concept.
Therefore, how to prepare the neodymium-iron-boron magnet with good biocompatibility and corrosion resistance is one of the problems which need to be solved in the industrialization of the magnetic device for magnetic anastomosis at present.
The invention comprises the following steps:
the invention aims to provide a method for protecting and modifying the surface of a neodymium-iron-boron magnet for magnetic pressing, which solves the problems of poor corrosion resistance and poor antibacterial property of a magnetic device for magnetic anastomosis in the prior art.
The invention is realized by the following technical scheme:
a method for protecting and modifying the surface of a neodymium-iron-boron magnet for magnetic pressing comprises the following steps: ti metal and Ti-Cu alloy are used as targets, a Ti metal transition layer is firstly prepared on the surface of a sintered NdFeB magnet matrix by magnetron sputtering, and then a TiN-Cu composite coating is prepared on the Ti metal transition layer, so that the NdFeB magnet for magnetic squeezing is prepared.
Preferably, the Ti metal transition layer has a thickness of 50-200nm.
The thickness of the TiN-Cu composite coating is 2-7 mu m.
Preferably, the purity of the Ti metal and Ti-Cu alloy target is 99.99%.
Preferably, in the Ti-Cu alloy target, the content of Ti is 85-98 wt.% and the content of Cu is 2-15 wt.% based on 100% of the total mass percent.
More preferably, the Ti-Cu alloy target contains 88-95 wt.% Ti and 5-12 wt.% Cu, based on 100% total mass.
The sintered NdFeB magnet used in the present invention is not particularly limited in its source, and is preferably of the brand N38 to N48.
Preferably, the substrate is sputtered and cleaned for 10-20 min under the negative bias of Ar gas pressure of 1Pa, -800 to-1000V before the Ti metal transition layer is prepared by magnetron sputtering.
Preferably, the magnetron sputtering deposition of the Ti metal transition layer is performed under Ar atmosphere with pressure of 0.5-1.0 Pa.
Preferably, the temperature of the matrix during magnetron sputtering deposition of the Ti metal transition layer is 20-200 ℃.
Preferably, the power density of the Ti metal transition layer is 5.5-6.5W/cm during magnetron sputtering deposition 2 。
Preferably, the base bias voltage is 0 to-300V in the magnetron sputtering deposition of the Ti metal transition layer.
Preferably, the sputtering time of the Ti metal transition layer is 3-8 min during magnetron sputtering deposition.
Preferably, the magnetron sputtering deposition of the TiN-Cu composite coating is carried out on N with the pressure of 0.5Pa to 1.0Pa 2 and/Ar under a mixed atmosphere.
Preferably, N is N during magnetron sputtering deposition of the TiN-Cu composite coating 2 N in Ar mixing atmosphere 2 The partial pressure ratio of Ar is (0.1-0.4): 1.
Preferably, the temperature of the matrix is 20-200 ℃ during magnetron sputtering deposition of the TiN-Cu composite coating.
Preferably, the power density of the TiN-Cu composite coating is 5.5-6.5W/cm during magnetron sputtering deposition 2 。
Preferably, the base bias voltage is 0 to 300V in the magnetron sputtering deposition of the TiN-Cu composite coating.
Preferably, the sputtering time of the TiN-Cu composite coating is 30-180 min during magnetron sputtering deposition.
Compared with the existing magnetic pressing magnet surface protection technology, the invention has the following advantages:
(1) The plating layer has good mechanical property, higher hardness, better toughness and good scratch resistance; the binding force between the plating layer and the magnet is good, and the plating layer is not easy to fall off.
(2) The plating layer has good chemical stability and good antibacterial property.
(3) The sputtering rate of the plating layer is accelerated, and thicker plating layers can be deposited on the surface of the magnet in shorter time.
(4) The preparation method of the coating is environment-friendly and accords with the environment-friendly idea of green development.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1:
in the embodiment, a Ti metal target and a Ti-Cu alloy target material with 6wt.% of Cu (Cu accounts for 6wt.% based on 100% of the total mass of the alloy target material) are adopted to prepare a surface coating of the neodymium-iron-boron magnet for magnetic squeezing through magnetron sputtering:
(1) Customizing a Ti metal target and a Ti-Cu alloy target containing 6wt.% Cu according to the size of the target of the magnetron sputtering system;
(2) Using an N42 sintered NdFeB magnet as a matrix, polishing the matrix to a mirror surface, ultrasonically cleaning the matrix in acetone and absolute ethyl alcohol for 15 minutes, and then placing the matrix in a 50 ℃ oven for drying;
(3) Mounting a Ti metal target and a Ti-Cu alloy sputtering target to two target positions connected with a direct current sputtering power supply, adjusting the distance between a matrix and the target to 80mm, placing a dried sample on a sample table, vacuumizing, starting infrared baking to 150 ℃, vacuumizing to the background vacuum degree, closing the vacuum baking, and cooling the matrix to the room temperature;
(4) Argon (Ar) is introduced into the vacuum chamber to 1Pa, negative bias of-900V is applied to the substrate, the direct current sputtering system is started, and the sample is sputtered and cleaned for 15min under the negative bias;
(5) Gradually reducing Ar gas flow, maintaining vacuum degree at 0.8Pa, adjusting negative bias to-80V, setting substrate temperature at 150deg.C, and using 6.0W/cm 2 The power density deposition of (2) is 5min, and a Ti transition layer with the thickness of 100nm can be deposited;
(6) Gradually reducing Ar gas flow, introducing N 2 N in mixed atmosphere 2 The partial pressure ratio of Ar was 0.3:1 to maintain the vacuum at 0.8Pa, the negative bias was adjusted to-80V, the substrate temperature was set at 150℃and 6.0W/cm was used 2 The power density deposition of (2) is 90min, and a TiN-Cu plating layer with the thickness of 5 mu m can be deposited;
(7) And after the deposition is finished, turning off a sputtering coating power supply, pumping to background vacuum, cooling the furnace to room temperature, and taking out the sample.
In the embodiment, after the surface coating process, the surface of the prepared Ti/TiN-Cu coating is compact and smooth, and the hardness is 6.3GPa; the binding force between the coating and the substrate is high, the critical load is 30N when the scratch test is completely dropped, the coating is not broken under the impact of the impact, the coating is not dropped, and the requirements of most scratch-resistant and corrosion-resistant coatings can be met. The magnetic properties of the magnet, such as coercive force, remanence and maximum magnetic energy product, are not significantly changed. The plating layer has good chemical stability, and the surface has no color change after being subjected to a salt spray test for 72 hours. The plating layer has good antibacterial property and can effectively inhibit the growth of escherichia coli, helicobacter pylori and staphylococcus.
Comparative example 1:
reference example 1 was different in that a Ti transition layer of 100nm thickness and a TiN-Cu plating layer of 5 μm were deposited by multi-arc ion plating instead of magnetron sputtering. It takes 30min to deposit a Ti transition layer with a thickness of 100nm and 180min to deposit a TiN-Cu plating layer with a thickness of 5 μm. The surface of the obtained Ti/TiN-Cu plating layer is compact and flat, and the hardness is 4.1GPa; the binding force between the coating and the substrate is high, and the critical load is 15N when the scratch test is completely dropped. The magnetic properties of the magnet, such as coercive force, remanence and maximum magnetic energy product, are not significantly changed. The plating layer has good chemical stability, and the surface has no color change after being subjected to a salt spray test for 72 hours. The plating layer has good antibacterial property and has a certain inhibition effect on the growth of escherichia coli, helicobacter pylori and staphylococcus.
Comparative example 2:
referring to example 1, a Ti metal transition layer was first prepared on the surface of a sintered neodymium-iron-boron magnet substrate by magnetron sputtering, except that an aluminum plating layer was then prepared on the Ti metal transition layer. The surface of the Ti/Al coating is compact and smooth, and the hardness is 3.4GPa; the binding force between the coating and the substrate is high, and the critical load is 15N when the scratch test is completely dropped. The magnetic properties of the magnet, such as coercive force, remanence and maximum magnetic energy product, are not significantly changed. The plating layer has good chemical stability, and the surface has no color change after being subjected to a salt spray test for 72 hours. The plating layer has good antibacterial property and has a certain inhibition effect on the growth of escherichia coli, helicobacter pylori and staphylococcus.
As can be seen from comparison between the example 1 and the comparative example 1, the magnetron sputtering rate is higher, the hardness of the obtained Ti/TiN-Cu plating layer is higher, the bonding force between the Ti/TiN-Cu plating layer and the magnet is good, and the Ti/TiN-Cu plating layer is not easy to fall off.
As can be seen from comparison between the example 1 and the comparative example 2, in the example 1, the Ti metal transition layer is first prepared on the surface of the sintered neodymium-iron-boron magnet matrix by magnetron sputtering, and then the TiN-Cu composite coating is prepared on the Ti metal transition layer, so that the TiN-Cu composite coating has higher hardness than the aluminum coating prepared on the Ti metal transition layer, has good binding force with the magnet, and is not easy to fall off.
Example 2:
in the embodiment, a Ti metal target and a Ti-Cu alloy target material with 2wt.% of Cu (Cu accounts for 2wt.% based on 100% of the total mass of the alloy target material) are adopted to prepare a surface coating of a neodymium-iron-boron magnet for magnetic squeezing through magnetron sputtering:
(1) Customizing a Ti metal target and a Ti-Cu alloy target containing 15wt.% Cu according to the size of the target of the magnetron sputtering system;
(2) Using an N48 sintered NdFeB magnet as a matrix, polishing the matrix to a mirror surface, ultrasonically cleaning the matrix in acetone and absolute ethyl alcohol for 15 minutes, and then placing the matrix in a 50 ℃ oven for drying;
(3) Mounting a Ti metal target and a Ti-Cu alloy sputtering target to two target positions connected with a direct current sputtering power supply, adjusting the distance between a matrix and the target to 80mm, placing a dried sample on a sample table, vacuumizing, starting infrared baking to 150 ℃, vacuumizing to the background vacuum degree, closing the vacuum baking, and cooling the matrix to the room temperature;
(4) Argon (Ar) is introduced into the vacuum chamber to 1Pa, negative bias of-800V is applied to the substrate, the direct current sputtering system is started, and the sample is sputtered and cleaned for 10min under the negative bias;
(5) Gradually reducing Ar gas flow, maintaining vacuum degree at 0.5Pa, adjusting negative bias to 0V, setting substrate temperature at 20deg.C, and using 5.5W/cm 2 The power density of the Ti transition layer is deposited for 3min, and the Ti transition layer with the thickness of about 50nm can be deposited;
(6) Gradually reducing Ar gas flow, introducing N 2 N in mixed atmosphere 2 Partial pressure of ArThe vacuum was maintained at 0.5Pa at a pressure ratio of 0.1:1, the negative bias was adjusted to 0V, the substrate temperature was set at 20deg.C, and the vacuum was maintained at 5.5W/cm 2 For 30min, can deposit TiN-Cu plating layer with the thickness of about 2 mu m;
(7) And after the deposition is finished, turning off a sputtering coating power supply, pumping to background vacuum, cooling the furnace to room temperature, and taking out the sample.
In the embodiment, after the surface coating process, the surface of the prepared Ti/TiN-Cu coating is compact and flat, and the hardness is 5.1GPa; the binding force between the coating and the substrate is high, the critical load is more than 27N when the scratch test is completely fallen, the coating is not broken under the impact of the impact, and the coating is not fallen, so that the coating can meet the requirements of most scratch-resistant and corrosion-resistant coatings. The magnetic properties of the magnet, such as coercive force, remanence and maximum magnetic energy product, are not significantly changed. The plating layer has good chemical stability, and the surface has no color change after being subjected to a salt spray test for 72 hours. The plating layer has good antibacterial property and can effectively inhibit the growth of escherichia coli, helicobacter pylori and staphylococcus.
Example 3:
in the embodiment, a Ti metal target and a Ti-Cu alloy target material with 2wt.% of Cu (Cu accounts for 2wt.% based on 100% of the total mass of the alloy target material) are adopted to prepare a surface coating of a neodymium-iron-boron magnet for magnetic squeezing through magnetron sputtering:
(1) Customizing a Ti metal target and a Ti-Cu alloy target containing 2wt.% Cu according to the size of the target of the magnetron sputtering system;
(2) Using an N38 sintered NdFeB magnet as a matrix, polishing the matrix to a mirror surface, ultrasonically cleaning the matrix in acetone and absolute ethyl alcohol for 15 minutes, and then placing the matrix in a 50 ℃ oven for drying;
(3) Mounting a Ti metal target and a Ti-Cu alloy sputtering target to two target positions connected with a direct current sputtering power supply, adjusting the distance between a matrix and the target to 80mm, placing a dried sample on a sample table, vacuumizing, starting infrared baking to 150 ℃, vacuumizing to the background vacuum degree, closing the vacuum baking, and cooling the matrix to the room temperature;
(4) Argon (Ar) is introduced into the vacuum chamber to 1Pa, negative bias of-1000V is applied to the substrate, the direct current sputtering system is started, and the sample is sputtered and cleaned for 20min under the negative bias;
(5) Gradually becomeReducing Ar gas flow, maintaining vacuum degree at 1.0Pa, adjusting negative bias to-300V, setting substrate temperature at 200deg.C, and using 6.5W/cm 2 For 8min, a Ti transition layer with a thickness of about 200nm can be deposited;
(6) Gradually reducing Ar gas flow, introducing N 2 N in mixed atmosphere 2 The partial pressure ratio of Ar was 0.4:1 to maintain the vacuum at 1.0Pa, the negative bias was adjusted to-300V, the substrate temperature was set at 200℃and 6.5W/cm was used 2 180min, can deposit TiN-Cu plating layer with the thickness of about 7 mu m;
(7) And after the deposition is finished, turning off a sputtering coating power supply, pumping to background vacuum, cooling the furnace to room temperature, and taking out the sample.
In the embodiment, after the surface coating process, the surface of the prepared Ti/TiN-Cu coating is compact and flat, and the hardness is 7.6GPa; the binding force between the coating and the substrate is high, the critical load is more than 32N when the scratch test is completely fallen, the coating is not broken under the impact of the impact, and the coating is not fallen, so that the requirements of most scratch-resistant and corrosion-resistant coatings can be met. The magnetic properties of the magnet, such as coercive force, remanence and maximum magnetic energy product, are not significantly changed. The plating layer has good chemical stability, and the surface has no color change after being subjected to a salt spray test for 72 hours. The plating layer has good antibacterial property and can effectively inhibit the growth of escherichia coli, helicobacter pylori and staphylococcus.
Claims (10)
1. The method for protecting and modifying the surface of the neodymium-iron-boron magnet for magnetic pressing is characterized by comprising the following steps of: ti metal and Ti-Cu alloy are used as targets, a Ti metal transition layer is firstly prepared on the surface of a sintered NdFeB magnet matrix by magnetron sputtering, and then a TiN-Cu composite coating is prepared on the Ti metal transition layer, so that the NdFeB magnet for magnetic squeezing is prepared.
2. The method according to claim 1, wherein the Ti metal transition layer has a thickness of 50-200nm; the thickness of the TiN-Cu composite coating is 2-7 mu m.
3. The method of claim 1, wherein the Ti metal and Ti-Cu alloy target has a purity of 99.99%.
4. The method according to claim 1, wherein the Ti-Cu alloy target has a Ti content of 85-98 wt.% and a Cu content of 2-15 wt.%, based on 100% by mass of the total.
5. The method according to claim 1, wherein the Ti-Cu alloy target has a Ti content of 88 to 95wt.% and a Cu content of 5 to 12wt.%, based on 100% by mass of the total.
6. The method according to claim 1, wherein the substrate is sputter cleaned for 10-20 min under a negative bias of Ar gas pressure of 1Pa, -800 to-1000V before the Ti metal transition layer is prepared by magnetron sputtering.
7. The method according to claim 1, wherein the magnetron sputter deposition of the Ti metal transition layer is performed under Ar atmosphere at a pressure of 0.5 to 1.0 Pa; the temperature of the matrix is 20-200 ℃ and the bias voltage of the matrix is 0-300V during magnetron sputtering deposition; the power density is 5.5-6.5W/cm during the magnetron sputtering deposition 2 The method comprises the steps of carrying out a first treatment on the surface of the The sputtering time is 3-8 min.
8. The method according to claim 1, wherein the TiN-Cu composite coating is deposited by magnetron sputtering at a pressure of 0.5 to 1.0Pa of N 2 and/Ar under a mixed atmosphere.
9. The method of claim 8, wherein N 2/ N in Ar Mixed atmosphere 2/ Ar has a partial pressure ratio of (0.1 to 0.4): 1.
10. The method according to claim 1, wherein the temperature of the substrate during the magnetron sputtering deposition of the TiN-Cu composite coating is 20-200 ℃; the substrate bias voltage is 0 to-300V, the sputtering time is 30 to 180min, and the power density is 5.5 to 6.5W/cm 2 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310322019.7A CN116497325A (en) | 2023-03-29 | 2023-03-29 | Surface protection modification method for neodymium-iron-boron magnet for magnetic squeezing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310322019.7A CN116497325A (en) | 2023-03-29 | 2023-03-29 | Surface protection modification method for neodymium-iron-boron magnet for magnetic squeezing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116497325A true CN116497325A (en) | 2023-07-28 |
Family
ID=87327576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310322019.7A Pending CN116497325A (en) | 2023-03-29 | 2023-03-29 | Surface protection modification method for neodymium-iron-boron magnet for magnetic squeezing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116497325A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104195508A (en) * | 2014-09-15 | 2014-12-10 | 佳木斯大学 | Method for preparing Cr/CrN/Cu-TiN film on surface of stainless steel operation instrument |
| JP2015185850A (en) * | 2014-03-22 | 2015-10-22 | 沈陽中北通磁科技股▲ふん▼有限公司Ｓｈｅｎｙａｎｇ Ｇｅｎｅｒａｌｍａｇｎｅｔｉｃ Ｃｏ．，Ｌｔｄ． | Composite plating method of neodymium iron boron rare earth permanent magnet component |
| CN107419231A (en) * | 2017-07-26 | 2017-12-01 | 威海蓝膜光热科技有限公司 | The preparation method of Nd-Fe-B permanent magnetic anti-corrosion insulation coating and the Nd-Fe-B permanent magnet with the coating |
| CN107937875A (en) * | 2017-11-21 | 2018-04-20 | 合肥工业大学 | A kind of preparation method of Sintered NdFeB magnet surface protection coating |
| CN108070829A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院金属研究所 | A kind of Ti-Cu-N nano composite antibacterials coating and preparation method thereof |
| CN109576651A (en) * | 2017-09-29 | 2019-04-05 | 中国科学院金属研究所 | A kind of stainless steel ware antibacterial surface wear-resistant coating and its preparation method and application |
-
2023
- 2023-03-29 CN CN202310322019.7A patent/CN116497325A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015185850A (en) * | 2014-03-22 | 2015-10-22 | 沈陽中北通磁科技股▲ふん▼有限公司Ｓｈｅｎｙａｎｇ Ｇｅｎｅｒａｌｍａｇｎｅｔｉｃ Ｃｏ．，Ｌｔｄ． | Composite plating method of neodymium iron boron rare earth permanent magnet component |
| CN104195508A (en) * | 2014-09-15 | 2014-12-10 | 佳木斯大学 | Method for preparing Cr/CrN/Cu-TiN film on surface of stainless steel operation instrument |
| CN108070829A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院金属研究所 | A kind of Ti-Cu-N nano composite antibacterials coating and preparation method thereof |
| CN107419231A (en) * | 2017-07-26 | 2017-12-01 | 威海蓝膜光热科技有限公司 | The preparation method of Nd-Fe-B permanent magnetic anti-corrosion insulation coating and the Nd-Fe-B permanent magnet with the coating |
| CN109576651A (en) * | 2017-09-29 | 2019-04-05 | 中国科学院金属研究所 | A kind of stainless steel ware antibacterial surface wear-resistant coating and its preparation method and application |
| CN107937875A (en) * | 2017-11-21 | 2018-04-20 | 合肥工业大学 | A kind of preparation method of Sintered NdFeB magnet surface protection coating |
Non-Patent Citations (2)
| Title |
|---|
| 田波彦 等: "不同表面改性钕铁硼磁体抗胃液腐蚀的体外研究", 《中国医疗设备》, vol. 34, no. 3, pages 5 - 8 * |
| 田波彦 等: "不同镀层钕铁硼磁体抗胆汁腐蚀的体外研究", 《现代生物医学进展》, vol. 19, no. 6, pages 1006 - 1010 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102618829B (en) | Medical magnesium alloy material with amorphous film and preparation method thereof | |
| CN103031523B (en) | The preparation method of the cupric compound coating on a kind of metal parts of medicine equipment and medicine equipment | |
| WO2021083166A1 (en) | Method for improving coercivity, wear resistance and corrosion resistance properties of neodymium iron boron magnet | |
| WO2012000401A1 (en) | Composite structure and method of preparing the same | |
| CN106555162A (en) | A kind of preparation method of high rigidity sterilization PVD films | |
| CN102676991B (en) | Process for preparing superhard nanocomposite laminated coating by PVD (plating vacuum deposition) technology | |
| JPH0234737A (en) | Corrosion-resistant and heat-resistant aluminum-base alloy thin film and its manufacture | |
| CN116497325A (en) | Surface protection modification method for neodymium-iron-boron magnet for magnetic squeezing | |
| CN101429648A (en) | Method for aluminum-copper-iron quasi-crystal coating preparation by three-target magnetic controlled cosputtering and use thereof | |
| CN103243306A (en) | Method for preparing Cu doped TiN alloy layer on surface of titanium alloy | |
| CN102453849B (en) | Film-coated part and preparation method thereof | |
| CN111041433B (en) | Medical copper-containing composite coating and preparation method thereof | |
| CN102453852A (en) | Plated member and preparation method thereof | |
| US20130022835A1 (en) | Coated article having antibacterial effect and method for making the same | |
| CN105586576A (en) | Method for plating physical vapor deposition (PVD) anti-microbial film | |
| CN112359319B (en) | Preparation method of double-period wear-resistant antibacterial and high-toughness composite film | |
| CN110055495B (en) | CrFe + (Cr, Fe) N-substituted chromium coating and preparation method thereof | |
| CN114959613A (en) | Method for enhancing corrosion resistance of medium-entropy alloy CoCrNi film | |
| CN1736493A (en) | Method for preparing TiO2-HA biological medical nanometer structured film | |
| CN108411265A (en) | A kind of preparation method of low stress dense coating | |
| JP3423299B2 (en) | Fe-BR type permanent magnet having corrosion-resistant film | |
| CN114150267B (en) | Preparation method of alumina/silver nanoparticle layer/alumina multilayer antibacterial film | |
| CN115807208A (en) | Multilayer compact composite membrane on surface of pure magnesium and preparation method thereof | |
| CN116808300A (en) | Antibacterial composite coating for titanium alloy implant and preparation method thereof | |
| CN115058688B (en) | Composite lubricating film and preparation method and application 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 |