CN101444983B - Coating material and preparation method thereof - Google Patents
Coating material and preparation method thereof Download PDFInfo
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- CN101444983B CN101444983B CN2007101954089A CN200710195408A CN101444983B CN 101444983 B CN101444983 B CN 101444983B CN 2007101954089 A CN2007101954089 A CN 2007101954089A CN 200710195408 A CN200710195408 A CN 200710195408A CN 101444983 B CN101444983 B CN 101444983B
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Abstract
The invention provides a coating material which comprises base material and a film plating on the base material, wherein, the film comprises a plurality of metal layers and a plurality of nitride layers of metal, and the nitride layers of metal are used for separating the adjacent metal layers, wherein, one of the metal layers is contacted with the surface of the base material, and one of the nitride layers of metal is the outmost layer. The film of the coating material provided by the invention has less defect concentration and has better inoxidability, wearing resistance and bonding force between the film and the base material. Furthermore, when the base material of the coating material is a permanent-magnet, the remnant magnetism of the coating material can basically achieve the level of a permanent-magnet before the film is plated, coercive force and magnetic energy product are both higher than the permanent-magnet before the film is plated, and the maximum working temperature is higher than the temperature of the permanent-magnet before the film is plated.
Description
Technical field
The invention relates to a kind of Coating Materials and preparation method thereof.
Background technology
Nd-Fe-B rare earth permanent magnetic material is the third generation rare earth powder metallurgy material that grows up the eighties.New era of rare earth permanent-magnetic material has been started in its discovery; Because of it has the excellent magnetism ability; Cheap relatively price and sufficient resources deposit and to replace traditional Sm-Co rapidly be rare earth permanent-magnetic material have obtained in fields such as voice coil motor, magnetic resonance imaging, motor, sensor, instrument to use widely.But there is the shortcoming of corrosion resisting property difference in the NdFeB magnet, has a strong impact on its service behaviour, handles and must carry out surfacecti proteon to it.The surface treatment method of routines such as plating, electrophoresis has characteristics such as cost is low, efficient is high, adaptation is wide, simple to operate, in the neodymium iron boron surfacecti proteon is handled, occupies leading position always.But; Because the corrosion resistance of the film of the permanent magnet surfaces plating after these disposal methods and the adhesion of wearability and film and permanent magnet base material are strong inadequately; And there is pollution problem; When adopting electrophoresis in addition, its acidity or alkaline electrophoresis liquid are prone to remain in the magnet hole, and magnet is prone to inhale hydrogen and cause coating embrittlement in electroplating process; Therefore these conventional methods have certain limitation.
Recently; There is report to propose method at substrate surface plating one deck titanium and nitride multilayer titanium or layer of aluminum and nitride multilayer aluminium; But the defect concentration of the film of this method plating is bigger, so the adhesion of the corrosion resistance of film and wearability and film and base material is good inadequately.
Summary of the invention
The objective of the invention is imperfect defective, all Coating Materials of film and preparation method thereof preferably of a kind of adhesion that comprises corrosion resistance and wearability and film and base material are provided for the adhesion of the corrosion resistance of the film that overcomes existing Coating Materials and wearability and film and base material.
The invention provides a kind of Coating Materials; This material comprises base material and the film that is plated on substrate surface; Wherein, said film comprises the nitride layer of a plurality of metal levels and a plurality of metals, and is separated by the nitride layer of metal between the adjacent metal layer; One deck in wherein a plurality of metal levels contacts with substrate surface, and the one deck in the nitride layer of a plurality of metals is an outermost layer.
The preparation method of Coating Materials provided by the invention is included under the magnetron sputtering condition; Make the target material sputter on the magnetic control target and deposit on the base material applying power supply on the magnetic control target; Be formed on the film of substrate surface; Wherein, the method that is formed on the film of substrate surface comprises the nitride layer that forms a plurality of metal levels and a plurality of metals, and the nitride layer by metal between the adjacent metal layer separates; One deck in wherein a plurality of metal levels contacts with substrate surface, and the one deck in the nitride layer of a plurality of metals is an outermost layer.
Compare with existing Coating Materials, the defect concentration of the film of Coating Materials provided by the invention is less, and therefore, the adhesion of the corrosion resistance of film and wearability and film and base material is all better.And; When the base material of Coating Materials is permanent magnet; The remanent magnetism of Coating Materials provided by the invention can reach the level of the permanent magnet before the plating film basically, and coercivity and magnetic energy product be all than the height of the permanent magnet before the plated film, the permanent magnetism height of maximum operating temperature before than plated film; And remanent magnetism, coercivity, magnetic energy product and the maximum operating temperature of existing Coating Materials are all poor than the permanent magnet before the plating film.
The specific embodiment
The invention provides a kind of Coating Materials; This material comprises base material and the film that is plated on substrate surface; Wherein, said film comprises the nitride layer of a plurality of metal levels and a plurality of metals, and is separated by the nitride layer of metal between the adjacent metal layer; One deck in wherein a plurality of metal levels contacts with substrate surface, and the one deck in the nitride layer of a plurality of metals is an outermost layer.
According to the present invention, said outermost layer is meant from substrate surface thin layer from inside to outside, also promptly away from the thin layer of substrate surface.
The present invention is to the not restriction of the number of plies of film, and from principle, the many more films of the number of plies of film are thick more; The defect concentration of film is less, and the adhesion of the corrosion resistance of film and wearability and film and base material is good more, still; The many more films of the number of plies of film are thick more, and the cost that then prepares this film is high more, therefore; Under the preferable case, said film is the 4-8 layer, and the said metal layer thickness that contacts with substrate surface is the 0.01-2 micron; The thickness of the nitride layer of said outermost metal is the 0.1-8 micron, and the metal layer thickness of other layer is the 0.01-0.5 micron, and the thickness of the nitride of the metal of other layer is the 0.2-1.6 micron.More preferably said film is 4 layers, and said film is followed successively by the nitride layer of nitride layer, metal level and the metal of metal level, metal from inside to outside from substrate surface.
Metal in each of said film layer can be identical, also can be different, preferably identical, and be titanium, aluminium or chromium, be preferably titanium or aluminium, more preferably titanium; According to this optimal way, the defect concentration of the film of Coating Materials is less, and the adhesion of the corrosion resistance of film and wearability and film and base material is all better; And when the base material of Coating Materials was permanent magnet, the remanent magnetism of permanent magnet, coercivity and magnetic energy product were all better, and the maximum operating temperature of permanent magnet is higher.Said base material is a permanent magnet.
Coating Materials provided by the invention can be through magnetic controlled sputtering ion plating method or the preparation of multi-arc ion coating method; Preferably through the preparation of magnetic controlled sputtering ion plating method; The defect concentration of the film of the Coating Materials through magnetic controlled sputtering ion plating method preparation is less, and the adhesion of the corrosion resistance of film and wearability and film and base material is all better; And when the base material of Coating Materials was permanent magnet, the remanent magnetism of permanent magnet, coercivity and magnetic energy product were all better, and the maximum operating temperature of permanent magnet is higher.
The preparation method of Coating Materials provided by the invention is included under the magnetron sputtering condition; Make the target material sputter on the magnetic control target and deposit on the base material applying power supply on the magnetic control target; Be formed on the film of substrate surface; Wherein, the method that is formed on the film of substrate surface comprises the nitride layer that forms a plurality of metal levels and a plurality of metals, and the nitride layer by metal between the adjacent metal layer separates; One deck in wherein a plurality of metal levels contacts with substrate surface, and the one deck in the nitride layer of a plurality of metals is an outermost layer.
Above-mentioned Coating Materials is to use the preparation of magnetic controlled sputtering ion plating equipment, and said magnetic controlled sputtering ion plating equipment comprises vacuum chamber, heater, work rest and magnetic control target, and said base material is placed on the work rest.
Said target contains target material, can be preferably the single element target for single element target (promptly only containing a kind of target material in a target) or multielement target (promptly containing multiple target material in a target), and the purity of target material is preferably more than 99.9%.Can select the kind of target thing Gu according to the composition of rete.For example, when titanizing on base material, target material is a titanium; When on base material, aluminizing, target material is an aluminium.
Said magnetic control target is preferably target structure, can use a pair of or several to magnetic control target as required; Every pair of magnetic control target is supplied power by a power supply, and two magnetic control targets extremely link to each other with one of power supply separately, and insulate mutually with whole vacuum chamber.Can be 10-25 centimetre to the distance between two magnetic control targets of target, be preferably 14-22 centimetre.Movements and postures of actors part can be around the central shaft of vacuum chamber clockwise or rotate counterclockwise, and its rotating speed can be 0.5-10 rev/min, is preferably 2-6 rev/min.
According to the present invention; Said film is preferably the 4-8 layer; The said metal layer thickness that contacts with substrate surface is the 0.01-2 micron; The thickness of the nitride layer of said outermost metal is the 0.1-8 micron, and the metal layer thickness of other layer is 0.0 1-0.5 micron, and the thickness of the nitride of the metal of other layer is the 0.2-1.6 micron.More preferably said film is 4 layers, and said film is followed successively by the nitride layer of nitride layer, metal level and the metal of metal level, metal from inside to outside from substrate surface.
Said power supply can be preferably intermediate frequency power supply for the existing various power supplys that are used for magnetic controlled sputtering ion plating, and the frequency of intermediate frequency power supply is generally the 10-150 kilohertz, is preferably the 10-100 kilohertz.
Said magnetron sputtering condition comprises that the power of power supply is 8-20 kilowatt, is preferably 12-18 kilowatt, and the absolute pressure of magnetron sputtering is the 0.1-1.0 handkerchief, is preferably the 0.3-0.8 handkerchief, and temperature is 20-200 ℃, is preferably 50-150 ℃; The sputtering time that forms every layer film is 1-25 minute, and the atmosphere that forms metal level is inert gas, and the atmosphere that forms the nitride layer of metal is nitrogen.
Said sputtering time can be selected according to the thickness of the power of power supply and required each layer; For example; When in above-mentioned power scope of the present invention, forming the film of above-mentioned thickness, the time that forms the metal level that contacts with substrate surface can be 5-10 minute, and the time that forms the nitride layer of outermost metal can be 1-10 minute; The time that forms the metal level of other layer can be 5-15 minute, and the time of nitride that forms the metal of other layer can be 15-25 minute.
The atmosphere of said formation metal level is inert gas, as long as the pressure the when consumption of said inert gas makes sputter reaches the 0.1-1.5 handkerchief, is preferably the 0.3-1.0 handkerchief.Can vacuumize earlier, make the absolute pressure in the vacuum chamber reach 4 * 10
-3Handkerchief to 6 * 10
-3In the scope of handkerchief, and then charge into inert gas, make the absolute pressure in the vacuum chamber reach the 0.1-1.5 handkerchief.Said inert gas for example can be helium and/or argon gas for not participating in the gas of sputter reaction.
The atmosphere of the nitride layer of said metal is nitrogen.The consumption of said nitrogen can be preferably 10-500sccm, more preferably 10-200sccm for 10-800 standard ml/min (sccm).
Before carrying out sputter, the preparation method of Coating Materials provided by the invention cleans base material before can also being included in plated film.The method of said cleaning has been conventionally known to one of skill in the art; Can use existing various cleaning method among the present invention; Only otherwise can damage base material and can remove the dirt of substrate surface again, guarantee that the substrate surface cleaning get final product, for example can use reverse sputtering method to clean substrate surface, specifically can pass through under the pressure of inert gas atmosphere 0.3-0.5 handkerchief; On base material, apply grid bias power supply; The bias voltage initial value of grid bias power supply can be-300 to-500 volts, the bias adjustment step-length can lie prostrate for 5-50/minute, cleaned base material 30-50 minute.Said magnetic controlled sputtering ion plating equipment can also comprise biasing device, and biasing device can be grid bias power supply, and the positive pole of grid bias power supply links to each other with work rest, and negative pole links to each other with the housing of vacuum chamber.Said inert gas can be helium and/or argon gas.
In order in sputter procedure, the film that forms to be cleaned, improve adhesion of thin film, can on base material, apply grid bias power supply, the bias voltage of grid bias power supply can lie prostrate for 50-2000, is preferably the 100-1500 volt; Dutycycle is 15-90%, is preferably 30-80%.Said magnetic controlled sputtering ion plating equipment can also comprise biasing device, and biasing device can be grid bias power supply, and the positive pole of grid bias power supply links to each other with the housing of vacuum chamber, and negative pole links to each other with work rest.
Under the preferable case; The preparation method of Coating Materials provided by the invention carries out annealing in process to Coating Materials after can also being included in and forming outermost layer; According to this optimal way; The defect concentration of the film of Coating Materials be can further reduce, the corrosion resistance of film and the adhesion of wearability and film and base material improved; And when the base material of Coating Materials was permanent magnet, the remanent magnetism of permanent magnet, coercivity and magnetic energy product were all better, and the maximum operating temperature of permanent magnet is higher.
The method of said annealing in process comprises makes Coating Materials be incubated 10-30 minute down at 400-600 ℃; The said method that makes Coating Materials reach 400-600 ℃ can be cooled to 25-30 ℃ naturally for the Coating Materials that will form earlier behind the outermost layer, is warmed up to 400-600 ℃ with 5-15 ℃/minute speed again.
Come to describe in more detail the present invention through embodiment below.
Embodiment 1
This embodiment is used to explain Coating Materials provided by the invention and preparation method thereof.
Adopt magnetic controlled sputtering ion plating equipment (magnetron sputtering ion plating machine; Beijing Beiyi Innovation Vacuum Technology Co., Ltd. makes; Model is JP-700); This magnetic controlled sputtering ion plating equipment comprises vacuum chamber, heater, work rest, magnetic control target and biasing device, and heater, work rest and magnetic control target are arranged in vacuum chamber.Magnetic control target is to target structure, comprises a pair of titanium target.Distance between two targets of a pair of titanium target is 18 centimetres, and two targets link to each other with the both positive and negative polarity that a frequency is 40 kilo hertzs a power supply.Rubidium iron boron permanent magnet base material (35UH model) is fixed on the work rest, and rubidium iron boron permanent magnet base material equates with distance between two targets of a pair of target between to target.Biasing device is a grid bias power supply.
Earlier absolute pressure in the vacuum chamber is transferred to 5 * 10
-3Handkerchief charges into argon gas then in vacuum chamber, be 0.5 handkerchief until pressure; Temperature transfers to 100 ℃; Start grid bias power supply (positive pole of grid bias power supply links to each other with work rest, and negative pole links to each other with the housing of vacuum chamber), regulate and be biased into-500 volts; The bias adjustment step-length is 20 volts/minute, and permanent magnet was carried out reverse sputter clean 40 minutes.
Keep aforesaid operations, different is to start titanium target (promptly opening the power supply that is connected with the titanium target) and carry out magnetic controlled sputtering ion plating; The power of the power supply that is connected with the titanium target is 15 kilowatts, and (at this moment, the positive pole of grid bias power supply links to each other with the housing of vacuum chamber to regulate grid bias power supply simultaneously; Negative pole links to each other with work rest) bias voltage be 200 volts, dutycycle is 50%, the rotating speed of work rest is 2 rev/mins; Time is 5 minutes, forms metal level-titanium layer at the permanent magnet substrate surface.
Then, keep aforesaid operations, different is, stops to feed argon gas, feeds nitrogen simultaneously, and the consumption of nitrogen is 100sccm, and the time is 15 minutes, on above-mentioned layer on surface of metal, forms the nitride layer of the nitride layer-titanium of metal.
Keep aforesaid operations again, different is, stops to feed nitrogen, feeds argon gas simultaneously, is 0.5 handkerchief until pressure, and the time is 5 minutes, on the nitride layer surface of above-mentioned metal, forms metal level-titanium layer.
Keep aforesaid operations again, different is, stops to feed argon gas, feeds nitrogen simultaneously, and the consumption of nitrogen is 100sccm, and the time is 1 minute, forms the nitride layer of outermost layer-titanium.
At last, close titanium target, grid bias power supply and stop to feed nitrogen, naturally cool to 30 ℃; Be warmed up to 500 ℃ with 10 ℃/minute speed again; Be incubated 20 minutes, take out the permanent magnet base material behind the above-mentioned plated film, record with the microscope of the Shanghai Cai Kang DMM-660D of Instr Ltd. model; From the permanent magnet substrate surface from inside to outside, the thickness of the nitride layer of the nitride layer of metal level, metal, metal level and metal is respectively 0.01 micron, 0.2 micron, 0.01 micron and 0.1 micron.Note is made Coating Materials A1.
Comparative Examples 1
This Comparative Examples is used to explain existing Coating Materials and preparation method thereof.
Adopt magnetic controlled sputtering ion plating equipment (magnetron sputtering ion plating machine; Beijing Beiyi Innovation Vacuum Technology Co., Ltd. makes; Model is JP-700); This magnetic controlled sputtering ion plating equipment comprises vacuum chamber, heater, work rest, magnetic control target and biasing device, and heater, work rest and magnetic control target are arranged in vacuum chamber.Magnetic control target is to target structure, comprises a pair of titanium target.Distance between two targets of a pair of titanium target is 18 centimetres, and two targets link to each other with the both positive and negative polarity that a frequency is 40 kilo hertzs a power supply.Rubidium iron boron permanent magnet base material (35UH model) is fixed on the work rest, and between to target, the distance between two targets of permanent magnet base material and a pair of target equates.Biasing device is a grid bias power supply.
Earlier absolute pressure in the vacuum chamber is transferred to 5 * 10
-3Handkerchief charges into argon gas then in vacuum chamber, be 0.5 handkerchief until pressure; Temperature transfers to 100 ℃; Start grid bias power supply (positive pole of grid bias power supply links to each other with work rest, and negative pole links to each other with the housing of vacuum chamber), regulate and be biased into-500 volts; The bias adjustment step-length is 20 volts/minute, and permanent magnet was carried out reverse sputter clean 40 minutes.
Keep aforesaid operations, different is to start titanium target (promptly opening the power supply that is connected with the titanium target) and carry out magnetic controlled sputtering ion plating; The power of the power supply that is connected with the titanium target is 15 kilowatts, and (at this moment, the positive pole of grid bias power supply links to each other with the housing of vacuum chamber to regulate grid bias power supply simultaneously; Negative pole links to each other with work rest) bias voltage be 200 volts, dutycycle is 50%, the rotating speed of work rest is 2 rev/mins; Time is 5 minutes, forms metal level-titanium layer at the permanent magnet substrate surface.
Then, keep aforesaid operations, different is, stops to feed argon gas, feeds nitrogen simultaneously, and the consumption of nitrogen is 100sccm, and the time is 15 minutes, on above-mentioned layer on surface of metal, forms the nitride layer of the nitride layer-titanium of metal.
Keep aforesaid operations again 5 minutes, and on the nitride layer surface of above-mentioned titanium, formed the nitride layer of titanium.
Keep aforesaid operations again 1 minute, and formed the nitride layer of outermost layer-titanium.
At last; Close titanium target, grid bias power supply and stop to feed nitrogen, naturally cool to 30 ℃, take out the permanent magnet base material behind the above-mentioned plated film; Microscope with the Shanghai Cai Kang DMM-660D of Instr Ltd. model records; From the permanent magnet substrate surface from inside to outside, the thickness of the nitride layer of metal level and metal is respectively 0.01 micron and 0.31 micron, and note is made Coating Materials AC1.
Embodiment 2
This embodiment is used to explain Coating Materials provided by the invention and preparation method thereof.
According to preparing Coating Materials with embodiment 1 identical method; Different is; Time when the permanent magnet substrate surface forms the nitride layer of nitride layer, metal level and metal of metal level, metal from inside to outside successively was respectively 7 minutes, 20 minutes, 10 minutes and 5 minutes, and the thickness of the rete of formation is respectively 1 micron, 1 micron, 0.2 micron and 3 microns.Note is made Coating Materials A2.
Embodiment 3
This embodiment is used to explain Coating Materials provided by the invention and preparation method thereof.
According to preparing Coating Materials with embodiment 1 identical method; Different is; Time when the permanent magnet substrate surface forms the nitride layer of nitride layer, metal level and metal of metal level, metal from inside to outside successively was respectively 10 minutes, 25 minutes, 15 minutes and 10 minutes, and the thickness of the rete of formation is respectively 2 microns, 1.6 microns, 0.5 micron and 8 microns.Note is made Coating Materials A3.
Embodiment 4
This embodiment is used to explain Coating Materials provided by the invention and preparation method thereof.
According to preparing Coating Materials A4 with embodiment 1 identical method, different is to replace the titanium target with the aluminium target.
Embodiment 5
This embodiment is used to explain Coating Materials provided by the invention and preparation method thereof.
According to preparing Coating Materials A5 with embodiment 1 identical method, different is to replace the titanium target with the chromium target.
Embodiment 6
This embodiment is used to explain Coating Materials provided by the invention and preparation method thereof.
According to preparing Coating Materials A6 with embodiment 1 identical method, different is, after forming outermost layer, Coating Materials is not carried out annealing in process, promptly naturally cools to 30 ℃, directly takes out the permanent magnet base material.
Embodiment 7
This embodiment is used to explain Coating Materials provided by the invention and preparation method thereof.
Adopt multi-arc ion plating equipment (multi-arc ion plating film machine; Beijing Beiyi Innovation Vacuum Technology Co., Ltd. makes; Model is a LDH series); This multi-arc ion plating equipment comprises vacuum chamber, heater, work rest, multiple arc target and biasing device, and heater, work rest and multiple arc target are arranged in vacuum chamber.Multiple arc target is a titanium target.Rubidium iron boron permanent magnet base material (35UH model) is fixed on the work rest, and the permanent magnet base material is over against target.Biasing device is a grid bias power supply.
Earlier absolute pressure in the vacuum chamber is transferred to 5 * 10
-3Handkerchief charges into argon gas then in vacuum chamber, be 0.5 handkerchief until pressure; Temperature transfers to 100 ℃; Start grid bias power supply (positive pole of grid bias power supply links to each other with work rest, and negative pole links to each other with the housing of vacuum chamber), regulate and be biased into-500 volts; The bias adjustment step-length is 20 volts/minute, and permanent magnet was oppositely cleaned 40 minutes.
Keep aforesaid operations, different is to start titanium target (promptly opening the power supply that is connected with the titanium target) and carry out multi-arc ion coating; The electric current that is connected with arc is 70 peaces, and (at this moment, the positive pole of grid bias power supply links to each other with the housing of vacuum chamber to regulate grid bias power supply simultaneously; Negative pole links to each other with work rest) bias voltage be 200 volts, dutycycle is 50%, the rotating speed of work rest is 2 rev/mins; Time is 5 minutes, forms metal level-titanium layer at the permanent magnet substrate surface.
Then, keep aforesaid operations, different is, stops to feed argon gas, feeds nitrogen simultaneously, and the consumption of nitrogen is 100sccm, and the time is 15 minutes, on above-mentioned layer on surface of metal, forms the nitride layer of the nitride layer-titanium of metal.
Keep aforesaid operations again, different is, stops to feed nitrogen, feeds argon gas simultaneously, is 0.5 handkerchief until pressure, and the time is 5 minutes, on the nitride layer surface of above-mentioned metal, forms metal level-titanium layer.
Keep aforesaid operations again, different is, stops to feed argon gas, feeds nitrogen simultaneously, and the consumption of nitrogen is 100sccm, and the time is 1 minute, forms the nitride layer of outermost layer-titanium.
At last, close titanium target, grid bias power supply and stop to feed nitrogen, naturally cool to 30 ℃; Be warmed up to 500 ℃ with 10 ℃/minute speed again; Be incubated 20 minutes, take out the permanent magnet base material behind the above-mentioned plated film, record with the microscope of the Shanghai Cai Kang DMM-660D of Instr Ltd. model; From the permanent magnet substrate surface from inside to outside, the thickness of the nitride layer of the nitride layer of metal level, metal, metal level and metal is respectively 0.01 micron, 0.2 micron, 0.01 micron and 0.1 micron.Note is made Coating Materials A7.
Embodiment 8-14
This embodiment is used to measure the performance of the film of the Coating Materials that embodiment 1-7 makes.
Use following method to measure defect concentration, corrosion resistance and wearability and the adhesion of film and base material of film of the Coating Materials A1-A7 of embodiment 1-7 preparation.
(1) defect concentration test
Adopt light microscope respectively 160 times with 640 times of multiplication factors under observe the film surface defective, the recording surface defect situation, wherein, dimensional discrepancy is 4.5%.Defect concentration is more little, explains that film quality is good more, and promptly the adhesion of the corrosion resistance of film and wearability and film and base material is all good more, and test result is as shown in table 1 below.
(2) corrosion resistance test
Corrosion resistance is weighed through salt spray test; The salt spray test method places respectively in the YWX/Q-250 type salt-mist corrosion tester of Wuxi City southern Jiangsu testing equipment Co., Ltd production for the Coating Materials A1-A9 with embodiment 1-9 preparation; Using down concentration at 35 ℃ is that the sodium-chloride water solution splash of 5 weight % is after 2 hours; Again goods being placed the another one temperature after the taking-up is that 40 ℃, relative humidity are 80% climatic chamber, observes alloy product, is recorded in how long the back product surface occurs unusual; Time is long more, explains that the corrosion resistance of rete is good more.Test result is as shown in table 1 below.
(3) wearability is measured
Adopt the ball-dish friabilator of WTM-1 type aluminium ball (6 millimeters of φ), the wearability of testing film under following test condition: the sliding speed of 5 Ns load, 100 meter per seconds, 300 meters sliding distance, room temperature and unlubricated.The wearing depth of the film of record Coating Materials and wearing and tearing width, wearing depth is more little with the wearing and tearing width, explains that the wearability of film is good more.
(4) adhesion of film and base material test
On the surface of the Coating Materials A1-A7 that embodiment 1-7 prepares, mark the lattice number 100 (scratch depth is controlled at and guarantees film lower substrate metal exposed) that is spaced apart 1 millimeter of uniform size respectively with sharp blade; The lattice that the statistics film comes off is counted N1; To stick width be 24 millimeters adhesive tape (Permacell-99) in the lattice zone of drawing on film, and guarantee to combine between adhesive tape and the film that grid is arranged tight.After 5 minutes, adhesive tape is uncovered, and added up the lattice that film comes off once more and count N2 with the power of a vertical face.Appraisal procedure is following: adopt hundred-mark system, and binding force of membrane mark=100-(N1+N2), the binding force of membrane mark is big more, explains that the adhesion of film and base material is good more.Evaluation result is described in table 1 below.
The NIM-200C type permanent-magnet material hysteresiscope that re-uses the production of China metering institute is measured remanent magnetism, coercivity, magnetic energy product and the maximum operating temperature of the Coating Materials A1-A7 of embodiment 1-7 preparation respectively.Test result is as shown in table 2 below respectively.The remanent magnetism of the rubidium iron boron permanent magnet base material (35UH model) (before being the plating film) that wherein, uses among the embodiment 1-7 is 150 ℃ as 11.74kGs, coercivity 18.89kOe, magnetic energy product as 35.20MGOe, maximum operating temperature.
Comparative Examples 2
This Comparative Examples is used to measure the performance of the film of the Coating Materials that Comparative Examples 1 makes.
Adopt the method identical to measure defect concentration, corrosion resistance and wearability and the adhesion of film and base material of film of the Coating Materials AC1 of Comparative Examples 1 preparation with embodiment 8-14.Mensuration result is as shown in table 1 below.
Table 1
| The embodiment numbering | The Coating Materials numbering | Defect concentration (every square centimeter) | Corrosion resistance (hour) | Wearability | The binding force of membrane mark | |
| Wearing depth (micron) | Wearing and tearing width (micron) | |||||
| Embodiment 8 | A1 | 49 | 360 | 0.12 | 0.16 | 99 |
| Embodiment 9 | A2 | 49 | 360 | 0.12 | 0.16 | 99 |
| Embodiment 10 | A3 | 49 | 360 | 0.12 | 0.16 | 99 |
| Embodiment 11 | A4 | 50 | 350 | 0.13 | 0.17 | 98 |
| Embodiment 12 | A5 | 52 | 340 | 0.15 | 0.19 | 97 |
| Embodiment 13 | A6 | 53 | 340 | 0.15 | 0.19 | 97 |
| Embodiment 14 | A7 | 53 | 340 | 0.15 | 0.19 | 97 |
| Comparative Examples 2 | AC1 | 68 | 160 | 0.18 | 0.24 | 70 |
Can find out that from the data of table 1 compare with existing Coating Materials, the defect concentration of the film of Coating Materials provided by the invention is less, therefore, the adhesion of the corrosion resistance of film and wearability and film and base material is all better.
Table 2
| The embodiment numbering | The Coating Materials numbering | Remanent magnetism (kGrs) | Coercivity (kOe) | Magnetic energy product (MGOe) | Maximum operating temperature (℃) |
| Embodiment 8 | A1 | 11.71 | 19.85 | 36.20 | 180 |
| Embodiment 9 | A2 | 11.71 | 19.85 | 36.20 | 180 |
| Embodiment 10 | A3 | 11.71 | 19.85 | 36.20 | 180 |
| Embodiment 11 | A4 | 11.68 | 19.75 | 36.10 | 170 |
| Embodiment 12 | A5 | 11.64 | 19.65 | 35.84 | 160 |
| Embodiment 13 | A6 | 11.68 | 19.70 | 35.96 | 160 |
| Embodiment 14 | A7 | 11.68 | 19.70 | 35.96 | 160 |
| Comparative Examples 2 | AC1 | 11.54 | 16.20 | 34.1 | 140 |
Can find out that from the data of table 2 remanent magnetism of Coating Materials provided by the invention can reach the level of the permanent magnet before the plating film basically, coercivity and magnetic energy product be all than the height of the permanent magnet before the plated film, the permanent magnetism height of maximum operating temperature before than plated film; And remanent magnetism, coercivity, magnetic energy product and the maximum operating temperature of existing Coating Materials are all poor than the permanent magnet before the plating film.
Claims (9)
1. Coating Materials, this material comprise base material and the film that is plated on substrate surface, it is characterized in that; Said film comprises the nitride layer of a plurality of metal levels and a plurality of metals; And the nitride layer by metal between the adjacent metal layer separates, and the one deck in wherein a plurality of metal levels contacts with substrate surface, and the one deck in the nitride layer of a plurality of metals is an outermost layer; Wherein, said base material is a permanent magnet.
2. Coating Materials according to claim 1; Wherein, Said film is the 4-8 layer, and the said metal layer thickness that contacts with substrate surface is the 0.01-2 micron, and the thickness of the nitride layer of said outermost metal is the 0.1-8 micron; The metal layer thickness of other layer is the 0.01-0.5 micron, and the thickness of the nitride of the metal of other layer is the 0.2-1.6 micron.
3. Coating Materials according to claim 2, wherein, said film is 4 layers, said film is followed successively by the nitride layer of nitride layer, metal level and the metal of metal level, metal from inside to outside from substrate surface.
4. according to any described Coating Materials among the claim 1-3, wherein, the metal in each of said film layer is identical, and is titanium, aluminium or chromium.
5. the preparation method of the said Coating Materials of claim 1, this method is included under the magnetron sputtering condition, makes the target material sputter on the magnetic control target and deposits on the base material applying power supply on the magnetic control target; Be formed on the film of substrate surface; It is characterized in that the method that is formed on the film of substrate surface comprises the nitride layer that forms a plurality of metal levels and a plurality of metals, the nitride layer by metal between the adjacent metal layer separates; One deck in wherein a plurality of metal levels contacts with substrate surface; One deck in the nitride layer of a plurality of metals is an outermost layer, and wherein, said base material is a permanent magnet.
6. method according to claim 5; Wherein, Said film is the 4-8 layer, and the said metal layer thickness that contacts with substrate surface is the 0.01-2 micron, and the thickness of the nitride layer of said outermost metal is the 0.1-8 micron; The metal layer thickness of other layer is the 0.01-0.5 micron, and the thickness of the nitride of the metal of other layer is the 0.2-1.6 micron.
7. method according to claim 6, wherein, said film is 4 layers, said film is followed successively by the nitride layer of nitride layer, metal level and the metal of metal level, metal from inside to outside from substrate surface.
8. method according to claim 5, wherein, said magnetron sputtering condition comprises that the power of power supply is 8-20 kilowatt, and the absolute pressure of magnetron sputtering is the 0.1-1.0 handkerchief, and temperature is 20-200 ℃; The sputtering time that forms every layer film is 1-25 minute, and the atmosphere that forms metal level is inert gas, and the atmosphere that forms the nitride layer of metal is nitrogen.
9. according to claim 5,6 or 7 described methods, wherein, this method is carried out annealing in process to Coating Materials after also being included in and forming outermost layer.
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| CN102810321A (en) * | 2011-03-07 | 2012-12-05 | 南通万宝实业有限公司 | Method for manufacturing magnetic recording magnetic film |
| CN103915918B (en) * | 2014-03-30 | 2016-05-25 | 南通保来利轴承有限公司 | The large radian permanent ferrite magnetic tile of a kind of high-performance |
| 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 |
| CN107419231B (en) * | 2017-07-26 | 2019-11-15 | 沈阳广泰真空科技有限公司 | The preparation method of Nd-Fe-B permanent magnetic anti-corrosion insulation coating and Nd-Fe-B permanent magnet with the coating |
| CN113451038B (en) * | 2021-06-07 | 2023-05-02 | 杭州永磁集团有限公司 | Preparation method of samarium cobalt permanent magnet suitable for high-temperature high-pressure pure hydrogen environment |
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| CN1066835A (en) * | 1991-06-17 | 1992-12-09 | 伟光镀膜玻璃有限公司 | Four layer series film plating glass |
| CN1712553A (en) * | 2004-06-15 | 2005-12-28 | 鸿富锦精密工业（深圳）有限公司 | Magnesium surface treatment and product therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1066835A (en) * | 1991-06-17 | 1992-12-09 | 伟光镀膜玻璃有限公司 | Four layer series film plating glass |
| CN1712553A (en) * | 2004-06-15 | 2005-12-28 | 鸿富锦精密工业（深圳）有限公司 | Magnesium surface treatment and product therefrom |
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