CN115216726A - High-performance thin film material and preparation method thereof - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 239000010409 thin film Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000010408 film Substances 0.000 claims abstract description 61
- 238000000151 deposition Methods 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 229910052786 argon Inorganic materials 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 238000007733 ion plating Methods 0.000 claims abstract description 5
- 238000005137 deposition process Methods 0.000 claims abstract description 3
- 238000005530 etching Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 239000011651 chromium Substances 0.000 claims description 46
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052804 chromium Inorganic materials 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000013077 target material Substances 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 16
- 239000010410 layer Substances 0.000 description 38
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000001050 lubricating effect Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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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
- C23C14/0664—Carbonitrides
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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
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- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to a high-performance thin film material and a preparation method thereof, belonging to the technical field of thin film materials, wherein the thin film material is a multilayer composite structure which is formed by sequentially depositing a Cr layer, a CrN layer and a CrCN layer on the surface of a base material upwards and alternately and circularly depositing the three layers, the preparation method adopts a multi-arc ion plating technology, and the vacuum degree of a cavity is not higher than 5.0 multiplied by 10 ‑3 Depositing under the conditions of Pa and the workpiece rotating speed of 2.0-6.0 rmp; in the deposition process, high bias voltage and argon plasma are adopted to carry out substrate etching cleaning. The high-performance film material and the preparation method thereof have the advantages that the film has higher corrosion resistance and lower wear rate, can play a good surface protection role in corrosive media, and improve the equipment performanceThe operation stability and the service life of the film material, and the preparation process and the application field of the film material of the multilayer system are widened.
Description
Technical Field
The invention relates to a high-performance thin film material and a preparation method thereof, in particular to a high-performance thin film material deposited by multiple layers of alternate circulation and a preparation method thereof, and belongs to the technical field of thin film materials.
Background
CrN films are often used as protective films due to their high hardness, good chemical stability, excellent wear and corrosion resistance. However, defects such as microporosities during the deposition of CrN films inhibit the wear life of the films and their protective properties in corrosive media, severely limiting the wide use of the films.
The multi-element composite and multi-layer structure design is often used for refining crystal grains and improving the corrosion resistance of the film, and the element C is often used as a composite element to improve the wear resistance and the corrosion resistance of the film. Ye et al, in 2015, doping carbon to improve the tribological performance of CrN coatings in sea water, tribology International (C Doping to improve tribological performance in a CrN coating seawater environment), vol 90, pp 362-371, states: the abrasion resistance of the CrCN film prepared by adopting the multi-arc ion plating technology in the seawater environment is obviously superior to that of the CrN film;
hardcrcn/CrN multilayer Coatings for tribological applications surface and Coatings Technology, published by warchonski et al in 2010 (development of Hard CrCN/CrN multilayer Coatings based on tribological applications), vol 204, pages 2289-2293 indicated: the CrCN/CrN multilayer film has higher hardness, low friction and wear resistance;
warcholinski et al, in 2020, "Improvement in the tribological performance of CrCN coating by multilayered design for marine protective application. Applied Surface Science" (Improvement of the abrasion performance of CrCN coatings in marine protective applications by multilayer design), vol. 528, 147061, states: the prepared CrN/CrCN multilayer film has higher toughness, film-substrate bonding strength and higher abrasion resistance in a seawater environment. In conclusion, the density and mechanical properties of the film can be improved by the C element composite and multilayer structure design, so that the wear resistance, corrosion resistance and other properties of the CrN film are improved.
Many research reports are reported on CrN-based multielement composite and multilayer systems, however, the research reports mostly focus on multilayer structures obtained by alternately depositing two layers, and the research on the multilayer structure system formed by alternately and circularly depositing three layers is only reported, and the beneficial effects and excellent performances of the multilayer structure system are not known, so that the beneficial effects and performances of the multilayer system thin film material and the preparation method thereof are needed to be verified.
Disclosure of Invention
The purpose of the invention is: in order to broaden the research on the thin film material and the preparation process thereof in the prior art, a high-performance thin film material with multi-layer cycle alternate deposition and a preparation method thereof are provided, and the design and the preparation of a new thin film system material, namely a Cr/CrN/CrCN multi-layer composite thin film material with three-layer alternate cycle deposition are realized by combining the synergistic effect of gradient transition and three-layer alternate cycle deposition.
The technical scheme for solving the technical problems is as follows:
a high-performance thin film material is a multilayer composite structure which is formed by sequentially depositing a Cr layer, a CrN layer and a CrCN layer on the surface of a base material upwards and alternately and circularly depositing the three layers.
A process for preparing high-performance film material by multi-arc ion plating technique features that the vacuum degree in cavity is not higher than 5.0X 10 -3 Depositing under the conditions of Pa and workpiece rotating speed of 2.0-6.0 rmp; in the deposition process, high bias voltage and argon plasma are adopted to carry out substrate etching cleaning.
The preparation method comprises the following specific steps:
step 1, carrying out ultrasonic cleaning on a base material, drying the base material by using common nitrogen, fixing the base material on a sample rack, then placing the base material into a vacuum chamber, wherein the distance between a target material and the base material is 10-15 cm, the temperature of the heating chamber is raised to 400 ℃, and vacuumizing is carried out until the vacuum degree of the chamber is not higher than 5 multiplied by 10 -3 When Pa, introducing argon and bombarding and cleaning the surface of the sample for 10-30 min by high bias voltage;
step 2, adjusting the argon flow to be 300-600 sccm, the substrate bias voltage to be-20 to-70V, the chromium target current to be 50-70A, and depositing a Cr layer for 0-30 min;
step 3, closing the argon valve, simultaneously opening the nitrogen valve, adjusting the flow of the nitrogen valve to be 300-800 sccm, controlling the substrate bias voltage to be-20 to-70V, controlling the chromium target current to be 50-70A, and depositing a CrN layer for 1-10 min;
step 4, keeping the current of the chromium target at 50-70A and the nitrogen flow at 300-800 sccm, introducing acetylene gas at 30-100 sccm, and depositing a CrCN layer for 1-10 min;
and 5, circulating the steps 2, 3 and 4 to obtain the Cr/CrN/CrCN multilayer composite film with the expected thickness.
Further, in step 1, the argon flow is 300 to 800sccm, and the high bias is-800 to-1100V.
The invention has the beneficial effects that: the gradient transition of the Cr component of the prepared Cr/CrN/CrCN multilayer composite film and the multilayer structure system formed by alternately depositing the Cr layer, the CrN layer and the CrCN layer improve the mechanical properties of the film such as density, hardness, film-substrate bonding strength, toughness and the like, meanwhile, the C element in the film can be subjected to graphitizing conversion in the friction process so as to play a good lubricating role, the film presents a lower wear rate due to the synergistic effect of the mechanical properties of higher hardness and the like and the lubricating effect of the C element, the penetration and permeation of a corrosive medium in the film can be effectively inhibited due to higher density and multilayer interface structure, and the corrosion resistance of the film in the corrosive medium can be effectively improved; the multilayer composite film has the advantages of high hardness, small internal stress and high film-substrate adhesion, the film has higher corrosion resistance and lower wear rate, can play a good surface protection role in a corrosive medium, improves the running stability and service life of equipment, and widens the preparation process and application field of multilayer system film materials.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
A high-performance thin film material is a multilayer composite structure which is formed by sequentially depositing a Cr layer, a CrN layer and a CrCN layer on the surface of a base material upwards and alternately and circularly depositing the three layers.
The preparation method of the high-performance film material adopts the multi-arc ion plating technology, and the vacuum degree of a chamber is 5.0 multiplied by 10 - 3 The deposition is carried out under the conditions of Pa and workpiece rotating speed of 4.0rmp, and the specific steps are as follows:
example 1
Step 1, carrying out ultrasonic cleaning on a substrate in acetone and absolute ethyl alcohol in sequence, drying the substrate by using common nitrogen, fixing the substrate on a sample rack, then placing the sample rack into a vacuum chamber, wherein the distance between a target material and the substrate is 10cm, the temperature of the heating chamber is raised to 400 ℃, and vacuumizing the chamber until the vacuum degree of the chamber is 5 multiplied by 10 -3 When Pa, introducing argon and bombarding and cleaning the surface of the sample by using a high bias voltage of-1000V for 10min, wherein the flow of the argon is 400sccm;
step 2, adjusting the argon flow to 350sccm, the substrate bias voltage to-20V and the chromium target current to 60A, and depositing a Cr layer for 10min;
step 3, closing the argon gas valve, simultaneously opening the nitrogen gas valve, adjusting the flow of the nitrogen gas valve to 600sccm, controlling the substrate bias voltage to be-20V and the chromium target current to be 60A, and depositing a CrN layer for 10min;
step 4, keeping the current of the chromium target at 60A and the flow rate of nitrogen at 600sccm, introducing acetylene gas and adjusting the flow rate to 30sccm, and depositing a CrCN layer for 10min;
and 5, circulating the steps 2, 3 and 4 for four times to obtain the Cr/CrN/CrCN multilayer composite film with the thickness of about 4 mu m.
Test analysis shows that:
the prepared Cr/CrN/CrCN multilayer composite film is well combined with a substrate, the hardness is higher, an indentation experiment shows that the film has higher toughness, and the wear rate of the film in the atmospheric environment is about 4.4 multiplied by 10 -7 mm 3 Nm, corrosion current density of the thin film in 3.5% NaCl solution as low as 10 -8 A/cm 2 。
Example 2
Step 1, carrying out ultrasonic cleaning on a substrate in acetone and absolute ethyl alcohol in sequence, drying the substrate by using common nitrogen, fixing the substrate on a sample rack, then placing the sample rack into a vacuum chamber, wherein the distance between a target material and the substrate is 10cm, the temperature of the heating chamber is raised to 400 ℃, and vacuumizing the chamber until the vacuum degree of the chamber is 5 multiplied by 10 -3 When Pa, introducing argon and bombarding and cleaning the surface of the sample by using a high bias voltage of-1000V for 10min, wherein the flow of the argon is 400sccm;
step 2, adjusting the argon flow to 350sccm, the substrate bias voltage to-20V and the chromium target current to 60A, and depositing a Cr layer for 5min;
step 3, closing the argon valve, simultaneously opening the nitrogen valve, adjusting the flow of the nitrogen valve to 600sccm, setting the substrate bias voltage to-20V and the chromium target current to 60A, and depositing a CrN layer for 5min;
step 4, keeping the current of the chromium target at 60A and the flow rate of nitrogen at 600sccm, introducing acetylene gas and adjusting the flow rate to 30sccm, and depositing a CrCN layer for 10min;
and 5, circulating the steps 2, 3 and 4 for six times to obtain the Cr/CrN/CrCN multilayer composite film with the thickness of about 4 mu m.
Test analysis shows that:
the prepared Cr/CrN/CrCN multilayer composite film is well combined with a substrate, the hardness is higher, an indentation experiment shows that the film has higher toughness, and the wear rate of the film in the atmospheric environment is about 4.9 multiplied by 10 -7 mm 3 /Nm, corrosion current density of the film in 3.5% NaCl solution as low as 10 -8 A/cm 2 。
Example 3
Step 1, carrying out ultrasonic cleaning on a base material in acetone and absolute ethyl alcohol in sequence, drying the base material by using common nitrogen, fixing the base material on a sample rack, then placing the sample rack into a vacuum chamber, wherein the distance between a target material and the base material is 10cm, the temperature of the heating chamber is raised to 400 ℃, and vacuumizing the chamber until the vacuum degree of the chamber is 5 multiplied by 10 -3 When Pa, introducing argon and bombarding and cleaning the surface of the sample by using a high bias voltage of-1000V for 10min, wherein the flow of the argon is 400sccm;
step 2, adjusting the argon flow to 350sccm, the substrate bias voltage to-20V and the chromium target current to 60A, and depositing a Cr layer for 10min;
step 3, closing the argon gas valve, simultaneously opening the nitrogen gas valve, adjusting the flow of the nitrogen gas valve to 600sccm, controlling the substrate bias voltage to be-20V and the chromium target current to be 60A, and depositing a CrN layer for 5min;
step 4, keeping the current of the chromium target at 60A and the flow rate of nitrogen at 600sccm, introducing acetylene gas and adjusting the flow rate to 30sccm, and depositing a CrCN layer for 5min;
and 5, circulating the steps 2, 3 and 4 for six times to obtain the Cr/CrN/CrCN multilayer composite film with the thickness of about 4 mu m.
Test analysis shows that:
the prepared Cr/CrN/CrCN multilayer composite film is well combined with a substrate and is hardThe degree is higher, indentation experiments show that the film has higher toughness, and the wear rate of the film in the atmospheric environment is about 5.2 multiplied by 10 -7 mm 3 Nm, corrosion current density of the thin film in 3.5% NaCl solution as low as 10 -8 A/cm 2 。
Comparative example 1
Step 1, carrying out ultrasonic cleaning on a base material in acetone and absolute ethyl alcohol in sequence, drying the base material by using common nitrogen, fixing the base material on a sample rack, then placing the sample rack into a vacuum chamber, wherein the distance between a target material and the base material is 10cm, the temperature of the heating chamber is raised to 400 ℃, and vacuumizing the chamber until the vacuum degree of the chamber is 5 multiplied by 10 -3 When Pa, introducing argon and bombarding and cleaning the surface of the sample by using a high bias voltage of-1000V for 10min, wherein the flow of the argon is 400sccm;
step 2, adjusting the argon flow to 350sccm, the substrate bias voltage to-20V and the chromium target current to 60A, and depositing a Cr layer for 10min;
step 3, closing the argon gas valve, simultaneously opening the nitrogen gas valve, adjusting the flow of the nitrogen gas valve to 600sccm, controlling the substrate bias voltage to be-20V and the chromium target current to be 60A, and depositing a CrN layer for 10min;
step 4, keeping the current of the chromium target at 60A and the flow rate of nitrogen at 600sccm, introducing acetylene gas and adjusting the flow rate to 30sccm, and depositing a CrCN layer for 10min;
and 5, circulating the steps 3 and 4 for six times to obtain the CrN/CrCN multilayer film with the thickness of about 4 mu m.
Test analysis shows that:
the prepared CrN/CrCN multilayer film is well combined with a substrate, has higher hardness and toughness, and has the wear rate of about 8.3 multiplied by 10 under the atmospheric environment -7 mm 3 /Nm, corrosion current density of the film in 3.5% NaCl solution about 10 - 7 A/cm 2 。
Comparative example 2
Step 1, carrying out ultrasonic cleaning on a base material in acetone and absolute ethyl alcohol in sequence, drying the base material by using common nitrogen, fixing the base material on a sample rack, then placing the sample rack into a vacuum chamber, wherein the distance between a target material and the base material is 10cm, the temperature of the heating chamber is raised to 400 ℃, and vacuumizing the chamber until the vacuum degree of the chamber is 5 multiplied by 10 -3 When Pa is required, argon is introduced and the mixture is used at-100Bombarding and cleaning the surface of the sample for 10min at a high bias voltage of 0V, wherein the flow of argon is 400sccm;
step 2, adjusting the argon flow to 350sccm, the substrate bias voltage to-20V and the chromium target current to 60A, and depositing a Cr layer for 10min;
and 3, closing the argon valve, keeping the bias voltage at-20V and the chromium target current at 60A, simultaneously opening the nitrogen valve and regulating the flow rate to be 600sccm, introducing acetylene and regulating the flow rate to be 20sccm, and depositing the CrCN layer for 120min to obtain the single-layer CrCN thin film material.
Test analysis shows that:
the thickness of the prepared CrCN film material is about 4 mu m, and the wear rate of the film in the atmospheric environment is about 8.0 multiplied by 10 - 7 mm 3 /Nm, corrosion current density of the film in 3.5% NaCl solution about 10 -7 A/cm 2 。
In conclusion, from the comparison of the data of the above 3 examples and 2 comparative examples, it can be seen that the corrosion current density of the Cr/CrN/CrCN multilayer composite film prepared by the present technique in 3.5% NaCl solution is reduced by about 1 order of magnitude as compared with the corresponding CrN/CrCN multilayer film and CrCN film, and the wear rate in the atmospheric environment can be reduced by about 50%, exhibiting good corrosion and wear resistance.
Therefore, the Cr/CrN/CrCN multilayer composite film prepared by the preparation method has the advantages that the gradient transition of the Cr component and the multilayer structure system formed by the alternate deposition of the Cr layer, the CrN layer and the CrCN layer improve the mechanical properties of the film, such as density, hardness, film-substrate bonding strength, toughness and the like, meanwhile, the C element in the film can generate graphite conversion in the friction process so as to play a good lubricating role, the film has a lower wear rate due to the synergistic effect of the mechanical properties of higher hardness and the like and the lubricating effect of the C element, the penetration and permeation of a corrosive medium in the film can be effectively inhibited by the higher density and the multilayer interface structure, and the corrosion resistance of the film in the corrosive medium can be effectively improved;
the multilayer composite film has the advantages of high hardness, small internal stress and high film-substrate adhesion, has higher corrosion resistance and lower wear rate, can play a good surface protection role in a corrosive medium, improves the running stability and service life of equipment, and widens the preparation process and application field of multilayer system film materials.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (4)
1. A high performance thin film material, characterized by: the film material is a multilayer composite structure which is formed by sequentially depositing a Cr layer, a CrN layer and a CrCN layer on the surface of a base material upwards and alternately and circularly depositing the three layers.
2. The preparation method of the high-performance thin film material based on claim 1 is characterized by comprising the following steps: the preparation method adopts multi-arc ion plating technology, and the vacuum degree of the chamber is not higher than 5.0 multiplied by 10 -3 Depositing under the conditions of Pa and the workpiece rotating speed of 2.0-6.0 rmp; in the deposition process, high bias voltage and argon plasma are adopted to carry out substrate etching cleaning.
3. The preparation method of the high-performance thin film material according to claim 2, which comprises the following steps:
step 1, carrying out ultrasonic cleaning on a substrate, drying the substrate by using common nitrogen, fixing the substrate on a sample rack, then placing the substrate into a vacuum chamber, wherein the distance between a target material and the substrate is 10-15 cm, the temperature of the heating chamber is raised to 400 ℃, and vacuumizing the chamber until the vacuum degree of the chamber is not higher than 5 multiplied by 10 -3 When Pa, introducing argon and bombarding and cleaning the surface of the sample for 10-30 min by high bias voltage;
step 2, adjusting the argon flow to be 300-600 sccm, the substrate bias voltage to be-20 to-70V, the chromium target current to be 50-70A, and depositing a Cr layer for 0-30 min;
step 3, closing the argon valve, simultaneously opening the nitrogen valve, adjusting the flow of the nitrogen valve to be 300-800 sccm, controlling the substrate bias voltage to be-20 to-70V, controlling the chromium target current to be 50-70A, and depositing a CrN layer for 1-10 min;
step 4, keeping the current of the chromium target at 50-70A and the nitrogen flow at 300-800 sccm, introducing acetylene gas at 30-100 sccm, and depositing a CrCN layer for 1-10 min;
and 5, circulating the steps 2, 3 and 4 to obtain the Cr/CrN/CrCN multilayer composite film with the expected thickness.
4. The method for preparing high-performance thin film material according to claim 3, wherein: in step 1, the argon flow is 300-800 sccm, and the high bias voltage is-800V-1100V.
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