CN118996371A - Graphene-diamond composite coating and preparation method and application thereof - Google Patents
Graphene-diamond composite coating and preparation method and application thereof Download PDFInfo
- Publication number
- CN118996371A CN118996371A CN202411100326.1A CN202411100326A CN118996371A CN 118996371 A CN118996371 A CN 118996371A CN 202411100326 A CN202411100326 A CN 202411100326A CN 118996371 A CN118996371 A CN 118996371A
- Authority
- CN
- China
- Prior art keywords
- diamond
- graphene
- coating
- composite coating
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/271—Diamond only using hot filaments
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开了一种石墨烯‑金刚石复合涂层及其制备方法与应用，属于材料技术领域。该石墨烯‑金刚石复合涂层包括金刚石涂层和石墨烯涂层；石墨烯sp2键结构与金刚石sp3键结构共价结合；石墨烯涂层具有呈垂直为主的非平行生长的石墨烯结构。其中，金刚石和石墨烯的晶格失配小，避免了摩擦热过程中引起的体积膨胀；金刚石涂层可为石墨烯提供支撑层，并在交界面形成超强的C‑C共价键，显著提升石墨烯的附着强度；石墨烯可避免金刚石发生脆性断裂，并显著提升金刚石涂层表面的润滑性能。该复合涂层具有较佳的耐磨性、低摩擦系数和优异的抗氧化性能，还能在高温、高负荷的工作条件下保持稳定，从而提高耐磨件的使用寿命和加工效率。
The present invention discloses a graphene-diamond composite coating and a preparation method and application thereof, belonging to the field of material technology. The graphene-diamond composite coating includes a diamond coating and a graphene coating; the graphene sp2 bond structure is covalently bonded to the diamond sp3 bond structure; the graphene coating has a graphene structure that is mainly vertical and non-parallel growth. Among them, the lattice mismatch between diamond and graphene is small, which avoids the volume expansion caused by the friction heat process; the diamond coating can provide a support layer for graphene and form a super strong C-C covalent bond at the interface, significantly improving the adhesion strength of graphene; graphene can avoid brittle fracture of diamond and significantly improve the lubrication performance of the surface of the diamond coating. The composite coating has good wear resistance, low friction coefficient and excellent oxidation resistance, and can also remain stable under high temperature and high load working conditions, thereby improving the service life and processing efficiency of wear-resistant parts.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a graphene-diamond composite coating, and a preparation method and application thereof.
Background
With the rapid development of the mechanical and energy fields, higher requirements are put on the durability, energy loss and lubricating performance of key power components in extreme environments such as high temperature, high pressure and the like. Graphene has become a hotspot in material science research due to its excellent lubricating properties. However, the low flexural rigidity of graphene causes it to be susceptible to wrinkling when loaded, creating additional energy dissipation during sliding friction, which is detrimental to maintaining its ideal layered structure, and correspondingly affects its wear resistance.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a graphene-diamond composite coating, and a preparation method and application thereof, so as to solve or improve the technical problems.
The invention can be realized as follows:
in a first aspect, the present invention provides a graphene-diamond composite coating comprising a diamond coating and a graphene coating;
the diamond coating is used for being arranged on the surface of the hard alloy substrate, and a graphene sp2 bond structure in the graphene coating is covalently combined with a diamond sp3 bond structure in the diamond coating; the graphene coating has a non-parallel grown graphene structure that is predominantly perpendicular from an interface with the diamond coating to a direction away from the diamond coating.
In alternative embodiments, the graphene-diamond composite coating has at least one of the following features:
feature 1: the thickness of the diamond coating is 1-15 mu m;
Feature 2: the diamond in the diamond coating is super nanocrystalline diamond, nanocrystalline diamond or microcrystalline diamond;
feature 3: the thickness of the graphene coating is 1-5 mu m.
In an alternative embodiment, the average grain size of the super nanocrystalline diamond is 5nm to 30nm; or the average grain size of the nanocrystalline diamond is 40 nm-100 nm; or the average grain size of the micron-sized diamond is 1000 nm-3000 nm.
In an alternative embodiment, the graphene-diamond composite coating further has at least one of the following features:
Feature 4: the friction coefficient of the graphene-diamond composite coating is not more than 0.1;
Feature 5: the abrasion rate of the graphene-diamond composite coating is not more than 1X 10 -6mm3/Nm.
In a second aspect, the present invention provides a method for preparing a graphene-diamond composite coating according to any one of the preceding embodiments, comprising the steps of: preparing a diamond coating on the surface of the hard alloy substrate, preparing a liquid catalyst layer on the surface of the diamond coating, and preparing a graphene coating on the surface of the liquid catalyst layer; and etching the residual liquid catalyst layer.
In an alternative embodiment, the cemented carbide substrate is etched and cleaned prior to preparing the diamond coating.
In an alternative embodiment, the diamond coating is prepared using a hot wire chemical vapor deposition technique, and the preparation conditions of the diamond coating include: the deposition power is 1500-2500W, the deposition air pressure is 1-10 mbar, the hydrogen flow is 9000-18000 sccm, the methane flow is 100-500 sccm, the deposition temperature is 800-1000 ℃, and the deposition time is 6-30 h.
In an alternative embodiment, a liquid metal is applied to the surface of the diamond coating using a instillation process to form a liquid catalyst layer.
In an alternative embodiment, the liquid metal is applied in an amount of 0.5g/cm 2～5g/cm2.
In an alternative embodiment, the liquid metal includes at least one of liquid gallium, liquid copper, and liquid nickel.
In an alternative embodiment, the liquid metal comprises liquid gallium.
In an alternative embodiment, the graphene coating is prepared by using a tube furnace high-temperature treatment technology, and the preparation conditions of the graphene coating include: the vacuum degree of the quartz tube is 10-30 mtorr, the hydrogen flow is 100-1000 sccm, the growth temperature is 700-1200 ℃, and the growth time is 10-40 min.
In a third aspect, the present invention provides a graphene-diamond composite coating material comprising a substrate and a graphene-diamond composite coating according to any one of the preceding embodiments disposed on a surface of the substrate.
In a fourth aspect, the present invention provides a wear part having a graphene-diamond composite coating material as described in the previous embodiments.
The beneficial effects of the invention include:
The invention provides a graphene-diamond composite coating, which comprises a diamond coating and a graphene coating. The diamond coating can be used as a bearing phase and a solid carbon source of the graphene coating. The diamond has higher mechanical properties, can provide firm support, and reduces wrinkling and edge wrapping phenomena of graphene, thereby maintaining a more orderly sliding interface and potentially improving the wear resistance of graphene.
In the invention, the graphene structure of the graphene coating grows vertically and mainly from the interface combined with the diamond coating to the direction far away from the diamond coating. Compared with graphene growing in a parallel mode, the graphene structure growing in a non-parallel orientation mainly in a vertical mode can endow the coating with excellent wear resistance, low friction coefficient and excellent oxidation resistance, and can be kept stable under high-temperature and high-load working conditions, so that the service life and the processing efficiency of the wear-resistant part are remarkably improved.
In addition, in the invention, the diamond coating provides a solid carbon source for the growth of the graphene coating, and a carbon precursor is not required to be introduced from outside, so that the preparation process is simplified. From the microstructure, the lattice mismatch of diamond and graphene is small, and the volume expansion caused in the friction heat process is avoided. In addition, the diamond and the graphene are allotropes of carbon, the high hardness of the diamond coating can provide a supporting layer for the graphene, and a super strong C-C covalent bond is formed at the interface, so that the adhesion strength of the graphene is obviously improved; the graphene with the flexibility characteristic can prevent the diamond from brittle fracture, remarkably improve the lubricating performance of the surface of the diamond coating, and form complementary advantages.
It is further emphasized that, in the current prior art, graphene is generally grown in layers, not more than 10 layers, and has a thickness of about 1nm to 4nm; the invention provides the idea of vertically and mainly growing the graphene in a non-parallel manner (namely vertically growing), namely successfully provides a specific scheme for realizing the idea, and comprises a preparation method and preparation conditions, so that the graphene material with better wear resistance and skid resistance is effectively provided.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a structural morphology diagram of a graphene-diamond composite coating prepared in example 1 of the present invention;
FIG. 2 is a Raman spectrum of the diamond coating in example 1 of the present invention;
FIG. 3 shows a Raman spectrum of the graphene-diamond composite coating prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The graphene-diamond composite coating provided by the invention, and a preparation method and application thereof are specifically described below.
The invention provides a graphene-diamond composite coating, which comprises a diamond coating and a graphene coating. The diamond coating is used for being arranged on the surface of the hard alloy substrate, and a graphene sp2 bond structure in the graphene coating is covalently combined with a diamond sp3 bond structure in the diamond coating; the graphene coating has a non-parallel grown graphene structure that is predominantly perpendicular from an interface with the diamond coating to a direction away from the diamond coating.
The diamond coating can be used as a bearing phase and a solid carbon source of the graphene coating. The diamond has higher mechanical properties, can provide firm support, and reduces wrinkling and edge wrapping phenomena of graphene, thereby maintaining a more orderly sliding interface and potentially improving the wear resistance of graphene. However, in the prior art, the bonding of the graphene coating and the diamond coating mainly depends on weak van der waals force, and the bonding force is generally insufficient to bear a high-load friction environment, so that the application on workpieces with complex shapes or irregular shapes is difficult.
Based on the above, in the preparation process, a liquid catalyst layer is introduced between the graphene coating and the diamond coating, and the liquid catalyst layer is used for inducing the graphene coating to grow on the diamond coating in situ under the high-temperature condition so as to form the graphene-diamond composite coating. By introducing the catalyst layer, the self-limiting dynamics characteristic of the catalyst layer can be utilized to promote the seamless growth of the graphene sp2 bond structure on the diamond sp3 bond structure, so that the graphene coating and the diamond coating have excellent bonding strength, and the application of the composite coating on workpieces with complex shapes or irregular shapes is realized. And, in the preparation process, the residual liquid catalyst layer is etched, so that most of the catalyst layer can be removed.
In the invention, the graphene structure of the graphene coating grows vertically and mainly from the interface combined with the diamond coating to the direction far away from the diamond coating. Wherein "non-parallel" growth forms include growth in a direction perpendicular to the binding interface, and growth in a direction at an angle (e.g., 5 °, 10 °,20 °, 30 °, 40 °, 50 °, 60 °, 70 °, 80 °, etc.) to the binding interface. Compared with graphene grown in parallel, the graphene grown in the direction guided by the crystal face of the catalyst can generate larger graphene crystals, and the larger graphene crystals are stacked into an irregular structure. The structure can endow the coating with excellent wear resistance, low friction coefficient and excellent oxidation resistance, and can be kept stable under high-temperature and high-load working conditions, so that the service life and the processing efficiency of the wear-resistant part are obviously improved.
In addition, in the invention, the diamond coating can also provide a solid carbon source for the growth of the graphene coating, and a carbon precursor is not required to be introduced from outside, so that the preparation process is simplified. From the microstructure, the lattice mismatch of diamond and graphene is small, and the volume expansion caused in the friction heat process is avoided. In addition, the diamond and the graphene are allotropes of carbon, the high hardness of the diamond coating can provide a supporting layer for the graphene, and a super strong C-C covalent bond is formed at the interface, so that the adhesion strength of the graphene is obviously improved; the graphene with the flexibility characteristic can prevent the diamond from brittle fracture, remarkably improve the lubricating performance of the surface of the diamond coating, and form complementary advantages.
In some alternative embodiments, the diamond coating may have a thickness of 1 μm to 15 μm, such as 1 μm,2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 15 μm, etc., and may have other values in the range of 1 μm to 15 μm.
If the thickness of the diamond coating is less than 1 mu m, the shortage of solid carbon source supply is easy to occur, and the growth of vertical graphene is not facilitated; if the thickness of the diamond coating is larger than 15 mu m, the number of layers and the thickness of the graphene are easy to increase, and even parallel graphite states are formed.
The diamond in the diamond coating can be super-nanocrystalline diamond, nanocrystalline diamond or micro-crystalline diamond. The average grain size of the super nanocrystalline diamond may be 5nm to 30nm, such as 5nm, 10nm, 15nm, 20nm, 25nm or 30nm, or may be other values within the range of 5nm to 30 nm. The average grain size of the nanocrystalline diamond may be 40nm to 100nm, such as 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 100nm, or may be other values in the range of 40nm to 100 nm. The average grain size of the microcrystalline diamond may be 1000nm to 3000nm, such as 1000nm, 1500nm, 2000nm, 2500nm or 3000nm, and may be other values in the range of 1000nm to 3000 nm.
If the average grain size of diamond in the diamond coating is too large, larger grain boundaries are easy to appear in the coating, and the grain boundaries are potential stress concentration points, so that the possibility of microcracking of the coating is increased when the coating is stressed, and the overall fracture toughness of the coating is reduced.
In some alternative embodiments, the thickness of the graphene coating may be 1 μm to 5 μm, such as 1 μm,2 μm, 3 μm, 4 μm, or 5 μm, etc., and may be other values in the range of 1 μm to 5 μm.
If the thickness of the graphene coating is too thin, a continuous and uniform protective barrier cannot be formed, and the force applied to the surface is not sufficiently absorbed and dispersed, so that the coating is easy to crack or peel when being subjected to mechanical impact or pressure; if the thickness of the graphene coating is too thick, the overall flexibility of the coating will be affected, reducing its applicability in applications requiring bending or stretching. Also, increased layer thickness may lead to uneven stress between interfaces, resulting in layer-by-layer separation or overall spalling of the coating.
In some embodiments, the friction coefficient of the graphene-diamond composite coating layer does not exceed 0.1, and may be, for example, 0.081 to 0.099, such as 0.081, 0.082, 0.088, 0.091, 0.095, or 0.099, and may be other values within the range of 0.081 to 0.099. In some more typical embodiments, the graphene-diamond composite coating has a coefficient of friction of 0.081 to 0.082.
In some embodiments, the graphene-diamond composite coating has a wear rate of no more than 1×10 -6mm3/Nm, for example, 1×10 -7mm3/Nm～1×10-6mm3/Nm, such as 1×10-7mm3/Nm、2.1×10-7mm3/Nm、2.2×10- 7mm3/Nm、2.5×10-7mm3/Nm、3.6×10-7mm3/Nm or 1×10 -6mm3/Nm, and other values within the range of 1×10 -7mm3/Nm～1×10-6mm3/Nm. In some more typical embodiments, the graphene-diamond composite coating has a wear rate of 1X 10 -6mm3/Nm～1.0×10-7mm3/Nm.
Correspondingly, the invention also provides a preparation method of the graphene-diamond composite coating, which can comprise the following steps: preparing a diamond coating on the surface of the hard alloy substrate, preparing a liquid catalyst layer on the surface of the diamond coating, and preparing a graphene coating on the surface of the liquid catalyst layer; and etching the residual liquid catalyst layer.
In some embodiments, the cemented carbide substrate is etched and cleaned prior to preparing the diamond coating.
The specific material, shape and size of the cemented carbide substrate are not limited, and the corresponding substrate, such as a cemented carbide planar sample, a cemented carbide milling cutter and other workpiece substrates, can be selected according to the application scene of the required part.
The time of ultrasonic etching can be 1 min-6 min, such as 1min, 2min, 3min, 4min, 5min or 6 min. The cleaning time can be 10 min-20 min, such as 10min, 15min or 20 min.
In some embodiments, a hot wire chemical vapor deposition technique may be used to prepare the diamond coating. The hot filament chemical vapor deposition technology is adopted, so that diamond coating can be deposited on the surface of the irregular workpiece substrate uniformly.
The preparation conditions of the diamond coating may include: the deposition power is 1500-2500W, the deposition air pressure is 1-10 mbar, the hydrogen flow is 9000-18000 sccm, the methane flow is 100-500 sccm, the deposition temperature is 800-1000 ℃, and the deposition time is 6-30 h.
The deposition power may be 1500W, 1600W, 1700W, 1800W, 1900W, 2000W, 2100W, 2200W, 2300W, 2400W, 2500W, or the like, or may be other values in the range of 1500W to 2500W.
The deposition gas pressure may be 1mbar, 2mbar, 3mbar, 4mbar, 5mbar, 6mbar, 7mbar, 8mbar, 9mbar or 10mbar, etc., but may also be other values in the range of 1mbar to 10 mbar.
The hydrogen flow rate may be 9000sccm, 10000sccm, 11000sccm, 12000sccm, 13000sccm, 14000sccm, 15000sccm, 16000sccm, 17000sccm, 18000sccm, or the like, or may be another value within a range of 9000sccm to 18000 sccm.
The methane flow rate may be 100sccm, 150sccm, 200sccm, 250sccm, 300sccm, 350sccm, 400sccm, 450sccm, 500sccm, or the like, or may be another value in the range of 100sccm to 500 sccm.
The deposition temperature may be 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, or the like, or may be other values within the range of 800 ℃ to 1000 ℃.
The deposition time may be 6h, 12h, 18h, 24h, 30h, or the like, or may be other values in the range of 6h to 30 h.
Under the condition of hot wire chemical vapor deposition, the surface of the substrate of the complex workpiece can be covered with a diamond layer with large area and uniform height, the diamond layer is not influenced by the special-shaped structure of the substrate, and the high bearing and excellent adhesive force of the graphene are ensured.
In some embodiments, a liquid metal may be applied to the surface of the diamond coating using a instillation process to form a liquid catalyst layer. The metal catalytic layer can effectively promote the growth rate of graphene, reduce the temperature and pressure conditions for graphene growth, remarkably reduce the production cost of the composite coating and facilitate the large-scale popularization and application of the technology.
The liquid metal may be applied in an amount of 0.5g/cm 2～5g/cm2, such as 0.5g/cm 2、1g/cm2、2g/cm2、3g/cm2、4g/cm2 or 5g/cm 2, etc., or may have other values in the range of 0.5g/cm 2～5g/cm2. Accordingly, the thickness of the liquid metal catalyst layer may be 10nm to 300nm, such as 10nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, or the like.
If the dosage of the liquid metal is too small, the liquid metal is easy to prevent the liquid metal from playing a catalytic role in the growth of graphene; if the amount of liquid metal is too large, a parallel graphene layer with weak van der waals force is easily formed, and growth of a non-parallel graphene structure is inhibited.
By way of example and not limitation, the liquid metal may include at least one of liquid gallium, liquid copper, and liquid nickel. In some preferred embodiments, the liquid metal comprises liquid gallium.
In some embodiments, a tube furnace high temperature processing technique may be used to prepare the graphene coating. By placing the substrate with the diamond coating and the liquid metal catalytic layer in a high temperature environment, the diffusion of carbon atoms in the diamond coating onto the liquid metal catalytic layer can be promoted; under the action of the liquid metal catalytic layer, the carbon atoms rearrange and form a non-parallel form of graphene coating in a non-parallel orientation.
The preparation conditions of the graphene coating can include: the vacuum degree of the quartz tube is 10-30 mtorr, the hydrogen flow is 100-1000 sccm, the growth temperature is 700-1200 ℃, and the growth time is 10-40 min.
The vacuum degree of the quartz tube can be 10mtorr, 15mtorr, 20mtorr, 25mtorr or 30mtorr, etc., and can also be other values in the range of 10mtorr to 30 mtorr.
The hydrogen flow rate may be 100sccm, 200sccm, 300sccm, 400sccm, 500sccm, 600sccm, 700sccm, 800sccm, 900sccm, 1000sccm, or the like, or may be another value in the range of 100sccm to 1000 sccm.
If the hydrogen flow is too low, enough hydrogen is not needed to etch the defect edges, the edge structure defects of the diamond and graphene coatings are increased, and the adhesive force of the diamond coatings and the graphene coatings is reduced.
The growth temperature may be 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, or the like, or may be other values within the range of 700 ℃ to 1200 ℃.
Under the high-temperature preparation condition, carbon atoms in the diamond layer can be effectively migrated to the liquid metal catalytic layer, and stable growth of non-parallel graphene is facilitated. If the growth temperature is lower than 700 ℃, the graphene is easy to grow slowly; if the growth temperature is higher than 1200 ℃, the coating and the matrix structure are easily damaged, and the bonding strength of the coating interface is reduced.
The growth time may be 10min, 15min, 20min, 25min, 30min, 35min or 40min, or may be other values within the range of 10min to 40 min.
In some embodiments, etching the remaining liquid catalyst layer may be performed with reference to the following: and (3) etching by using concentrated hydrochloric acid, wherein the etching time can be 1min.
On the contrary, the existing preparation technology relies on weak van der Waals force to realize the combination of the graphene coating and the diamond coating, but in a high-temperature friction environment, the insufficient bonding force caused by weak interaction can accelerate attenuation due to thermodynamic instability, and the service life and the performance of the graphene coating in the friction field are limited. According to the invention, the diamond coating is deposited on the surface of the complex workpiece substrate by adopting a hot wire chemical vapor deposition technology, and the graphene coating which mainly grows vertically and is not parallel is grown in situ and stably attached on the diamond coating by utilizing a liquid metal catalytic layer and a high-temperature technology, so that the durability of the graphene-diamond composite coating in a friction environment is improved. In addition, the technology is simple, efficient and high in adaptability, solves the problems of high equipment cost, low production efficiency, complex process control and the like of the conventional method, can cover workpiece substrates with various complex shapes and sizes, and greatly expands the application potential in the industrial field.
Further, the invention also provides a graphene-diamond composite coating material, which comprises a substrate and the graphene-diamond composite coating arranged on the surface of the substrate.
Furthermore, the invention also provides a wear-resistant piece which is provided with the graphene-diamond composite coating material, and other structures can be arranged on the basis of the wear-resistant piece according to requirements.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a graphene-diamond composite coating material, which is prepared by the following method:
step (1): etching and cleaning.
Sequentially soaking YG6 hard alloy planar sample pieces in a mixed strong acid solution containing HCl and HNO 3, a Murakami strong base solution and a mixed strong acid containing HCl and HNO 3, respectively performing ultrasonic etching for 1min, 3min and 2min, sequentially placing into isopropanol and deionized water, respectively performing ultrasonic cleaning for 10min, and then drying by nitrogen.
Step (2): and depositing the nanocrystalline diamond coating by adopting a hot filament chemical vapor deposition technology.
The diamond coating had a thickness of 2 μm and an average grain size of 40nm. The main process parameters of the hot wire chemical vapor deposition are as follows: the deposition power was 2000W, the deposition pressure was 5mbar, the hydrogen flow rate was 10000sccm, the methane flow rate was 200sccm, the deposition temperature was 800℃and the deposition time was 8 hours.
Step (3): the liquid gallium metal catalytic layer is coated by a instillation method.
The thickness of the coating was 30nm, the mass of liquid gallium metal used was 1g, and the area of the coating was 2cm 2.
Step (4): and (3) inducing the growth of the non-parallel graphene coating by adopting a tube furnace high-temperature technology.
Specifically, the base material on which the nano diamond coating and the liquid gallium metal catalytic layer are deposited is placed in a tube furnace, the vacuum degree is pumped to 10mtorr, the hydrogen flow is set to be 200sccm, the growth temperature is 800 ℃, the growth time is 10min, and the graphene coating with the thickness of 2 mu m is obtained.
Step (5): and etching the residual liquid gallium metal catalytic layer. Specifically, concentrated hydrochloric acid is used for etching for 1min.
After the prepared nano diamond coating is annealed at a high temperature by a tube furnace, carbon atoms in diamond diffuse to a liquid gallium metal catalytic layer, so that the rearrangement of the carbon atoms is promoted, the graphene sp2 bond structure is promoted to grow seamlessly on the diamond sp3 bond structure in a non-parallel orientation mode mainly perpendicular, and a graphene-diamond composite coating is formed, as shown in figure 1. Experiments show that the graphene-diamond composite coating prepared above is converted from a diamond sp3 characteristic Raman peak to a sp2 characteristic Raman peak, and the Raman spectrum curves are shown in figures 2 and 3. After 1800s of long-time friction, the graphene-diamond composite coating still has good wear resistance.
Example 2
The embodiment provides a graphene-diamond composite coating material, which is prepared by the following method:
step (1): etching and cleaning.
Sequentially soaking the milling cutter in a mixed strong acid solution containing HCl and HNO 3, a Murakami strong base solution and a mixed strong acid containing HCl and HNO 3, respectively performing ultrasonic etching for 1min, 3min and 2min, sequentially placing the milling cutter in isopropanol and deionized water, respectively performing ultrasonic cleaning for 10min, and then drying by nitrogen.
Step (2): and depositing the micron-sized crystal diamond coating by adopting a hot filament chemical vapor deposition technology.
The diamond coating had a thickness of 4 μm and an average grain size of 2000nm. The main process parameters of the hot wire chemical vapor deposition are as follows: the deposition power was 2300W, the deposition pressure was 1mbar, the hydrogen flow rate was 18000sccm, the methane flow rate was 300sccm, the deposition temperature was 900℃and the deposition time was 12 hours.
Step (3): the liquid gallium metal catalytic layer is coated by a instillation method.
The thickness of the coating was 100nm, the mass of liquid gallium metal used was 3g, and the area of the coating was 6cm 2.
Step (4): and (3) inducing the growth of the non-parallel graphene coating by adopting a tube furnace high-temperature technology.
Specifically, the substrate on which the microcrystalline diamond coating and the liquid gallium metal catalytic layer are deposited is placed in a tube furnace, the vacuum degree is pumped to 20mtorr, the hydrogen flow is set to be 500sccm, the growth temperature is 900 ℃, the growth time is 20min, and the graphene coating with the thickness of 3 μm is obtained.
Step (5): as in example 1.
After the prepared microcrystalline diamond coating is annealed at a high temperature by a tube furnace, carbon atoms in the diamond diffuse to the liquid gallium metal catalytic layer, so that the rearrangement of the carbon atoms is promoted, the graphene sp2 bond structure is promoted to grow seamlessly on the diamond sp3 bond structure in a non-parallel orientation mode, and the graphene-diamond composite coating is formed. Experiments show that the graphene-diamond composite coating prepared by the method is converted from a diamond sp3 characteristic Raman peak to a sp2 characteristic Raman peak, has a stable interface and good bonding strength. In the friction process, the wear-resisting performance and the service life are good.
Example 3
The embodiment provides a graphene-diamond composite coating material, which is prepared by the following method:
step (1): etching and cleaning.
Sequentially soaking the micro-drill in a mixed strong acid solution containing HCl and HNO 3, a Murakami strong base solution and a mixed strong acid containing HCl and HNO 3, respectively performing ultrasonic etching for 1min, 3min and 2min, sequentially placing the micro-drill in isopropanol and deionized water, respectively performing ultrasonic cleaning for 10min, and then drying by nitrogen.
Step (2): and depositing the ultra-nanocrystalline diamond coating by adopting a hot filament chemical vapor deposition technology.
The diamond coating had a thickness of 5 μm and an average grain size of 20nm. The main process parameters of the hot wire chemical vapor deposition are as follows: the deposition power was 1500W, the deposition pressure was 8mbar, the hydrogen flow rate was 9000sccm, the methane flow rate was 100sccm, the deposition temperature was 1000℃and the deposition time was 14h.
Step (3): the liquid gallium metal catalytic layer is coated by a instillation method.
The thickness of the coating was 200nm, the mass of liquid gallium metal used was 4g, and the area of the coating was 8cm 2.
Step (4): and (3) inducing the growth of the non-parallel graphene coating by adopting a tube furnace high-temperature technology.
Specifically, the substrate on which the ultra-nanocrystalline diamond coating and the liquid gallium metal catalytic layer are deposited is placed in a tube furnace, the vacuum degree is increased to 30mtorr, the hydrogen flow is set to be 100sccm, the growth temperature is 1000 ℃, the growth time is 30min, and the graphene coating with the thickness of 4 mu m is obtained.
Step (5): as in example 1.
After the prepared ultra-nanocrystalline diamond coating is annealed at a high temperature by a tube furnace, carbon atoms in the diamond diffuse to the liquid gallium metal catalytic layer, so that the rearrangement of the carbon atoms is promoted, the graphene sp2 bond structure is promoted to grow seamlessly on the diamond sp3 bond structure in a non-parallel orientation mode, and the graphene-diamond composite coating is formed. Experiments show that the graphene-diamond composite coating prepared by the method is converted from a diamond sp3 characteristic Raman peak to a sp2 characteristic Raman peak, has a stable interface and good bonding strength. In the friction process, the wear-resisting performance and the service life are good.
Example 4
The embodiment provides a graphene-diamond composite coating material, which is prepared by the following method:
step (1): etching and cleaning: as in example 2.
Step (2): and depositing the nanocrystalline diamond coating by adopting a hot filament chemical vapor deposition technology.
The diamond coating had a thickness of 8 μm and an average grain size of 70nm. The main process parameters of the hot wire chemical vapor deposition are as follows: the deposition power was 2100W, the deposition pressure was 2mbar, the hydrogen flow rate was 12000sccm, the methane flow rate was 300sccm, the deposition temperature was 1000℃and the deposition time was 20 hours.
Step (3): the liquid gallium metal catalytic layer is coated by a instillation method.
The thickness of the coating was 300nm, the mass of liquid gallium metal used was 5g, and the area of the coating was 10cm 2.
Step (4): and (3) inducing the growth of the non-parallel graphene coating by adopting a tube furnace high-temperature technology.
Specifically, the base material on which the nanocrystalline diamond coating and the liquid gallium metal catalytic layer are deposited is placed in a tube furnace, the vacuum degree is pumped to 15mtorr, the hydrogen flow is set to be 400sccm, the growth temperature is 1100 ℃, the growth time is 40min, and the graphene coating with the thickness of 5 mu m is obtained.
Step (5): as in example 1.
After the prepared nanocrystalline diamond coating is annealed at a high temperature by a tube furnace, carbon atoms in the diamond diffuse to the liquid gallium metal catalytic layer, so that the rearrangement of the carbon atoms is promoted, the graphene sp2 bond structure is promoted to grow seamlessly on the diamond sp3 bond structure in a non-parallel orientation mode, and the graphene-diamond composite coating is formed. Experiments show that the graphene-diamond composite coating prepared by the method is converted from a diamond sp3 characteristic Raman peak to a sp2 characteristic Raman peak, has a stable interface and good bonding strength. Under the cutting working condition, the wear-resisting alloy has good wear-resisting performance and service life.
Example 5
The embodiment provides a graphene-diamond composite coating material, which is prepared by the following method:
Step (1): as in example 1.
Step (2): and depositing the ultra-nanocrystalline diamond coating by adopting a hot filament chemical vapor deposition technology.
The diamond coating had a thickness of 1 μm and an average grain size of 5nm. The main process parameters of the hot wire chemical vapor deposition are as follows: the deposition power was 1500W, the deposition pressure was 1mbar, the hydrogen flow rate was 9000sccm, the methane flow rate was 100sccm, the deposition temperature was 900℃and the deposition time was 30 hours.
Step (3): the liquid copper catalytic layer is coated by a instillation method.
The liquid copper metal used had a mass of 0.5g and the coated area was the same as in example 1.
Step (4): and (3) inducing the growth of the non-parallel graphene coating by adopting a tube furnace high-temperature technology.
Specifically, the base material on which the nano diamond coating and the liquid copper metal catalytic layer are deposited is placed in a tube furnace, the vacuum degree is pumped to 20mtorr, the hydrogen flow is set to be 100sccm, the growth temperature is 700 ℃, the growth time is 40min, and the graphene coating with the thickness of 1.5 mu m is obtained.
Step (5): as in example 1.
After the prepared ultra-nano diamond coating is annealed at a high temperature by a tube furnace, carbon atoms in diamond diffuse to a liquid copper metal catalytic layer, so that rearrangement of carbon atoms is promoted, and graphene sp2 bond structures are promoted to grow seamlessly on diamond sp3 bond structures in a non-parallel orientation mode, so that a graphene-diamond composite coating is formed.
Example 6
The embodiment provides a graphene-diamond composite coating material, which is prepared by the following method:
Step (1): as in example 1.
Step (2): and depositing the micron-sized crystal diamond coating by adopting a hot filament chemical vapor deposition technology.
The diamond coating had a thickness of 15 μm and an average grain size of 3000nm. The main process parameters of the hot wire chemical vapor deposition are as follows: the deposition power was 2500W, the deposition gas pressure was 10mbar, the hydrogen flow rate was 18000sccm, the methane flow rate was 500sccm, the deposition temperature was 1000℃and the deposition time was 6 hours.
Step (3): the liquid nickel metal catalytic layer is coated by a instillation method.
The mass of liquid nickel metal used was 5g and the area coated was the same as in example 1.
Step (4): and (3) inducing the growth of the non-parallel graphene coating by adopting a tube furnace high-temperature technology.
Specifically, the base material on which the nano diamond coating and the liquid nickel metal catalytic layer are deposited is placed in a tube furnace, the vacuum degree is pumped to 30mtorr, the hydrogen flow is set to be 1000sccm, the growth temperature is 1200 ℃, the growth time is 20min, and the graphene coating with the thickness of 5 mu m is obtained.
Step (5): as in example 1.
After the prepared micron diamond coating is annealed at a high temperature by a tube furnace, carbon atoms in the diamond diffuse to the liquid nickel metal catalytic layer, so that the rearrangement of the carbon atoms is promoted, the graphene sp2 bond structure is promoted to grow seamlessly on the diamond sp3 bond structure in a non-parallel orientation mode, and the graphene-diamond composite coating is formed.
Comparative example 1
The preparation method provided in this comparative example is substantially the same as in example 1, except that: the liquid metal catalytic layer in the step (3) and the step (5) is replaced by a non-liquid metal catalytic layer.
Experimental results show that the graphene coating obtained in the comparative example is in parallel orientation. The same friction and wear test parameters are adopted, so that the friction curve is severely dithered after long-time friction, and the wear resistance is poor.
Comparative example 2
The preparation method provided in this comparative example is substantially the same as in example 1, except that: step (3) is not performed.
Experimental results show that the liquid gallium metal catalytic layer is not deposited on the surface of the diamond coating, so that the growth of the vertical graphene cannot be catalyzed. In addition, the diamond surface loses the lubrication antifriction effect of graphene, so that a large number of abrasion particles appear at a friction interface, abrasion of abrasive particles occurs, and poor lubrication performance is achieved.
Comparative example 3
The preparation method provided in this comparative example is substantially the same as in example 1, except that: the deposition time in step (2) was replaced with 5h.
Experimental results show that the thickness of the diamond coating obtained by the comparative example is only 500nm, the surface of the complex workpiece substrate cannot be completely covered, the catalytic layer cannot effectively catalyze the growth of graphene, and the diamond coating has poor lubrication and wear resistance.
Comparative example 4
The preparation method provided in this comparative example is substantially the same as in example 1, except that: the growth temperature in step (4) was set to 600 ℃.
Experimental results show that at lower annealing temperatures, carbon atoms in the diamond layer cannot migrate to the catalytic layer effectively, resulting in slow growth and uneven coverage of non-parallel oriented graphene, poor adhesion between diamond and graphene, and poor wear resistance.
Comparative example 5
The preparation method provided in this comparative example is substantially the same as in example 1, except that: the hydrogen flow rate in step (4) was set to 50sccm.
Experimental results show that under the condition of less hydrogen flow, insufficient hydrogen is used for etching the defect edges, so that the edge structure defects of the diamond and graphene coatings are increased, and the adhesive force of the diamond coatings and the graphene coatings is reduced.
Comparative example 6
The preparation method provided in this comparative example is substantially the same as in example 1, except that: in step (2), the thickness of the diamond coating was 20. Mu.m.
Comparative example 7
The preparation method provided in this comparative example is substantially the same as in example 2, except that: in the step (2), the average grain size of the microcrystalline diamond is 5000nm.
Comparative example 8
The preparation method provided in this comparative example is substantially the same as in example 1, except that: in the step (4), the thickness of the graphene coating is 0.6nm.
Comparative example 9
The preparation method provided in this comparative example is substantially the same as in example 1, except that: in the step (4), the thickness of the graphene coating is 6 μm.
Comparative example 10
The preparation method provided in this comparative example is substantially the same as in example 1, except that: in the step (3), the coating amount of the liquid gallium is 0.1g, and the coating area is unchanged.
Comparative example 11
The preparation method provided in this comparative example is substantially the same as in example 1, except that: in the step (3), the coating amount of the liquid gallium is 8g, and the coating area is unchanged.
Test examples
The composite coatings obtained in examples 1 to 6 and comparative examples 1 to 11 were subjected to performance comparison, and the results are shown in Table 1.
The testing condition of the friction coefficient of the diamond coating and the graphene coating is ball disc friction, the rotating speed is 0.2m/s, the load is 5N, and the rotating radius is 5mm; the calculation formula of the wear rate is w=v/(f×s); wherein V is the abrasion loss, and the unit is mm 3; f is the sliding distance, and the unit is m; s is the load in N.
Table 1 table of performance versus results
As can be seen from table 1, the graphene-diamond composite coating provided by the invention has better wear resistance and low friction coefficient, and is beneficial to prolonging the service life of corresponding wear-resistant parts.
In summary, the scheme provided by the invention has at least the following advantages:
The graphene-diamond composite coating provided by the invention can provide firm support due to the high mechanical property of diamond, and reduce wrinkling and edge wrapping phenomena of graphene, so that an ordered sliding interface is maintained, and the wear resistance of graphene is potentially improved. By introducing the liquid metal catalytic layer, the self-limiting dynamics characteristic of the liquid metal catalytic layer can be utilized to promote the seamless growth of the graphene sp2 bond structure on the diamond sp3 bond structure, so that the possibility is provided for the direct synthesis of graphene and the combination of the graphene and diamond, more covalent bond connection with the graphene is facilitated, the combination strength of the graphene-diamond composite coating interface is enhanced, and the stability of the graphene-diamond composite coating interface under the friction condition is improved. In addition, the preparation method of the graphene-diamond composite coating is simple and efficient, can be widely deposited on workpiece substrates with complex shapes and sizes, and can be applied to wear-resistant devices.
In the preferred embodiment of the invention, the thickness and the crystal grain of the diamond in the hot wire chemical vapor deposition are controlled within a proper range, so that the uniform coverage of the diamond coating on the surface of the irregular workpiece substrate can be ensured, and the sufficient carbon source and bearing capacity are ensured to be provided for the growth of the graphene coating.
In a preferred embodiment of the invention, the migration of carbon atoms in the diamond coating to the surface of the liquid metal catalytic layer can be activated by controlling the amount of liquid metal in the liquid metal catalytic layer within a proper range, so that the growth of the graphene coating in a non-parallel orientation direction mainly perpendicular to the carbon atoms is promoted.
In the preferred embodiment of the invention, the prepared graphene-diamond composite coating has better wear resistance by controlling the growth temperature and time of graphene within a proper range.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411100326.1A CN118996371A (en) | 2024-08-12 | 2024-08-12 | Graphene-diamond composite coating and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411100326.1A CN118996371A (en) | 2024-08-12 | 2024-08-12 | Graphene-diamond composite coating and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118996371A true CN118996371A (en) | 2024-11-22 |
Family
ID=93480971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411100326.1A Pending CN118996371A (en) | 2024-08-12 | 2024-08-12 | Graphene-diamond composite coating and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118996371A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120181501A1 (en) * | 2011-01-13 | 2012-07-19 | Chien-Min Sung | Graphene on Diamond Devices and Associated Methods |
| CN109722642A (en) * | 2017-10-30 | 2019-05-07 | 深圳先进技术研究院 | Workpiece provided with diamond/graphene composite lubricating film and preparation method thereof |
| CN113582173A (en) * | 2021-08-18 | 2021-11-02 | 上海交通大学 | Graphene-diamond covalent heterostructure connected through covalent bond and preparation method thereof |
-
2024
- 2024-08-12 CN CN202411100326.1A patent/CN118996371A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120181501A1 (en) * | 2011-01-13 | 2012-07-19 | Chien-Min Sung | Graphene on Diamond Devices and Associated Methods |
| CN109722642A (en) * | 2017-10-30 | 2019-05-07 | 深圳先进技术研究院 | Workpiece provided with diamond/graphene composite lubricating film and preparation method thereof |
| CN113582173A (en) * | 2021-08-18 | 2021-11-02 | 上海交通大学 | Graphene-diamond covalent heterostructure connected through covalent bond and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHEJI等: "Enhanced lubricity of CVD diamond films by in-situ synthetization of top-layered graphene sheets", 《CARBON》, vol. 184, 31 October 2021 (2021-10-31), pages 680 - 688, XP086809885, DOI: 10.1016/j.carbon.2021.08.077 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10836132B2 (en) | Graphene reinforced materials and related methods of manufacture | |
| CN102586777B (en) | Preparation method for CBN (Cubic Boron Nitride) coated cutter based on micrometer/nanometer diamond transition layer | |
| CN109930129B (en) | Composite diamond coating hard alloy cutter and preparation method thereof | |
| CN103952660B (en) | Composite material with a nitride film as well as preparation method and application of composite material | |
| CN105543803A (en) | Diamond/boron carbide composite coating of hard alloy substrate and preparation method thereof | |
| CN110803941A (en) | Carbon-silicon carbide composite material surface oxidation resistant coating and preparation method thereof | |
| CN118996371A (en) | Graphene-diamond composite coating and preparation method and application thereof | |
| CN110453176A (en) | Preparation method of long-life ultra-nano diamond periodic multilayer coating cutter | |
| CN108300967A (en) | High temperature resistant low friction DLC/AlTiSiN multi-layer composite coatings and preparation method thereof | |
| CN109081332A (en) | Graphene nano graphical sapphire substrate and preparation method thereof | |
| CN113278939A (en) | Fullerene-like nano-structure hydrogen-containing carbon film and preparation method thereof | |
| CN1727410A (en) | A kind of nanocomposite diamond-like carbon coating and preparation method thereof | |
| CN114351088B (en) | Solid self-lubricating coating and preparation method thereof | |
| CN116200822A (en) | Wafer carrier plate and its preparation method | |
| JP7613829B2 (en) | Carbon Composite Materials | |
| CN108946701A (en) | A kind of carbon nanotube double-sided adhesive and its preparation method and application | |
| CN116426875A (en) | Preparation method of AlN/Si/SiN/AlSiN/AlN/Al multilayer gradient structure coating and coating | |
| CN114481030A (en) | Solid neutron conversion layer and preparation method and application thereof | |
| CN206635411U (en) | Wire-drawing die with a variety of coatings | |
| KR101562950B1 (en) | Diamond coated cutting tool and method for fabricating the same | |
| CN112941475A (en) | DLC film for removing floating oil in water treatment process and preparation method thereof | |
| CN115821206B (en) | Ultra-thick carbon-based composite coating with heterogeneous multilayer structure and preparation method and application thereof | |
| CN110359029B (en) | Coating for cutting tools and method for producing the same | |
| CN115341191B (en) | Material with graphene coating on surface, preparation method of graphene coating and wear-resistant part | |
| CN115505157B (en) | Application of organic-inorganic composite wear-resistant antifriction coating in polyether-ether-ketone surface protection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |