CN116288153A - Titanium/lanthanum co-doped diamond-like carbon coating and preparation method thereof - Google Patents
Titanium/lanthanum co-doped diamond-like carbon coating and preparation method thereof Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 86
- 239000010936 titanium Substances 0.000 title claims abstract description 70
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 42
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 39
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 39
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 238000000151 deposition Methods 0.000 claims abstract description 29
- 230000007704 transition Effects 0.000 claims abstract description 26
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000992 sputter etching Methods 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 7
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- 238000000861 blow drying Methods 0.000 claims description 3
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- 239000011195 cermet Substances 0.000 claims 1
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- 238000013461 design Methods 0.000 abstract description 7
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- 229910052727 yttrium Inorganic materials 0.000 description 4
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- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
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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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
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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
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Mechanical Engineering (AREA)
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- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to a titanium/lanthanum co-doped diamond-like coating and a preparation method thereof, wherein the diamond-like coating comprises a transition layer (2) and a gradient layer (3) on the surface of a substrate (1), the transition layer (2) adopts a TiN layer, and the gradient layer (3) adopts a gradient power titanium/lanthanum co-doped diamond-like layer; the gradient layer (3) comprises three gradient layers; the method comprises the steps of ion etching and cleaning of a substrate (1), deposition of a transition layer (2) and deposition of a gradient layer (3); the substrate (1) is pretreated before ion etching and cleaning of the substrate (1). Compared with the prior art, the diamond-like carbon coating has high hardness, low friction coefficient and good chemical inertness, and simultaneously shows lower internal stress, and the design of the transition layer and the gradient layer improves the film-based binding force, so that the cutter coated by the diamond-like carbon coating has excellent cutting life when cutting nonferrous metals.
Description
Technical Field
The invention belongs to the technical field of surface modification, and relates to a titanium/lanthanum co-doped diamond-like carbon coating and a preparation method thereof.
Background
With the continuous development of modern industry, the requirements on mechanical surface properties are gradually increased, and in order to adapt to different requirements of high strength, high hardness, wear resistance, high temperature resistance, corrosion resistance and the like, various surface treatment technologies are generally adopted to process the surface of the material, so that the material is suitable for various complex environments. Meanwhile, the development concepts of energy conservation, emission reduction, environmental protection and the like also put forward higher requirements on the design and application of materials. The surface modification of the metal material can prolong the service life of the parts, reduce abrasion and improve economic benefit. The surface coating technology is a material surface modification, and plays an important role in improving wear resistance, corrosion resistance, oxidation resistance and the like. Coating techniques can be generally classified into Chemical Vapor Deposition (CVD) and Physical Vapor Deposition (PVD), and CVD and PVD techniques have been widely used for surface treatment of tools since the 60s of the 20 th century, so that various aspects of the tool performance, particularly, life span, have been greatly improved. Meanwhile, the coating technology has wide application prospect in the aerospace field, intelligent manufacturing, novel composite materials and other aspects.
Diamond-like carbon (DLC) coatings are used as an amorphous carbon film in many fields such as machinery, electronics, optics, etc. because of their excellent tribological properties, high hardness, good chemical inertness, etc. At the same time, however, DLC coatings also have the disadvantage of higher internal stress, poorer film-based bonding forces, which limits their use in many applications.
Patent CN102925862a discloses a method for preparing a DLC coating doped with Ti, putting a pretreated substrate on a rotating rack rod of an arc and magnetron sputtering composite coating device, taking a cylindrical arc Ti target as a Ti source, taking a plane C target as a source of C, arranging three pairs of plane C targets on the inner wall of a furnace body in an evenly distributed manner, adopting high-purity Ar as main ionization gas, and ensuring an effective glow discharge process; adopts high-purity N 2 As a reaction gas, the reaction gas is ionized and combined with Ti and C elements, and then the reaction gas is formedAnd depositing a Ti-doped DLC coating on the surface of the body. Although the preparation method of Ti doped DLC is adopted in the patent, the dry friction coefficient of the coating is 0.2, the wear resistance and antifriction performance are weaker, and the internal stress of the coating is increased by the doping of Ti.
Patent CN110306153A discloses a preparation method of a Cr-doped DLC coating, fully utilizes the advantages of high smoothness, uniformity and compactness of a high-power pulse magnetron sputtering film, and adopts a bottom layer and transition layer design method for improving the defects of poor bonding force of the DLC coating and poor toughness of the film. The patent adopts gradient design, but the sputtering power difference of each gradient coating is larger, the thickness of the coating is 1.45 mu m, and the prepared diamond-like coating has larger internal stress.
Patent CN113913735a discloses a vanadium/yttrium co-doped DLC coating and a preparation method thereof, the preparation method comprising: first, depositing a Cr or Ti bottom layer on a substrate, then depositing a CrC or TiC transition layer on the surface of the bottom layer, and then depositing a vanadium-yttrium co-doped DLC coating on the surface of the transition layer by taking vanadium and yttrium as doped metal sources. Although the preparation method of the DLC coating with the co-doped vanadium/yttrium is adopted in the patent, the dry friction coefficient of the coating is 0.15, the wear resistance and the antifriction performance are weak, and the prepared coating has larger internal stress due to the fact that the charge density is smaller due to the yttrium doping.
Disclosure of Invention
The invention aims to overcome at least one defect in the prior art and provide a titanium/lanthanum co-doped diamond-like coating and a preparation method thereof, and the invention not only has the advantages of high hardness, low friction coefficient, good chemical inertness, low internal stress, and the design of a transition layer and a gradient layer improves the film-based binding force, and a cutter coated by the coating has excellent cutting life when cutting nonferrous metals.
The aim of the invention can be achieved by the following technical scheme:
the technical scheme of the invention is that the titanium/lanthanum co-doped diamond-like coating comprises a transition layer and a gradient layer on the surface of a substrate, wherein the transition layer adopts a TiN layer, the gradient layer adopts a gradient power titanium/lanthanum co-doped diamond-like carbon (DLC) layer, and the coating of TiN/(Ti, la) -DLC is finally formed by utilizing a radio frequency magnetron sputtering technology for deposition preparation.
Further, the thickness of the gradient layer is 3.2-3.5 mu m.
Further, the gradient layer comprises three gradient layering layers, and the thickness of each gradient layering layer is 1.0-1.2 mu m.
Further, the thickness of the transition layer is 0.1-0.3 mu m.
One of the technical schemes of the invention is to provide a preparation method of a titanium/lanthanum co-doped diamond-like carbon coating, which comprises the following steps:
s1, substrate ion etching cleaning: filling the substrate into a vacuum chamber, introducing ionized gas, cleaning the substrate, removing oxide skin on the surface of the substrate, and activating the surface of the substrate;
s2, depositing a transition layer: placing the cleaned substrate on a rotating frame clamp of a magnetron sputtering equipment cavity, introducing reaction gas, keeping the flux of ionized gas unchanged, opening a Ti target, taking the Ti target as one of Ti element sources, and depositing a transition layer;
s3, gradient layer deposition: after the deposition of the transition layer is completed, the reaction gas is closed, the flux of ionized gas is increased, the graphite target and the LaTi target are opened, the graphite target is used as a source of C element, the LaTi target is used as a doping source, the power of the graphite target is kept, and gradient layers are deposited in a multi-layer gradient mode with different LaTi target powers.
Further, the substrate pretreatment before the step S1 comprises the following steps: and (3) after degreasing and polishing the surface of the substrate, ultrasonically cleaning and finally drying.
Further, the ultrasonic cleaning is sequentially carried out in ethanol or acetone and water, the frequency is 30-40 kHz, and the time is 10-15 min;
the blow-drying gas is nitrogen or dry air.
Further, in the step S1, the matrix is hard alloy or metal ceramic;
the vacuum degree is 0.25-0.50 Pa, the ionized gas is argon, the glow discharge process is ensured, and the flow is 200-220 sccm;
the ionization voltage is 800-1100V, the substrate bias voltage is-1000-900V, and the cleaning time is 20-25 min.
Further, in the step S2, the rotating speed of the transfer frame is 5-10 r/min, so that the uniformity of the coating is ensured;
the air pressure is 0.5-0.6 Pa, the reaction gas is nitrogen, and the flow is 120-130 sccm;
the Ti target power is 100-110W, and the deposition time is 25-30 min.
Further, in step S3, the LaTi target is La 0.03 Ti 0.97 Target, la to Ti atomic ratio is 3:97;
the air pressure is 0.5-0.6 Pa, the ionized gas is argon, and the flow is 240-260 sccm;
the power of the graphite target is 120-125W;
the power of the first LaTi target is 20-25W, and the deposition time is 2.0-2.2 h;
the power of the second LaTi target is 40-45W, and the deposition time is 2.0-2.2 h;
the third LaTi target power is 60-65W, and the deposition time is 2.0-2.2 h.
The method adopts the design of a TiN transition layer and gradient La/Ti codoped DLC coating with different powers, so that the thermal expansion coefficient difference between the coating and a matrix and between each layer is reduced, thereby reducing the internal stress of the coating and improving the binding force of a film base.
After being doped with trace La element and Ti element, the crosslinking degree of the carbon network in the coating can be changed, and sp is inhibited 2 The formation of C bonds reduces the surface roughness of the coating, forming a very smooth surface.
The doped trace La element exists in a nanocrystalline form, internal stress caused by bond length and bond angle distortion is released through dislocation movement in the crystal, and meanwhile, a pinning effect is achieved on C atoms at the crystal boundary of the nanocrystalline, so that the internal stress is greatly reduced while the hardness of the coating is almost unchanged.
Compared with the prior art, the invention has the following advantages:
(1) The invention adopts the titanium/lanthanum co-doped diamond-like carbon coating, has high hardness, good chemical inertia and tribological property;
(2) The doping of rare earth lanthanum greatly reduces the residual internal stress of the coating;
(3) The invention adopts the design of the transition layer and the gradient layer, improves the binding force between the coating and the matrix, and ensures that the cutter has excellent cutting life when cutting nonferrous metals.
Drawings
FIG. 1 is a schematic diagram of a titanium/lanthanum co-doped diamond-like coating in accordance with an embodiment of the present invention;
FIG. 2 is a graph showing the internal stress test results of a titanium/lanthanum co-doped diamond-like coating according to an embodiment of the present invention;
FIG. 3 is a graph showing the hardness test results of titanium/lanthanum co-doped diamond-like coatings in accordance with embodiments of the present invention;
FIG. 4 is a graph showing the results of film-based bonding force test of a titanium/lanthanum co-doped diamond-like coating in an embodiment of the present invention;
FIG. 5 is a graph showing the results of the friction coefficient test of a titanium/lanthanum co-doped diamond-like coating in an embodiment of the present invention;
fig. 6 is a graph showing the cutting distance test results of the titanium/lanthanum co-doped diamond-like coating applied to a tool in an embodiment of the present invention.
The figure indicates:
1-matrix, 2-transition layer, 3-gradient layer.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
The equipment used in the following examples is representative of conventional equipment in the art unless otherwise specified; unless otherwise indicated, all reagents used are commercially available or prepared by methods conventional in the art, and all of the following examples, not specifically described, are accomplished by means of conventional experimentation in the art.
Examples:
a titanium/lanthanum co-doped diamond-like carbon coating is shown in figure 1, and comprises a TiN transition layer 2 and a gradient power titanium/lanthanum co-doped diamond-like carbon (DLC) gradient layer 3 which are TiN/(Ti, la) -DLC coatings deposited on the surface of a substrate 1 in sequence by adopting a radio frequency magnetron sputtering technology. Wherein the thickness of the transition layer 2 is 0.2 μm, the thickness of the gradient layer 3 is 3.3 μm, and the thickness of each gradient layer is 1.1 μm.
A preparation method of a titanium/lanthanum co-doped diamond-like carbon coating comprises the following specific steps:
(1) Pretreatment of a substrate 1: cemented carbide with the size of 25 multiplied by 4mm is taken as a substrate 1, the surface of the substrate 1 is degreased and polished, then is sequentially ultrasonically cleaned in ethanol (with the concentration of 95%) and deionized water for 10min at 30kHz, and finally is dried by using nitrogen (with the purity of 99.99%).
(2) Ion etching and cleaning of a substrate 1: filling a substrate 1 into a vacuum chamber, wherein the vacuum degree is 0.25Pa, introducing ionized gas argon (the purity is 99.99%), ensuring the glow discharge process, wherein the argon flow is 200sccm, the argon ion ionization voltage is 1000V, biasing the substrate 1 to 900V, cleaning the substrate 1, removing oxide skin on the surface of the substrate 1, activating the surface of the substrate 1, and lasting for 20min;
(3) Deposition of a transition layer 2: placing the surface-treated substrate 1 on a rotating frame fixture of a magnetron sputtering device cavity, rotating the whole rotating frame at 5r/min to ensure the uniformity of the coating, setting the air pressure in a furnace chamber to be 0.5Pa, introducing reaction gas nitrogen, the nitrogen flow to be 120sccm, keeping the argon flow unchanged, opening a Ti target (the purity is 99.9%), taking the cylindrical Ti target as one of Ti element sources, preparing a TiN layer with the Ti target power of 100W, and lasting for 25min;
(4) Gradient layer 3 deposition: after the preparation of the transition layer 2 is completed, closing nitrogen, increasing the flux of ionized gas, ensuring the air pressure in the furnace to be 0.5Pa with the argon flow of 240sccm, and opening a graphite target (purity is 99.99%) and La 0.03 Ti 0.97 Target (La to Ti atomic ratio is 3:97), cylindrical graphite target is used as source of C element, cylindrical La is used as source of C element 0.03 Ti 0.97 The target is used as a doping source, the power of the graphite target is kept to be 120W, la 0.03 Ti 0.97 Target power was maintained at 20W for a deposition time of 2.0h, la 0.03 Ti 0.97 Target power was maintained at 40W for a deposition time of 2.0h, la 0.03 Ti 0.97 The target power is 60W, the deposition time is 2.0h, and La/Ti codoped DLC coating is prepared by different LaTi target power multilayer gradients.
The internal stress test of the titanium/lanthanum co-doped diamond-like coating comprises the following specific steps:
the internal stress of the coating is calculated by a Stonely formula through a curvature method, and the calculation formula is as follows:
wherein: e (E) s For Young's modulus, v of the matrix 1 s Poisson's ratio, t, of the matrix 1 s For the thickness of the substrate 1, t c For the thickness of the coating, R 0 For the radius of curvature of the sample before coating, R is the radius of curvature of the sample after coating, and the radius of curvature of the sample before and after coating is measured by a surface profiler (FORM TALYSURF 200).
As shown in FIG. 2, the minimum internal stress of the coating can be 0.6GPa after three measurements and calculations, and the average internal stress of the coating is 0.7GPa.
The hardness test of the titanium/lanthanum co-doped diamond-like carbon coating comprises the following specific steps:
the hardness of the coating is obtained by a continuous stiffness test method (CSM), applying a certain pressure on the surface of a sample, releasing after a specified time, and obtaining the hardness of the coating by a Nano indentation instrument (MTS-Nano indicator II). The indentation load is set to be 15mN, the thermal drift rate is 0.05nm/s, the load holding time is 5s, and the maximum indentation depth is within 1/10 of the coating thickness to ensure the accuracy of the measurement result.
As shown in FIG. 3, the five times of measurement taken as an arithmetic average value, the coating hardness was finally measured to be 27.05GPa.
The film-based binding force test of the titanium/lanthanum co-doped diamond-like coating comprises the following specific steps:
the coated substrate was first fixed by scoring, and then passed through at a speed of 2mm/s using a scoring pin with a smooth conical tip, the scoring pin being perpendicular to the surface of the coating. The pressure is gradually increased on the scriber at 20N/min, the maximum pressure is 100N, the sliding distance is 4mm, so that the coating cracks, and the minimum applied acting force is the film base binding force of the coating.
As shown in FIG. 4, the maximum film-base bonding force of the coating layer measured by three tests can be 65N, and the average value is 61.67N.
The friction coefficient test of the titanium/lanthanum co-doped diamond-like carbon coating comprises the following specific steps:
a friction experiment machine (UMT-3) is adopted, zirconia ceramic beads with the diameter of 8mm are selected as a pair friction pair through a reciprocating friction experiment, the load is 10N, the reciprocating linear motion is 0.2m/s, the reciprocating motion amplitude is 10mm, and the friction condition is 40% of atmospheric humidity. During the experiment, the coating sample is fixed on a test bed, so that the friction pair reciprocates on the surface of the coating, the real-time friction force of the surface of the coating is measured by a sensor in a friction experiment machine, and the friction coefficient can be estimated by the ratio of the friction force to the positive pressure.
As shown in FIG. 5, the minimum coefficient of friction of the coating can reach 0.1 by three tests, and the average coefficient of friction is 0.12.
The titanium/lanthanum co-doped diamond-like carbon coating is applied to cutting distance test of a cutter, and comprises the following specific steps:
through cutting experiments, a VMC-100 II machine tool is used as a carrier, a 2A50 aluminum alloy is used as a cutting material, dry cutting is adopted, and the service life of the cutter is calculated by the length of the cutter passing through the surface of the aluminum alloy. The cutting parameters are as follows: feed amount a f 0.05mm, a shaft rotation speed n of 3980rev/min and a back cutting tool draft a p Is 2mm.
As shown in fig. 6, the cutting distance was found to be 210m by taking an average of three experiments.
Under the above technological conditions, the titanium/lanthanum co-doped diamond-like coating can be obtained. The titanium/lanthanum co-doped diamond-like carbon coating prepared by the method of the embodiment has smooth and compact surface, internal stress of 0.7GPa, coating hardness of 27.05GPa, film base binding force of 61.67N, friction coefficient of 0.12 when the friction pair is zirconia and cutting distance of 210m when 2A50 aluminum alloy is cut. The titanium/lanthanum co-doped diamond-like carbon coating has good wear resistance and antifriction performance, high hardness, low internal stress and higher film-based binding force.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The titanium/lanthanum co-doped diamond-like coating is characterized by comprising a transition layer (2) and a gradient layer (3) on the surface of a substrate (1), wherein the transition layer (2) adopts a TiN layer, and the gradient layer (3) adopts a gradient power titanium/lanthanum co-doped diamond-like layer.
2. A titanium/lanthanum co-doped diamond-like coating according to claim 1, wherein the gradient layer (3) has a thickness of 3.2-3.5 μm.
3. A titanium/lanthanum co-doped diamond-like coating according to claim 1, wherein the gradient layer (3) comprises three gradient layers, each gradient layer having a thickness of 1.0-1.2 μm.
4. A titanium/lanthanum co-doped diamond-like coating according to claim 1, wherein the thickness of the transition layer (2) is 0.1-0.3 μm.
5. A method of preparing a titanium/lanthanum co-doped diamond-like coating as claimed in any one of claims 1 to 4, comprising the steps of:
s1, ion etching and cleaning of a substrate (1): filling a substrate (1) into a vacuum chamber, introducing ionized gas, and cleaning the substrate (1);
s2, depositing a transition layer (2): placing the cleaned substrate (1) on a rotating frame clamp of a magnetron sputtering equipment cavity, introducing reaction gas, keeping the flux of ionized gas unchanged, opening a Ti target, and depositing a transition layer (2);
s3, depositing a gradient layer (3): and after the deposition of the transition layer (2), closing the reaction gas, increasing the flux of the ionized gas, opening the graphite target and the LaTi target, maintaining the power of the graphite target, and depositing the gradient layer (3) by using different LaTi target powers in a multilayer gradient manner.
6. The method for preparing a titanium/lanthanum co-doped diamond-like carbon coating according to claim 5, wherein the substrate (1) is pretreated before step S1, and the steps are as follows: after degreasing and polishing the surface of the substrate (1), ultrasonic cleaning and finally blow-drying.
7. The titanium/lanthanum co-doped diamond-like carbon coating according to claim 6, wherein the ultrasonic cleaning is performed in ethanol or acetone and water sequentially at a frequency of 30-40 kHz for 10-15 min;
the blow-drying gas is nitrogen or dry air.
8. The method for preparing a titanium/lanthanum co-doped diamond-like carbon coating according to claim 5, wherein in step S1, the substrate (1) is cemented carbide or cermet;
the vacuum degree is 0.25-0.50 Pa, the ionized gas is argon, and the flow is 200-220 sccm;
the ionization voltage is 800-1100V, the bias voltage of the substrate (1) is-1000-900V, and the cleaning time is 20-25 min.
9. The method for preparing a titanium/lanthanum co-doped diamond-like carbon coating according to claim 5, wherein the rotating speed of the rotating frame in the step S2 is 5-10 r/min;
the air pressure is 0.5-0.6 Pa, the reaction gas is nitrogen, and the flow is 120-130 sccm;
the Ti target power is 100-110W, and the deposition time is 25-30 min.
10. The method for preparing a titanium/lanthanum co-doped diamond-like carbon coating according to claim 5, wherein in step S3, the target LaTi is La 0.03 Ti 0.97 Target, la to Ti atomic ratio is 3:97;
the air pressure is 0.5-0.6 Pa, the ionized gas is argon, and the flow is 240-260 sccm;
the power of the graphite target is 120-125W;
the power of the first LaTi target is 20-25W, and the deposition time is 2.0-2.2 h;
the power of the second LaTi target is 40-45W, and the deposition time is 2.0-2.2 h;
the third LaTi target power is 60-65W, and the deposition time is 2.0-2.2 h.
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