CN116641023A - Molybdenum disulfide-based coating with strong binding force on zirconia ceramic surface, and preparation method and application thereof - Google Patents

Molybdenum disulfide-based coating with strong binding force on zirconia ceramic surface, and preparation method and application thereof Download PDF

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CN116641023A
CN116641023A CN202310643230.9A CN202310643230A CN116641023A CN 116641023 A CN116641023 A CN 116641023A CN 202310643230 A CN202310643230 A CN 202310643230A CN 116641023 A CN116641023 A CN 116641023A
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target
layer
molybdenum disulfide
zirconia ceramic
chromium
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李泽清
徐明龙
张虹虹
邵恕宝
宋思扬
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Xian Jiaotong University
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Xian Jiaotong University
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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
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—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
    • 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
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • 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
    • C23C14/0623—Sulfides, selenides or tellurides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/48—Ion implantation

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Abstract

The invention discloses a zirconia ceramic surface strong-binding molybdenum disulfide-based coating, a preparation method and application thereof, wherein the coating is composed of a substrate surface modification layer, a Cr bonding layer, a hard gradient transition layer and a molybdenum disulfide-based target layer, wherein: the modified layer is formed by high-energy chromium ion implantation, and the hard gradient transition layer consists of a chromium doped amorphous carbon layer, a chromium and molybdenum co-doped amorphous carbon layer, a molybdenum doped amorphous carbon layer and a molybdenum disulfide layer, namely, the transition from a Cr metal layer to MoS 2 The composition is changed into Cr/a-C, cr/Mo/a-C, mo/a-C, M in detailoS 2 /a‑C、MoS 2 . The invention can strengthen the film-based bonding strength of the zirconia and molybdenum disulfide-based coating, effectively improve the tribological performance of zirconia ceramics, and provide technical support for realizing high-performance and long-service life of zirconia friction pairs.

Description

Molybdenum disulfide-based coating with strong binding force on zirconia ceramic surface, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of coating materials, and particularly relates to a molybdenum disulfide-based coating with strong binding force on the surface of zirconia ceramic, and a preparation method and application thereof.
Background
Zirconia (ZrO) 2 ) The ceramic has the characteristics of high hardness, high wear resistance, high temperature resistance, corrosion resistance and the like, and has been successfully used in the fields of aerospace, biomedicine, electronic information and the like. However, the friction stability of zirconia self-assembled pairs remains to be improved. In the atmosphere and vacuum environment, the sliding friction force and the dry friction coefficient of the friction pair can be gradually increased along with time, the performance and the reliable service life of the friction pair are directly affected, and the long-service requirement of high-end equipment under severe working conditions cannot be met. Currently, research on zirconia ceramics is mainly focused on improving the mechanical properties of the zirconia ceramics, and research on improving the stability of the tribological properties of the zirconia ceramics is less.
Solid lubricating coatings are an effective method of improving the tribological properties of contact surfaces. Molybdenum disulfide-based coatings are typical solid lubrication coatings, and are widely used in the field of aerospace lubrication because they exhibit a stable ultra-low coefficient of friction (less than 0.01) in a vacuum or high vacuum environment. However, because of the good chemical inertness of the zirconia ceramic surface, it is difficult to form strong chemical bonds with the coating material, resulting in poor bonding strength with the molybdenum disulfide coating, and peeling off is very easy to occur during the reciprocating friction process to fail.
It can be seen that the weak bond strength of zirconia ceramic and molybdenum disulfide coating is a key bottleneck restricting its use in the field of severe operating mode lubrication. Therefore, the film-based binding force between the inert surface of the zirconia ceramic and molybdenum disulfide is enhanced, and the method has important significance for further expanding the application of the zirconia ceramic in the field of high-end equipment.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a molybdenum disulfide-based coating with strong bonding force on the surface of zirconia ceramic, and a preparation method and application thereof, so as to solve the technical problem of weak bonding strength of the zirconia ceramic and the molybdenum disulfide coating, thereby effectively improving the tribological performance of the zirconia ceramic.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a design and a preparation method of a molybdenum disulfide-based coating with strong binding force on the surface of zirconia ceramic, wherein the coating is a composite system consisting of a modified layer, a Cr binding layer, a hard gradient transition layer and a molybdenum disulfide-based target layer; wherein:
the modified layer is formed by implanting chromium metal ions on the surface of zirconia;
the hard transition layer is composed of a chromium doped amorphous carbon layer, a chromium and molybdenum co-doped amorphous carbon layer, a molybdenum doped amorphous carbon layer and a molybdenum disulfide layer;
the molybdenum disulfide-based target layer comprises a pure molybdenum disulfide coating and a metal or compound doped molybdenum disulfide coating.
Preferably, the total thickness of the molybdenum disulfide-based coating with strong binding force on the surface of the zirconia ceramic is 1.0-4.5 μm.
The invention also discloses a preparation method of the molybdenum disulfide-based coating with strong binding force on the zirconia ceramic surface, which comprises the following steps:
1) Grinding, polishing, ultrasonic cleaning and drying the surface of the matrix in sequence;
2) Chromium metal ions are injected into the surface of the dried matrix;
3) Vacuum argon ion (Ar) treatment of chromium ion implantation surface + ) Etching;
4) In Ar + Depositing a Cr bonding layer on the surface of the etched substrate;
5) Depositing a hard gradient transition layer on the surface of the Cr bonding layer;
6) And depositing a molybdenum disulfide-based target layer on the surface of the hard gradient transition layer.
Preferably, in step 1), the zirconia substrate is polished to a roughness (Ra) below 0.1 μm.
Preferably, in step 2), the polished surface is subjected to chromium metal ion implantation, the main process parametersThe number is as follows: the injection voltage is 30 kV-50 kV, and the injection dosage is 10 17 ～10 18 ions/cm 2 。
Preferably, in step 3), the chromium ion implantation surface is subjected to vacuum argon ion (Ar) + ) Etching, wherein the main technological parameters are as follows: the bias voltage of the substrate is-600V to-750V, the rotating speed of the sample stage is 6rpm to 12rpm, and the etching time is 10min to 20min.
Preferably, in the step 5), a multi-target unbalanced magnetron sputtering system is adopted to deposit a hard gradient transition layer on the surface of the Cr bonding layer, and the specific steps and technological parameters are as follows:
1) The current of the chromium target is set to be 2.0A-3.5A, the chromium target is kept for 5 min-15 min,
2) The target current of the chromium target is linearly reduced from 2.0A to 3.5A to 0A, the target current of the Mo target is linearly increased from 0A to 0.3A to 0.6A, the target current of the graphite target is linearly increased from 0A to 2.0A to 3.5A, and the change time of each target current is 10min to 30min;
3) The current of the molybdenum target and the graphite target is respectively kept between 0.3A and 0.6A and between 2.0A and 3.5A for 5min to 15min;
4) The current of the molybdenum target and the graphite target is linearly reduced to 0A, and meanwhile, the current of the molybdenum disulfide target is linearly increased from 0A to 0.6-1.0A, and the change time of each target current is 5-15 min.
Preferably, in the steps 1) to 4), the bias voltage is-60V to-100V, the rotation speed of the sample is 6rpm to 12rpm, and the thickness of the hard gradient transition layer is 150nm to 500nm.
Preferably, in the step 6), a multi-target unbalanced magnetron sputtering system is adopted to deposit a molybdenum disulfide-based coating on the surface of the hard transition layer, and the thickness of the target layer is 0.5-3.5 mu m.
Preferably, the substrate is a zirconia-based ceramic.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a molybdenum disulfide-based coating with strong binding force on the surface of zirconia ceramic, which consists of a substrate surface modification layer, a Cr bonding layer, a hard gradient transition layer and a molybdenum disulfide-based target layer, wherein: the modified layer is formed by high-energy chromium ion implantation, and the hard gradient transition layer is doped with chromium and is not doped with chromiumThe crystalline carbon layer, the chromium and molybdenum co-doped amorphous carbon layer, the molybdenum doped amorphous carbon layer and the molybdenum disulfide layer are formed, namely transition from a Cr metal layer to MoS 2 The composition is changed into Cr/a-C, cr/Mo/a-C, mo/a-C, moS in detail 2 /a-C、MoS 2 The specific advantages are as follows:
1) The high-energy ion implantation technology and the multi-target unbalanced magnetron sputtering technology are combined, the high-energy chromium ion implantation is carried out on the zirconia surface, so that the chemical inertia of the film coating surface is reduced, the metallurgical bonding is easily formed with a Cr bonding layer deposited by the magnetron sputtering, no obvious interface exists, and the film base bonding strength of a zirconia substrate and a coating is obviously improved.
2) The research shows that the mechanical property of the coating transition layer has obvious influence on the binding force and the bearing performance of the coating, the invention designs the hard transition layer with high hardness, namely, amorphous carbon, chromium and molybdenum carbide hard phases are introduced, the components of the hard transition layer are graded gradually, interfaces with abrupt changes of the components and the physical and chemical properties are avoided, and the binding force and the bearing capacity of the coating are improved.
3) According to the preparation method, the high-bonding-strength molybdenum disulfide-based coating is prepared on the surface of the zirconia ceramic, so that the tribological performance of the surface of a matrix can be remarkably improved, a stable low friction coefficient is shown, and the friction stability of the zirconia ceramic is effectively improved.
Drawings
FIG. 1 is a schematic diagram of a strong-binding molybdenum disulfide-based coating on the surface of zirconia ceramic disclosed by the invention;
FIG. 2 is a schematic diagram of the target installation of the four-target unbalanced magnetron sputtering system for coating preparation of example 1, example 2 and comparative example 1;
FIG. 3 is a schematic diagram of the target installation of the six-target unbalanced magnetron sputtering system for coating preparation of example 3 and example 4;
FIG. 4 shows a comparison of the film-based bonding force of example 1 of the present invention and comparative example 1.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the attached drawing figures:
example 1
Preparation of high-binding-force MoS on surface of yttria-stabilized zirconia ceramic 2 A method of lubricating a coating comprising the steps of:
1) Yttria stabilized zirconia substrate surface treatment
Grinding and polishing the surface of the substrate until the roughness of the surface is lower than 0.1 mu m; then, sequentially adopting acetone and absolute ethanol solution to ultrasonically clean for 15min, and drying the surface of the matrix by using dry nitrogen.
2) Cr ion implantation
Adopting a metal vapor vacuum arc ion implantation system, installing a high-purity Cr metal target, applying a 35kV accelerating voltage, and performing ion implantation on the polished surface of the zirconia matrix, wherein the implantation dosage is 2 multiplied by 10 17 ions/cm 2 。
3) Argon ion etching
Mounting the zirconium oxide substrate after ion implantation treatment on a fixture of a four-target unbalanced magnetron sputtering system, and vacuumizing to be lower than 1 multiplied by 10 -4 And setting the bias voltage to be-650V during Pa, and carrying out argon ion etching on the ion implantation surface of the zirconia matrix, wherein the etching duration is 1500s.
4) Cr binding layer preparation
And depositing a chromium metal bonding layer on the etched surface of the zirconia matrix by utilizing a high-purity chromium metal target arranged in the four-target unbalanced magnetron sputtering system. The technological parameters are as follows: the chromium target current was 3.0A, ar gas flow was 15sccm, bias voltage-100V, sample rotation speed 10rpm, deposition time 600s.
5) Hard gradient transition layer (Cr- & gtCr/a-C- & gtCr/Mo/a-C- & gtMo/a-C- & gtMoS 2 ) Preparation
High-purity chromium targets, graphite targets, molybdenum targets and molybdenum disulfide targets installed in a four-target unbalanced magnetron sputtering system are utilized to control target currents of the targets to realize a hard gradient transition layer Cr- & gtCr/a-C- & gtMo/a-C- & gtMoS 2 And (3) preparation. The process flow is as follows: first, the chromium target current linearly decreased from 3.0A to 0A, while the Mo target current linearly increased from 0A to 0.4A, and the graphite target current linearly increased from 0A to 3.0A; secondly, the currents of the molybdenum target and the graphite target are respectively kept unchanged for 300 seconds; then, the molybdenum target and graphite target currents linearly decrease to 0A while the molybdenum disulfide target current increases linearly from 0A to 0.8A; wherein the time of change of each target current was 300s.
6)MoS 2 Layer preparation
MoS is deposited on the surface of the transition layer by utilizing a high-purity molybdenum disulfide target installed in a four-target unbalanced magnetron sputtering system 2 A layer. The technological parameters are as follows: the molybdenum disulfide target current is 0.8A and the bias voltage is-60V.
Example 2
Preparation of high-binding-force MoS on surface of yttria-stabilized zirconia ceramic 2 A method of base lubrication coating comprising the steps of:
1) Yttria stabilized zirconia substrate surface treatment
Grinding and polishing the surface of the substrate until the roughness of the surface is lower than 0.1 mu m; then, sequentially adopting acetone and absolute ethanol solution to ultrasonically clean for 15min, and drying the surface of the matrix by using dry nitrogen.
2) Cr ion implantation
Adopting a metal vapor vacuum arc ion implantation system, installing a high-purity Cr metal target, applying a 35kV accelerating voltage, and performing ion implantation on the polished surface of the zirconia matrix, wherein the implantation dosage is 4 multiplied by 10 17 ions/cm 2 。
3) Argon ion etching
Mounting the zirconium oxide substrate after ion implantation treatment on a fixture of a four-target unbalanced magnetron sputtering system, and vacuumizing to be lower than 1 multiplied by 10 -4 And setting the bias voltage to 600V at Pa, and carrying out argon ion etching on the ion implantation surface of the zirconia matrix for 1500s.
4) Cr binding layer preparation
And depositing a chromium metal bonding layer on the etched surface of the zirconia matrix by utilizing a high-purity chromium metal target arranged in the four-target unbalanced magnetron sputtering system. The technological parameters are as follows: the chromium target current was 3.0A, ar gas flow was 15sccm, bias voltage-100V, sample rotation speed 10rpm, deposition time 600s.
5) Hard gradient transition layer (Cr- & gtCr/a-C- & gtCr/Mo/a-C- & gtMo/a-C- & gtMoS 2 ) Preparation
High-purity chromium targets, graphite targets, molybdenum targets and molybdenum disulfide targets installed in a four-target unbalanced magnetron sputtering system are utilized to control target currents of the targets to realize a hard gradient transition layer Cr- & gtCr/a-C- & gtMo/a-C- & gtMoS 2 And (3) preparation. The process flow is as follows: first, the chromium target current linearly decreased from 3.0A to 0A, while the Mo target current linearly increased from 0A to 0.4A, and the graphite target current linearly increased from 0A to 3.0A; secondly, the currents of the molybdenum target and the graphite target are respectively kept unchanged for 300 seconds; then, the molybdenum target and graphite target currents linearly decrease to 0A while the molybdenum disulfide target current increases linearly from 0A to 0.8A; wherein the time of change of each target current was 300s.
6) Cr doped MoS 2 Layer preparation
High-purity molybdenum disulfide targets installed in four-target unbalanced magnetron sputtering system are utilized to form a hard gradient transition layer surfaceDeposition of Ti doped MoS 2 A target layer. The technological parameters are as follows: the sputtering current of the Cr target is 0.3A, the current of the molybdenum disulfide target is 0.8A, the bias voltage is-70V, and the rotating speed of the sample stage is 10rpm.
Example 3
Preparation of high-binding-force MoS on surface of yttria-stabilized zirconia ceramic 2 A method of base lubrication coating comprising the steps of:
1) Yttria stabilized zirconia substrate surface treatment
Grinding and polishing the surface of the substrate until the roughness of the surface is lower than 0.1 mu m; then, sequentially adopting acetone and absolute ethanol solution to ultrasonically clean for 15min, and drying the surface of the matrix by using dry nitrogen.
2) Cr ion implantation
Adopting a metal vapor vacuum arc ion implantation system, installing a high-purity Cr metal target, applying 40kV accelerating voltage, and performing ion implantation on the polished surface of the zirconia matrix, wherein the implantation dosage is 5 multiplied by 10 17 ions/cm 2 。
3) Argon ion etching
Mounting the zirconium oxide substrate after ion implantation treatment on a fixture of a four-target unbalanced magnetron sputtering system, and vacuumizing to be lower than 1 multiplied by 10 -4 And setting the bias voltage to 700V at Pa, and carrying out argon ion etching on the ion implantation surface of the zirconia matrix for 1500s.
4) Cr binding layer preparation
And depositing a chromium metal bonding layer on the etched surface of the zirconia matrix by utilizing a high-purity chromium metal target arranged in the six-target unbalanced magnetron sputtering system. The technological parameters are as follows: the chromium target current was 3.0A, ar gas flow was 15sccm, bias voltage-100V, sample rotation speed 10rpm, deposition time 600s.
5) Hard gradient transition layer (Cr- & gtCr/a-C- & gtCr/Mo/a-C- & gtMo/a-C- & gtMoS 2 ) Preparation
High-purity chromium targets, graphite targets, molybdenum targets and molybdenum disulfide targets installed in a six-target unbalanced magnetron sputtering system are utilized to control target currents of the targets to realize a hard gradient transition layer Cr- & gtCr/a-C- & gtMo/a-C- & gtMoS 2 And (3) preparation. The process flow is as follows: first, chromium targetsThe current linearly decreased from 3.0A to 0A while the Mo target current increased linearly from 0A to 0.4A, and the graphite target current increased linearly from 0A to 3.0A; secondly, the currents of the molybdenum target and the graphite target are respectively kept unchanged for 300 seconds; then, the molybdenum target and graphite target currents linearly decrease to 0A while the molybdenum disulfide target current increases linearly from 0A to 0.8A; wherein the time of change of each target current was 300s.
6)Ti/MoS 2 Layer preparation
High-purity titanium metal targets and molybdenum disulfide targets installed in six-target unbalanced magnetron sputtering system are utilized to jointly sputter and deposit Ti/MoS on the surface of transition layer 2 A target layer. The technological parameters are as follows: the current of the titanium metal target is 0.3A, the current of the molybdenum disulfide target is 0.8A, the bias voltage is-70V, and the rotating speed of the sample stage is 10rpm.
Example 4
Preparation of high-binding-force MoS on surface of yttria-stabilized zirconia ceramic 2 A method of base lubrication coating comprising the steps of:
1) Yttria stabilized zirconia substrate surface treatment
Grinding and polishing the surface of the substrate until the roughness of the surface is lower than 0.1 mu m; then, sequentially adopting acetone and absolute ethanol solution to ultrasonically clean for 15min, and drying the surface of the matrix by using dry nitrogen.
2) Cr ion implantation
Adopting a metal vapor vacuum arc ion implantation system, installing a high-purity Cr metal target, applying a 35kV accelerating voltage, and performing ion implantation on the polished surface of the zirconia matrix, wherein the implantation dosage is 7.5X10% 17 ions/cm 2 。
3) Argon ion etching
Mounting the zirconium oxide substrate after ion implantation treatment on a fixture of a four-target unbalanced magnetron sputtering system, and vacuumizing to be lower than 1 multiplied by 10 -4 And setting the bias voltage to 700V at Pa, and carrying out argon ion etching on the ion implantation surface of the zirconia matrix for 1500s.
4) Cr binding layer preparation
And depositing a chromium metal bonding layer on the etched surface of the zirconia matrix by utilizing a high-purity chromium metal target arranged in the six-target unbalanced magnetron sputtering system. The technological parameters are as follows: the chromium target current was 3.0A, ar gas flow was 15sccm, bias voltage-100V, sample rotation speed 10rpm, deposition time 600s.
5) Hard gradient transition layer (Cr- & gtCr/a-C- & gtCr/Mo/a-C- & gtMo/a-C- & gtMoS 2 ) Preparation
High-purity chromium targets, graphite targets, molybdenum targets and molybdenum disulfide targets installed in a six-target unbalanced magnetron sputtering system are utilized to control target currents of the targets to realize a hard gradient transition layer Cr- & gtCr/a-C- & gtMo/a-C- & gtMoS 2 And (3) preparation. The process flow is as follows: first, the chromium target current linearly decreased from 3.0A to 0A, while the Mo target current linearly increased from 0A to 0.4A, and the graphite target current linearly increased from 0A to 3.0A; secondly, the currents of the molybdenum target and the graphite target are respectively kept unchanged for 300 seconds; then, the molybdenum target and graphite target currents linearly decrease to 0A while the molybdenum disulfide target current increases linearly from 0A to 0.8A; wherein the time of change of each target current was 300s.
6)Ti/Pb/MoS 2 Layer preparation
High-purity titanium targets, lead targets and molybdenum disulfide targets installed in six-target unbalanced magnetron sputtering system are utilized to jointly sputter and deposit Ti/Pb/MoS on the surface of the transition layer 2 A target layer. The technological parameters are as follows: the titanium target current is 0.15A, the lead target current is 0.15A, the molybdenum disulfide target current is 0.8A, and the bias voltage is-100V.
Comparative example 1
Preparation of traditional MoS on yttria-stabilized zirconia ceramic surface 2 A method of lubricating a coating comprising the steps of:
1) Yttria stabilized zirconia substrate surface treatment
Grinding and polishing the surface of the substrate until the roughness of the surface is lower than 0.1 mu m; then, sequentially adopting acetone and absolute ethanol solution to ultrasonically clean for 15min, and drying the surface of the matrix by using dry nitrogen.
2) Argon ion etching
Mounting the dried zirconia matrix on a fixture of a four-target unbalanced magnetron sputtering system, and vacuumizing to be lower than 1 multiplied by 10 -4 At Pa, the bias voltage is set to-650V, and the oxygen is suppliedArgon ion etching is carried out on the ion implantation surface of the zirconium oxide substrate, and the etching time is 1500s.
3) Cr binding layer preparation
And depositing a chromium metal bonding layer on the etched surface of the zirconia matrix by utilizing a high-purity chromium metal target arranged in the four-target unbalanced magnetron sputtering system. The technological parameters are as follows: the chromium target current was 3.0A, ar gas flow was 15sccm, bias voltage-100V, sample rotation speed 10rpm, deposition time 600s.
4) Gradient transition layer (Cr-Cr/MoS) 2 →MoS 2 ) Preparation
High-purity chromium targets and molybdenum disulfide targets installed in a four-target unbalanced magnetron sputtering system are utilized to realize a gradient transition layer Cr-Cr/MoS 2 →MoS 2 And (3) preparation. The process flow is as follows: the chromium target current was controlled to linearly decrease from 3.0A to 0A while the molybdenum disulfide target current was linearly increased from 0A to 0.8A with a change time of 300s for each target current.
5)MoS 2 Layer preparation
High-purity molybdenum disulfide targets installed in a four-target unbalanced magnetron sputtering system are utilized to form a gradient transition layer (Cr-Cr/MoS 2 →MoS 2 ) Surface deposition MoS 2 A layer. The technological parameters are as follows: the molybdenum disulfide target current is 0.8A and the bias voltage is-60V.
FIG. 1 shows a schematic diagram of the structure of a strong-binding molybdenum disulfide-based coating on the surface of zirconia ceramic. Fig. 2 shows the relative positions of the targets of the four-target unbalanced magnetron sputtering systems used in example 1, example 2 and comparative example 1. Fig. 3 shows the relative positions of the targets of the six-target unbalanced magnetron sputtering systems used in examples 3 and 4.
As shown in fig. 4, the binding force of the coatings of example 1 and comparative example 1 was compared. The results of the same scratch method and parameter test show that the average bonding force of the example 1 is improved by more than 63.6 percent compared with that of the comparative example 1, and the molybdenum disulfide coating prepared by the example has obviously better bonding strength with the zirconia matrix.
In summary, the method disclosed by the invention adopts a combination of a high-energy ion implantation system and a multi-target magnetron sputtering system to realize preparation, and sequentially comprises zirconiaGrinding and polishing ceramic matrix, chromium ion implantation, depositing Cr metal adhesive layer and hard gradient transition layer (Cr- & gtCr/a-C- & gtCr/Mo/a-C- & gtMo/a-C- & gtMoS) on the surface of matrix 2 ) And depositing a molybdenum disulfide-based coating on the surface of the transition layer. The composite molybdenum disulfide-based coating has higher bonding strength with the zirconia ceramic matrix.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (10)

1. The molybdenum disulfide-based coating with strong binding force on the surface of zirconia ceramic is characterized by being a composite coating formed by a modified layer, a chromium metal bonding layer, a hard gradient transition layer and a molybdenum disulfide-based target layer which are sequentially arranged on the surface of zirconia ceramic; wherein:
the modified layer is formed by implanting chromium metal ions into the surface of zirconia;
the hard gradient transition layer is composed of a chromium doped amorphous carbon layer, a chromium and molybdenum co-doped amorphous carbon layer, a molybdenum doped amorphous carbon layer and a molybdenum disulfide layer;
the molybdenum disulfide-based target layer is a pure molybdenum disulfide coating and a metal or compound doped molybdenum disulfide coating.
2. The zirconia ceramic surface strongly bonded molybdenum disulfide-based coating of claim 1, wherein the total thickness of the coating is 1.0 μm to 4.5 μm.
3. The method for preparing the molybdenum disulfide-based coating with strong binding force on the surface of zirconia ceramic as claimed in claim 1 or 2, which is characterized by comprising the following steps:
1) Grinding, polishing, ultrasonic cleaning and drying the surface of the zirconia ceramic substrate in sequence;
2) Chromium metal ions are injected into the surface of the zirconia ceramic after the drying treatment;
3) Vacuum argon ion Ar for chromium metal ion implantation surface + Etching;
4) In Ar + Depositing a Cr bonding layer on the surface of the etched substrate;
5) Depositing a hard gradient transition layer on the surface of the Cr bonding layer;
6) And depositing a molybdenum disulfide-based target layer on the surface of the hard gradient transition layer to finish the preparation of the coating.
4. The method for preparing a strong binding molybdenum disulfide-based coating on the surface of zirconia ceramic according to claim 3, wherein in the step 1), the zirconia ceramic substrate is polished to a roughness Ra of less than 0.1 μm.
5. The method for preparing a strong binding molybdenum disulfide-based coating on the surface of zirconia ceramic according to claim 3, wherein in the step 2), the operation process parameters of injecting chromium metal ions are as follows: the injection voltage is 30 kV-50 kV, and the injection dosage is 10 17 ～10 18 ions/cm 2 。
6. The method for preparing a strong binding molybdenum disulfide-based coating on a zirconia ceramic surface according to claim 3, wherein in the step 3), vacuum argon ion Ar is performed on the chromium ion implantation surface + The operation technological parameters of etching are as follows: the bias voltage of the substrate is-600V to-750V, the rotating speed of the sample table is 6rpm to 12rpm, and the etching time is 15min to 30min.
7. The method for preparing the molybdenum disulfide-based coating with strong bonding force on the surface of the zirconia ceramic according to claim 3, wherein in the step 5), a multi-target unbalanced magnetron sputtering system is adopted to deposit a hard gradient transition layer on the surface of the Cr bonding layer, and the method comprises the following steps:
s1: the current of the chromium target is set to be 2.0A-3.5A, the chromium target is kept for 5 min-30 min,
s2: the target current of the chromium target is linearly reduced from 2.0A to 3.5A to 0A, the target current of the Mo target is linearly increased from 0A to 0.3A to 0.6A, the target current of the graphite target is linearly increased from 0A to 2.0A to 3.5A, and the change time of each target current is 5min to 15min;
s3: the current of the molybdenum target and the graphite target is respectively kept between 0.3A and 0.6A and between 2.0A and 3.5A for 5min to 15min;
s4: the current of the molybdenum target and the graphite target is linearly reduced to 0A, and meanwhile, the current of the molybdenum disulfide target is linearly increased from 0A to 0.6-1.0A, and the change time of each target current is 5-15 min.
8. The method for preparing the molybdenum disulfide-based coating with strong binding force on the zirconia ceramic surface according to claim 7, wherein in S1-S4, the bias voltage is-60V to-100V, the sample rotating speed is 6 rpm-12 rpm, and the thickness of the hard gradient transition layer is 150 nm-500 nm.
9. The method for preparing the molybdenum disulfide-based coating with strong bonding force on the surface of zirconia ceramic according to claim 1, wherein in the step 6), a multi-target unbalanced magnetron sputtering system is adopted to deposit the molybdenum disulfide-based coating on the surface of the hard transition layer, and the thickness of the molybdenum disulfide-based target layer is 0.5-3.5 μm.
10. The use of a strongly bonded molybdenum disulfide-based coating on the surface of a zirconia ceramic as claimed in claim 1 or 2 in the field of aerospace high-end equipment.
CN202310643230.9A 2023-06-01 2023-06-01 Molybdenum disulfide-based coating with strong binding force on zirconia ceramic surface, and preparation method and application thereof Pending CN116641023A (en)

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