CN203938726U - Carbon back anti-friction wear-resistant coating and workpiece - Google Patents

Abstract

The utility model provides a carbon-based friction-reducing and wear-resistant coating and a workpiece. The carbon-based anti-friction and wear-resistant coating is a multilayer film structure formed by alternately depositing bonding layers and working layers; the bonding layer is a simple substance or nitride or carbide of one of Ti, Cr, and W elements. Thin film of material, or thin film of Si element; The working layer is a graphite-like amorphous carbon film, and the atomic percentage of graphite structure in the graphite-like amorphous carbon film is greater than 70%. The carbon-based anti-friction and wear-resistant coating realizes the large-thickness preparation of graphite-like amorphous carbon coating through the alternate deposition of bonding layer and working layer, so that the graphite-like amorphous carbon coating has excellent tribological properties in water environment It can be used stably for a long life; and the multi-interface design of alternate deposition further improves the corrosion/erosion resistance of graphite-like amorphous carbon coatings in various water-based fluid environments.

Description

Carbon-based anti-friction and wear-resistant coating and workpiece

technical field

The utility model relates to the technical field of surface engineering, in particular to a carbon-based friction-reducing and wear-resistant coating and a workpiece. the

Background technique

For friction pair components such as hard-sealed valves, water-lubricated bearings, and water-environment gear transmission parts, the low lubrication characteristics of water media make them often in a semi-dry friction state when they are frequently opened/closed (or started/stopped) and instantaneously overloaded , the coefficient of friction between the frictional contact surfaces will increase sharply, and the accompanying wear damage will also increase sharply. When there are acids, alkalis and salts in the water-based fluid, its chemical or electrochemical corrosion characteristics will further aggravate the friction and wear of the working surfaces of such friction pairs. Therefore, friction and wear are the key issues that restrict the working stability and service life of friction pair parts such as hard-sealed valves, water-lubricated bearings, and water-environment gear transmission parts. It is also a bottleneck that restricts the efficient operation of the entire hydraulic mechanical system. The coating protection technology can endow the working surface of the parts with more excellent service performance without changing the physical and chemical properties of the matrix and the processing and forming properties. technical approach. the

Graphite-like amorphous carbon has excellent environmental adaptive tribological properties, and can exhibit stable low friction and low wear under the conditions of dry friction with lack of lubrication, semi-dry friction with insufficient lubrication, and boundary lubrication or fluid lubrication with sufficient lubrication. The characteristics, especially its low friction, low wear and insensitivity to water molecules, make it suitable for various atmospheres or environments with water. the

However, the preparation thickness of traditional graphite-like amorphous carbon coatings is usually less than 5 μm, which makes it difficult to exert its excellent anti-friction and wear-resisting properties for a long life, and its load-carrying capacity is limited. At the same time, the interface structure of the traditional graphite-like amorphous carbon coating is single, and its single-layer (directly deposited graphite-like amorphous carbon layer on the substrate) or double-layer (transition layer + graphite-like amorphous carbon layer) structure is difficult to interrupt the continuous growth defects. , providing a potential channel for the erosion/corrosion of water molecules or corrosive molecules, so it is difficult to exhibit sufficient erosion/corrosion resistance in a water environment, resulting in a short service life. the

Utility model content

The utility model provides a carbon-based anti-friction and wear-resistant coating. The carbon-based anti-friction and wear-resistant coating can maintain low friction and wear in water-based fluids, and can make the carbon-based anti-friction and wear-resistant Coated water environment uses friction pair parts to achieve long-life and stable operation. the

For achieving technical purpose, the technical scheme that the utility model adopts is as follows:

A carbon-based anti-friction and wear-resistant coating, which is a multi-layer film structure formed by alternate deposition of bonding layers and working layers;

The bonding layer is a simple substance or a nitride or carbide film of one of Ti, Cr, W elements, or a film of Si element;

The working layer is a graphite-like amorphous carbon film, and the atomic percentage of graphite structure in the graphite-like amorphous carbon film is greater than 70%. the

In one embodiment, the thickness of the carbon-based anti-friction and wear-resistant coating is 10 μm to 50 μm, the hardness is 10 GPa to 20 GPa, the scratch binding force is greater than 50 N, and the friction coefficient in the water environment is less than 0.1. The wear rate is less than 10 ^-16 m ³ N ^-1 m ^-1 order of magnitude.

In one of the embodiments, the thickness of each layer of the bonding layer is 100nm-400nm, the thickness of each layer of the working layer is 1000nm-2000nm, and the bonding layer and the adjacent working layer The thickness ratio is 1:5 to 1:10. the

In one embodiment, the number of cycles of alternately depositing the adhesive layer and the working layer is 10-30. the

A workpiece includes a substrate, and the carbon-based friction-reducing and wear-resistant coating is deposited on the surface of the substrate. the

The carbon-based anti-friction and wear-resistant coating of the utility model realizes the large-thickness preparation of the graphite-like amorphous carbon coating through the alternate deposition of the bonding layer and the working layer, making the graphite-like amorphous carbon coating excellent in the water environment The tribological properties can be played stably for a long life; and the multi-interface design of alternate deposition further improves the corrosion/erosion resistance of graphite-like amorphous carbon coatings in various water-based fluid environments. the

Description of drawings

Fig. 1 is a schematic structural view of an embodiment of a workpiece deposited with a carbon-based anti-friction and wear-resistant coating of the present invention. the

Detailed ways

The utility model will be described in detail below in conjunction with the embodiments. It should be noted that, in the case of no conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. the

Referring to Fig. 1, the utility model provides a carbon-based anti-friction and wear-resistant coating, which is a multi-layer film structure formed by alternately depositing adhesive layers 200 and working layers 300; The junction layer 200 is a simple substance or a nitride or carbide film of one of Ti, Cr, and W elements, or a film of Si element; the working layer 300 is a graphite-like amorphous carbon film, and in the graphite-like amorphous carbon film The atomic percentage of the graphite structure is greater than 70%. Among them, graphite-like amorphous carbon film is also called GLC (Graphite-like carbon) film, and its main component is graphite structure (ie, sp ² bond). The number of cycles of alternately depositing the adhesive layer 200 and the working layer 300 is not strictly limited, and depends on specific circumstances. Preferably, the number of cycles for alternately depositing the adhesive layer 200 and the working layer 300 is 10 to 30 times.

It should be noted that, in the carbon-based anti-friction and wear-resistant coating of the present invention, the materials of different bonding layers 200 may be the same or different. the

As a possible embodiment, the thickness of the carbon-based anti-friction and wear-resistant coating is 10 μm to 50 μm, the hardness is 10 GPa to 20 GPa, the scratch binding force is greater than 50 N, the friction coefficient in the water environment is less than 0.1, and the wear rate in the water environment is Less than 10 ^-16 m ³ N ^-1 m ^-1 order of magnitude. It should be noted that the water environment for measuring the friction coefficient and wear rate here is distilled water environment.

In order to prepare a carbon-based anti-friction and wear-resistant coating with excellent performance, the thickness of each layer of bonding layer 200 and each layer of working layer 300 has strict regulations, in order to ensure the adhesion, anti-friction and wear resistance of the coating characteristics and corrosion resistance are brought into full play, combined with the physical and chemical properties of the used bonding layer 200 and working layer 300 and a large number of experiments, it is concluded that the thickness of each layer of bonding layer 200 is 100nm to 400nm, and each layer The thickness of the working layer 300 is 1000nm-2000nm, and the thickness ratio of the bonding layer 200 to the adjacent working layer 300 is 1:5-1:10. the

The utility model also provides a workpiece, including a substrate 100, the surface of the substrate 100 is deposited with the above-mentioned carbon-based anti-friction and wear-resistant coating. Generally, the base 100 in the present invention is a friction pair component for water environment, such as a hard-sealed valve, a water-lubricated bearing, and a water environment gear transmission part. Utilizing the carbon-based anti-friction and wear-resistant coating of the utility model can significantly improve the stability and service life of friction pair parts used in water environments such as hard-sealed valves, water-lubricated bearings, and water-environment gear transmission parts. It has a good application prospect in water environment mechanical systems such as fluid transmission equipment, petrochemical equipment and marine engineering equipment. the

This novel carbon-based anti-friction and wear-resistant coating can be prepared by the following methods: pre-treating the substrate 100; performing plasma cleaning on the surface of the pre-treated substrate 100; depositing the above-mentioned coating on the surface of the substrate 100 after plasma cleaning Carbon-based anti-friction and wear-resistant coating. the

In the above preparation method, the purpose of pretreatment and plasma cleaning is to expose the substrate 100 to a fresh surface, so that the subsequent deposition can proceed smoothly, and at the same time, it can also increase the adhesion between the substrate 100 and the coating, and improve the durability of the product. Quality, enhanced service life. the

As a possible implementation, the pretreatment of the substrate 100 includes the following steps: firstly, the substrate 100 is preliminarily treated with a common detergent to remove oil stains on the surface of the substrate 100 and impurities adsorbed during processing, transportation or long-term storage. object; then sandblasting is carried out on the surface of the substrate 100 after preliminary treatment, to remove rust, oxide layer and machining burrs on the surface, in this processing step, the sandblasting pressure is preferably 0.2MPa～0.5MPa; The industrial detergent performs ultrasonic cleaning on the sandblasted substrate 100 to further remove physical and chemical adsorbates on its surface. Preferably, the ultrasonic cleaning time is 5 minutes to 30 minutes; finally, the ultrasonic cleaned substrate 100 is rinsed with plasma water Put it in an oven, heat and dry its surface water stains, preferably, the temperature of the oven is 50°C-80°C. In one of the embodiments, the pretreatment of the base body 100 can be part of the process of the above solution, and the specific situation depends on the actual situation of the base body 100 . the

As a possible implementation, the plasma cleaning includes the following steps: placing the pre-treated substrate 100 on the sample holder in the vacuum chamber of the magnetron sputtering system, and vacuuming; wait until the air pressure in the vacuum chamber is pumped to 5×10 ⁻ When it is ³ Pa or below, feed Ar gas and adjust the air pressure to 1Pa ~ 10Pa; turn on the bias power supply, adjust the bias voltage to 500V ~ 1000V, and the bias duty ratio to 40% ~ 60%; Ar gas under the action of the electric field The plasma is excited to etch the surface of the substrate 100 after the pretreatment, and the etching time is 5 minutes to 50 minutes. Plasma cleaning is to use high-energy particles to bombard the surface of the substrate 100, which can remove stubborn stains or scale remaining in the pretreatment, so that the surface of the substrate 100 has a higher degree of cleanliness and enhance the deposition quality of subsequent coatings.

Compared with the graphite-like amorphous carbon coating, the bonding layer 200 in the present invention has better compatibility with the friction pair parts materials (stainless steel, titanium alloy, engineering ceramics, etc.) used in the actual water environment. To improve the bonding force between the coating and the substrate 100, first deposit the bonding layer 200 on the surface of the substrate 100 after plasma cleaning, then deposit the working layer 300, and then alternately deposit the bonding layer 200 and the working layer 300 successively. the

As a possible implementation manner, the carbon-based anti-friction and wear-resistant coating is deposited by magnetron sputtering technology. The specific operation steps are as follows:

First turn on the metal or non-metallic target power supply to deposit the bonding layer 200 on the surface of the substrate 100, then turn on the graphite target power supply to deposit a graphite-like amorphous carbon layer on the bonding layer 200, and then alternately deposit the bonding layer 200 and the graphite-like layer to form Large thickness carbon-based anti-friction and wear-resistant coating. the

Among them, the metal thin films of Ti, Cr, and W are sputtered and deposited under Ar atmosphere by intermediate frequency or DC magnetron sputtering technology; the non-metallic Si films are sputtered by radio frequency or DC magnetron sputtering technology under Ar atmosphere Obtained by deposition; thin films of Ti, Cr, and W nitrides are obtained by sputtering deposition under N ₂ atmosphere by intermediate frequency or DC reactive magnetron sputtering technology; Ti, Cr, and W carbide films are obtained by intermediate frequency or DC reactive magnetron sputtering The sputtering technology was obtained by sputtering deposition in C ₂ H ₂ atmosphere; the graphite-like amorphous carbon film was obtained by sputtering deposition in Ar atmosphere by DC magnetron sputtering technology.

As a possible implementation, during the deposition process of the adhesive layer 200 and the working layer 300, the gas pressure in the vacuum chamber of the magnetron sputtering equipment is 0.5Pa-1.5Pa; the current of the intermediate frequency magnetron sputtering power supply is 1.5A ～2.5A, the current of the DC magnetron sputtering power supply is 1.0A～2.0A, and the power of the RF magnetron sputtering power supply is 300W～500W. the

As a possible implementation manner, during the deposition process of the adhesive layer 200 and the working layer 300 , the applied bias voltage is a pulse bias voltage of 400V-600V, and the duty cycle of the bias voltage is 40%-60%. the

The carbon-based anti-friction and wear-resistant coating of the utility model realizes the large-thickness preparation of the graphite-like amorphous carbon coating through the alternate deposition of the bonding layer 200 and the working layer 300, making the graphite-like amorphous carbon coating excellent The tribological properties of the water environment can be played stably for a long time, and the multi-interface design of alternate deposition further improves the corrosion/erosion resistance of the graphite-like amorphous carbon coating in various water-based fluid environments. the

The preparation of the carbon-based anti-friction and wear-resistant coating of the utility model is carried out in three steps. The first step is the pretreatment of the substrate 100, the second step is the plasma cleaning of the substrate 100, and the third step is the bonding layer 200 and the working layer. Alternate deposition of 300. The following will be described in detail in conjunction with specific embodiments. the

Example 1

The carbon-based anti-friction and wear-resistant coating is prepared on the hard sealing surface of the titanium alloy ball valve. In this embodiment, the substrate 100 is a titanium alloy ball valve, the bonding layer 200 is a metal Ti film, and the metal Ti film and graphite-like amorphous carbon film are alternately deposited to form a composite coating with a thickness of 45 μm. The specific implementation steps are as follows:

1) Pre-processing

Use ordinary detergent to treat the substrate 100 to remove oil stains on the hard sealing surface of the titanium alloy ball valve and impurities adsorbed during processing, transportation or long-term storage; then sandblast the hard sealing surface of the titanium alloy ball valve, Remove the oxide film and machining burrs; then use an industrial cleaning agent to ultrasonically clean the hard sealing surface of the titanium alloy ball valve to further remove the physical and chemical adsorbates on the surface; finally rinse the hard sealing surface of the titanium alloy ball valve with deionized water and put it in an oven. Heat to dry surface water stains. In this embodiment, the blasting pressure is 0.3 MPa, the ultrasonic cleaning time is 20 min, and the oven temperature is 80°C. the

2) Plasma cleaning

Place the pre-treated titanium alloy ball valve on the sample holder in the vacuum chamber of the magnetron sputtering system, and vacuumize; when the air pressure in the vacuum chamber is pumped to 5×10 ^-3 , introduce Ar gas and adjust the air pressure to 1.0Pa ; Turn on the bias power supply, adjust the bias voltage to 1000V, and the bias duty cycle to 50%; Ar gas is excited into plasma under the action of an electric field, and the hard sealing surface of the pre-treated titanium alloy ball valve is etched. The etching time is 10min.

3) Alternate deposition by magnetron sputtering

The Ti target and the graphite target were respectively installed in the corresponding target positions of the magnetron sputtering equipment. Among them, the Ti target is connected to the intermediate frequency magnetron sputtering power supply, the graphite target is connected to the DC magnetron sputtering power supply, and the pressure of Ar gas in the vacuum chamber is kept at 1.0 Pa. the

First, turn on the intermediate frequency power supply, and deposit a 200nm metal Ti thin film on the hard sealing surface of the titanium alloy ball valve after plasma cleaning as the adhesive layer 200 . During the deposition process, the current of the intermediate frequency power supply was set to 2.0A, the pulse bias voltage applied to the titanium alloy ball valve was 500V, and the duty cycle of the bias voltage was 50%. the

Then a graphite-like amorphous carbon film with a thickness of 1300 nm is deposited on the surface of the metal Ti film. During the deposition process, the DC power supply current was 1.2A, the pulse bias voltage applied to the titanium alloy ball valve was 500V, and the bias duty cycle was 50%. the

Metal Ti thin films and graphite-like amorphous carbon thin films were deposited alternately in sequence, and a carbon-based anti-friction and wear-resistant coating with a thickness of 45 μm was obtained after 30 cycles. the

Example 2

The carbon-based anti-friction and wear-resistant coating is prepared on the surface of the silicon nitride ceramic water-lubricated bearing rolling body. In this embodiment, the substrate 100 is a silicon nitride ceramic water-lubricated bearing rolling body, the bonding layer 200 is a Si film, and the Si film and graphite-like amorphous carbon film are alternately deposited to form a composite coating with a thickness of 45 μm. The specific implementation steps as follows:

1) Pre-processing

Use industrial cleaning agent to ultrasonically clean the silicon nitride ceramic water-lubricated bearing rolling body to remove the physical and chemical adsorption on its surface; then rinse the silicon nitride ceramic water-lubricated bearing rolling body with deionized water, put it in an oven, and heat and dry the surface water stains. In this embodiment, the ultrasonic cleaning time is 20 minutes, and the oven temperature is 60°C. the

2) Plasma cleaning

Place the silicon nitride ceramic water-lubricated bearing rolling body that has been pretreated on the sample holder in the vacuum chamber of the magnetron sputtering system, and vacuumize; when the air pressure in the vacuum chamber is pumped to 5× ¹⁰ And adjust the air pressure to 1.0Pa; turn on the bias power supply, adjust the bias voltage to 1000V, and the bias duty cycle to 50%; Ar gas is excited into plasma under the action of an electric field, and the silicon nitride ceramic water that has been pretreated The surface of the lubricated bearing rolling body is etched for 10 minutes.

3) Alternate deposition by magnetron sputtering

The Si target and the graphite target were respectively installed in the corresponding target positions of the magnetron sputtering equipment. Wherein, the Si target is connected to the radio frequency magnetron sputtering power supply, the graphite target is connected to the DC magnetron sputtering power supply, and the pressure of Ar gas in the vacuum chamber is kept at 1.0Pa. the

Firstly, the radio frequency power is turned on, and a 300nm Si film is deposited on the surface of the silicon nitride ceramic water-lubricated bearing rolling element cleaned by plasma as the adhesive layer 200 . During the deposition process, the radio frequency power was set to 300W, the pulse bias voltage applied to the silicon nitride ceramic water-lubricated bearing rolling element was 500V, and the bias duty cycle was 50%. the

Then a 1200nm graphite-like amorphous carbon film is deposited on the surface of the Si film. During the deposition process, the DC power supply current was set to 1.2A, the pulse bias voltage applied to the rolling element of the silicon nitride ceramic water-lubricated bearing was 500V, and the duty cycle of the bias voltage was 50%. the

Si film and graphite-like amorphous carbon film were deposited alternately in sequence, and a carbon-based anti-friction and wear-resistant coating with a thickness of 45 μm was obtained after 30 cycles. the

Example 3

The above-mentioned carbon-based anti-friction and wear-resistant coating was prepared on the working surface of the stainless steel gear. In this embodiment, the substrate 100 is a stainless steel gear, the bonding layer 200 is a CrN film, and the CrN film and graphite-like amorphous carbon film are alternately deposited to form a composite coating with a thickness of 40 μm. The specific implementation steps are as follows:

1) Pre-processing

Use ordinary detergent to treat the substrate 100 to remove oil stains on the working surface of the stainless steel gear and impurities adsorbed during processing, transportation or long-term storage; then sandblast the working surface of the stainless steel gear to remove the oxide film and Machining burrs; then use industrial cleaning agent to ultrasonically clean the working surface of stainless steel gears to further remove physical and chemical adsorbates on the surface; finally rinse the working surface of rusty steel gears with deionized water, put them in an oven, and heat and dry the surface water stains. In this embodiment, the blasting pressure is 0.3 MPa, the ultrasonic cleaning time is 30 min, and the oven temperature is 80°C. the

2) Plasma cleaning

Place the pre-treated stainless steel gear on the sample rack in the vacuum chamber of the magnetron sputtering system, and vacuumize; when the air pressure in the vacuum chamber reaches 5×10 ^-3 , introduce Ar gas and adjust the air pressure to 1.0Pa; Turn on the bias power supply, adjust the bias voltage to 1000V, and the bias duty cycle to 50%; Ar gas is excited into plasma under the action of an electric field to etch the working surface of the pre-treated stainless steel gear, and the etching time for 20min.

3) Alternate deposition by magnetron sputtering

The Cr target and the graphite target are respectively installed in the corresponding target positions of the magnetron sputtering equipment. Among them, the Cr target is connected to the intermediate frequency magnetron sputtering power supply, the graphite target is connected to the DC magnetron sputtering power supply, _N2 gas is introduced into the vacuum chamber and the pressure is kept at 1.5Pa.

First, turn on the intermediate frequency power supply, and deposit a 400nm CrN film on the working surface of the stainless steel gear after plasma cleaning as the bonding layer 200 . During the deposition process, the current of the intermediate frequency power supply was set to 2.5A, the pulse bias voltage applied to the titanium alloy ball valve was 500V, and the duty cycle of the bias voltage was 50%. the

Then a 1600nm graphite-like amorphous carbon film is deposited on the surface of the CrN film. During the deposition process, the DC power supply current was set to 1.2A, a pulse bias voltage of 500V was applied to the titanium alloy ball valve, and the duty cycle of the bias voltage was 50%. the

CrN films and graphite-like amorphous carbon films were deposited alternately in sequence, and a carbon-based anti-friction and wear-resistant coating with a thickness of 40 μm was obtained after 30 cycles. the

In the above embodiment, the thicknesses of the bonding layer 200 and the working layer 300 are constant during the deposition process. As a possible implementation mode, during the deposition process, the thickness of the bonding layer 200 is constant, and the thickness of the working layer 300 decreases layer by layer ( If the thickness of the bonding layer 200 remains constant at 300nm, as the deposition progresses, the working layer 300 is gradually reduced from 2000nm to 1000nm), which can enhance the overall bonding force of the coating, so that the coating has more stable mechanical properties and tribological properties. the

The above-mentioned embodiments only express several implementations of the utility model, and the description thereof is relatively specific and detailed, but it should not be construed as limiting the patent scope of the utility model. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the scope of protection of the utility model patent should be based on the appended claims. the

Claims (5)

1. A carbon-based anti-friction and wear-resistant coating, characterized in that, is a multi-layer film structure formed by alternately depositing bonding layers and working layers; The bonding layer is a simple substance or a nitride or carbide film of one of Ti, Cr, W elements, or a film of Si element; The working layer is a graphite-like amorphous carbon film, and the atomic percentage of graphite structure in the graphite-like amorphous carbon film is greater than 70%; The number of cycles of the alternate deposition of the bonding layer and the working layer is arbitrary. the 2. The carbon-based anti-friction and wear-resistant coating according to claim 1, characterized in that, the thickness of the carbon-based anti-friction and wear-resistant coating is 10 μm to 50 μm, the hardness is 10 GPa to 20 GPa, and the scratch binding force Greater than 50N, the friction coefficient in the water environment is less than 0.1, and the wear rate in the water environment is less than 10 ^-16 m ³ N ^-1 m ^-1 order of magnitude. 3. The carbon-based anti-friction and wear-resistant coating according to claim 1, characterized in that, the thickness of each bonding layer is 100nm-400nm, and the thickness of each working layer is 1000nm-2000nm , and the thickness ratio of the adhesive layer to the adjacent working layer is 1:5˜1:10. the 4 . The carbon-based anti-friction and wear-resistant coating according to claim 1 , characterized in that, the number of cycles for the alternate deposition of the bonding layer and the working layer is 10 to 30 times. the 5. A workpiece, comprising a substrate, characterized in that the carbon-based anti-friction and wear-resistant coating according to any one of claims 1-4 is deposited on the surface of the substrate. the