CN115341191B - Material with graphene coating on surface, preparation method of graphene coating and wear-resistant part - Google Patents
Material with graphene coating on surface, preparation method of graphene coating and wear-resistant part Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000000576 coating method Methods 0.000 title claims abstract description 135
- 239000011248 coating agent Substances 0.000 title claims abstract description 130
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 124
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 59
- 239000002184 metal Substances 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000004050 hot filament vapor deposition Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000137 annealing Methods 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 238000011065 in-situ storage Methods 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 9
- 239000006104 solid solution Substances 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000005204 segregation Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims 1
- 230000001050 lubricating effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 59
- 230000003197 catalytic effect Effects 0.000 description 18
- 230000007547 defect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000005019 vapor deposition process Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000531 Co alloy Inorganic materials 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
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- 238000001514 detection method Methods 0.000 description 2
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- 238000007772 electroless plating Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000009643 growth defect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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
-
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0209—Pretreatment of the material to be coated by heating
-
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
- C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
-
- 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
- C23C16/44—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 method of coating
Landscapes
- Chemical & Material Sciences (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)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of preparation of coatings, and discloses a material with a graphene coating on the surface, a preparation method of the coating and a wear-resistant part. A method of preparing a coating comprising: forming a catalyst-containing layer on the surface of the metal substrate; organic gas and hydrogen are introduced into the reaction chamber by using a hot wire chemical vapor deposition method, the organic gas is decomposed by using a heat source generated by the hot wire, and carbon atoms cracked in the reaction chamber are adsorbed on the surface of the catalyst-containing layer under the assistance of the hydrogen to form the self-lubricating graphene coating. The self-lubricating graphene coating is formed on the surface of the metal substrate by adopting the preparation method. The wear-resistant piece is prepared from the material or is prepared by preparing a graphene coating on the surface of a base material by the preparation method. The preparation method of the coating provided by the application can prepare the graphene coating with good lubricating performance, and the method is wide in practicability.
Description
Technical Field
The invention relates to the technical field of preparation of coatings, in particular to a material with a graphene coating on the surface, a preparation method of the coating and a wear-resistant part.
Background
It is counted that about 20% of the annual energy consumption on earth is due to friction, wherein the wear-resistant devices mostly adopt liquid or grease lubricants to eliminate friction and wear, but are more difficult to meet the service requirements of severe environments such as ultra-high and low temperature, vacuum, radiation and the like, while MoS 2 The solid lubricating coating such as graphite, hexagonal boron nitride, diamond-like carbon, graphene and the like can provide an alternative scheme for improving the quality and prolonging the service life of the wear-resistant device. The graphene has low shear strength, high thermal conductivity, low surface energy, excellent mechanical strength and chemical stability, and has great application value in the field of friction and wear control. Currently, the ultra-lubricity of graphene coatings can only be achieved on the nano-scale and micro-scale, and how to extend it to the macro-scale is a major challenge today.
The preparation method of the graphene coating comprises a physical method and a chemical method, wherein the physical method is mainly used for obtaining graphene with higher purity through stripping, and the preparation method is simple to operate, takes longer time and cannot be applied to large-scale industrial production. The chemical method is mainly divided into three types: redox, epitaxial growth and chemical vapor deposition. The oxidation-reduction method is a main preparation method for growing large-area graphene, but has more growth defects, so that the performance of the graphene is affected. The number of layers and thickness of the graphene prepared by the epitaxial growth method can be controlled by temperature, but the quality of the graphene is greatly influenced by silicon carbide crystals, and the transfer and separation processes are complex, so that the requirement of large-area preparation cannot be met. The traditional CVD tube furnace vapor deposition process can grow a large-area graphene coating in situ, so that pollution and loss caused by a transfer process are avoided, but the preparation temperature is generally higher than 800 ℃, the phase change of a wear-resistant device matrix material is easy to occur, and many materials cannot be engineered.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a material with a graphene coating on the surface, a preparation method of the graphene coating and a wear-resistant part.
The invention is realized in the following way:
in a first aspect, the present invention provides a method for preparing a self-lubricating graphene coating, comprising:
forming a catalyst-containing layer on the surface of the metal substrate;
organic gas and hydrogen are introduced into the reaction chamber by using a hot wire chemical vapor deposition method, the organic gas is decomposed by using a heat source generated by the hot wire, and carbon atoms cracked in the reaction chamber are adsorbed on the surface of the catalyst-containing layer under the assistance of the hydrogen to form the self-lubricating graphene coating.
In an alternative embodiment, the catalyst-containing layer is formed on the surface of the metal substrate by:
depositing a metal catalyst layer on the surface of the metal substrate;
high temperature annealing is used to displace solid solution between the metal substrate and the metal catalyst layer to form an alloyed catalyst-containing layer.
In an alternative embodiment, the metal catalyst is at least one of nickel and copper.
In an alternative embodiment, the metal catalyst layer has a thickness of 3 to 20 μm.
In an alternative embodiment, the average grain size of the metal catalyst layer is 1 to 12 μm.
In an alternative embodiment, the thickness of the alloyed catalyst-containing layer is 6 to 12 μm.
In an alternative embodiment, the alloyed catalyst-containing layer formed after high temperature annealing has an average grain size of 4 to 11 μm.
In an alternative embodiment, the high temperature anneal is performed by: heating to 450-700 ℃ at a heating rate of 8-20 ℃/min, and preserving heat for 40-80 min.
In an alternative embodiment, the organic gas is methane.
In alternative embodiments, the metal substrate is cemented carbide or X70 pipeline steel.
In an alternative embodiment, the hydrogen flow is 1000 to 2000sccm; the flow rate of the organic gas is 5-12 sccm, the working air pressure is 100-500 Pa, and the deposition time is 8-15 min.
In an alternative embodiment, in the hot wire chemical vapor deposition process, the hot wires are tantalum wires or tungsten wires, the number of the hot wires is 2-24, the distance between two adjacent hot wires is 10-40 mm, and the distance between each hot wire and a metal substrate is 100-200mm.
In an alternative embodiment, in the hot wire chemical vapor deposition process, the heating temperature of the hot wire is 1900-2500 ℃, and the temperature of the metal substrate is controlled to be 500-700 ℃.
In an alternative embodiment, the hot filament chemical vapor deposition process is performed at an operating pressure of 100 to 500Pa for a deposition time of 8 to 15 minutes.
In an alternative embodiment, the self-lubricating graphene coating is formed and then cooled with a furnace at a cooling rate of 3-6 ℃/min.
In a second aspect, the present invention provides a material having a graphene coating on a surface, which is obtained by preparing a self-lubricating graphene coating on a surface of a metal substrate by a preparation method according to any one of the foregoing embodiments.
In a third aspect, the present invention provides a wear-resistant member prepared from a material according to the foregoing embodiments, or prepared by preparing a self-lubricating graphene coating on a surface of a metal substrate according to the preparation method according to any one of the foregoing embodiments.
The invention has the following beneficial effects:
according to the preparation method of the coating, the self-lubricating graphene coating is deposited on the surface of the catalyst-containing layer by adopting a hot filament chemical vapor deposition method, and hydrogen is used as an activator of surface-bonded carbon to promote graphene growth, so that graphene in-situ low-temperature growth is realized, and the problems of pollution, loss and the like caused by transfer are avoided; on the other hand, the etching effect is achieved to avoid the formation of a plurality of edge defects and phase changes of the graphene coating, so that the graphene coating has the advantages of low defects, high quality, low friction coefficient, low abrasion loss and the like. The temperature of the metal substrate can be controlled below 800 ℃ during coating preparation, and compared with the existing CVD tube furnace vapor deposition process, the method has wider applicability. In addition, the preparation method of the graphene coating is simple and efficient, can realize large-scale industrial production, and can be applied to wear-resistant devices.
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 schematic diagram of graphene coating structure and deposition provided in the present application;
FIG. 2 is a Raman spectrum of a graphene coating at a hydrogen flow rate of 1000 sccm;
FIG. 3 is a graph of the coefficient of friction of a graphene coating at a hydrogen flow rate of 1000 sccm;
FIG. 4 is a schematic Raman spectrum of a graphene coating at a hydrogen flow rate of 400 sccm;
FIG. 5 is a graph of the coefficient of friction of a graphene coating at a hydrogen flow rate of 400sccm.
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 preparation temperature of the graphene coating grown in situ based on the existing traditional CVD tube furnace vapor deposition process is generally higher than 800 ℃, and the phase transition temperature of most steel materials is lower than 800 ℃, so that the temperature higher than 800 ℃ easily causes the phase transition of the wear-resistant device matrix material, and many materials cannot be engineered.
By adopting a hot filament chemical vapor deposition method, organic gas can be decomposed into a carbon source at a hot filament position with the temperature of up to 2000 ℃, and is diffused and adsorbed on the surface of a substrate to grow the graphene coating in situ, and the temperature at the substrate can be controlled below 800 ℃, so that a reference is provided for growing the graphene coating in situ at low temperature.
However, graphene coatings grown at low temperature in situ are prone to more defects and thinner in thickness, while the friction performance of the graphene coatings is affected by the size of the defects and has layer number dependence, which can lose the super-slip performance due to a number of edge defects and phase changes, thereby limiting the application of the technology to wear-resistant devices.
The inventor proposes the technical scheme of the application, and the problems can be effectively overcome.
The material with the graphene coating on the surface, the preparation method of the graphene coating, and the wear-resistant piece provided by the embodiment of the invention are specifically described below.
As shown in fig. 1, a preparation method of a self-lubricating graphene coating provided in an embodiment of the present application includes:
forming a catalyst-containing layer on the surface of the metal substrate;
organic gas and hydrogen are introduced into the reaction chamber by using a hot wire chemical vapor deposition method, the organic gas is decomposed by using a heat source generated by the hot wire, and carbon atoms cracked in the reaction chamber are adsorbed on the surface of the catalyst-containing layer under the assistance of the hydrogen to form the self-lubricating graphene coating.
Therefore, according to the preparation method, the carbon layer is deposited on the surface of the catalyst-containing layer by adopting the hot filament chemical vapor deposition method, and hydrogen is used as an activator for combining carbon on the surface to promote the growth of graphene, so that the graphene in-situ low-temperature growth is realized, and the problems of pollution, loss and the like caused by transfer are avoided; on the other hand, the etching effect is achieved to avoid the formation of a plurality of edge defects and phase changes of the graphene coating, so that the graphene coating has the advantages of low defects, high quality, low friction coefficient, low abrasion loss and the like. The temperature of the metal substrate can be controlled below 800 ℃ during coating preparation, and compared with the existing CVD tube furnace vapor deposition process, the method has wider applicability. In addition, the preparation method of the graphene coating is simple and efficient, can realize large-scale industrial production, and can be applied to wear-resistant devices.
Specifically, the preparation method comprises the following steps:
s1, depositing a catalyst-containing layer
(1) And depositing a metal catalyst layer on the surface of the metal substrate. The deposition method may be electroless deposition, electroplating deposition, vacuum deposition, or the like. The metal catalyst may be, for example, at least one of nickel and copper, which is used to convert catalytically cracked carbon into graphene.
Preferably, the metal catalyst layer has a thickness of 3 to 20 μm and an average crystal grain size of 1 to 12 μm.
The thickness of the metal catalyst layer may be 3 μm, 5 μm, 7 μm, 10 μm, 14 μm, 16 μm, 18 μm, 20 μm, or the like, or any other value in the range of 3 to 20 μm.
The particle diameter of the metal catalyst layer may be 1 μm, 3 μm, 5 μm, 7 μm, 9 μm, 11 μm, 12 μm or the like, or may be any other value in the range of 1 to 12 μm.
If the thickness of the metal catalytic layer is less than 3 μm, it is easy to cause that it cannot catalyze the in-situ growth of the graphene coating, and if it is more than 20 μm, it is easy to cause that it cannot form a substitutional solid solution with the substrate in the subsequent high-temperature annealing.
Preferably, the specific material of the metal substrate is not limited, and the corresponding alloy material, such as cemented carbide, X70 pipeline steel or other base materials of some wear-resistant devices, can be selected according to the mechanical properties of the required parts.
(2) High temperature annealing is used to displace solid solution between the metal substrate and the metal catalyst layer to form an alloyed catalyst-containing layer.
The metal catalyst layer is alloyed to form an alloy coating, so that the coating and the base material are in alloy combination, and the combination strength between the coating and the base material is greatly improved.
Preferably, the high temperature annealing mode is as follows: heating to 450-700 ℃ at a heating rate of 8-20 ℃/min, and preserving heat for 40-80 min.
The heating rate can be 8 ℃/min, 10 ℃/min, 12 ℃/min, 14 ℃/min, 16 ℃/min, 18 ℃/min or 20 ℃/min, or any other value within the range of 8-20 ℃/min.
The temperature may be 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ or 700 ℃, or any other value within the range of 450 to 700 ℃.
The heat preservation time can be 40min, 50min, 60min, 70min or 80min, or any other value within the range of 40-80 min.
Under the annealing condition, the alloying coating with good gold phase, good grain size and high bonding strength can be obtained. If the annealing temperature of the metal catalytic layer is lower than 450 ℃, elements in the base material cannot diffuse into the metal catalytic layer, namely the substitutional solid solution alloy coating cannot be formed, and if the annealing temperature is higher than 700 ℃, the metal catalytic layer is easy to recrystallize, the grain size is reduced, and the segregation growth of the graphene coating is affected.
Preferably, the thickness of the alloyed coating after high temperature annealing is 6-13 μm and the average grain size is 4-11 μm.
The thickness of the alloyed coating layer may be 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm or 13 μm, or any other value in the range of 6 to 13 μm.
The particle size of the alloyed coating may be 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm or 11 μm, or any other value in the range of 4 to 11 μm.
The thickness of the coating and the grain size can ensure the segregation growth of the graphene coating.
S2, hot filament chemical vapor deposition
Organic gas and hydrogen are introduced into the reaction chamber by using a hot wire chemical vapor deposition method, so that a heat source generated by the hot wire decomposes the organic gas, and carbon atoms cracked in the reaction chamber are adsorbed on the surface of the alloyed catalyst-containing layer under the assistance of the hydrogen to form a self-lubricating graphene coating.
Specifically:
(1) Setting hot wire
Preferably, in order to ensure that a coating with good performance can be prepared, the hot wires arranged in the hot wire chemical vapor deposition chamber are tantalum wires or tungsten wires, the number of the hot wires is 2-24, the distance between two adjacent hot wires is 10-40 mm, and the distance between each hot wire and a base material is 100-200mm;
the number of the hot wires can be 2, 4, 6, 8, 10, 12, 14, 16, 18, 20 or 24, etc., or any other value in the range of 2-24.
The hot wire spacing can be 10mm, 20mm, 30mm or 40mm, etc., or any other value in the range of 10-40 mm.
The distance between the hot wire and the substrate can be 100mm, 120mm, 140mm, 160mm, 180mm or 200mm, etc., and can be any other value in the range of 100-200mm.
(2) Heating temperature regulation and control
Preferably, before introducing gas into the reaction chamber, the reaction chamber is vacuumized to a vacuum degree of 0.3Pa, the heating temperature of a hot wire is 1900-2500 ℃, and the temperature of a metal substrate is 500-700 ℃.
The heating temperature of the filament may be 1900 ℃, 2000 ℃, 2100 ℃, 2200 ℃, 2300 ℃, 2400 ℃, 2500 ℃, or any other value within the range of 1900 to 2500 ℃.
The substrate temperature may be 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, or the like, or may be any other value in the range of 500 to 700 ℃.
Further, to ensure that the heating temperature of the heater is within the above range, taking the heater material defined in the application as an example, the heating power of the heater can be 1800-2500W.
The hot wire power may be 1800W, 1900W, 2000W, 2100W, 2200W, 2300W, 2400W, 2500W, or any other value in the range of 1800 to 2500W.
The heating temperature of the hot wire has a remarkable influence on the in-situ segregation growth of the graphene coating, and if the heating temperature is lower than 1900 ℃, the capability of cracking a carbon source of the graphene coating can be reduced, and the capability of diffusing, adsorbing and accumulating active carbon species on the surface of the alloyed catalyst-containing layer can be reduced, so that the in-situ segregation growth of the graphene coating can be remarkably influenced. If the temperature of the hot wire is higher than 2500 ℃, the graphene coating is easy to cause the graphene coating to be incapable of epitaxial growth, the uniformity of the coating is reduced, and the phase change of the base material is caused.
(3) Introducing gas
And introducing organic gas and hydrogen into the reaction chamber, wherein the flow rate of the hydrogen is 1000-2000 sccm, the flow rate of the organic gas is 5-12 sccm, the working air pressure is 100-500 Pa, and the deposition time is 8-15 min.
Preferably, the organic gas may be methane, ethane or other organic gas, and the more commonly used gas is methane.
The hydrogen flow rate may be 1000sccm, 1100sccm, 1200sccm, 1300sccm, 1400sccm, 1500sccm, 1600sccm, 1700sccm, 1800sccm, 1900sccm, 2000sccm, or any other value within a range of 1000 to 2000 sccm.
The methane flow rate may be 5sccm, 6sccm, 8sccm, 10sccm, or 12sccm, or any other value within the range of 5 to 12 sccm.
The operating air pressure may be 100Pa, 200Pa, 300Pa, 400Pa, 500Pa, or the like, or may be any other value within a range of 100 to 500 Pa.
In the hot wire chemical vapor deposition process, the growth quality and self-lubricating performance of the graphene coating can be improved by regulating and controlling the flow of gas related parameters such as hydrogen. Under the conditions of the gas flow and working pressure, the growth of graphene can be promoted, the etching effect is also realized, and the size of the generated graphene defects is controlled, so that a coating with better self-lubricating property is obtained.
In the range limited by the conditions of the air pressure, the organic gas flow and the like, if the hydrogen flow is smaller than 1000sccm, the activated carbon species cannot be activated easily, so that the in-situ segregation growth of the graphene coating is inhibited, and if the hydrogen flow is larger than 2000sccm, a large amount of hydrogen is easily caused to etch the intact graphene coating, so that defects are increased, and the self-lubricating performance is reduced.
If the conditions such as the gas pressure and the organic gas flow rate are not within the above-described limited ranges, the optimum hydrogen flow rate may vary, and therefore, the optimum hydrogen flow rate is not limited to the above-described ranges, but may vary according to the variation of other operating conditions.
(4) Cooling
In order to avoid oxidation of the high-temperature self-lubricating graphene coating by air after being discharged from the furnace, the graphene coating is cooled to room temperature by adopting a furnace-following cooling mode and then taken out, preferably, the cooling rate is 3-6 ℃/min, and the cooling rate can be 3 ℃/min, 4 ℃/min, 5 ℃/min or 6 ℃/min, for example.
The material with the graphene coating on the surface is obtained by adopting the preparation method provided by the embodiment of the application to prepare the self-lubricating graphene coating on the surface of the metal substrate.
The wear-resistant part is prepared from the material provided by the embodiment of the application, or is prepared from the self-lubricating graphene coating on the surface of the metal substrate by adopting the preparation method of the coating.
The material with the graphene coating on the surface or the wear-resistant piece has better wear resistance because the self-lubricating graphene coating is prepared on the surface.
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 preparation method of a self-lubricating graphene coating, which comprises the following steps:
(1) Cleaning: sequentially placing the YG6 hard alloy base material into cleaning agent, deionized water and absolute ethyl alcohol to ultrasonically clean the YG6 hard alloy base material for 10min respectively, and drying.
(2) And adopting electroless plating to deposit a nickel catalyst layer, wherein the thickness of the nickel catalyst layer is 3 mu m, and the average grain diameter is 1 mu m.
(3) High temperature annealing forms an alloyed catalyst-containing layer: and (3) placing a nickel-plated substrate, vacuumizing the tube furnace by using a mechanical pump, continuously introducing argon-hydrogen mixed gas for three times, removing impurity gas in the furnace, setting the heating temperature to 450 ℃, and keeping the temperature for 40min at a heating rate of 8 ℃/min.
An alloyed catalyst-containing layer having a thickness of 6 μm and an average grain size of 4 μm was produced.
(4) Preparing two tantalum wires, setting the interval between the two tantalum wires to be 10mm, placing a base material containing an alloy catalytic layer into a hot wire chemical vapor deposition chamber, and placing the tantalum wires above the base material for 100mm.
(5) Vacuum degree is pumped to 0.3Pa, hot wire power is set to 1800W, hot wire temperature is about 1900 ℃, and substrate temperature is 500 ℃.
(6) And introducing hydrogen at a flow rate of 1000sccm and methane at a flow rate of 5sccm, setting the working air pressure to be 100Pa, and depositing the graphene coating for 8min.
(7) Cooling along with the furnace. The cooling rate was 3℃per minute.
And diffusing Co element in the prepared annealed hard metal substrate to the nickel catalytic layer to form a nickel-cobalt alloy coating for replacing the solid solution. Experiments show that D, G and 2D peaks exist in the prepared graphene coating, the surface scanning ID/IG value is 0.2, and the Raman spectrum is shown as a curve in FIG. 2, and the graphene coating belongs to a graphene coating with low defects and high quality. The frictional wear result showed an average friction coefficient of 0.02068 (as shown in FIG. 3) and an amount of wear of 1.2X10 -5 mm 3 Nm, has excellent self-lubricating properties.
Example 2
The embodiment provides a preparation method of a self-lubricating graphene coating, which comprises the following steps:
(1) Cleaning: sequentially placing the YG8 hard metal base materials into cleaning agent, deionized water and absolute ethyl alcohol, ultrasonically cleaning the YG8 hard metal base materials for 15min each, and drying the YG8 hard metal base materials.
(2) The nickel catalytic layer is deposited by electroplating, the thickness reaches 10 mu m, and the average grain diameter of the crystal grains is 6 mu m.
(3) High temperature annealing forms an alloyed catalyst-containing layer: and (3) placing a nickel-plated substrate, vacuumizing the tube furnace by using a mechanical pump, continuously introducing argon-hydrogen mixed gas for three times, removing impurity gas in the furnace, setting the heating temperature to 500 ℃, and keeping the heating rate to 14 ℃/min for 60min.
The thickness of the resulting alloyed catalyst-containing layer was 8. Mu.m, and the average grain size was 8. Mu.m.
(4) 6 tantalum wires are prepared, 6 tantalum wires are arranged at intervals of 20mm, a base material containing an alloy catalytic layer is placed into a hot wire chemical vapor deposition chamber, and the tantalum wires are placed above the base material for 130mm.
(5) Vacuum degree is pumped to 0.3Pa, hot wire power is set to 2000W, hot wire temperature is between 1950 and 2000 ℃, and substrate temperature is 600 ℃.
(6) Introducing hydrogen at a flow rate of 1500sccm and methane at a flow rate of 8sccm, setting the working air pressure to 300Pa, and depositing the graphene coating for 10min.
(7) Cooling along with the furnace. The cooling rate was 4℃per minute.
And diffusing Co element in the prepared annealed hard metal substrate to the nickel catalytic layer to form a nickel-cobalt alloy coating for replacing the solid solution. Experiments show that D, G and 2D peaks exist in the prepared graphene coating, the surface scanning ID/IG value is 1.5, and the graphene coating belongs to a low-defect high-quality graphene coating. The frictional wear result showed an average friction coefficient of 0.05763 and an abrasion loss of 3.4X10 -5 mm 3 Nm, has excellent self-lubricating properties and wear resistance.
Example 3
The embodiment provides a preparation method of a self-lubricating graphene coating, which comprises the following steps:
(1) Cleaning: sequentially placing the YG12 hard metal base materials into cleaning agent, deionized water and absolute ethyl alcohol, ultrasonically cleaning the YG12 hard metal base materials for 20min respectively, and drying the YG12 hard metal base materials.
(2) The nickel catalytic layer was deposited by vacuum plating to a thickness of 14 μm and a particle size of 8. Mu.m.
(3) High temperature annealing forms an alloyed catalyst-containing layer: and (3) placing a nickel-plated base material, vacuumizing the tube furnace by using a mechanical pump, continuously introducing argon-hydrogen mixed gas for three times, removing impurity gas in the furnace, setting the heating temperature to 650 ℃, the heating rate to 16 ℃/min, and the heat preservation time to 70min.
The thickness of the resulting alloyed catalyst-containing layer was 10. Mu.m, and the average grain size of the crystal grains was 9. Mu.m.
(4) Preparing 12 hot wires, setting the interval of the 12 hot wires to be 30mm, placing the base material containing the alloy catalytic layer into a hot wire chemical vapor deposition chamber, and placing the hot wire above the base material for 150mm.
(5) Vacuum degree is pumped to 0.3Pa, tantalum wire power is set to 2300W, hot wire temperature is about 2300 ℃, and substrate temperature is 650 ℃.
(6) And introducing 1800sccm of hydrogen and 10sccm of methane, setting the working air pressure to 400Pa, and depositing the graphene coating for 12min.
(7) Cooling along with the furnace. The cooling rate was 5℃per minute.
And diffusing Co element in the prepared annealed hard metal substrate to the nickel catalytic layer to form a nickel-cobalt alloy coating for replacing the solid solution. Experiments show that D, G and 2D peaks exist in the prepared graphene coating, the surface scanning ID/IG value is 1.9, and the graphene coating belongs to a low-defect high-quality graphene coating. The frictional wear result showed an average friction coefficient of 0.0664 and an abrasion loss of 5.1X10 -5 mm 3 Nm, has excellent self-lubricating properties and wear resistance.
Example 4
The embodiment provides a preparation method of a self-lubricating graphene coating, which comprises the following steps:
(1) Cleaning: sequentially placing the steel base material of the X70 pipeline into cleaning agent, deionized water and absolute ethyl alcohol to ultrasonically clean the steel base material of the X70 pipeline for 10 minutes respectively, and drying.
(2) The nickel catalytic layer is deposited by electroless plating, the thickness is 20 mu m, and the average grain diameter is 12 mu m.
(3) High temperature annealing forms an alloyed catalyst-containing layer: and (3) placing a nickel-plated base material, vacuumizing the tube furnace by using a mechanical pump, continuously introducing argon-hydrogen mixed gas for three times, removing impurity gas in the furnace, setting the heating temperature at 700 ℃, and keeping the temperature for 80 minutes at a heating rate of 20 ℃/min.
The thickness of the resulting alloyed catalyst-containing layer was 13 μm and the average grain size was 11. Mu.m.
(4) Preparing 24 hot wires, setting the interval between the 24 hot wires to 40mm, placing the hot wires 200mm above the base material, placing the alloy catalytic layer into a hot wire chemical vapor deposition chamber, and cleaning dust and impurities in the chamber by using a dust collector.
(5) Vacuum degree is pumped to 0.3Pa, tantalum wire power is set to 2500W, hot wire temperature is about 2500 ℃, and substrate temperature is 700 ℃.
(6) And introducing 2000sccm of hydrogen flow and 12sccm of methane flow, setting the working air pressure to be 500Pa, and depositing the graphene coating for 15min.
(7) Cooling along with the furnace. The cooling rate was 6℃per minute.
Fe element in the annealed X70 pipeline steel substrate prepared by the method is oriented to a metallic nickel layerAnd diffusing to form an iron-nickel alloy catalytic layer for replacing the solid solution. Experiments show that D, G and 2D peaks exist in the prepared graphene coating, the surface scanning ID/IG value is 0.5, the graphene coating belongs to a low-defect high-quality graphene coating, and the X70 pipeline steel does not undergo phase change. The frictional wear result showed an average coefficient of friction of 0.0454 and an amount of wear of 3.5X10 -5 mm 3 Nm, has excellent self-lubricating properties and wear resistance.
Comparative example 1
The preparation method provided in this comparative example is substantially the same as that in example 1, except that: the flow rate of the hydrogen introduced in the step (6) is replaced by 400sccm.
Experimental results show that the graphene coating obtained in the comparative example also has D, G and 2D peaks, but the 2D peak intensity is lower, and in addition, the ID/IG value is 4, so that the graphene coating has higher defects, and the quality of the graphene coating is poor (shown in figure 4). The same friction and wear test parameters are adopted, and the friction coefficient is higher, the friction coefficient reaches 0.10449, and the wear amount is 2.7X10 -5 mm 3 and/Nm, wear after 2000 cycles, has poor self-lubricating and wear-resistant properties, as shown in FIG. 5.
Comparative example 2
The preparation method provided in this comparative example is substantially the same as in example 1, except that: step (2) and step (3) are not performed.
The raman results show that no 2D peak exists in the coating, indicating that the graphene coating does not grow in situ on the substrate surface, and no subsequent frictional wear detection is performed.
Comparative example 3
The preparation method provided in this comparative example is substantially the same as in example 1, except that: and (3) replacing the thickness of the nickel catalytic layer in the step (2) with 800nm, and diffusing a small part of Co element in the base material to the nickel catalytic layer after annealing.
Experimental results show that D, G and 2D peaks exist in the prepared graphene coating, and defects are more. The frictional wear results showed an average coefficient of friction of 0.0836, which was worn through at a friction time of 4min, with poor wear resistance.
Comparative example 4
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 substrate which is not annealed at high temperature is poorly combined with the nickel catalytic layer, and the shedding phenomenon occurs, so that the subsequent friction and wear detection is not performed.
Comparative example 5
The preparation method provided in this comparative example is substantially the same as in example 1, except that: the deposition time in step (6) was replaced with 30min.
Experimental results show that graphene curls to form a morphology similar to that of a carbon nano tube, a 2D peak does not exist in the coating, the friction coefficient exceeds 0.2, and the self-lubricating performance is poor.
In summary, according to the preparation method of the self-lubricating graphene coating, the self-lubricating graphene coating is deposited on the surface of the catalyst-containing layer by adopting the hot filament chemical vapor deposition method, and hydrogen is used as an activator of surface-bound carbon to promote graphene growth, so that graphene in-situ low-temperature growth is realized, and the problems of pollution, loss and the like caused by transfer are avoided; on the other hand, the etching effect is achieved to avoid the formation of a plurality of edge defects and phase changes of the graphene coating, so that the graphene coating has the advantages of low defects, high quality, low friction coefficient, low abrasion loss and the like. The temperature of the metal substrate can be controlled below 800 ℃ during coating preparation, and compared with the existing CVD tube furnace vapor deposition process, the method has wider applicability. In addition, the preparation method of the graphene coating is simple and efficient, can realize large-scale industrial production, and can be applied to wear-resistant devices.
In the preferred embodiments of the present application, the effect of further improving the self-lubricity of the graphene coating can be achieved by controlling the hydrogen flow rate within a suitable range.
In the preferred embodiment of the application, the metal catalyst layer is alloyed by annealing treatment, so that the bonding strength between the metal catalyst layer and an alloy matrix is improved, and the material is ensured to have good wear resistance.
In the preferred embodiments of the present application, by controlling the thickness of the alloy catalyst layer within a suitable range, better wear resistance of the resulting coating can be ensured.
In the preferred embodiments of the present application, by controlling the deposition time within a suitable range, it is further ensured that a coating is produced that is a graphene phase.
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 (11)
1. The preparation method of the self-lubricating graphene coating is characterized by comprising the following steps of:
depositing a metal catalyst layer on the surface of a metal substrate, wherein the thickness of the metal catalyst layer is 3-20 mu m, and the metal substrate is hard alloy or X70 pipeline steel;
performing solid solution displacement between the metal substrate and the metal catalyst layer by adopting high-temperature annealing so as to form an alloyed catalyst-containing layer;
introducing organic gas and hydrogen into the reaction chamber by using hot filament chemical vapor deposition, decomposing the organic gas by using a heat source generated by the hot filament, and adsorbing carbon atoms cracked in the reaction chamber to the surface of the catalyst-containing layer under the assistance of the hydrogen to enable graphene to grow in situ in a segregation manner to form a self-lubricating graphene coating; the hydrogen flow is 1100-2000 sccm; the flow rate of the organic gas is 5-12 sccm, the working air pressure is 100-500 Pa, the deposition time is 8-15 min, and the organic gas is methane;
in the hot wire chemical vapor deposition process, the heating temperature of the hot wire is 1900-2500 ℃, and the temperature of the metal substrate is controlled to be 500-700 ℃.
2. The method for preparing a self-lubricating graphene coating according to claim 1, wherein the metal catalyst is at least one of nickel and copper.
3. The method for preparing the self-lubricating graphene coating according to claim 1, wherein the average grain size of the metal catalyst layer is 1-12 mu m.
4. The method for preparing the self-lubricating graphene coating according to claim 1, wherein the thickness of the alloyed catalyst-containing layer is 6-12 [ mu ] m.
5. The preparation method of the self-lubricating graphene coating according to claim 1, wherein the average grain size of the alloyed catalyst-containing layer formed after high-temperature annealing is 4-11 mu m.
6. The method for preparing a self-lubricating graphene coating according to claim 1, wherein the high-temperature annealing mode is as follows: heating to 450-700 ℃ at a heating rate of 8-20 ℃/min, and preserving heat for 40-80 min.
7. The method for preparing the self-lubricating graphene coating according to claim 1, wherein in the hot wire chemical vapor deposition process, the hot wires are tantalum wires or tungsten wires, the number of the hot wires is 2-24, the distance between two adjacent hot wires is 10-40 mm, and the distance between each hot wire and the metal substrate is 100-200mm.
8. The method for preparing a self-lubricating graphene coating according to claim 1, wherein the self-lubricating graphene coating is formed and then cooled in a furnace.
9. The method for preparing the self-lubricating graphene coating according to claim 8, wherein the cooling rate is 3-6 ℃/min.
10. The material with the graphene coating on the surface is characterized in that the self-lubricating graphene coating is prepared on the surface of the metal substrate by adopting the preparation method according to any one of claims 1-9.
11. A wear part prepared from the material of claim 10.
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