CN109161845B - Marine environment wear-resistant self-lubricating nano composite coating and preparation method and application thereof - Google Patents

Marine environment wear-resistant self-lubricating nano composite coating and preparation method and application thereof Download PDF

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CN109161845B
CN109161845B CN201811089085.XA CN201811089085A CN109161845B CN 109161845 B CN109161845 B CN 109161845B CN 201811089085 A CN201811089085 A CN 201811089085A CN 109161845 B CN109161845 B CN 109161845B
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tibon
nano composite
coating
tibo
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CN109161845A (en
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邹长伟
李达
梁枫
田灿鑫
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Lingnan Normal 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
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • 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
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3485—Sputtering using pulsed power to the 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
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering

Abstract

The invention relates to a marine environment wear-resistant self-lubricating nano composite coating and a preparation method and application thereof. The nano composite coating comprises a TiN transition layer and a nano composite layer which are sequentially arranged on the surface of the substrate, and the nano composite layer comprises a TiBON layer and a TiBO layer which are sequentially and alternately arranged on the surface of the TiN transition layer. The nano composite coating provided by the invention takes TiN as a transition layer, so that the connection between the nano composite layer and the substrate is enhanced, and the bonding force of the whole coating is increased; the nano composite layer formed by the TiBON layer and the TiBO layer has high hardness and low friction coefficient, and has self-lubricating property in marine environment, and the TiBON layer and the TiBO layer are sequentially alternated to reduce the stress of the coating, so that the wear resistance and the corrosion resistance are further improved. Experimental results show that the hardness of the wear-resistant self-lubricating nano composite coating provided by the invention can reach 32GPa, and the service life of marine equipment components applying the coating can be prolonged by more than 5 times.

Description

Marine environment wear-resistant self-lubricating nano composite coating and preparation method and application thereof
Technical Field
The invention belongs to the technical field of hard coatings, and particularly relates to a marine environment wear-resistant self-lubricating nano composite coating, and a preparation method and application thereof.
Background
The hard coating is an effective way for strengthening the surface of a material, exerting the potential of the material and improving the production efficiency, is a surface coating, and is a surface coating with the microhardness greater than a certain value deposited on the surface of a substrate by a physical or chemical method. Hard coatings have been widely used in the cutting industry, the mold industry, geological drilling, the textile industry, mechanical manufacturing, and aerospace, and have played an increasingly important role. The application of the hard coating in the cutting industry can process materials which are difficult to process, such as common cutting tools, cutters, drill bits and the like, can improve the cutting accuracy, and has the advantages of super hardness, toughness, wear resistance, self lubrication and the like, so that the hard coating is considered as a revolution in the cutting history. However, since the seawater contains high concentration of acid ions such as Cl-, SO42-, HCO 3-and the like, the seawater has strong corrosion damage effect on the marine machinery of metal materials, and the failure of mechanical parts and even a mechanical main body is easily caused, SO that the machinery for producing petroleum, the ship body for marine transportation and the like are required to have good corrosion resistance. Through research for many years, it is found that surface treatment of materials, especially the formation of a protective layer with strong corrosion resistance on the surface of the materials, is the most effective and lowest-cost method, and therefore, research of corrosion-resistant films in seawater environment is important for the development of ocean resources at present.
A great deal of research shows that the polymer material and the ceramic material have respective defects under the condition of water lubrication, so that in order to meet the requirements of low friction coefficient and low wear rate of the water-lubricated friction part, a nano composite film with the thickness of only a few microns or even hundreds of nanometers, short running-in period and good water-lubricated friction characteristic is prepared on the surface of the metal part, which becomes a better solution. However, there are many kinds of nanocomposite films, not all hard films have good water-lubricated tribological properties, many films have poorer tribological properties (coefficient of friction and wear rate) under water-lubricated conditions than under dry-friction conditions, and are prone to peeling and fail quickly due to problems of bonding force.
Therefore, the research on the water lubrication tribology characteristics of different hard films and the obtaining of the coating with high hardness, corrosion resistance and wear resistance have important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects and defects of a hard film on the water lubrication tribology characteristic in the prior art and provide a marine environment wear-resistant self-lubricating nano composite coating. The TiBON/TiBO coating with the multilayer nano composite structure in the nano composite coating has the corrosion resistance of a hardness tester, and simultaneously generates borate in a seawater friction environment, so that the TiBON/TiBO coating has a self-lubricating function, further reduces the friction coefficient and improves the wear resistance; the multilayer nano composite structure boron oxide can reduce the internal stress of the coating, improve the binding force and prolong the service life, and has important application value in the field of surface protection of marine equipment.
The invention also aims to provide a preparation method of the nano composite coating.
The invention also aims to provide the application of the nano composite coating in surface protection of marine equipment.
In order to achieve the purpose, the invention adopts the following technical scheme:
a marine environment wear-resistant self-lubricating nano composite coating comprises a TiN transition layer and a nano composite layer which are sequentially arranged on the surface of a substrate, wherein the nano composite layer comprises a TiBON layer and a TiBO layer which are sequentially and alternately arranged on the surface of the TiN transition layer; the TiBON layer comprises TiN and TiB2Nanocrystalline, amorphous BN and amorphous oxide TiO2In the TiBON layer, the atomic percent of titanium element is 29-40%, the atomic percent of boron element is 16-22%, the atomic percent of oxygen element is 7-16%, and the atomic percent of nitrogen element is 35-46%; the TiBO layer comprises TiB2Nanocrystalline and amorphous oxide TiO2The nanocomposite structure of (a); in the TiBO layer, the atomic percent of titanium element is 30-40%, the atomic percent of boron element is 9-25%, and the atomic percent of oxygen element is 40-52%.
The amorphous oxide referred to in the present invention means TiO2。
The hard film represented by the nitrogen-boron-based film has a plurality of excellent physicochemical properties, particularly high hardness, abrasion resistance, oxidation resistance and corrosion resistance, and the unique friction reducing and abrasion reducing performance expressed in the water environment widens a new visual field for the vigorous development of related industries such as river shipping, offshore operation, water conservancy devices and the like. However, the improvement of the hardness is not the only index for evaluating the hard nano composite coating, and is more important for improving the corrosion resistance and the wear resistance of the coating in the occasion of marine environment application.
The TiN transition layer can improve the binding force between the nano composite layer and the substrate, enhance the using effect of the coating and prolong the service life of the coating.
The function of the TiBON layer is as follows: the layer has excellent wear resistance and low friction coefficient, and simultaneously has high hardness and self-lubricating property.
The function of the TiBO layer is as follows: the layer has excellent wear resistance, low stress and low friction coefficient, and simultaneously has high hardness and self-lubricating property.
The TiBON layer and the TiBO layer are sequentially arranged alternately and periodically, so that the stress of the coating can be reduced, the crystal face structure and the crystal boundary of the coating are increased, and the wear resistance and the corrosion resistance are further improved.
The nano composite coating provided by the invention takes TiN as a transition layer, so that the connection between the nano composite layer and the substrate is enhanced, and the bonding force of the whole coating is increased; the nano composite layer formed by the TiBON layer and the TiBO layer has high hardness and low friction coefficient, and has self-lubricating property in marine environment, and the TiBON layer and the TiBO layer are sequentially alternated to reduce the stress of the coating, so that the wear resistance and the corrosion resistance are further improved. Experimental results show that the hardness of the wear-resistant self-lubricating nano composite coating provided by the invention can reach 32GPa, and the service life of marine equipment components applying the coating can be prolonged by more than 5 times.
Preferably, the thickness of each TiBON layer and the TiBO layer is respectively and independently selected from 2-50 nm.
More preferably, the thickness of each TiBON layer and the TiBO layer is respectively and independently selected from 10-30 nm.
More preferably, the thickness of each TiBON layer and the TiBO layer is respectively and independently selected from 15-25 nm.
Preferably, the number of the TiBON layers is 10-100.
More preferably, the number of the TiBON layers is 20-80,
more preferably, the number of the TiBON layers is 40-50.
Preferably, in the TiBON layer, the atomic percentage of titanium element is 32%, the atomic percentage of boron element is 19%, the atomic percentage of oxygen element is 13%, and the atomic percentage of nitrogen element is 36%.
Preferably, the grain size of the TiBON layer is 2-15 nm.
More preferably, the grain size of the TiBON layer is 3-8 nm.
Preferably, in the TiBO layer, the atomic percent of the titanium element is 33%, the atomic percent of the boron element is 19%, and the atomic percent of the oxygen element is 48%.
Preferably, the grain size of the TiBO layer is 3-12 nm.
More preferably, the grain size of the TiBO layer is 4-6 nm.
Preferably, in the TiN transition layer, the atomic percent of the titanium element is 50-58%, and the atomic percent of the nitrogen element is 42-50%; the thickness of the TiN transition layer is 100-800 nm.
More preferably, the thickness of the TiN transition layer is 200-500 nm.
More preferably, the thickness of the TiN transition layer is 300-400 nm.
Preferably, the substrate is an aluminum-titanium alloy or stainless steel.
More preferably, the substrate is a Ti-6Al-4V alloy.
It should be understood that the composition of Ti-6Al-4V is not particularly limited in the present invention, and Ti-6Al-4V alloy for high temperature corrosion resistant parts of engines and marine equipment, which is well known to those skilled in the art, may be used.
The preparation method of the nano composite coating comprises the following steps:
s1: depositing a TiN transition layer on the surface of the substrate;
s2: and (5) alternately depositing a TiBON layer and a TiBO layer on the surface of the TiN transition layer obtained in the step S1 in sequence to obtain the marine environment wear-resistant self-lubricating nano composite coating.
Preferably, the TiBON layer is prepared by the following process: with TiB2For deposition of the target material, N is introduced2And O2Depositing to obtain the TiBON layer; said N is2And O2The volume ratio of (A) to (B) is 1: 2-4: 1.
Preferably, the TiBO layer is prepared by the following process: with TiB2For depositing the target material, Ar and O are introduced2Depositing the TiBO layer, the Ar and the O2The volume ratio of (A) to (B) is 1: 2-3: 1.
Preferably, in S1, a TiN transition layer is deposited on the surface of the substrate by using a cathodic arc ion plating technique.
The invention has no special limitation on the operation of the cathode arc ion plating technology of the TiN transition layer, and can adopt the technical scheme of the cathode arc ion plating technology which is well known by the technical personnel in the field.
Preferably, the parameters of the cathodic arc ion plating technology are as follows: the rotating speed of the matrix is 2-8 rpm, the sputtering temperature is 300-500 ℃, the pressure of the deposition gas is 1.0-1.8 Pa, the bias voltage is 100-180V, the target current is 40-100A, and the deposition time is 10-30 min.
Preferably, the parameters of the cathodic arc ion plating technology are as follows: the rotating speed of the substrate is 3-6 rpm, the sputtering temperature is 400-450 ℃, the pressure of the deposition gas is 1.3-1.5 Pa, the bias voltage is 130-160V, the target current is 60-75A, and the deposition time is 15-25 min.
Preferably, in S2, a TiBON layer and a TiBO layer are alternately deposited in sequence by using a high power pulsed magnetron sputtering technique.
According to the invention, the high-power pulse magnetron sputtering deposition can further enable the coating to have excellent film-substrate binding force, reduce the internal stress of the coating and improve the wear resistance and the coating hardness.
More preferably, the high-power pulse magnetron sputtering technology comprises the following processes: opening TiB2Target, depositing TiBO layer; then N is turned on2A flow valve for depositing a TiBON layer; and repeatedly depositing a TiBO layer and a TiBON layer until the deposition of the nano composite layer is finished.
Preferably, the parameters for depositing the TiBO layer are: the method comprises the following steps of sputtering argon gas, reacting oxygen gas, wherein the total pressure of the argon gas and the oxygen gas is 0.4-1.2 Pa, the pressure ratio of the argon gas to the oxygen gas is 1-3: 3-1, the rotating speed of a matrix is 2-10 rpm, the sputtering temperature is 300-500 ℃, the average current of a target is 3-8A, the peak current of the target is 300-800A, the peak voltage of the target is 300-800V, and the duty ratio is 1-8%.
More preferably, the parameters for depositing the TiBON layer are as follows: the method comprises the following steps of sputtering argon gas, reacting oxygen gas and nitrogen gas, wherein the total pressure of the argon gas and the oxygen gas is 0.6-1.0 Pa, the pressure ratio of the nitrogen gas to the oxygen gas is 1-2: 2-1, the rotating speed of a matrix is 3-6 rpm, the sputtering temperature is 300-500 ℃, the average current of a target is 2-6A, the peak current of the target is 400-700A, the peak voltage of the target is 500-800V, and the duty ratio is 3-6%.
Preferably, S2 further comprises the step of cooling the deposited product after the alternating deposition.
Preferably, the cooling is performed in the atmosphere of the deposition.
Preferably, the end point temperature of the cooling is below 120 ℃.
Preferably, the end temperature of the cooling is below 80 ℃.
Preferably, the method further comprises the step of performing pretreatment, sputtering cleaning and activation on the substrate in sequence before the step of S1.
The operation of the pretreatment is not particularly limited in the present invention, and the pretreatment technical scheme known to those skilled in the art can be adopted.
Preferably, the pretreatment process is washing and drying.
Preferably, the washing is sequentially ultrasonic in acetone and absolute ethyl alcohol; the time of ultrasonic treatment in acetone and absolute ethyl alcohol is independently 15-30 min.
More preferably, the time of the ultrasonic treatment in acetone and absolute ethyl alcohol is 20 min.
Preferably, the drying is blow-drying with clean compressed air.
Preferably, the parameters of the sputter cleaning are: the rotating speed of the matrix is 2-8 rpm, the sputtering temperature is 300-500 ℃, the sputtering gas is argon, the sputtering gas pressure is 0.3-1.2 Pa, the bias voltage is 800-1200V, and the sputtering cleaning time is 10-30 min.
In the invention, the sputtering cleaning can improve the bonding capability between the substrate and the TiN transition layer.
More preferably, the parameters of the sputter cleaning are: the rotating speed of the substrate is 4-6 rpm, the sputtering temperature is 350-400 ℃, the sputtering gas is argon, the sputtering gas pressure is 0.5-0.8 Pa, the bias voltage is 900-1100V, and the sputtering cleaning time is 20-35 min.
Preferably, the activation is performed using a Ti cathodic arc target; the parameters of the activation are: the rotating speed of the substrate is 2-9 rpm, the sputtering temperature is 300-500 ℃, the sputtering gas is argon, the sputtering gas pressure is 0.8-1.5 Pa, the bias voltage is 400-800V, the target current is 40-100A, and the deposition time is 5-25 min.
In the invention, the activation increases the energy state of particles on the surface of the substrate by bombarding the surface of the substrate by Ti ions, generates a metal layer and enhances the binding force between the coating and the substrate.
Preferably, the parameters of the activation are: the rotating speed of the substrate is 3-6 rpm, the sputtering temperature is 400-450 ℃, the sputtering gas is argon, the sputtering gas pressure is 1.0-1.2 Pa, the bias voltage is 500-700V, the target current is 60-80A, and the deposition time is 10-15 min.
The application of the nano composite coating in the surface protection of marine equipment is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
the nano composite coating provided by the invention takes TiN as a transition layer, so that the connection between the nano composite layer and the substrate is enhanced, and the bonding force of the whole coating is increased; the nano composite layer formed by the TiBON layer and the TiBO layer has high hardness and low friction coefficient, and has self-lubricating property in marine environment, and the TiBON layer and the TiBO layer are sequentially alternated to reduce the stress of the coating, so that the wear resistance and the corrosion resistance are further improved. Experimental results show that the hardness of the wear-resistant self-lubricating nano composite coating provided by the invention can reach 32GPa, and the service life of marine equipment components applying the coating can be prolonged by more than 5 times.
Drawings
Fig. 1 is an XRD diffraction pattern of the wear-resistant self-lubricating nanocomposite coating provided in example 1 of the present invention.
FIG. 2 is a TEM image of the wear-resistant self-lubricating nanocomposite coating provided in example 1 of the present invention;
fig. 3 is a friction wear image of the abrasion resistant self-lubricating nanocomposite coating (b) provided in example 2 of the present invention and the comparative example 3 (a).
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
This example provides a nanocomposite coating (coating 1) that is prepared as follows.
Uniformly fixing the pretreated Ti-6Al-4V substrate on a support, loading into a coating machine, adjusting the rotating speed of the workpiece support to 3rpm, and pumping to a background vacuum of 1.0 × 10-3Pa, simultaneously turning on a heater, and heating to 300 ℃; opening an argon flow valve, adjusting the vacuum chamber to be about 0.3Pa, adding a negative bias voltage 1200V to the substrate, and carrying out glow sputtering cleaning for 10 min;
then reducing the negative bias voltage of the substrate to 400V, opening an argon flow valve, controlling the gas pressure to be 0.8Pa, opening a Ti cathode electric arc target, adjusting the target current to be 40A, depositing at the temperature of 500 ℃, and bombarding the substrate for 5min by Ti ions at high energy to activate the surface of the substrate; closing the argon flow valve, opening the nitrogen flow valve, reducing the substrate bias voltage to 100V, coating the film at the pressure of 1.0pa, the substrate temperature of 500 ℃, and depositing the TiN transition layer for 10min at the target current of 40A; argon and oxygen are introduced to control the total air pressure to be 0.6Pa, the ratio of nitrogen to oxygen is 1/2, the rotating speed of a workpiece rack is 3rpm, and TiB is opened2Target, adjusting high power pulse magnetron sputtering average current 3A, peak current 700A, peak voltage 500V and duty ratio 3%, and depositing TiBON layer for 5 minutes; and (3) closing a nitrogen flow valve, controlling the ratio of argon to oxygen to be 1/3, controlling the average current of the target to be 3A, controlling the peak current of the target to be 800A, controlling the peak voltage of the target to be 300V, controlling the duty ratio to be 1%, and depositing TiBO for 5 minutes. And (3) alternately opening and closing the nitrogen flow valve, depositing the TiBON/TiBO layer for 60min, closing the power supply, closing the flow valve, and cooling the substrate to 80 ℃ along with the furnace after the film coating is finished, and taking out the substrate for normal temperature cooling.
The prepared sample surface coating is named as coating 1, and an XRD image and a TEM transmission electron microscope image of the coating are shown in figures 1 and 2. The nanocrystalline TiN and TiB are clearly visible in FIG. 12X-ray diffraction peak of (1), BN and oxygen were not foundDiffraction peaks of the compound, which are presumed to be an amorphous phase; the structure of the nano-grains and the amorphous matrix can be seen in fig. 2. Therefore, the whole coating is TiN and TiB2A nano-composite structure of nanocrystalline, amorphous BN and amorphous oxide.
The atomic percentages and thicknesses of the layers of coating 1 are as follows:
TiN transition layer: titanium 52 at.%, nitrogen 48 at.%; the thickness is 120 nm;
a TiBON layer: titanium 30 at.%, boron 20 at.%, oxygen 14 at.% and nitrogen 36 at.%; the thickness is 10 nm;
a TiBO layer: titanium 35 at.%, boron 16 at.%, and oxygen 49 at.%; the thickness is 12 nm.
Example 2
This example provides a nanocomposite coating (coating 2) that is prepared as follows.
Uniformly fixing the pretreated Ti-6Al-4V substrate on a support, loading into a coating machine, adjusting the rotating speed of the workpiece support to 3rpm, and pumping to a background vacuum of 1.0 × 10-3Pa, simultaneously turning on a heater, and heating to 300 ℃; opening an argon flow valve, adjusting the vacuum chamber to be about 1.2Pa, adding negative bias voltage 1200V to the substrate, and carrying out glow sputtering cleaning for 35 min;
then reducing the negative bias voltage of the substrate to 800V, opening an argon flow valve, controlling the gas pressure to be 0.5Pa, opening a Ti cathode electric arc target, adjusting the target current to be 40A, depositing at the temperature of 500 ℃, and bombarding the substrate for 5min by Ti ions at high energy to activate the surface of the substrate; closing the argon flow valve, opening the nitrogen flow valve, reducing the substrate bias voltage to 100V, coating the film at the pressure of 1.0pa, the substrate temperature of 500 ℃, and depositing the TiN transition layer for 10min at the target current of 40A; argon and oxygen are introduced to control the total air pressure to be 0.6Pa, the ratio of nitrogen to oxygen is 1/2, the rotating speed of a workpiece rack is 3rpm, and TiB is opened2Target, adjusting high power pulse magnetron sputtering average current 3A, peak current 700A, peak voltage 500V and duty ratio 8%, and depositing TiBON layer for 5 minutes; and (3) closing a nitrogen flow valve, controlling the ratio of argon to oxygen to be 1/3, controlling the average current of the target to be 3A, the peak current of the target to be 800A, the peak voltage of the target to be 300V, controlling the duty ratio to be 6%, and depositing TiBO for 5 minutes. Thus, the nitrogen flow valve is alternately opened and closed, the TiBON/TiBO layer is deposited for 100min, the power supply is closed, and the flow is closedAnd (4) measuring a valve, and after the film coating is finished, cooling the substrate to 120 ℃ along with the furnace, taking out the substrate, and cooling the substrate at normal temperature.
The prepared sample surface coating is named coating 2, and fig. 3 is a friction wear image of the wear-resistant self-lubricating nanocomposite coating (b) in example 2 and the friction wear image of the comparative example 3 (a). It is evident from the figure that the wear resistance of the coating 2 is better in a marine environment than in comparative example 3.
The atomic percentages and thicknesses of coating 2 are as follows:
TiN transition layer: titanium 51 at.%, nitrogen 49 at.%; the thickness is 400 nm;
a TiBON layer: titanium 32 at.%, boron 19 at.%, oxygen 13 at.% and nitrogen 36 at.%; the thickness is 25 nm;
a TiBO layer: titanium 33 at.%, boron 19 at.%, and oxygen 48 at.%; the thickness is 30 nm.
Example 3
This example provides a nanocomposite coating (coating 3) that is prepared as follows.
Uniformly fixing the pretreated Ti-6Al-4V substrate on a support, loading into a coating machine, adjusting the rotating speed of the workpiece support to 5rpm, and vacuumizing to 1.0 multiplied by 10 of background vacuum-3Pa, simultaneously turning on a heater, and heating to 400 ℃; opening an argon flow valve, adjusting the vacuum chamber to be about 1.2Pa, adding a negative bias voltage 1200V to the substrate, and carrying out glow sputtering cleaning for 20 min;
then reducing the negative bias voltage of the substrate to 800V, opening an argon flow valve, controlling the gas pressure to be 0.5Pa, opening a Ti cathode electric arc target, adjusting the target current to be 80A, depositing at the temperature of 500 ℃, and bombarding the substrate for 15min by Ti ions at high energy to activate the surface of the substrate; closing the argon flow valve, opening the nitrogen flow valve, reducing the bias voltage of the substrate to 120V, reducing the coating pressure to 1.0pa, reducing the substrate temperature to 500 ℃, and depositing the TiN transition layer for 10min at the target current of 60A; argon and oxygen are introduced to control the total air pressure to be 0.6Pa, the ratio of nitrogen to oxygen is 2/1, the rotating speed of a workpiece rack is 3rpm, and TiB is opened2Target, adjusting high power pulse magnetron sputtering average current 3A, peak current 700A, peak voltage 500V and duty ratio 3%, and depositing TiBON layer for 5 minutes; closing a nitrogen flow valve, controlling the ratio of argon to oxygen to be 3/1, controlling the average current of the target to be 3A, the peak current of the target to be 800A, controlling the peak voltage of the target to be 300V, and controlling the ratio of argon to oxygen to be in the range of3% air ratio, and 8 minutes of TiBO deposition. And (3) alternately opening and closing the nitrogen flow valve, depositing the TiBON/TiBO layer for 90min, closing the power supply, closing the flow valve, and cooling the substrate to 120 ℃ along with the furnace after the film coating is finished, and taking out the substrate for normal temperature cooling.
The prepared sample surface coating is named as coating 3, and the atomic percentage and the thickness of the coating are as follows:
TiN transition layer: titanium 55 at.%, nitrogen 45 at.%; the thickness is 380 nm;
a TiBON layer: titanium 30 at.%, boron 20 at.%, oxygen 15 at.% and nitrogen 35 at.%; the thickness is 18 nm;
a TiBO layer: titanium 40 at.%, boron 15 at.%, and oxygen 45 at.%; the thickness is 9 nm.
It should be understood that other atomic percentages and thicknesses of the TiN transition layer, the TiBON layer and the TiBO layer can be obtained by controlling the deposition conditions, and will not be described in detail herein.
Comparative example 1
A sample of a buffer layer containing only titanium and nitrogen prepared on a Ti-6Al-4V alloy substrate using the method described in example 1 was designated as coating 4.
Comparative example 2
Samples of the TiBON-only buffer layer and TiBON layer on Ti-6Al-4V alloy substrates prepared using the method described in example 1 were designated as coating 5.
Comparative example 3
Samples of the TiBO layer and the Tinitrogen containing buffer layer only prepared on Ti-6Al-4V alloy substrates using the method described in example 1 were designated as coating 6.
The performance of the coatings obtained in examples 1 to 3 and comparative examples 1 to 3 was examined, and the results are shown in Table 1.
TABLE 1 test results of coating properties of examples 1 to 3 and comparative examples 1 to 3
Numbering Hardness (C)GPa) Combining force (N) Coefficient of friction of sea water
Coating 1 24 63 0.08
Coating 2 32 65 0.12
Coating 3 18 60 0.12
Coating 4 20 45 0.56
Coating 5 22 46 0.42
Coating 6 24 37 0.48
According to the comparative example and the embodiment, the wear-resistant self-lubricating nano composite coating provided by the invention has the advantages of high hardness, low friction coefficient in a seawater environment and strong binding force between the coating and a substrate.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (10)

1. The marine environment wear-resistant self-lubricating nano composite coating is characterized by comprising a TiN transition layer and a nano composite layer which are sequentially arranged on the surface of a substrate, wherein the nano composite layer comprises a TiBON layer and a TiBO layer which are sequentially and alternately arranged on the surface of the TiN transition layer; the TiBON layer comprises TiN and TiB2Nanocrystalline, amorphous BN and amorphous oxide TiO2In the TiBON layer, the atomic percent of titanium element is 29-40%, the atomic percent of boron element is 16-22%, the atomic percent of oxygen element is 7-16%, and the atomic percent of nitrogen element is 35-46%; the TiBO layer comprises TiB2Nanocrystalline and amorphous oxide TiO2The nanocomposite structure of (a); in the TiBO layer, the atomic percent of titanium element is 30-40%, the atomic percent of boron element is 9-25%, and the atomic percent of oxygen element is 40-52%.
2. The nanocomposite coating according to claim 1, wherein the thickness of each of the TiBON layer and the TiBO layer is independently selected from 2 to 50 nm.
3. The nanocomposite coating according to claim 1, wherein the number of TiBON layers is 10 to 100.
4. The nanocomposite coating according to claim 1, wherein in the TiBON layer, the atomic percentage of titanium is 32%, the atomic percentage of boron is 19%, the atomic percentage of oxygen is 13%, and the atomic percentage of nitrogen is 36%.
5. The nanocomposite coating according to claim 1, wherein the TiBO layer comprises 33 atomic percent of titanium, 19 atomic percent of boron and 48 atomic percent of oxygen.
6. The nanocomposite coating according to claim 1, wherein in the TiN transition layer, the atomic percent of the titanium element is 50-58%, and the atomic percent of the nitrogen element is 42-50%; the thickness of the TiN transition layer is 100-800 nm.
7. A method for preparing a nanocomposite coating according to any one of claims 1 to 6, comprising the steps of:
s1: depositing a TiN transition layer on the surface of the substrate;
s2: and (5) alternately depositing a TiBON layer and a TiBO layer on the surface of the TiN transition layer obtained in the step S1 in sequence to obtain the marine environment wear-resistant self-lubricating nano composite coating.
8. The method according to claim 7, wherein the TiBON layer is prepared by the following steps: with TiB2For deposition of the target material, N is introduced2And O2Depositing to obtain the TiBON layer; said N is2And O2The volume ratio of (A) to (B) is 1: 2-4: 1.
9. The method according to claim 7, wherein the TiBO layer is prepared by the following steps: with TiB2For depositing the target material, Ar and O are introduced2Depositing the TiBO layer, the Ar and the O2The volume ratio of (A) to (B) is 1: 2-3: 1.
10. Use of the nanocomposite coating according to any one of claims 1 to 6 for surface protection of marine equipment.
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