CN116240492A - Friction structural member for polymer matching pair, preparation method and application thereof - Google Patents
Friction structural member for polymer matching pair, preparation method and application thereof Download PDFInfo
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- CN116240492A CN116240492A CN202310241367.1A CN202310241367A CN116240492A CN 116240492 A CN116240492 A CN 116240492A CN 202310241367 A CN202310241367 A CN 202310241367A CN 116240492 A CN116240492 A CN 116240492A
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Images
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/354—Introduction of auxiliary energy into the plasma
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/16—Sealings between relatively-moving surfaces
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/16—Sealings between relatively-moving surfaces
- F16J15/162—Special parts or details relating to lubrication or cooling of the sealing itself
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a friction structural member for a polymer pair, a preparation method and application thereof. The friction structural member comprises a substrate and a composite coating arranged on the friction surface of the substrate, wherein the composite coating comprises a transition layer and an amorphous carbon layer which are sequentially laminated along the direction far away from the substrate, and the amorphous carbon layer is doped with Cr element. According to the invention, the friction interface between the coating and the polymer is regulated and controlled by doping metal element Cr, so that the excellent lubricity of the carbon-based coating is maintained, the formation process of the amorphous carbon graphitized friction film is not influenced, meanwhile, the adhesion chemical reaction can be inhibited, an excellent metal and amorphous carbon lubrication interface is formed, the friction running-in period of the matched pair is shortened, the friction coefficient is reduced, and the application potential of the matched pair is increased; the preparation method combines the high-power pulse magnetron sputtering and the direct-current magnetron sputtering technology, can deposit the composite coating with no gap and high density at the low matrix temperature, has safe operation environment and simple and easily controlled process, and is beneficial to industrial production and application.
Description
Technical Field
The invention relates to the technical field of surface protection, in particular to a friction structural member for matching with a polymer, a preparation method and application thereof, and particularly relates to a low-abrasion control structure and method for shortening the friction running-in period of a carbon-based coating and the polymer matching pair.
Background
Mechanical seals, also known as end face seals, are commonly used in pumps, kettles, compressors, hydraulic transmission and other equipment, are important components of these mechanical equipment, and have great influence on normal operation and safe production. And frictional wear of the sealing material is a main cause of accidents such as mechanical seal failure and leakage.
Soft sealing polymer materials commonly used in mechanical sealing, such as Polyetheretherketone (PEEK), polytetrafluoroethylene (PTFE), polyimide (PI), polyphenylene sulfide (PPS), etc., are often used in stainless steel-stainless steel friction systems as commonly used solid lubricants to achieve low coefficients of friction due to their good antifriction lubrication and sealing properties.
It is widely accepted by researchers that one of the important roles of polymers in improving lubricating properties is the formation of transfer films on steel surfaces. Amorphous carbon coating is a type of carbon-derived sp 2 And sp (sp) 3 The metastable state material formed by hybridization has the properties of high hardness, wear resistance, chemical inertness and the like. Generally, the amorphous carbon coating can be transferred to the surface of the counter-milled metal to form a graphitized friction film in the friction process, thereby realizing antifriction lubrication characteristics. Therefore, the amorphous carbon coating is adopted to modify the metal part and the polymer pair, so that antifriction lubrication with high sealing requirements can be realized under multiple working conditions.
However, it has been confirmed that when two materials with solid self-lubricating properties are rubbed together, severe adhesion chemical reactions such as cleavage of surface ether, diphenyl ether and other bonds after rubbing of PEEK, formation of ROC, RO, RC radicals and re-bonding with amorphous carbon surface C are generated, and the adhesion chemical reactions significantly affect the tribological properties of the friction pair.
Typically, for example, in dry friction conditions lacking liquid lubrication, the running-in period of friction due to the adhesive chemistry may be as high as 5 hours, with a coefficient of friction up to 0.55, which greatly limits the practical application of amorphous carbon coatings and polymer formulations.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a friction structural member for matching with a polymer, a preparation method and application thereof.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the invention provides a friction structural member for matching with a polymer, which comprises a substrate and a composite coating arranged on a friction surface of the substrate, wherein the composite coating comprises a transition layer and an amorphous carbon layer which are sequentially laminated along a direction away from the substrate, and the amorphous carbon layer is doped with Cr element.
In a second aspect, the present invention also provides a method for manufacturing the friction structural member, which includes:
providing a substrate;
forming a transition layer on the friction surface of the substrate;
and forming an amorphous carbon layer on the surface of the transition layer, wherein the amorphous carbon layer is doped with Cr element.
In a third aspect, the invention also provides a friction pair, which comprises the friction structural member and a friction body in friction fit with the friction structural member;
the friction body is made of polymer on the friction surface.
In a fourth aspect, the invention also provides the use of the friction fit pair in a mechanical seal.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
according to the invention, the friction interface between the coating and the polymer is regulated by doping metal element Cr, so that the excellent lubricity of the carbon-based coating can be maintained, the formation process of the amorphous carbon graphitized friction film is not influenced, meanwhile, the adhesion chemical reaction of free radicals formed after the friction of the polymer surface and the amorphous carbon surface C can be inhibited, an excellent metal-amorphous carbon lubrication interface is formed, the friction running-in period of the auxiliary pair is shortened, the friction coefficient is reduced, and the potential of the auxiliary pair applied to other fields is increased.
The preparation method provided by the invention combines the high-power pulse magnetron sputtering and the direct-current magnetron sputtering technology, can deposit the composite coating with no gap and high density at low matrix temperature, has safe operation environment and simple and easily controlled process, and is beneficial to industrialized production and application.
The above description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical means of the present application, the present invention may be implemented according to the content of the specification, the following description is given of the preferred embodiments of the present invention with reference to the accompanying drawings.
Drawings
FIG. 1 is an XPS survey spectrum of a composite coating provided by some exemplary embodiments of the invention;
FIG. 2 is a graph showing the coefficient of friction test of composite coatings provided by some exemplary embodiments of the present invention and comparative examples;
FIG. 3 is a graph showing the coefficient of friction test of composite coatings provided by other exemplary embodiments of the present invention and comparative examples;
FIG. 4a is a surface SEM image of a composite coating provided by an exemplary comparative case of the present invention;
FIG. 4b is a surface SEM image of a composite coating provided by an exemplary embodiment of the invention;
fig. 5 is a graph showing the bonding force test of the composite coating provided by some exemplary embodiments of the present invention and comparative examples.
Detailed Description
In the prior art, the amorphous carbon coating is formed by sp of carbon 2 And sp (sp) 3 Hybrid bond composite compositionThe material has high hardness and high elastic modulus, and the friction coefficient can be as low as 0.03, so that the material is one of the preferable materials of the precise auxiliary protective coating. However, it is empirically known that the formation of a graphite transfer layer from an amorphous carbon coating to a metal counter surface is a key factor in reducing COF during sliding. However, studies have found that these two materials with solid self-lubricating properties undergo severe adhesive chemical reactions when rubbed together, which greatly limits the practical application of amorphous carbon coatings and polymer partners.
In view of the defects in the prior art, the inventor discovers through long-term research and mass practice that a metal transfer film can be formed on the surface of a polymer by doping a proper amount of Cr content, so that a friction interface between amorphous carbon and the polymer is converted into a metal and amorphous carbon friction interface, the adhesion chemical reaction can be obviously inhibited, the friction running-in period of a matched pair is shortened, and the friction coefficient is reduced, and therefore the technical scheme of the invention is provided.
The technical scheme, the implementation process, the principle and the like are further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
According to one aspect of the embodiment of the invention, the friction structural member for matching with the polymer comprises a substrate and a composite coating arranged on the friction surface of the substrate, wherein the composite coating comprises a transition layer and an amorphous carbon layer which are sequentially laminated along the direction away from the substrate, and the amorphous carbon layer is doped with Cr element.
In the technical scheme, the invention relates to a low-wear control method for shortening the friction running-in period of a carbon-based coating and a polymer pair, and the friction interface lubrication behavior of the carbon-based coating and polyether-ether-ketone is improved through a metal doping design, wherein the metal doping design is a Cr-doped hydrogen-free carbon-based composite coating, and in a very specific embodiment, the composite coating comprises a Cr/CrN transition layer and a Cr-doped hydrogen-free amorphous carbon layer which are sequentially formed on the surface of a stainless steel substrate.
And, a metal doped carbon-based composite coating is preferably prepared on the surface of stainless steel by using a multi-target magnetron sputtering technology, particularly as exemplified below.
Wherein the substrate may be, for example, a metal substrate, preferably a stainless steel substrate, more preferably, the substrate may be selected from 316, 304, 17-4PH stainless steel, and most preferably, 17-4PH stainless steel, and is not limited thereto. The main technical means of the technical proposal provided by the invention is that Cr doped component and high sp 2 The combination of the amorphous carbon layer with carbon content and the surface of the polymer material brings about excellent running-in performance, and the material selection of the matrix material can be carried out, so that the matrix material meeting certain strength standards, such as ceramic material or other metal material, and the like.
The material selection of the transition layer may be different based on different materials, and a person skilled in the art may appropriately select a suitable transition layer in the common prior art, so as to ensure a good binding force between the substrate and the amorphous carbon layer. Therefore, the material selection and structure of the specific substrate and the transition layer disclosed in the present invention are not limited to the scope of the following specific examples.
In some embodiments, the amorphous carbon layer is formed from a hydrogen-free amorphous carbon material formed by mixing a diamond phase and a graphite phase.
In some embodiments, the amorphous carbon layer has a molar ratio of diamond phase to graphite phase of from 1:2 to 1:5.
In some embodiments, the amorphous carbon layer may preferably have an atomic percentage of Cr of 2.15 to 15.52%, and particularly preferably 2.15 to 4%. In the invention, the Cr content greatly influences the hardness, modulus and internal stress of the Cr-doped amorphous carbon composite coating. If the Cr doping content in the amorphous carbon coating is too high, the hardness of the coating is reduced too low, the plastic deformation resistance is weak, and the anti-friction performance is reduced. The appropriate Cr content can inhibit the chemical reaction of the friction interface adhesion between the coating and the polymer, and maintain a proper mechanical property, so that the friction coefficient is reduced and the wear resistance of the amorphous carbon coating is maintained.
In some embodiments, the thickness of the composite coating may be 300-500nm.
In some embodiments, the thickness of the transition layer may be 150-240nm.
In some embodiments, the transition layer comprises a Cr layer and a CrN layer stacked in sequence in a direction away from the substrate.
In some embodiments, the Cr layer may have a thickness of 80-120nm and the CrN layer may have a thickness of 80-120nm.
In some embodiments, the amorphous carbon layer may have a thickness of 150-300nm.
The second aspect of the embodiment of the present invention further provides a method for manufacturing a friction structural member according to any one of the above embodiments, including the steps of:
providing a substrate;
forming a transition layer on the friction surface of the substrate;
and forming an amorphous carbon layer on the surface of the transition layer, wherein the amorphous carbon layer is doped with Cr element.
In some embodiments, the method of preparation specifically comprises:
and sequentially depositing a Cr layer and a CrN layer on the surface of the substrate by adopting magnetron sputtering. In the invention, the hardness of the metal and amorphous carbon coating is greatly different, and the hardness of CrN is between Cr and amorphous carbon, so that the three-layer structure using the CrN layer as the intermediate layer can effectively relieve the problem of interface mismatch, and improve the binding force of the coating.
And C target material is sputtered by direct current magnetron sputtering, and Cr target material is sputtered by pulse magnetron sputtering, so that the amorphous carbon layer is formed on the surface of the CrN layer by codeposition.
In some embodiments, the sputtering mode of the Cr layer and the CrN layer may be selected from direct current magnetron sputtering.
In some embodiments, the substrate may be subjected to a cleaning process and an etching process prior to performing magnetron sputtering. The specific cleaning agent etching treatment is mainly used for improving the binding force between the substrate and the composite coating and achieving the corresponding function, and is not limited to the cleaning/etching mode specifically exemplified in the following embodiments.
In some embodiments, the CrN layer may be deposited by introducing a nitrogen source based on magnetron sputtering of the Cr layer.
In some embodiments, the nitrogen source may include nitrogen.
In some embodiments, the Ar flow rate during deposition of the Cr layer and the CrN layer may be 45-65sccm, the pulsed negative bias may be 80-120V, the chamber pressure may be 2.0-2.5mTorr, the chamber temperature may be 130-170 ℃, and the deposition time may be 5-10 minutes.
In some embodiments, N when depositing the CrN layer 2 The flow rate may be 15-25sccm.
In some embodiments, the Ar flow rate when depositing the amorphous carbon layer may be 45-65sccm, the pulsed negative bias may be 180-220V, the DC current may be 2.5-3.5A, the power of the pulsed magnetron sputtering may be 100-400W, and the deposition time may be 30-50min.
As some typical application examples of the above technical solution, the following steps may be adopted to implement the above preparation method:
1) And (5) carrying out ultrasonic cleaning on the surface of the stainless steel matrix.
And 2) adopting a multi-target magnetron sputtering technology, placing the stainless steel matrix obtained after cleaning in a reaction cavity and vacuumizing; ar is introduced to carry out etching treatment on the matrix, then a direct current power supply is adopted to prepare a Cr/CrN transition layer, and the technological parameters comprise: ar flow is 55sccm, N 2 The flow is 20sccm, the pulse negative bias is 100V, the cavity air pressure is 2.0-2.5mTorr, the cavity temperature is 150 ℃, and the deposition time is 8min; and finally, adopting a Direct Current (DC) power supply and a high-power pulse magnetron sputtering technology (HiPIMS) to deposit a Cr-doped amorphous carbon layer, wherein the technological parameters comprise: ar flow is 55sccm, pulse negative bias is 200V, DC current is 3.0A, hiPIMS power is 100-300W, and deposition time is 30-50min.
Wherein, the targets used for the multi-target magnetron sputtering preferably comprise Cr targets and C targets with the purity of 99.99 percent.
Therefore, the technical scheme of the invention adopts a multi-target magnetron sputtering technology to form a Cr-doped amorphous carbon composite coating on the surface of the stainless steel substrate; the deposition process parameters are optimized by adopting the direct-current magnetron sputtering combined with the high-power pulse magnetron sputtering technology, and the Cr doping content can be precisely controlled, so that the adhesion chemical reaction of a coating and a polymer interface is inhibited, the friction running-in period is shortened, the friction coefficient is reduced, and the dry friction solid lubrication application has great potential.
On the basis, as an application, a third aspect of the embodiment of the invention also provides a friction fit pair, which comprises the friction structural member in any one of the above embodiments and a friction body in friction fit with the friction structural member; the friction body is made of polymer on the friction surface.
In some embodiments, the polymer may comprise, for example, any one or a combination of two or more of PEEK, PTFE, PI, PPS. But is not limited thereto.
In some embodiments, the friction fit is a dry friction fit.
In some embodiments, the break-in period of the friction fit is less than 30 minutes.
In some embodiments, the friction coefficient of the friction fit is below 0.2 after the running-in.
In a further application, as a fourth aspect of the embodiment of the present invention, there is also provided an application of the friction fit pair in any of the above embodiments in mechanical sealing. The coating structure provided by the invention is very suitable for the field of mechanical sealing with dynamic friction.
However, in the above embodiment, the invention adopts a multi-target magnetron sputtering device to prepare a Cr doped carbon-based coating, and positive ions generated by gas discharge bombard a target serving as a cathode under the action of an electric field, so that atoms (or molecules) in the target material escape and are deposited on the surface of a substrate to form a required coating; in the prior art, magnetic filtration vacuum cathode arc equipment is adopted, and ion plating is realized by utilizing arc discharge and evaporation as plating particle sources in a vacuum environment. The preparation method and the preparation principle are completely different.
In particular, the Cr-doped carbon-based coating in the embodiment of the invention is hydrogen-free high sp 2 The amorphous carbon coating with the content has high environmental adaptability and good lubricating performance; in the comparison document, the difference of the preparation principle leads to very high deionization rate, and the prepared carbon-based coating sp 3 The content is ultra-high, and the coating can be graphitized only by heating or metal catalysis, etc., so as to achieve the due technical effect.
And in terms of purposes, the invention aims at a system mainly comprising a carbon-based coating and a polymer pair, and the purposes of Cr doping modification are as follows: improving the lubricating property of the polymer-carbon-based coating auxiliary system, and mainly aiming at reducing the abrasion of the polymer; the comparison document is mainly aimed at protecting the surface of the metal material, so that the specific effect of chromium doping in the two materials is not the same.
The technical scheme of the invention is further described in detail below through a plurality of embodiments and with reference to the accompanying drawings. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a metal doped carbon-based composite coating/structural member and a preparation method thereof, and the specific steps are as follows:
(1) Firstly, adopting absolute ethanol and acetone to clean a stainless steel substrate, and placing the cleaned and dried substrate into a vacuum degree of less than 4 x 10- 5 Argon is introduced into the vacuum cavity of Torr, 35sccm is introduced, and when the pressure of the cavity is 1.8mTorr, 200V pulse negative bias is applied to the stainless steel substrate, and the etching time is 40min.
(2) Heating the cavity to 150 ℃, introducing argon gas of 55sccm, applying a pulse negative bias voltage of 100V and a current of 3.5A, and depositing a Cr layer for 4min; then, nitrogen gas is introduced for 20sccm, the bias voltage and the current are not changed, and the CrN layer is deposited for 4min.
(3) Closing an air valve to cool the cavity temperature to room temperature (in the invention, the room temperature is 15-30 ℃, the same is true), introducing argon gas of 55sccm, and applying pulse negative bias voltage of 200V; sputtering a Cr target by using HiPIMS technology, wherein the sputtering power is 100W; the C target was DC sputtered at a current of 3.0A for a deposition time of 50 minutes.
Through the steps, the 402.8nm composite coating is obtained on the surface of the stainless steel substrate, the Cr atomic percent content on the surface of the coating is 2.15at percent, the C atomic percent content is 86.24at percent, and the XRD full spectrum is shown in figure 1, so that the doping structure is proved.
Besides Cr and C elements, the film layer has a small amount of O (10.54 at.%) and N (1.07 at.%) elements on its surface. The N element is derived from nitrogen remained in the cavity in the coating preparation process, and the O element is derived from oxygen adsorbed on the surface of the coating when the coating is exposed to air. For example, oxygen is more electronegative than nitrogen and is also more reactive, and is more readily adsorbed on the surface in air and oxidized by the C bond in the coating. Therefore, the sum of the percentages of Cr and C elements is not equal to 100%.
The structural member is subjected to tribological test, in particular to a friction test with a polymer pair, and the friction test is specifically as follows: the PEEK balls with a diameter of 6mm were subjected to a finish-grinding for 120min under a dry friction condition with a load of 5N, a frequency of 2Hz and a distance of 5mm, and the result was shown in FIG. 2, wherein the friction coefficient was 0.12 and the running-in period was 30min.
Example 2
The embodiment provides a metal doped carbon-based composite coating/structural member and a preparation method thereof, and the specific steps are as follows:
(1) Firstly, adopting absolute ethanol and acetone to clean a stainless steel matrix, and placing the cleaned and dried matrix into a vacuum degree of less than 4 x 10 -5 Argon is introduced into the vacuum cavity of Torr, 35sccm is introduced, and when the pressure of the cavity is 1.8mTorr, 200V pulse negative bias is applied to the stainless steel substrate, and the etching time is 40min.
(2) Heating the cavity to 150 ℃, introducing argon gas of 55sccm, applying a pulse negative bias voltage of 100V and a current of 3.5A, and depositing a Cr layer for 4min; then, nitrogen gas is introduced for 20sccm, the bias voltage and the current are not changed, and the CrN layer is deposited for 4min.
(3) Closing an air valve, reducing the temperature of the cavity to room temperature, introducing argon gas of 55sccm, and applying a pulse negative bias voltage of 200V; sputtering a Cr target by using a HiPIMS technology, wherein the sputtering power is 200W; the C target was DC sputtered at a current of 3.0A for a deposition time of 50 minutes.
By the steps, the 417.5nm composite coating is obtained on the surface of the stainless steel substrate, the Cr atom percentage content on the surface of the coating is 3.73at percent, and the C atom percentage content is 80.14at percent.
The structural member is subjected to tribological test, in particular to a friction test with a polymer pair, and the friction test is specifically as follows: the PEEK ball with the diameter of 6mm is subjected to counter-grinding for 120min under the dry friction condition of 5N load and 2Hz frequency, the distance of 5mm, the friction coefficient is 0.2, and the grinding period is 80min.
Example 3
The embodiment provides a metal doped carbon-based composite coating/structural member and a preparation method thereof, and the specific steps are as follows:
(1) Firstly, adopting absolute ethanol and acetone to clean a stainless steel matrix, and placing the cleaned and dried matrix into a vacuum degree of less than 4 x 10 -5 Argon is introduced into the vacuum cavity of Torr, 35sccm is introduced, and when the pressure of the cavity is 1.8mTorr, 200V pulse negative bias is applied to the stainless steel substrate, and the etching time is 40min.
(2) Heating the cavity to 150 ℃, introducing argon gas of 55sccm, applying a pulse negative bias voltage of 100V and a current of 3.5A, and depositing a Cr layer for 4min; then, nitrogen gas is introduced for 20sccm, the bias voltage and the current are not changed, and the CrN layer is deposited for 4min.
(3) Closing an air valve, reducing the temperature of the cavity to room temperature, introducing argon gas of 55sccm, and applying a pulse negative bias voltage of 200V; sputtering a Cr target by using HiPIMS technology, wherein the sputtering power is 300W; the C target was DC sputtered at a current of 3.0A for a deposition time of 40min.
Through the steps, the 398.5nm composite coating is obtained on the surface of the stainless steel substrate, the Cr atom percentage content on the surface of the coating is 6.63at percent, and the C atom percentage content is 79.74at percent.
The structural member is subjected to tribological test, in particular to a friction test with a polymer pair, and the friction test is specifically as follows: the PEEK ball with the diameter of 6mm is subjected to counter-grinding for 120min under the dry friction condition of 5N load and 2Hz frequency and 5mm distance, the friction coefficient is 0.5, and the grinding period is 65min.
Example 4
The embodiment provides a metal doped carbon-based composite coating/structural member and a preparation method thereof, and the specific steps are as follows:
(1) Firstly, adopting absolute ethanol and acetone to clean a stainless steel matrix, and placing the cleaned and dried matrix into a vacuum degree of less than 4 x 10 -5 Argon is introduced into the vacuum cavity of Torr, 35sccm is introduced, and when the pressure of the cavity is 1.8mTorr, 200V pulse negative bias is applied to the stainless steel substrate, and the etching time is 40min.
(2) Heating the cavity to 150 ℃, introducing argon gas of 55sccm, applying a pulse negative bias voltage of 100V and a current of 3.5A, and depositing a Cr layer for 4min; then, nitrogen 20seem is introduced, the bias voltage and the current are not changed, and the CrN layer is deposited for 4min.
(3) Closing an air valve, reducing the temperature of the cavity to room temperature, introducing argon gas of 55sccm, and applying a pulse negative bias voltage of 200V; sputtering a Cr target by using HiPIMS technology, wherein the sputtering power is 400W; the C target was DC sputtered at a current of 3.0A for a deposition time of 30min.
Through the steps, the 410.5nm composite coating is obtained on the surface of the stainless steel substrate, the Cr atomic percent on the surface of the coating is 15.52at percent, and the C atomic percent is 70.85at percent.
The structural member is subjected to tribological test, in particular to a friction test with a polymer pair, and the friction test is specifically as follows: the PEEK ball with the diameter of 6mm is subjected to counter-grinding for 120min under the dry friction condition of 5N load and 2Hz frequency, the distance of 5mm, the friction coefficient is 0.38, and the grinding period is 35min.
Example 5
This example illustrates the running wear performance test of the composite coating/structure prepared in example 1 with other polymers, as follows:
the same method was used to perform a running-in test with a friction coefficient of 0.16 and a running-in period of 4 minutes, by replacing the PEEK ball having a diameter of 6mm in example 1 with a PTFE ball having the same size.
The PEEK ball of 6mm diameter in example 1 was replaced with a PI ball of the same size, and the running-in test was performed in the same manner, with a friction coefficient of 0.19 and a running-in period of 3min.
The PEEK ball having a diameter of 6mm in example 1 was replaced with a PSS ball of the same size, and a running-in test was performed by the same method, with a friction coefficient of 0.15 and a running-in period of 8min.
A graph of the friction test described above is shown in particular in fig. 3.
Still to be noted, the technical scheme provided by the invention is not only suitable for the selection range of the auxiliary materials in the examples shown in the embodiments, but also common polymers capable of generating self-adhesion chemical reaction can be suitable for the composite coating, and better technical effects are obtained compared with those before undoped.
Example 6
The present embodiment provides a metal-doped carbon-based composite coating/structural member and a method for preparing the same, which are substantially the same as those of embodiment 1, and are mainly different from those of step (2) and step (3), and specifically include the following steps:
(2) Heating the cavity to 130 ℃, introducing argon gas at 45sccm, applying a pulse negative bias voltage of 80V and a current of 3A, and depositing a Cr layer for 5min; then, 15sccm of nitrogen was introduced, and the CrN layer was deposited for 5min without changing the bias and current.
(3) Closing an air valve, reducing the temperature of the cavity to room temperature, introducing argon gas to 45sccm, and applying a pulse negative bias voltage of 180V; sputtering a Cr target by using HiPIMS technology, wherein the sputtering power is 100W; the C target was DC sputtered at a current of 2.5A for a deposition time of 50 minutes.
The friction structure member prepared in this example has the same level of running-in performance as in example 1, and has significantly reduced running-in time and friction coefficient compared to the undoped Cr film.
Example 7
The present embodiment provides a metal-doped carbon-based composite coating/structural member and a method for preparing the same, which are substantially the same as those of embodiment 1, and are mainly different from those of step (2) and step (3), and specifically include the following steps:
(2) Heating the cavity to 170 ℃, introducing argon gas of 65sccm, applying pulse negative bias voltage of 120V and current of 4A, and depositing a Cr layer for 10min; then, 25sccm of nitrogen was introduced, and the CrN layer was deposited for 10 minutes without changing the bias and current.
(3) Closing an air valve, reducing the temperature of the cavity to room temperature, introducing argon to 65sccm, and applying a pulse negative bias voltage of 220V; sputtering a Cr target by using HiPIMS technology, wherein the sputtering power is 400W; the C target was DC sputtered at a current of 3.5A for a deposition time of 30min.
The friction structure member prepared in this example has the same level of running-in performance as in example 1, and has significantly reduced running-in time and friction coefficient compared to the undoped Cr film.
Comparative example 1
The embodiment provides a pure carbon-based composite coating/structural member and a preparation method thereof, and the preparation method comprises the following specific steps:
(1) Firstly, adopting absolute ethanol and acetone to clean a stainless steel matrix, and placing the cleaned and dried matrix into a vacuum degree of less than 4 x 10 -5 Argon is introduced into the vacuum cavity of Torr, 35sccm is introduced, and when the pressure of the cavity is 1.8mTorr, 200V pulse negative bias is applied to the stainless steel substrate, and the etching time is 40min.
(2) Heating the cavity to 150 ℃, introducing argon gas of 55sccm, applying a pulse negative bias voltage of 100V and a current of 3.5A, and depositing a Cr layer for 4min; then, nitrogen gas is introduced for 20sccm, the bias voltage and the current are not changed, and the CrN layer is deposited for 4min.
(3) Closing an air valve, reducing the temperature of the cavity to room temperature, introducing argon gas of 55sccm, and applying a pulse negative bias voltage of 200V; the C target was DC sputtered at a current of 3.0A for a deposition time of 50 minutes.
Through the steps, the 447.9nm composite coating is obtained on the surface of the stainless steel substrate, and the Cr atomic percentage content on the surface of the coating is 0at percent.
The same test method is adopted to grind PEEK balls with the diameter of 6mm for 120min under the dry friction condition of 5N load, 2Hz frequency and 5mm distance, and the friction coefficient continuously oscillates and rises to 0.6 at 120 min.
Compared with the examples, the comparative example has high friction coefficient and long friction running-in period, which is mainly because the amorphous carbon coating which is not doped with metal has adhesion chemical reaction with the polymer, which is unfavorable for solid lubrication and stability of friction coefficient.
Comparative example 2
The embodiment provides a pure chromium composite coating/structural member and a preparation method thereof, and the preparation method comprises the following specific steps:
(1) Firstly, adopting absolute ethanol and acetone to clean a stainless steel matrix, and placing the cleaned and dried matrix into a vacuum degree of less than 4 x 10 -5 Argon is introduced into the vacuum cavity of Torr, 35sccm is introduced, and when the pressure of the cavity is 1.8mTorr, 200V pulse negative bias is applied to the stainless steel substrate, and the etching time is 40min.
(2) Heating the cavity to 150 ℃, introducing argon gas of 55sccm, applying a pulse negative bias voltage of 100V and a current of 3.5A, and depositing a Cr layer for 4min; then, nitrogen gas is introduced for 20sccm, the bias voltage and the current are not changed, and the CrN layer is deposited for 4min.
(3) Closing an air valve, reducing the temperature of the cavity to room temperature, introducing argon gas of 55sccm, and applying a pulse negative bias voltage of 200V; and sputtering a Cr target by adopting HIPIMS, wherein the sputtering power is 1800W, and the deposition time is 4min.
Through the steps, the 422.1nm composite coating is obtained on the surface of the stainless steel substrate, and the C atom percentage content of the surface of the coating is 0at percent.
The same test means is adopted, and the PEEK ball with the diameter of 6mm is subjected to counter-grinding for 120min under the dry friction condition of 5N load, 2Hz frequency and 5mm distance, wherein the friction coefficient is 0.7 in the first 60min and 0.73 in the last 60 min.
The coefficient of friction of this comparative example is very high compared to the examples, mainly due to the lack of solid lubricating phase of the pure metal coating and the severe abrasive wear that occurs when the polymer is rubbed against the mating surfaces.
Comparative example 3
The present embodiment provides a chromium doped composite coating/structural member and a method for producing the same, which are substantially the same as the embodiment, and differ mainly in that:
in the step (3), a direct current power supply (DCMS) is adopted to sputter the C target and the Cr target, and HiPIMS is not adopted to sputter the Cr target, and the carbon-based film with the same element composition ratio and the same thickness as those of the embodiment 1 is obtained by adjusting sputtering parameters.
The structural member obtained in this comparative example was subjected to surface morphology characterization, and the comparison with example 1 is sequentially shown in fig. 4a and 4b, and the surface compactness of the coating obtained in this comparative example was found to be poor. The method is characterized in that the ionization rate of the direct current power supply to the target material is low, high-ionization plasmas cannot be generated, the deposited transition layer columnar crystal size is large, the surface compactness is affected, and further the need of friction test on the transition layer columnar crystal is eliminated.
Comparative example 4
The present embodiment provides a chromium doped composite coating/structural member and a method for producing the same, which are substantially the same as the embodiment, and differ mainly in that:
in the step (2), only the Cr transition layer was sputtered or no transition layer was provided, and the sputtering parameters were adjusted to obtain a carbon-based thin film having the same element composition ratio and the same thickness as those of example 1.
The structural member obtained in this comparative example was subjected to a bonding force test, and the result of comparison with example 1 is shown in fig. 5, and it was found that the coating obtained in this example was poor in bonding. The main reason is that the hardness difference between the metal and the carbon-based coating is larger (the hardness of the amorphous carbon coating can reach 15-35 GPa), an eggshell effect is generated, the interface mismatch problem occurs, the coating is easy to damage, and the friction test is performed meaningless and related data are acquired.
Comparative example 5
The present embodiment provides a chromium doped composite coating/structural member and a method for producing the same, which are substantially the same as the embodiment, and differ mainly in that:
in step (3), a carbon-based coating is deposited using a magnetic filter cathodic arc, as described in detail below.
(3) Starting a pulse cathode arc evaporation device, setting pulse frequency to 10Hz, and evaporating the Cr-doped carbon-based film for 3min.
By the same test means, a PEEK ball having a diameter of 6mm was subjected to a pair of abrasion for 60 minutes under a dry abrasion condition of 5N under a frequency of 2Hz at a distance of 5mm, a friction coefficient of 0.6 and a friction run-in period of 8 minutes, it was noted that although the run-in period was short, it was caused by the fact that the larger friction coefficient which could be finally achieved by itself was not produced a gradual decrease in the friction coefficient similar to the run-in curve of example 1 by continuing to extend the run-in time, rather than representing that the run-in speed of this comparative example was more excellent.
The coefficient of friction of this comparative example is very high compared to the examples, mainly due to the higher sp of the evaporated carbon-based coating 3 The carbon bond content is not easy to form graphitized solid lubricating phase, the interaction synergistic effect of the chromium doping and the amorphous carbon layer cannot be generated, and serious fatigue abrasion can be generated when the carbon bond content and the polymer are rubbed.
Based on the above examples and comparative examples, it can be clarified that:
(1) According to the embodiment of the invention, the content of the doped metal element is optimized, the friction interface between the coating and the polymer is regulated and controlled, the proper Cr content can keep the excellent lubricity of the carbon-based coating, the formation process of the amorphous carbon graphitized friction film is not influenced, and meanwhile, the generation of adhesive chemical reactions of ROC, RO, RC, and other free radicals formed after the friction of the polymer surface and the amorphous carbon surface C can be inhibited, so that a metal-amorphous carbon lubrication interface is formed, the friction running-in period of a matched pair is shortened, the friction coefficient is reduced, and the potential of the matched pair applied to other fields is increased.
(2) The embodiment of the invention combines the high-power pulse magnetron sputtering and direct-current magnetron sputtering technologies, can deposit the coating with no gap and high density at low matrix temperature, has safe operating environment and simple and easily controlled process, and is beneficial to industrial production and application.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (10)
1. The friction structural member for matching with the polymer is characterized by comprising a matrix and a composite coating arranged on a friction surface of the matrix, wherein the composite coating comprises a transition layer and an amorphous carbon layer which are sequentially laminated along a direction far away from the matrix, and the amorphous carbon layer is doped with Cr.
2. A friction structure according to claim 1, wherein the amorphous carbon layer is formed of a hydrogen-free amorphous carbon material formed by mixing a diamond phase and a graphite phase;
preferably, the molar ratio of the diamond phase to the graphite phase in the amorphous carbon layer is 1:2-1:5;
and/or, the atomic percentage of Cr in the amorphous carbon layer is 2.15-15.52%.
3. A friction structure according to claim 1, wherein the composite coating has a thickness of 300-500nm;
and/or the thickness of the transition layer is 150-240nm;
preferably, the transition layer comprises a Cr layer and a CrN layer which are sequentially stacked along the direction far away from the substrate;
preferably, the thickness of the Cr layer is 80-120nm, and the thickness of the CrN layer is 80-120nm;
and/or the thickness of the amorphous carbon layer is 150-300nm.
4. A method of making a friction structure as claimed in any one of claims 1 to 3 comprising:
providing a substrate;
forming a transition layer on the friction surface of the substrate;
and forming an amorphous carbon layer on the surface of the transition layer, wherein the amorphous carbon layer is doped with Cr element.
5. The preparation method according to claim 4, which comprises the following steps:
sequentially depositing a Cr layer and a CrN layer on the surface of the substrate by adopting magnetron sputtering;
adopting a direct current magnetron sputtering C target material, and simultaneously adopting a pulse magnetron sputtering Cr target material to form the amorphous carbon layer on the surface of the CrN layer by codeposition;
preferably, the sputtering mode of the Cr layer and the CrN layer is selected from direct current magnetron sputtering;
preferably, before magnetron sputtering, the substrate is subjected to a cleaning treatment and an etching treatment.
6. The method according to claim 5, wherein the CrN layer is deposited by introducing a nitrogen source based on magnetron sputtering of the Cr layer;
preferably, the nitrogen source comprises nitrogen gas;
preferably, ar flow is 45-65sccm, pulse negative bias is 80-120V, cavity air pressure is 2.0-2.5mTorr, cavity temperature is 130-170 ℃, and deposition time is 5-10min;
preferably, the flow of N2 when depositing the CrN layer is 15-25sccm;
and/or Ar flow is 45-65sccm, pulse negative bias is 180-220V, direct current is 2.5-3.5A, pulse magnetron sputtering power is 100-400W, and deposition time is 30-50min.
7. A friction fit comprising the friction structure of any one of claims 1-3 and a friction body frictionally engaged with the friction structure;
the friction body is made of polymer on the friction surface.
8. A friction fit as set forth in claim 7 wherein said polymer comprises any one or a combination of two or more of PEEK, PTFE, PI, PPS;
preferably, the friction fit is a dry friction fit.
9. A friction fit according to claim 7, wherein the break-in period of the friction fit is below 30 minutes;
preferably, after running in, the friction coefficient of the friction fit pair is below 0.2.
10. Use of a friction fit as claimed in any one of claims 7 to 9 in the field of mechanical seals.
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