CN113832441A - Multilayer composite film and preparation method thereof - Google Patents
Multilayer composite film and preparation method thereof Download PDFInfo
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- CN113832441A CN113832441A CN202111127420.2A CN202111127420A CN113832441A CN 113832441 A CN113832441 A CN 113832441A CN 202111127420 A CN202111127420 A CN 202111127420A CN 113832441 A CN113832441 A CN 113832441A
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- film
- titanium alloy
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- transition layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—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
Abstract
The present invention provides a multilayer composite film comprising: the multilayer film comprises a transition layer and a plurality of film layers stacked with the transition layer, wherein the plurality of film layers comprise Ta and TaN film layers which are alternately deposited, and the thickness ratio of the Ta to the TaN film layers is 1: 1. The advantages are that: the mechanical property and the toughness of the film are improved, and the wear resistance of the film is improved.
Description
Technical Field
The invention relates to the technical field of film layers, in particular to a multilayer composite film and a preparation method thereof.
Background
In the preparation process of the nano oxide film, the defects that the surface of a sample adsorbs impurities to influence interface combination, the use performance of the coating is influenced under the condition of insufficient melting of metal powder exist, and the problems of large internal stress generated in the coating and poor wear resistance exist.
Disclosure of Invention
The present invention provides a multilayer composite film and a process for its preparation, with the aim of overcoming at least one of the above-mentioned technical drawbacks.
In order to achieve the above purpose, the invention provides the following technical scheme:
a first aspect of the present invention protects a multilayer composite film comprising: the multilayer film comprises a transition layer and a plurality of film layers stacked with the transition layer, wherein the plurality of film layers comprise Ta and TaN film layers which are alternately deposited, and the thickness ratio of the Ta to the TaN film layers is 1: 1.
Preferably, the transition layer is Ti/TiN/TaN or Ti-5 Ta.
Preferably, the transition layer is laminated to the titanium alloy substrate.
A second aspect of the present invention provides a method for manufacturing a multilayer composite film according to the first aspect, comprising: comprises the following steps
S1, replacing the target material into a magnetron sputtering device;
s2, grinding the substrate and polishing;
s3, carrying out acid washing, ultrasonic treatment and blow-drying on the substrate obtained in the step for later use;
s4, carrying out vacuum pumping treatment on the deposition chamber, cleaning the substrate and carrying out sputtering coating;
preferably, the substrate is a titanium alloy.
Preferably, in step S2, the titanium alloy is polished with 400#, 600#, 800#, 1000#, 1200#, 1500#, 2000# sandpaper, respectively.
Preferably, in step S3, the etching solution is used for acid cleaning, and the etching solution is made of nitric acid, hydrofluoric acid and deionized water, and the volume ratio of the solution is 5:5:90, and the acid cleaning time is 14-16 min.
Preferably, in step S3, the titanium alloy is ultrasonically cleaned with alcohol and deionized water for 9-11 min.
Preferably, in step S4, the deposition chamber is vacuumized to 2 × 10-3After Pa, the heating device is started to increase the temperature of the deposition chamber to 300 ℃ when the vacuum is appliedDegree of 2 x 10-3And after Pa, setting the deposition temperature to be 120 ℃, introducing 100sccm of argon, closing a ventilation valve when the temperature is reduced to 120 ℃, vacuumizing for 20min, introducing 100sccm of argon, inflating for 20min, closing the argon valve, continuously vacuumizing, and repeating for 2 or 3 times.
Preferably, in step S4, a transition layer and a plurality of film layers are sequentially deposited on the substrate by sputtering.
The multilayer composite film and the preparation method thereof have the advantages that:
1. according to the structure, the TiN/TaN film layer has higher hardness, plays a certain supporting role, and improves the mechanical property of the film layer;
2. the design of the Ti/TiN/TaN transition layer structure improves the combination degree of (Ta/TaN) and titanium alloy;
3. the alternating structure of the metal Ta film layer and the TaN ceramic film layer can improve the toughness of the film layer and improve the wear resistance of the film layer;
4. the TaN film layer is used as a transition layer, so that the combination degree of the Ta metal layer and the TiN layer is improved;
5. the Ti-5Ta film layer is used as a transition layer and is connected with the titanium alloy and the metal Ta layer, so that the continuity of the film layer and the base body is improved;
6. compared with a plasma spraying technology, the magnetron sputtering film has better film forming quality, less defects in the film and compact film layer;
7. TaN has excellent blood compatibility.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIGS. 1-3 are schematic diagrams of one to three multilayer composite films according to embodiments of the present invention;
fig. 4-6 are wear profiles of products obtained in accordance with one to three embodiments of the present invention, respectively.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example one
S1, replacing the Ti and Ta targets in a magnetron sputtering device before preparing the multilayer film;
s2, respectively using 400#, 600#, 800#, 1000#, 1200#, 1500# and 2000# sandpaper to polish the titanium alloy test sample, and polishing the surface of the polished titanium alloy test sample to a straight mirror surface;
s3, carrying out acid cleaning treatment on the titanium alloy by using an etching solution to remove an oxide film on the surface of the titanium alloy, wherein the etching solution is prepared from nitric acid, hydrofluoric acid and deionized water, and the volume ratio of the solution is 5:5: 90. And (3) pickling for 15min, then respectively carrying out ultrasonic cleaning on the titanium alloy sample by using alcohol and deionized water for 10 min, respectively carrying out blow-drying by using nitrogen after cleaning is finished, and placing the titanium alloy sample into a drying vessel for later use. Taking out the titanium alloy from the drying vessel, binding the titanium alloy with a metal wire, hanging the titanium alloy on a sample rotating stand in unbalanced magnetron sputtering equipment without shielding a polished surface, and closing a cavity door;
s4, before depositing the multilayer film, vacuumizing the deposition chamber by 2 x 10-3After Pa, the heating device is started to increase the temperature of the deposition chamber to 300 ℃ when the vacuum degree reaches 2 x 10-3After Pa, setting the deposition temperature to be 120 ℃, introducing 100sccm of argon, closing a ventilation valve when the temperature is reduced to 120 ℃, vacuumizing for 20min, introducing 100sccm of argon, inflating for 20min, closing the argon valve, continuously vacuumizing, and repeating for 2 or 3 times to reduce the oxygen content in the cavity;
setting the argon gas flow as 80sccm, turning on a power supply rotating frame to enable the sample rotating frame to rotate, turning on an ion source, turning on a substrate bias voltage power supply, cleaning the surface of the titanium alloy when the pulse bias voltage is-150V for 20min, then adjusting the pulse bias voltage to-400V, and cleaning for 30 min;
then the bias voltage of the substrate is adjusted to-100V, the flow of argon is adjusted to ensure that the pressure of the cavity is 0.5Pa, and sputtering coating is carried out in the following way;
(1) opening a metal Ta baffle, and depositing a metal Ta film layer on the surface of the titanium alloy for 20 min;
(2) then introducing nitrogen, and depositing a TaN film on the surface of the Ta film for 20 min;
(3) and (3) repeating the steps (1) and (2), and co-depositing 4 (Ta/TaN) film structures to obtain a multilayer composite film (shown in figure 1).
Example two
The difference from the first embodiment is that the following sputter coating step is performed in step S4:
(1) firstly, opening a metal Ti target baffle, sputtering metal Ti, and preparing a pure titanium film layer on the surface of the titanium alloy, wherein the deposition time is 20 min;
(2) opening a nitrogen gas valve, introducing nitrogen, depositing a TiN film layer on the surface of the metal Ti layer for 40min, and then closing the metal Ti target baffle;
(3) opening a metal Ta target baffle, and depositing a TaN film on the surface of the TiN film for 20 min;
(4) then closing the nitrogen gas valve, and depositing a metal Ta film layer on the surface of the TaN film layer for 20 min;
(5) then introducing nitrogen, and depositing a TaN film on the surface of the Ta film for 20 min;
(6) and (5) repeating the steps (4) and (5), and co-depositing 4 (Ta/TaN) film structures to obtain a multilayer composite film (shown in figure 2).
As shown in fig. 1 and fig. 2, the cross-sectional views of the coating show that the interfaces of the layers are continuous, which indicates that the layers have better bonding, the metal Ta layer has certain ductility and can deform under external force, which hinders crack propagation, and the TaN layer has higher hardness, better deformation resistance, better supporting effect, and better wear resistance. The Ti/TiN/TaN gradient transition layer is designed, so that the continuity and the bonding force of the (Ta/TaN) and the titanium alloy substrate are increased, and the stability of the film layer is increased.
EXAMPLE III
The difference from the first embodiment is that the following sputter coating step is performed in step S4:
(1) the Ti-5Ta transition layer is prepared on the surface of the titanium alloy, and the specific process flow is as follows: simultaneously opening the metal Ti and Ta target baffles, sputtering the metal Ti and Ta, preparing a Ti-5Ta transition layer on the surface of the titanium alloy, depositing for 30min, and then closing the metal Ti target baffles;
(2) depositing a metal Ta film layer on the surface of the Ti-5Ta film layer for 20 min;
(3) then introducing nitrogen, and depositing a TaN film on the surface of the Ta film for 20 min;
(4) and (3) repeating the steps (2) and (3), and co-depositing 4 (Ta/TaN) film structures to obtain a multilayer composite film (shown in figure 3).
As shown in FIG. 3, the interface of each layer is continuous as seen from the cross-sectional view of the coating, which shows that each layer has better bonding, and the design of the Ti-5Ta transition layer increases the continuity and bonding force of (Ta/TaN) and the titanium alloy substrate, and increases the stability of the film.
Hardness and frictional wear tests were performed on the first to third examples, and the experimental parameters and structures are shown in tables 1 and 2 below:
TABLE 1 test standards and hardness test results of the first, second and third examples of the present invention
TABLE 2 test standards and results of the frictional wear test for the first, second and third embodiments of the present invention
As shown in Table 1, compared with a titanium alloy matrix, the hidden rod of the invention has the advantages that the hardness of the sample is effectively improved after the film layer is prepared; as shown in fig. 4-6, in the first embodiment, the peeling phenomenon occurred at the edge of the wear scar of the sample without the transition layer, the film layer was broken, because the elastic modulus difference between the titanium alloy and the tantalum metal was large, while the edges of the wear scar of the sample with the transition layer, i.e., sample two and sample three, were relatively complete and the width of the wear scar was narrow, which indicates that the preparation of the transition layer has a mechanical transition effect, and therefore, the wear resistance of the film layer was improved. In addition, the wear scar edges of examples two and three were relatively complete, which also indicates that the film had a relatively low internal stress.
The steps not described in detail in the present technical solution and the experimental steps are achievable by conventional techniques, and therefore are not described in detail.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A multilayer composite film characterized by: the multilayer film comprises a transition layer and a plurality of film layers stacked with the transition layer, wherein the plurality of film layers comprise Ta and TaN film layers which are alternately deposited, and the thickness ratio of the Ta to the TaN film layers is 1: 1.
2. A multilayer composite film according to claim 1, wherein: the transition layer is Ti/TiN/TaN or Ti-5 Ta.
3. A multilayer composite film according to claim 1, wherein: the transition layer is laminated on the titanium alloy substrate.
4. A method of making a multilayer composite film according to any of claims 1 to 3, characterized in that: the method comprises the following steps:
s1, replacing the target material into a magnetron sputtering device;
s2, grinding the substrate and polishing;
s3, carrying out acid washing, ultrasonic treatment and blow-drying on the substrate obtained in the step for later use;
and S4, carrying out vacuum pumping treatment on the deposition chamber, cleaning the substrate and carrying out sputtering coating.
5. The method of claim 3, further comprising: the substrate is a titanium alloy.
6. The method of claim 3, further comprising: in step S2, the titanium alloy is polished with 400#, 600#, 800#, 1000#, 1200#, 1500#, and 2000# sandpaper, respectively.
7. The method of claim 3, further comprising: in step S3, an etching solution is used for acid cleaning, wherein the etching solution is prepared from nitric acid, hydrofluoric acid and deionized water, the volume ratio of the solution is 5:5:90, and the acid cleaning time is 14-16 min.
8. The method of claim 3, further comprising: in step S3, the titanium alloy is cleaned by ultrasonic wave with alcohol and deionized water for 9-11 min.
9. The method of claim 3, further comprising: in step S4, the deposition chamber is vacuumized to 2 × 10-3After Pa, the heating device is started to increase the temperature of the deposition chamber to 300 ℃ when the vacuum degree reaches 2 x 10-3And after Pa, setting the deposition temperature to be 120 ℃, introducing 100sccm of argon, closing a ventilation valve when the temperature is reduced to 120 ℃, vacuumizing for 20min, introducing 100sccm of argon, inflating for 20min, closing the argon valve, continuously vacuumizing, and repeating for 2 or 3 times.
10. The method of claim 3, further comprising: in step S4, a transition layer and a plurality of layers are sequentially deposited on the substrate.
Priority Applications (1)
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| CN202111127420.2A CN113832441A (en) | 2021-09-26 | 2021-09-26 | Multilayer composite film and preparation method thereof |
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| CN202111127420.2A CN113832441A (en) | 2021-09-26 | 2021-09-26 | Multilayer composite film and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114990485A (en) * | 2022-07-01 | 2022-09-02 | 嘉兴云浩纳米技术有限公司 | Super-wear-resistant composite coating, preparation method and application thereof to dental plate mold |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108054162A (en) * | 2017-12-27 | 2018-05-18 | 成都海威华芯科技有限公司 | A kind of MIM capacitor manufacturing process |
| CN109261958A (en) * | 2018-11-15 | 2019-01-25 | 西北有色金属研究院 | Surface coats the medical porous titanium of tantalum coating or the preparation method of titanium alloy material |
-
2021
- 2021-09-26 CN CN202111127420.2A patent/CN113832441A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108054162A (en) * | 2017-12-27 | 2018-05-18 | 成都海威华芯科技有限公司 | A kind of MIM capacitor manufacturing process |
| CN109261958A (en) * | 2018-11-15 | 2019-01-25 | 西北有色金属研究院 | Surface coats the medical porous titanium of tantalum coating or the preparation method of titanium alloy material |
Non-Patent Citations (3)
| Title |
|---|
| ALI SHANAGHI等: "Efects of the tantalum intermediate layer on the nanomechanical properties and biocompatibility of nanostructured tantalum/ tantalum nitride bilayer coating deposited by magnetron sputtering on the nickel titanium alloy", 《APPLIED NANOSCIENCE》, vol. 11 * |
| CÉSAR D. RIVERA-TELLO等: "Micro and Macro-Tribology Behavior of a Hierarchical Architecture of a Multilayer TaN/Ta Hard Coating", 《COATINGS》, vol. 263, no. 10, pages 2 * |
| LIXIA WANG等: "Polylaminate TaN/Ta coating modified ferritic stainless steel bipolar plate for high temperature proton exchange membrane fuel cell", 《JOURNAL OF POWER SOURCES》, vol. 399 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114990485A (en) * | 2022-07-01 | 2022-09-02 | 嘉兴云浩纳米技术有限公司 | Super-wear-resistant composite coating, preparation method and application thereof to dental plate mold |
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