CN114686823B - Steel collar with periodic carbon film coating and preparation method thereof - Google Patents

Steel collar with periodic carbon film coating and preparation method thereof Download PDF

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Publication number
CN114686823B
CN114686823B CN202210395458.6A CN202210395458A CN114686823B CN 114686823 B CN114686823 B CN 114686823B CN 202210395458 A CN202210395458 A CN 202210395458A CN 114686823 B CN114686823 B CN 114686823B
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chromium
carbon
target
doped
layer
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CN114686823A (en
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杨忠仪
李洪涛
刘灿灿
徐彤
张宁
钱潮浪
陈波
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Nanjing Tech University
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Nanjing Tech 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
    • C23C14/22—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
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01H—SPINNING OR TWISTING
    • D01H7/00—Spinning or twisting arrangements
    • D01H7/02—Spinning or twisting arrangements for imparting permanent twist
    • D01H7/52—Ring-and-traveller arrangements
    • D01H7/60—Rings or travellers; Manufacture thereof not otherwise provided for ; Cleaning means for rings
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01H—SPINNING OR TWISTING
    • D01H7/00—Spinning or twisting arrangements
    • D01H7/02—Spinning or twisting arrangements for imparting permanent twist
    • D01H7/52—Ring-and-traveller arrangements
    • D01H7/60—Rings or travellers; Manufacture thereof not otherwise provided for ; Cleaning means for rings
    • D01H7/602—Rings

Abstract

The invention provides a steel collar with a periodic carbon film coating and a preparation method thereof, wherein a micro-arc ion plating technology is adopted, and after degreasing, water washing and ultrasonic cleaning are carried out on the steel collar to be treated, hot air drying is carried out; then placing the steel collar substrate in a workpiece table in a vacuum chamber of micro-arc ion plating equipment, sequentially performing the steps of ion cleaning, depositing a pure chromium priming layer, depositing a later-stage working layer and the like, and alternately depositing a carbon-doped chromium-based layer and a chromium-doped carbon-based layer on the surface of the steel collar substrate, so that on the basis of ensuring the tribological performance of the carbon-based coating, the rich sp can be effectively avoided 3 Residual compressive stress in the carbon coating builds up, thereby improving the toughness of the film. The obtained ring surface has the characteristics of high wear resistance, high rotating speed, low vibration and low friction, and can effectively meet the requirement that the ring is used for spinning and spinning, and the high-speed transfer of cotton threads can effectively improve the running stability of the whole machine.

Description

Steel collar with periodic carbon film coating and preparation method thereof
Technical Field
The invention relates to the technical field of spinning ring processing, in particular to a ring with a periodic carbon film coating and a preparation method thereof.
Background
The surface properties of rings (base materials are usually GCr15 bearing steel and 20Cr alloy structural steel) are used as one of important connecting parts in the spinning field, and directly influence the working performance of textile machinery equipment. The steel collar is usually in a working condition of local high-temperature high-speed (more than 1500 r/min) operation, is easy to wear and has large consumption, so that the friction coefficient of the surface of the steel collar is required to be low enough, the hardness is high, the maturing period is short, and the service life is long, so that the surface of the steel collar can be subjected to coating modification in actual application to meet the use requirement. However, the common wear-resistant layer materials of the rings, such as electroplated hard chrome rings, CVD TiC-plated rings, PVD CrN-plated rings, tiTaN-coated rings and the like, often generate defects of cracks, fractures and the like in practical application, and finally lead to peeling of the thin film, so that the defects caused by the defects cause serious adverse effects on the rings in practical operation, even directly influence the operation stability of the whole machine, and finally lead to the worry of yarn quality.
Amorphous carbon (a-C) based coatings are widely focused on due to their high hardness, low friction and abrasion resistance, and although such coatings solve the above problems to some extent, such coatings are sp-rich with increasing hardness 3 The problem of film quality caused by residual compressive stress in the carbon coating limits its performance in a variety of engineering applications.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the steel collar with the periodic carbon film coating and the preparation method thereof, and the coating of the steel collar can effectively avoid residual compressive stress accumulation in the sp 3-rich carbon coating on the basis of ensuring the tribological performance of the carbon-based coating, improve the toughness of a film, and the obtained steel collar surface has the characteristics of high wear resistance, high rotating speed, low vibration and low friction, thereby effectively meeting the requirement that the steel collar is used for high-speed transfer of cotton threads in spinning and effectively improving the running stability of a complete machine.
According to a first aspect of the object of the present invention, there is provided a steel collar with a periodic carbon film coating, comprising a steel collar substrate, the surface of the steel collar substrate is attached with the carbon film coating, the carbon film coating comprises a plurality of carbon-doped chromium-based film layers and chromium-doped carbon-based film layers which are sequentially and alternately arranged, and the carbon-doped chromium-based film layers are arranged on the surface of the steel collar substrate.
Preferably, the number of layers of the carbon-doped chromium-based film layer and the chromium-doped carbon-based film layer is n, and n is more than or equal to 2 and less than or equal to 11.
Preferably, in the carbon-doped chromium-based film layer, the atomic percentage of Cr is 80-90 at%.
Preferably, the thickness of the carbon-doped chromium-based film layer is 10 nm-100 nm.
Preferably, in the chromium-doped carbon-based film layer, the atomic content of C is 10-20at%.
Preferably, the thickness of the chromium-doped carbon-based film layer is 10 nm-50 nm.
Preferably, in the plurality of carbon-doped chromium-based film layers, the atomic percentage of Cr in each carbon-doped chromium-based film layer is the same; and/or, in the plurality of carbon-doped chromium-based film layers, the thickness of each carbon-doped chromium-based film layer is equal;
the atom percentage content of C in each chromium-doped carbon-based film layer is the same in the chromium-doped carbon-based film layers; and/or, in the plurality of chromium-doped carbon-based film layers, the thickness of each chromium-doped carbon-based film layer is equal.
Preferably, the surface of the ring matrix further comprises a chromium priming layer, and the carbon-doped chromium-based film layer is arranged on the surface of the chromium priming layer.
According to a second aspect of the object of the present invention, there is provided a method for preparing the aforementioned steel collar with a periodic carbon film coating, comprising the following specific steps:
s1, hanging a cleaned ring to be plated on a working disc in a vacuum chamber of micro-arc ion plating equipment, and starting the working disc; wherein, the vacuum chamber is internally provided with a chromium target and a pure graphite target;
s2, vacuumizing the vacuum chamber, introducing argon, then turning on a plasma power supply of the chromium target, setting current density of the chromium target, applying pulse bias to the steel collar of the workpiece to be plated in S1, cleaning the plasma, and cleaning impurities on the surface of the workpiece to obtain a first-stage workpiece;
s3, adjusting the target current density of the chromium target, applying pulse bias to the first-stage workpiece, and depositing a pure chromium priming layer on the surface of the first-stage workpiece to obtain a second-stage workpiece;
s4, adjusting the target current density of the chromium target, starting the target current density of the graphite target, applying pulse bias to the second-stage workpiece, and depositing a carbon-doped chromium-based film layer on the surface of the second-stage workpiece to obtain a third-stage workpiece;
s5, changing the target current density of the chromium target and the graphite target in the S4, applying pulse bias to the workpiece in the third stage, and depositing a chromium-doped carbon-based film layer on the surface of the workpiece in the third stage to obtain the workpiece in the fourth stage;
s6, on the basis of the work piece in the fourth stage, alternately repeating the steps S4 and S5, and finally obtaining the steel collar with the surface plated with the periodic carbon film coating.
Preferably, in the step S4, the specific steps are as follows:
maintaining the argon flow of 5-50 sccm and the working air pressure in the vacuum chamber at 1.0X10 -1 Pa～7×10 -1 Pa；
The target current density of the chromium target material is uniformly regulated and reduced to 0.02A/cm 2 ～0.60A/cm 2 At the same time, the target current density of the graphite target material is uniformly adjusted and increased to 0.001A/cm 2 ～0.030A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And simultaneously, pulse bias is applied to the second workpiece, wherein the negative bias value is kept at 10-120V, a transition layer is deposited on the surface of the second workpiece, and the deposition time is 5-20 min, so that the third-stage workpiece is obtained.
Preferably, in the step S5, the specific steps are as follows:
maintaining the argon flow of 5-50 sccm and the working air pressure in the vacuum chamber at 1.0X10 -1 Pa～7×10 -1 Pa；
The target current density of the chromium target material is uniformly regulated and reduced to 0.001A/cm 2 ～0.030A/cm 2 At the same time, the target current density of the graphite target material is uniformly regulated and increased to 0.02A/cm 2 ～0.50A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And simultaneously, pulse bias is applied to the second-stage workpiece, wherein the bias value is adjusted to 10-120V, a carbon layer is deposited on the surface of the second workpiece, and the deposition time is 5-20 min, so that the fourth-stage workpiece is obtained.
Preferably, in the step S6, the steps S4 and S5 are alternately repeated 1 to 10 times, and the working time of accumulated deposition is 100min to 400min, so as to obtain the ring with the surface plated with the periodic carbon film coating.
Preferably, the adjustment rate of the target current density on the chromium target is 0.002A/cm 2 /min～0.06A/cm 2 The target current adjusting rate of the graphite target material is 0.002A/cm per minute 2 /min～0.06A/cm 2 /min。
Compared with the prior art, the invention has the beneficial effects that:
1. the steel collar with the periodic carbon film coating comprises a carbon-doped chromium-based film layer (Cr-C layer) and a chromium-doped carbon-based film layer (a-C: cr layer) which are alternately and repeatedly overlapped, wherein a nano-periodic multilayer structure is formed by introducing low-proportion amorphous carbon into Cr and introducing high-proportion Cr into the amorphous carbon and alternately depositing; in the nano periodic multilayer structure, the carbon-doped chromium-based film layer serving as the main guide layer is an impact-resistant buffer layer, more Cr atoms are gradually combined into the multilayer structure along with the internal diffusion effect of interface atoms, so that an sp2 structure and hard phase chromium carbide are promoted to be formed, and the finally formed nano periodic composite structure effectively relieves the stress in a film, prevents cracks from being rapidly diffused in the abrasion process, and further improves the plasticity, toughness and abrasion resistance of a multilayer film sample.
2. The micro-arc ion plating technology adopted by the invention is that by modulating a pulse voltage application mode, the voltage pulse width of opening is smaller than the critical time of inducing a micro-area molten pool, and the current pulse width is sufficient to maintain effective deposition, so that the grain structure of a plating layer is fine, a Cr priming layer in a composite plating layer has good adhesiveness, the film base binding force of the plating layer is effectively improved, and the prepared plating layer is compact, high in binding force and low in friction coefficient.
The binary periodic coating prepared on the surface of the ring by utilizing the micro-arc ion plating technology greatly improves the surface service performance of the ring, prolongs the service life of the ring, reduces and stabilizes the spinning tension of the treated ring, reduces broken ends and yarn hairiness, improves the yield and quality of spun yarn, and has great practical significance in saving energy sources.
Drawings
FIG. 1 is a schematic cross-sectional view of a periodic carbon film coating of the present invention.
FIG. 2 is a process flow diagram of a method of preparing a periodic carbon film coated ring of the present invention.
FIG. 3 is a surface micro-topography of a periodic carbon film coating of example 1 of the present invention.
Detailed Description
For a better understanding of the technical content of the present invention, specific examples are set forth below, along with the accompanying drawings.
Aspects of the invention are described in this disclosure with reference to the drawings, in which are shown a number of illustrative embodiments. The embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in more detail below, may be implemented in any of a wide variety of ways.
The steel collar has the advantages that the hardness of the base body is not high and the base body is not wear-resistant, so that a plating layer with more excellent wear-resistant and abrasion-resistant performance is required to improve the comprehensive mechanical property, and meanwhile, a metallurgical bonding interface with high bonding force is required between the coating layer and the base body, but the requirement is not satisfied by only relying on lower substrate temperature and the conventional chromium-doped graphite plating layer.
In view of the above, the invention provides a steel collar with a periodic carbon film coating, which adopts a micro-arc ion plating technology, and bombards more plasmas with stronger energy through larger current density, when the plasmas with higher energy are deposited on a substrate after collision, the surface of the substrate can generate high-density ion flow, so that deposited particles are more fully embedded and grown with atoms on the surface, the structure of a coating is more refined and compact, and a Cr dominant layer with proper thickness is introduced into an amorphous carbon layer to form a multi-layer structure, which is beneficial to the formation of more chromized carbon hard phases and influences the mechanical properties of the coating.
The impact-resistant middle layer (carbon-doped chromium base layer: cr-C layer) and the graphite-like self-lubricating interlayer (chromium-doped carbon base layer: a-C: cr layer) alternately deposited on the surface of the ring matrix can ensure the tribology of the carbon-based coatingCan effectively avoid rich sp on the basis 3 Residual compressive stress in the carbon coating builds up, thereby improving the toughness of the film.
In an exemplary embodiment of the present invention, in connection with fig. 1, there is provided a ring having a periodic carbon film coating, including a ring base 1, to the surface of which a carbon film coating 2 is attached, the carbon film coating 2 including a plurality of carbon-doped chromium-based film layers 21 and chromium-doped carbon-based film layers 22 sequentially and alternately disposed on each other, the carbon-doped chromium-based film layers 22 being disposed on the surface of the ring base.
In a preferred embodiment, the number of layers of the carbon-doped chromium-based film layer and the chromium-doped carbon-based film layer is n, and n is more than or equal to 2 and less than or equal to 11.
In a preferred embodiment, the carbon-doped chromium-based film layer contains 80-90at% of Cr.
In a preferred embodiment, the thickness of the carbon-doped chromium-based film layer is 10nm to 100nm.
In a preferred embodiment, the atomic percentage of C in the chromium doped carbon based film layer is 10 to 20at%.
In a preferred embodiment, the thickness of the chromium doped carbon based film layer is 10nm to 50nm.
In another preferred embodiment, the carbon-doped chromium-based film layers have the same atomic percentage of Cr; and/or, in the plurality of carbon-doped chromium-based film layers, the thickness of each carbon-doped chromium-based film layer is equal.
In another preferred embodiment, the plurality of chromium-doped carbon-based film layers each have the same atomic percentage of C; and/or, in the plurality of chromium-doped carbon-based film layers, the thickness of each chromium-doped carbon-based film layer is equal.
The carbon-doped chromium-based film layer takes chromium as a main material, and a small amount of carbon-doped nano-structure working layer ensures that the film layer has better toughness and low friction coefficient, and improves the mechanical property of the film layer.
The chromium-doped carbon-based film layer is a nano-structure working layer with carbon as a main component and a small amount of chromium doped, and the self-lubricating effect of the coating can be improved.
In a preferred embodiment, the surface of the ring matrix further comprises a chrome primer layer 3, and the carbon-doped chrome-based film layer 21 is disposed on the surface of the chrome primer layer 3.
In a more preferred embodiment, the thickness of the chrome primer layer is 200nm to 500nm.
At present, although the surface mechanical property of the steel collar is greatly improved by the common electroplating hard chromium in the market, the plating hardness and the hardenability of the steel collar are greatly improved, but the surface structure of the steel collar is complex and irregular, the thickness of the hard chromium plating layer can be uneven, the effect is unstable, and the electroplating solution can cause environmental pollution.
The wear-resistant coating with good bonding strength, low surface roughness and precisely controllable components can be obtained by various deposition technologies in the physical vapor deposition field, but the surface coating of a workpiece with a complex shape is difficult to prepare, the process for preparing the coating also comprises the working procedure of generating heavy metal ion wastewater, and the preparation flow is longer.
In view of the above, the present invention also provides a method for preparing the ring with the periodic carbon film coating, which adopts micro-arc ion plating technology to complete the preparation of the coating by ion cleaning, depositing a primer layer and designing a periodic structure working layer.
Referring to fig. 2, the steel collar to be treated is subjected to degreasing, water washing and ultrasonic cleaning and then dried by hot air; then placing the steel collar in a workpiece table in a vacuum chamber of micro-arc ion plating equipment, and sequentially performing the steps of ion cleaning, depositing a pure chromium priming layer, depositing a later working layer and the like to obtain the steel collar with the surface plating layer.
Firstly, in the ion cleaning process of micro-arc ion plating, compared with sputtering cleaning, the slightly strong bias is adopted to be beneficial to improving the coiling and plating property of the micro-arc ion plating technology, and for the complicated irregular workpiece of the ring, the good coiling and plating property can enable the plating layer to be more uniform. Meanwhile, the bias voltage is lifted to enable bombarded plasmas to be more active, and the surface of the base material is easy to sink in atomic level when the base material is bombarded, so that the bonding strength of the underlying chromium layer and the surface of the base body is increased.
In the deposition of the priming layer, although the current density of the chromium target is increased, after cascade collision of particles, the temperature of the matrix is very slow, so that the stress between layers is reduced, the binding force between the priming layer and the matrix is further ensured, and on the basis of better embedding of the priming layer bottom, the tissue structure of the coating can be combined with the surface of the matrix more tightly and rapidly to form a columnar structure, so that the good film-matrix binding force of the coating is ensured.
Finally, in the periodic working layer deposition, the Cr-C layer in the first stage is deposited in a higher proportion, so that the tissue defect caused by sudden drop of the current density of the Cr target of the working layer is avoided, the uniform change of the tissue is ensured, the priming layer is perfectly transited, the high current density deposition working layer in the transition layer deposition process is continuously maintained, the section of the working layer is in a periodic layered and compact columnar crystal structure, no gap exists, the surface tissue is compact and flat, almost no boundary line exists, and the roughness is small; meanwhile, aiming at the field intensity of a carbon target in micro-arc ion plating, the particles can be bombarded more rapidly by combining large current density, the deposition rate is improved, and the process efficiency is improved.
In another exemplary embodiment of the present invention, there is provided a method for preparing the aforementioned ring with a periodic carbon film coating, comprising the following specific steps:
s1, hanging a cleaned ring to be plated on a working disc in a vacuum chamber of micro-arc ion plating equipment, and starting the working disc; wherein, the vacuum chamber is internally provided with a chromium target and a pure graphite target.
S2, vacuumizing the vacuum chamber, introducing argon, then turning on a plasma power supply of the chromium target, setting current density of the chromium target, applying pulse bias to the steel collar of the workpiece to be plated in S1, performing plasma cleaning, and cleaning impurities on the surface of the workpiece to obtain the workpiece in the first stage.
S3, adjusting the target current density of the chromium target, applying pulse bias to the first-stage workpiece, and depositing a pure chromium priming layer on the surface of the first-stage workpiece to obtain the second-stage workpiece.
S4, adjusting the target current density of the chromium target, starting the target current density of the graphite target, applying pulse bias to the second-stage workpiece, and depositing a carbon-doped chromium-based film layer on the surface of the second-stage workpiece to obtain a third-stage workpiece.
S5, changing the target current density of the chromium target and the graphite target in the S4, applying pulse bias to the workpiece in the third stage, and depositing a chromium-doped carbon-based film layer on the surface of the workpiece in the third stage to obtain the workpiece in the fourth stage.
S6, on the basis of the work piece in the fourth stage, alternately repeating the steps S4 and S5 to finally obtain the steel collar with the surface plated with the periodic carbon film coating (Cr-C/a-C: cr periodic carbon film).
In a preferred embodiment, in the step S4, the specific steps are as follows:
maintaining the argon flow of 5-50 sccm and the working air pressure in the vacuum chamber at 1.0X10 -1 Pa～7×10 -1 Pa；
The target current density of the chromium target material is uniformly regulated and reduced to 0.02A/cm 2 ～0.60A/cm 2 At the same time, the target current density of the graphite target material is uniformly adjusted and increased to 0.001A/cm 2 ～0.030A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And simultaneously, pulse bias is applied to the second workpiece, wherein the negative bias value is kept at 10-120V, a transition layer is deposited on the surface of the second workpiece, and the deposition time is 5-20 min, so that the third-stage workpiece is obtained.
At this time, the chromium content in the chromium-based coating in the periodic layer is uniformly reduced to 80-90at%, the carbon content is gradually and uniformly increased to 10-20at%, and the thickness of the film layer is 100-150nm. The layer is deposited with a nano-structure working layer mainly containing chromium and a small amount of carbon doped, so that the film layer is ensured to have better toughness and low friction coefficient, and the mechanical property of the film layer is improved.
In a preferred embodiment, in the step S5, the specific steps are as follows:
maintaining the argon flow of 5-50 sccm and the working air pressure in the vacuum chamber at 1.0X10 -1 Pa～7×10 -1 Pa；
The target current density of the chromium target material is uniformly regulated and reduced to 0.001A/cm 2 ～0.030A/cm 2 At the same time, the target current density of the graphite target material is uniformly regulated and increased to 0.02A/cm 2 ～0.50A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Simultaneously, pulse bias is applied to the second stage workpiece,and the bias voltage value is regulated to 10-120V, a carbon layer is deposited on the surface of the second workpiece, and the deposition time is 5-20 min, so that the fourth-stage workpiece is obtained.
At this time, the carbon content of the film is uniformly increased and stabilized to 80-90at%, the chromium content is uniformly reduced and stabilized to 10-20at%, the thickness of the film layer is 100-150nm, and the self-lubricating effect of the coating can be improved.
In a preferred embodiment, in the step S6, the steps S4 and S5 are alternately repeated 1 to 10 times, and the accumulated deposition time is 100min to 400min, so as to obtain the ring with the surface plated with the periodic carbon film coating.
In a preferred embodiment, the adjustment rates of the target current densities on the chromium target are all 0.002A/cm 2 /min～0.06A/cm 2 The target current adjusting rate of the graphite target material is 0.002A/cm per minute 2 /min～0.06A/cm 2 /min。
In a preferred embodiment, in the step S2, the specific steps are as follows: vacuumizing the vacuum chamber to make the vacuum degree of the vacuum chamber smaller than 5.0X10 -3 Pa, introducing argon gas with the air flow of 5-50 sccm, and keeping the working air pressure in the vacuum chamber at 1.0X10 -1 Pa～7×10 -1 Pa；
Directly applying 0.01A/cm on chromium target 2 ～0.02A/cm 2 And simultaneously, applying a negative bias voltage value of 380V-420V to the steel collar to be plated, and performing sputter cleaning on the steel collar to be plated for 10 min-60 min.
In a preferred embodiment, in the step S3, the specific steps are as follows: maintaining the argon flow of 5-100 sccm and the working air pressure in the vacuum chamber at 1.0X10 -1 Pa～7×10 -1 Pa；
The target current density of the chromium target material is uniformly adjusted to 0.04A/cm 2 ～0.80A/cm 2 And simultaneously, pulse bias voltage is applied to the first workpiece, wherein the negative bias voltage value is 10-120V, a pure chromium priming layer is deposited on the surface of the first-stage workpiece, and the deposition time is 10-30 min, so that the second-stage workpiece is obtained.
In another preferred embodiment, the chromium target and the graphite target are placed adjacent to each other, and the number of each target is 2.
In another preferred embodiment, the distance between the chromium target and the axle center of the steel collar is 60-150 mm, the distance between the graphite target and the axle center of the steel collar is 60-150 mm, and the revolution/rotation speed of the working frame is 1-20 r/min.
In other preferred embodiments, the step S1 is performed by cleaning the steel collar to be coated after cleaning: degreasing, washing and ultrasonic cleaning the ring to be treated, and drying with hot air.
In the foregoing, the first-stage workpiece refers to a workpiece after plasma cleaning of the cleaned ring to be coated, the second-stage workpiece refers to a workpiece after deposition of a pure chromium primer layer on the surface of the first-stage workpiece, the third-stage workpiece refers to a workpiece after deposition of a transition layer on the surface of the second-stage workpiece, and the fourth-stage workpiece refers to a workpiece after deposition of a transition layer on the surface of the third-stage workpiece.
In the following, in connection with specific examples and tests, the preparation of the aforementioned surface periodic carbon film coating of the ring and its effects will be exemplarily tested and compared. Of course, the embodiments of the invention are not limited thereto.
The experimental methods used in the following examples are conventional methods unless otherwise specified. Materials, reagents, and the like used in the embodiments described below are commercially available unless otherwise specified.
[ example 1 ]
Micro-arc ion plating method for depositing Cr-C/a-C Cr periodic carbon film on steel collar
Step 1: firstly, ultrasonic dewaxing and degreasing cleaning are carried out, a long straight workpiece is directly placed into a vacuum chamber of magnetron sputtering equipment after being dried by an air compressor, a chromium target and a pure graphite target are placed in the vacuum chamber, and the vacuum degree of the vacuum chamber is increased to 5.0 multiplied by 10 -3 Argon is introduced under Pa, the gas flow is 30sccm, and the working pressure in the vacuum chamber is kept at 1.0X10 -3 Pa～5.0×10 -3 Pa。
Step 2: performing sputter bombardment cleaning on the ring in the step 1, and maintaining the ring in a vacuum chamberIs 1.0X10 g working pressure -3 Pa, applying a current of 0.5A to the chromium target, applying a current of 0.01A to the graphite target, and applying a negative bias of 400V to the ring for a bombardment cleaning time of 20min.
Step 3: depositing to form a pure chromium priming layer, continuously introducing argon after sputtering cleaning in the step 2, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, adjusting the target current of the chromium target to 1.5A, adjusting the current of the graphite target to 0A, and simultaneously adjusting the negative bias voltage applied to the ring to 120V for 10min to deposit and form the pure chromium primer layer.
Step 4: depositing a first periodic layer for forming a work periodic layer, continuously introducing argon after the step 3, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, adjusting the target current of the chromium target to 1.5A, and adjusting the target current of the graphite target to 0.5A; meanwhile, a negative bias of 50V was applied to the ring for a duration of 5min.
Step 5: the target current of the chromium target was adjusted to 0.05A while the target current of the graphite target was adjusted to 1.5A, while a negative bias of 50V was applied to the ring for 5min.
Step 6: and (5) alternately repeating the step (4) and the step (5) for 7 times to obtain the coated steel ring.
[ example 2 ]
Micro-arc ion plating method for depositing Cr-C/a-C Cr periodic carbon film on steel collar
Step 1: firstly, ultrasonic dewaxing and degreasing cleaning are carried out, a long straight workpiece is directly placed into a vacuum chamber of magnetron sputtering equipment after being dried by an air compressor, a chromium target and a pure graphite target are placed in the vacuum chamber, and the vacuum degree of the vacuum chamber is increased to 5.0 multiplied by 10 -3 Argon is introduced under Pa, the gas flow is 20sccm, and the working pressure in the vacuum chamber is kept at 1.0X10 -3 Pa～5.0×10 -3 Pa；
Step 2: performing sputter bombardment cleaning on the ring in the step 1, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, applying a current of 0.6A to the chromium target, applying a current of 0.02A to the graphite target, and applying a negative bias of 400V to the ringThe bombardment cleaning time is 20min.
Step 3: depositing to form a pure chromium priming layer, continuously introducing argon after sputtering cleaning in the step 2, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, adjusting the target current of the chromium target to 1.5A, adjusting the current of the graphite target to 0A, and simultaneously adjusting the negative bias voltage applied to the ring to 120V for 10min to deposit and form the pure chromium primer layer.
Step 4: depositing a first periodic layer for forming a work periodic layer, continuously introducing argon after the step 3, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, adjusting the target current of the chromium target to 2A, and adjusting the target current of the graphite target to 0.5A; meanwhile, a negative bias of 50V was applied to the ring for a deposition time of 6min.
Step 5: the target current of the chromium target was adjusted to 0.05A while the target current of the graphite target was adjusted to 1.5A, and simultaneously a negative bias of 50V was applied to the ring for a deposition time of 6min.
Step 6: and (5) alternately repeating the step (4) and the step (5) for 7 times to obtain the coated steel ring.
[ example 3 ]
Micro-arc ion plating method for depositing Cr-C/a-C Cr periodic carbon film on steel collar
Step 1: firstly, ultrasonic dewaxing and degreasing cleaning are carried out, a long straight workpiece is directly placed into a vacuum chamber of magnetron sputtering equipment after being dried by an air compressor, a chromium target and a pure graphite target are placed in the vacuum chamber, and the vacuum degree of the vacuum chamber is increased to 5.0 multiplied by 10 -3 Argon is introduced under Pa, the gas flow is 30sccm, and the working pressure in the vacuum chamber is kept at 1.0X10 -3 Pa～5.0×10 -3 Pa；
Step 2: performing sputter bombardment cleaning on the ring in the step 1, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, applying a current of 0.5A to the chromium target, applying a current of 0.01A to the graphite target, and applying a negative bias of 400V to the ring for a bombardment cleaning time of 20min.
Step 3: depositing to form a pure chromium priming layer, and continuously sputtering and cleaning in the step 2Argon is introduced and the working pressure in the vacuum chamber is kept to be 1.0 multiplied by 10 -3 Pa, adjusting the target current of the chromium target to 1.5A, adjusting the current of the graphite target to 0A, and simultaneously adjusting the negative bias voltage applied to the ring to 120V for 10min to deposit and form the pure chromium primer layer.
Step 4: depositing a first periodic layer for forming a work periodic layer, continuously introducing argon after the step 3, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, adjusting the target current of the chromium target to 1.8A, and adjusting the target current of the graphite target to 0.5A; simultaneously, a negative bias voltage of 50V is applied to the ring for 10min;
step 5: the target current of the chromium target was adjusted to 0.08A while the target current of the graphite target was adjusted to 1.5A while a negative bias of 50V was applied to the ring for a duration of 10min.
Step 6: and (5) alternately repeating the step (4) and the step (5) for 7 times to obtain the coated steel ring.
[ example 4 ]
Micro-arc ion plating method for depositing Cr-C/a-C Cr periodic carbon film on steel collar
Step 1: firstly, ultrasonic dewaxing and degreasing cleaning are carried out, a long straight workpiece is directly placed into a vacuum chamber of magnetron sputtering equipment after being dried by an air compressor, a chromium target and a pure graphite target are placed in the vacuum chamber, and the vacuum degree of the vacuum chamber is increased to 5.0 multiplied by 10 -3 Argon is introduced under Pa, the gas flow is 30sccm, and the working pressure in the vacuum chamber is kept at 1.0X10 -3 Pa～5.0×10 -3 Pa。
Step 2: performing sputter bombardment cleaning on the ring in the step 1, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, applying a current of 0.5A to the chromium target, applying a current of 0.01A to the graphite target, and applying a negative bias of 400V to the ring for a bombardment cleaning time of 20min.
Step 3: depositing to form a pure chromium priming layer, continuously introducing argon after sputtering cleaning in the step 2, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, adjusting the target current of the chromium target to 1.5A, and adjusting the current of the graphite target to be0A while adjusting the negative bias applied to the ring to 120V for a duration of 10min to deposit a pure chrome primer layer.
Step 4: depositing a first periodic layer for forming a work periodic layer, continuously introducing argon after the step 3, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, adjusting the target current of the chromium target to 1.5A, and adjusting the target current of the graphite target to 0.5A; meanwhile, a negative bias of 50V was applied to the ring for a duration of 5min.
Step 5: the target current of the chromium target was adjusted to 0.05A while the target current of the graphite target was adjusted to 1.5A, while a negative bias of 50V was applied to the ring for 5min.
Step 6: and (5) alternately repeating the step (4) and the step (5) for 10 times to obtain the coated steel ring.
[ example 5 ]
Micro-arc ion plating method for depositing Cr-C/a-C Cr periodic carbon film on steel collar
Step 1: firstly, ultrasonic dewaxing and degreasing cleaning are carried out, a long straight workpiece is directly placed into a vacuum chamber of magnetron sputtering equipment after being dried by an air compressor, a chromium target and a pure graphite target are placed in the vacuum chamber, and the vacuum degree of the vacuum chamber is increased to 5.0 multiplied by 10 -3 Argon is introduced under Pa, the gas flow is 30sccm, and the working pressure in the vacuum chamber is kept at 1.0X10 -3 Pa～5.0×10 -3 Pa。
Step 2: performing sputter bombardment cleaning on the ring in the step 1, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, applying a current of 0.5A to the chromium target, applying a current of 0.01A to the graphite target, and applying a negative bias of 400V to the ring for a bombardment cleaning time of 20min.
Step 3: depositing to form a pure chromium priming layer, continuously introducing argon after sputtering cleaning in the step 2, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, adjusting the target current of the chromium target to 1.5A, adjusting the current of the graphite target to 0A, and simultaneously adjusting the negative bias voltage applied to the ring to 120V for 10min to deposit and form the pure chromium primer layer.
Step (a)4: depositing a first periodic layer for forming a work periodic layer, continuously introducing argon after the step 3, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, adjusting the target current of the chromium target to 1.5A, and adjusting the target current of the graphite target to 0.5A; meanwhile, a negative bias of 50V was applied to the ring for a duration of 5min.
Step 5: the target current of the chromium target was adjusted to 0.05A while the target current of the graphite target was adjusted to 1.5A, while a negative bias of 50V was applied to the ring for 5min.
Step 6: and (5) alternately repeating the step (4) and the step (5) for 1 time to obtain the coated steel ring.
[ comparative example ]
Method for depositing graphite-like coating on ring by magnetron sputtering
Step 1: firstly, ultrasonic dewaxing and degreasing cleaning are carried out, a long straight workpiece is directly placed into a vacuum chamber of magnetron sputtering equipment after being dried by an air compressor, a chromium target and a pure graphite target are placed in the vacuum chamber, and the vacuum degree of the vacuum chamber is increased to 5.0 multiplied by 10 -3 Argon is introduced under Pa, the gas flow is 30sccm, and the working pressure in the vacuum chamber is kept at 1.0X10 -3 Pa～5.0×10 -3 Pa；
Step 2: performing sputter bombardment cleaning on the ring in the step 1, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, applying a current of 0.5A to the chromium target, applying a current of 0.01A to the graphite target, and applying a negative bias of 400V to the ring for a bombardment cleaning time of 20min.
Step 3: depositing to form a pure chromium priming layer, continuously introducing argon after sputtering cleaning in the step 2, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, adjusting the target current of the chromium target to 1.5A, adjusting the current of the graphite target to 0A, and simultaneously adjusting the negative bias voltage applied to the ring to 120V for 10min to deposit and form the pure chromium primer layer.
Step 4: depositing to form a transition layer, continuously introducing argon after the step 3, and keeping the working air pressure in the vacuum chamber to be 1.0 multiplied by 10 -3 Pa, adjusting the target current of the chromium target to 0.05A, simultaneously adjusting the target current of the graphite target to 1.5A; simultaneously, a negative bias of 50V is applied to the ring, and the transition layer is formed by deposition for 30 min.
Step 5: depositing to form graphite-like working layer, continuously introducing argon gas, and maintaining working air pressure in vacuum chamber at 1.0X10 -3 Pa; keeping the current parameters of the chromium target and the graphite target unchanged; and applying a negative bias voltage of 50V to the ring, and depositing for 360min to form a graphite-like working layer, wherein the graphite-like working layer is a graphite self-lubricating film.
[ test ]
Fig. 3 shows the surface morphology of the coating of example 1, and it can be seen that the surface of the coating is a graphite-like self-lubricating coating in a periodic film, which is flat, free of particles and agglomeration, and has a small roughness, so that the antifriction performance of the surface is ensured.
Meanwhile, as shown in table 1, it was found that the steel collar with the nano-periodic multi-layer structure obtained by the present invention has a slightly improved friction coefficient, but a higher bonding strength and an improved bonding force of at least 50% compared with the pure graphite-like coating (comparative example).
Hardness experiments show that in the nano periodic structure, the Cr-C layer taking soft metal as the main guide layer has reduced hardness to a certain extent, but nanocrystalline chromium formed by alternately deposited coatings is beneficial to absorbing energy in a shear test and also beneficial to preventing ductile shear damage in a single Cr-C layer.
Therefore, as can be seen from the final wear rate value, under the conditions that the friction coefficient is slightly improved and the hardness value is reduced, the wear rate of the nano-period plating layer is greatly reduced, which is beneficial to the fact that the chromium-based leading layer designed in the nano-period multilayer structure is used as an impact-resistant buffer layer, and along with the internal diffusion effect of interface atoms, more Cr atoms are gradually combined into the multilayer structure to promote the formation of an sp2 structure and hard phase chromium carbide, so that the finally formed nano-period composite structure can effectively relieve the stress in a film, prevent cracks from being rapidly diffused in the wear process, and further improve the wear resistance and the plastic toughness of a multilayer film sample.
TABLE 1
Figure BDA0003597177960000111
While the invention has been described with reference to preferred embodiments, it is not intended to be limiting. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.

Claims (11)

1. The steel collar with the periodic carbon film coating comprises a steel collar substrate, and is characterized in that the carbon film coating is attached to the surface of the steel collar substrate, and comprises a plurality of carbon-doped chromium-based film layers and chromium-doped carbon-based film layers which are sequentially and alternately arranged on the surface of the steel collar substrate;
wherein, in the carbon-doped chromium-based film layer, the atomic percentage content of Cr is 80-90at%;
in the chromium-doped carbon-based film layer, the atomic content of Cr is 10-20at%.
2. The steel collar with the periodic carbon film coating according to claim 1, wherein the number of layers of the carbon-doped chromium-based film layer and the chromium-doped carbon-based film layer is n, and n is more than or equal to 2 and less than or equal to 11.
3. The steel collar with the periodic carbon film coating according to claim 1, wherein the thickness of the carbon-doped chromium-based film layer is 10 nm-100 nm.
4. The steel collar with the periodic carbon film coating according to claim 1, wherein the thickness of the chromium-doped carbon-based film layer is 10 nm-50 nm.
5. The steel collar with the periodic carbon film coating according to claim 1, wherein the atomic percent of Cr in each of the plurality of carbon-doped chromium-based film layers is the same; and/or, in the plurality of carbon-doped chromium-based film layers, the thickness of each carbon-doped chromium-based film layer is equal;
the atom percentage content of C in each chromium-doped carbon-based film layer is the same in the chromium-doped carbon-based film layers; and/or, in the plurality of chromium-doped carbon-based film layers, the thickness of each chromium-doped carbon-based film layer is equal.
6. The steel ring with periodic carbon film coating according to claim 1, wherein the surface of the steel ring substrate further comprises a chrome-based layer, and the carbon-doped chrome-based film layer is disposed on the surface of the chrome-based layer.
7. A method for preparing a steel collar with a periodic carbon film coating according to any one of claims 1-6, characterized by comprising the following specific steps:
s1, hanging a cleaned ring to be plated on a working disc in a vacuum chamber of micro-arc ion plating equipment, and starting the working disc; wherein, the vacuum chamber is internally provided with a chromium target and a pure graphite target;
s2, vacuumizing the vacuum chamber, introducing argon, then turning on a plasma power supply of the chromium target, setting current density of the chromium target, applying pulse bias to the steel collar of the workpiece to be plated in S1, cleaning the plasma, and cleaning impurities on the surface of the workpiece to obtain a first-stage workpiece;
s3, adjusting the target current density of the chromium target, applying pulse bias to the first-stage workpiece, and depositing a pure chromium priming layer on the surface of the first-stage workpiece to obtain a second-stage workpiece;
s4, adjusting the target current density of the chromium target, starting the target current density of the graphite target, applying pulse bias to the second-stage workpiece, and depositing a carbon-doped chromium-based film layer on the surface of the second-stage workpiece to obtain a third-stage workpiece;
s5, changing the target current density of the chromium target and the graphite target in the S4, applying pulse bias to the workpiece in the third stage, and depositing a chromium-doped carbon-based film layer on the surface of the workpiece in the third stage to obtain the workpiece in the fourth stage;
s6, on the basis of the work piece in the fourth stage, alternately repeating the steps S4 and S5, and finally obtaining the steel collar with the surface plated with the periodic carbon film coating.
8. The method for producing a steel ring with a periodic carbon film coating according to claim 7, wherein in the step S4, the specific steps are as follows:
maintaining the argon flow of 5-50 sccm and the working air pressure in the vacuum chamber at 1.0X10 -1 Pa～7×10 -1 Pa；
The target current density of the chromium target material is uniformly regulated and reduced to 0.02A/cm 2 ～0.60A/cm 2 At the same time, the target current density of the graphite target material is uniformly adjusted and increased to 0.001A/cm 2 ～0.030 A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And simultaneously, pulse bias is applied to the second workpiece, wherein the negative bias value is kept at 10-120V, a transition layer is deposited on the surface of the second workpiece, and the deposition time is 5-20 min, so that the third-stage workpiece is obtained.
9. The method for producing a steel ring with a periodic carbon film coating according to claim 7, wherein in the step S5, the specific steps are as follows:
maintaining the argon flow of 5-50 sccm and the working air pressure in the vacuum chamber at 1.0X10 -1 Pa～7×10 -1 Pa；
The target current density of the chromium target material is uniformly regulated and reduced to 0.001A/cm 2 ～0.030 A/cm 2 At the same time, the target current density of the graphite target material is uniformly regulated and increased to 0.02A/cm 2 ～0.50A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And simultaneously, pulse bias is applied to the second-stage workpiece, wherein the bias value is adjusted to 10-120V, a carbon layer is deposited on the surface of the second workpiece, and the deposition time is 5-20 min, so that the fourth-stage workpiece is obtained.
10. The method for preparing a steel collar with a periodic carbon film coating according to claim 7, wherein in the step S6, the steps S4 and S5 are alternately repeated 1 to 10 times, and the accumulated deposition time is 100 to 400 minutes, so as to obtain the steel collar with the periodic carbon film coating on the surface.
11. The method for producing a steel collar with a periodic carbon film coating according to any one of claims 7 to 10, characterized in that the adjustment rates of the target current densities on the chromium target are all 0.002A/cm 2 /min～0.06A/cm 2 Per min, the regulating speed of the target current of the graphite target material is 0.002A/cm 2 /min～0.06A/cm 2 /min。
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