CN108425089B - Chromium carbide composite film and preparation method thereof - Google Patents
Chromium carbide composite film and preparation method thereof Download PDFInfo
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- CN108425089B CN108425089B CN201710076828.9A CN201710076828A CN108425089B CN 108425089 B CN108425089 B CN 108425089B CN 201710076828 A CN201710076828 A CN 201710076828A CN 108425089 B CN108425089 B CN 108425089B
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- 229910003470 tongbaite Inorganic materials 0.000 title claims abstract description 334
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 title claims 69
- 230000001965 increasing effect Effects 0.000 claims abstract description 61
- 239000000758 substrate Substances 0.000 claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims description 84
- 239000002184 metal Substances 0.000 claims description 84
- 239000007789 gas Substances 0.000 claims description 74
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 70
- 239000011651 chromium Substances 0.000 claims description 66
- 229910052804 chromium Inorganic materials 0.000 claims description 65
- 238000007747 plating Methods 0.000 claims description 61
- UMUXBDSQTCDPJZ-UHFFFAOYSA-N chromium titanium Chemical compound [Ti].[Cr] UMUXBDSQTCDPJZ-UHFFFAOYSA-N 0.000 claims description 43
- 238000000576 coating method Methods 0.000 claims description 43
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 42
- 239000010936 titanium Substances 0.000 claims description 42
- 229910052719 titanium Inorganic materials 0.000 claims description 42
- 239000011248 coating agent Substances 0.000 claims description 41
- 230000007704 transition Effects 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 150000004767 nitrides Chemical class 0.000 claims description 20
- 239000012495 reaction gas Substances 0.000 claims description 16
- 239000013077 target material Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001771 vacuum deposition Methods 0.000 claims description 6
- GVEHJMMRQRRJPM-UHFFFAOYSA-N chromium(2+);methanidylidynechromium Chemical compound [Cr+2].[Cr]#[C-].[Cr]#[C-] GVEHJMMRQRRJPM-UHFFFAOYSA-N 0.000 abstract description 265
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 239000003086 colorant Substances 0.000 abstract description 7
- 230000007935 neutral effect Effects 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000007921 spray Substances 0.000 abstract description 6
- 238000002474 experimental method Methods 0.000 abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 230000008859 change Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000010849 ion bombardment Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 4
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 241001268993 Heterochrosis Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical compound [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C23C14/0635—Carbides
-
- 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
- C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
-
- 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
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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
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/345—Applying energy to the substrate during sputtering using substrate bias
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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
- C23C14/3464—Sputtering using more than one target
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a chromium carbide composite film and a preparation method thereof. The mass contents of carbon in the first chromium carbide layer, the second chromium carbide layer, the third chromium carbide layer and the fourth chromium carbide layer of the chromium carbide composite film layer are gradually increased from the surface of the substrate to the outside layer by layer, and the mass contents of carbon in each layer are gradually increased. The chromium carbide composite film has good overall glossiness and uniform color, the L value of the chromium carbide composite film is reduced to below 30, the color is relatively black, and the chromium carbide composite film is not easy to generate different colors when attached to the surface of a product. The rubber does not discolor and rust for 96 hours in neutral salt spray, can bear 350g for 500 times in an eraser wear-resisting experiment, and has better wear resistance and corrosion resistance.
Description
Technical Field
The invention relates to the technical field of film preparation, in particular to a chromium carbide composite film and a preparation method thereof.
Background
With the rise of the global intelligent industry and the gradual and popular development of wearable equipment, the performance experience and appearance requirements of the market on terminal equipment are continuously improved. The intelligent wearing becomes the mainstream in future electronic products, and with the market demand and the increasing perfection of the MIM (metal injection molding) process, the MIM process, especially the PVD process (physical deposition coating) therein, is gradually applied to the processing of the main structures of metal bracelets and watches.
The traditional coating material generally adopts two film layers of chromium carbide (CrC) and titanium carbide (TiC), wherein the overall tone and the glossiness of CrC are better than those of TiC, and the fingerprint resistance is better than that of TiC. However, the sputtering coefficient of chromium is large, so that the film is directly changed from a solid state to a gas state during sputtering, and the film deposition rate is high. The L value of the chromium carbide film layer is at least more than 40, the color is white, the color is easy to generate different colors when the chromium carbide film layer is attached to the surface of a product, Cr is a brittle material, and the residual stress of the film layer seriously affects the wear resistance and the corrosion resistance of the CrC layer prepared by adopting a film coating mode.
Disclosure of Invention
Therefore, a chromium carbide composite film with good wear resistance and corrosion resistance and a preparation method thereof are needed.
The utility model provides a chromium carbide composite film layer, plates on the surface of substrate, chromium carbide composite film layer outwards includes first chromium carbide layer, second chromium carbide layer, third chromium carbide layer and fourth chromium carbide layer in proper order from the substrate surface, first chromium carbide layer, second chromium carbide layer, third chromium carbide layer and the quality content successive layer of carbon in the fourth chromium carbide layer increases progressively, just the quality content of carbon in first chromium carbide layer, second chromium carbide layer, third chromium carbide layer and fourth chromium carbide layer each layer gradually increases progressively.
In one embodiment, the substrate further comprises a transition layer, wherein the transition layer comprises a metal titanium layer, a metal chromium layer, a titanium-chromium mixed layer and a titanium-chromium mixed nitride layer which are sequentially stacked, the metal titanium layer is in direct contact with the substrate, and the first chromium carbide layer is in direct contact with the titanium-chromium mixed nitride layer.
In one embodiment, a fifth chromium carbide layer, a sixth chromium carbide layer, a seventh chromium carbide layer, an eighth chromium carbide layer, and a ninth chromium carbide layer are further stacked on the fourth chromium carbide layer in sequence, the mass contents of carbon in the fourth chromium carbide layer, the fifth chromium carbide layer, the sixth chromium carbide layer, the seventh chromium carbide layer, the eighth chromium carbide layer, and the ninth chromium carbide layer sequentially increase from layer to layer, and the mass contents of carbon in the fifth chromium carbide layer, the sixth chromium carbide layer, the seventh chromium carbide layer, the eighth chromium carbide layer, and the ninth chromium carbide layer gradually increase.
In one embodiment, the first, second, third, and fourth chromium carbide layers each have a thickness of 40nm to 60nm, and the first chromium carbide layer contains 10% to 15% by mass of carbon, the second chromium carbide layer contains 15% to 20% by mass of carbon, the third chromium carbide layer contains 20% to 25% by mass of carbon, and the fourth chromium carbide layer contains 25% to 30% by mass of carbon.
The preparation method of the chromium carbide composite film comprises the following steps:
placing a substrate in a vacuum coating machine, and performing glow cleaning treatment on the surface of the substrate;
adopting a metal chromium target as a target material, controlling the coating bias voltage to be 80V-120V, controlling the target current to be 20A-30A, and introducing C at a first air flow rate2H2As a reaction gas, and gradually increasing the C at a first rate2H2To a second gas flow, thereby plating a first chromium carbide layer on the surface of the substrate;
at the first stageGradually increasing C at a second rate based on a second flow rate2H2To a third gas flow, the second rate being less than the first rate, thereby plating a second chromium carbide layer on a surface of the first chromium carbide layer;
gradually increasing the C at a third rate based on the third airflow2H2To a fourth gas flow rate, the third rate being less than the second rate, thereby plating a third chromium carbide layer on a surface of the second chromium carbide layer; and
gradually increasing C at a fourth rate based on the fourth airflow2H2To a fifth gas flow, the fourth rate being less than the third rate, thereby plating a fourth chromium carbide layer on a surface of the third chromium carbide layer to obtain the chromium carbide composite film layer.
In one embodiment, more than three metal chromium targets are arranged in the vacuum coating machine, at least two metal chromium targets operate simultaneously in the process of coating the chromium carbide composite film, and the substrate is placed in an area surrounded by the metal chromium targets.
In one embodiment, the first gas flow rate is 80sccm to 100sccm, the first rate is 8sccm to 12sccm, the second gas flow rate is 180sccm to 200sccm, the second rate is 6sccm to 10sccm, the third gas flow rate is 260sccm to 280sccm, the third rate is 4sccm to 8sccm/min, the fourth gas flow rate is 320sccm to 340sccm, the fourth rate is 3sccm to 6sccm/min, and the fifth gas flow rate is 370sccm to 390 sccm.
In one embodiment, the plating of the fourth chromium carbide layer on the surface of the third chromium carbide layer further comprises:
gradually increasing said C at a fifth rate based on said fifth airflow rate2H2To a sixth gas flow rate, the fifth rate being less than the fourth rate, thereby plating a fifth chromium carbide layer on a surface of the fourth chromium carbide layer;
gradually increasing said C at a sixth rate based on said sixth airflow2H2To a seventh air flow rate, the sixth rate being less than the fifth rate, thereby plating a sixth chromium carbide layer on a surface of the fifth chromium carbide layer;
gradually increasing said C at a seventh rate based on said seventh airflow rate2H2To an eighth gas flow, the seventh rate being less than the sixth rate, thereby plating a seventh chromium carbide layer on a surface of the sixth chromium carbide layer;
gradually increasing C at an eighth rate based on the eighth airflow2H2To a ninth gas flow, the eighth rate being less than the seventh rate, thereby plating an eighth chromium carbide layer on a surface of the seventh chromium carbide layer; and
gradually increasing the C at a ninth rate based on the ninth airflow2H2To a tenth air flow rate, the ninth rate being less than the eighth rate, thereby plating a ninth chromium carbide layer on a surface of the eighth chromium carbide layer.
In one embodiment, the fifth flow rate is 370sccm to 390sccm, the fifth rate is 3sccm/min to 5sccm/min, the sixth flow rate is 410sccm to 430sccm, the sixth rate is 2sccm to 4sccm/min, the seventh flow rate is 440sccm to 460sccm, the seventh rate is 1sccm to 3sccm/min, the eighth flow rate is 460sccm to 480sccm, the eighth rate is 0.5sccm to 1.5sccm/min, the ninth flow rate is 470sccm to 490sccm, the ninth rate is 0.25sccm to 0.75sccm/min, and the tenth flow rate is 480sccm to 500 sccm.
In one embodiment, the step of plating the first chromium carbide layer on the surface of the substrate further comprises plating a transition layer on the surface of the substrate, wherein the transition layer comprises a metal titanium layer, a metal chromium layer, a mixed titanium-chromium layer and a mixed titanium-chromium nitride layer which are sequentially stacked, and the step of plating the transition layer comprises:
adopting a metallic titanium target as a target material, controlling the coating bias voltage to be 250-350V, controlling the target current to be 60-100A, and introducing Ar as a reaction gas so as to coat a metallic titanium layer on the surface of the substrate;
adopting a metal chromium target as a target material, controlling the coating bias voltage to be 250-350V and the target current to be 60-100A, and introducing Ar as a reaction gas, thereby coating a metal chromium layer on the surface of the metal titanium layer;
adopting a metal titanium target and a metal chromium target as target materials, controlling the coating bias voltage of the metal titanium target and the coating bias voltage of the metal chromium target to be 110V-130V, controlling the target current to be 60A-100A, and introducing Ar as a reaction gas, thereby coating a titanium-chromium mixed layer on the surface of the metal chromium layer; and
adopting a metal titanium target and a metal chromium target as target materials, controlling the coating bias voltage of the metal titanium target and the coating bias voltage of the metal chromium target to be 110V-130V, controlling the target current to be 60A-100A, and introducing N2As a reaction gas, thereby plating a titanium-chromium mixed nitride layer on the surface of the titanium-chromium mixed layer.
The mass contents of carbon in the first chromium carbide layer, the second chromium carbide layer, the third chromium carbide layer and the fourth chromium carbide layer of the chromium carbide composite film layer are gradually increased from the surface of the substrate to the outside layer by layer, and the mass contents of carbon in each layer are gradually increased. The experimental result shows that the chromium carbide composite film has good overall glossiness and uniform color, the L value of the chromium carbide composite film is reduced to below 30, the color is relatively black, and the chromium carbide composite film is not easy to generate different colors when attached to the surface of a product. The rubber does not discolor and rust for 96 hours in neutral salt spray, can bear 350g for 500 times in an eraser wear-resisting experiment, and has better wear resistance and corrosion resistance.
Drawings
FIG. 1 is a schematic structural view of an embodiment of a chromium carbide composite film;
FIG. 2 is a schematic structural view of another embodiment of a chromium carbide composite film;
FIG. 3 is a schematic structural view of another embodiment of a chromium carbide composite film;
FIG. 4 is a flow chart of a method for preparing a chromium carbide composite film according to an embodiment;
FIG. 5 shows the process C for preparing a chromium carbide composite film layer in example 12H2A graph of airflow versus time;
FIG. 6 is a schematic view of the distribution of targets in a vacuum coater according to one embodiment.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Referring to fig. 1, a chromium carbide composite film 100 according to an embodiment is plated on a surface of a substrate 200, the chromium carbide composite film 100 includes a first chromium carbide layer 110, a second chromium carbide layer 120, a third chromium carbide layer 130, and a fourth chromium carbide layer 140 in sequence from the substrate surface to the outside, the mass contents of carbon in the first chromium carbide layer 110, the second chromium carbide layer 120, the third chromium carbide layer 130, and the fourth chromium carbide layer 140 sequentially increase from layer to layer, and the mass contents of carbon in the first chromium carbide layer 110, the second chromium carbide layer 120, the third chromium carbide layer 130, and the fourth chromium carbide layer 140 gradually increase from layer to layer.
The substrate 200 may be, for example, the housing of various types of terminals, such as a cell phone housing, a computer housing, the housing of a smart watch, and the like. The material of the substrate 200 may be metal or plastic, etc.
Specifically, the thicknesses of the first, second, third, and fourth chromium carbide layers 110, 120, 130, and 140 are all 40nm to 60 nm. The thicknesses of the first, second, third, and fourth chromium carbide layers 110, 120, 130, and 140 may be the same or different. The mass content of carbon in the first chromium carbide layer is 10-15%, the mass content of carbon in the second chromium carbide layer is 15-20%, the mass content of carbon in the third chromium carbide layer is 20-25%, and the mass content of carbon in the fourth chromium carbide layer is 25-30%.
Further, the mass content of carbon in each of the first chromium carbide layer 110, the second chromium carbide layer 120, the third chromium carbide layer 130, and the fourth chromium carbide layer 140 increases gradually at a constant rate, and the mass content of carbon changes uniformly.
In the present embodiment, the thicknesses of the first chromium carbide layer 110, the second chromium carbide layer 120, the third chromium carbide layer 130, and the fourth chromium carbide layer 140 are all 50nm, and tests show that the average mass contents of carbon in the first chromium carbide layer 110, the second chromium carbide layer 120, the third chromium carbide layer 130, and the fourth chromium carbide layer 140 are 10%, 15%, 20%, and 25% in this order.
It is understood that there may be no definite interfaces between the first, second, third and fourth chromium carbide layers 110, 120, 130, 140 within the chromium carbide composite film layer 100. The layers are named separately for ease of description only.
Referring to fig. 2, in one embodiment, a fifth chromium carbide layer 150, a sixth chromium carbide layer 160, a seventh chromium carbide layer 170, an eighth chromium carbide layer 180, and a ninth chromium carbide layer 190 are further sequentially stacked on the fourth chromium carbide layer 140. The mass contents of carbon in the fourth chromium carbide layer 140, the fifth chromium carbide layer 150, the sixth chromium carbide layer 160, the seventh chromium carbide layer 170, the eighth chromium carbide layer 180, and the ninth chromium carbide layer 190 sequentially increase gradually from layer to layer, and the mass contents of carbon in the fifth chromium carbide layer 150, the sixth chromium carbide layer 160, the seventh chromium carbide layer 170, the eighth chromium carbide layer 180, and the ninth chromium carbide layer 190 gradually increase gradually. The chromium carbide composite film layer 100 consisting of the chromium carbide layers added by the multi-layer carbon content assembly has good overall glossiness and very uniform color.
Referring to fig. 3, in one embodiment, the chromium carbide composite film 100 further includes a transition layer 10, the transition layer 10 includes a metal titanium layer 11, a metal chromium layer 12, a titanium chromium mixed layer 13, and a titanium chromium mixed nitride layer 14, which are sequentially stacked, the metal titanium layer 11 directly contacts the substrate 200, and the first chromium carbide layer 110 directly contacts the titanium chromium mixed nitride layer 14. The transition layer 10 is arranged on the substrate 200, and the metal titanium layer 11 has strong adhesive force and is easy to be formed by sputtering coating, so that the chromium carbide composite film layer 100 can be coated on various types of substrates 200, and the application range is wide. The titanium layer 11, the chromium layer 12, the mixed titanium-chromium layer 13, and the mixed titanium-chromium nitride layer 14 are sequentially stacked, and gradually transition from the titanium-containing material layer to the chromium-containing material layer to the mixed chromium layer and the mixed titanium-chromium nitride layer, so that the change of each layer is gentle, the first chromium carbide layer 110 directly contacts with the mixed titanium-chromium nitride layer 14, and the overall glossiness is good.
Specifically, the thickness of the titanium metal layer 11 is 1nm to 2 nm. The thickness of the metallic chromium layer 12 is 1nm to 2 nm. The thickness of the titanium-chromium mixed layer 13 is 5nm to 10 nm. The thickness of the titanium chromium mixed nitride layer 14 is 10nm to 20 nm.
The mass contents of carbon in the first chromium carbide layer 110, the second chromium carbide layer 120, the third chromium carbide layer 130 and the fourth chromium carbide layer 140 of the chromium carbide composite film layer 10 are gradually increased from the surface of the substrate 200 to the outside, and the mass contents of carbon in each layer are gradually increased. Compared with the traditional chromium carbide layer, the whole glossiness is good, the color is very uniform, the L value of the chromium carbide composite film layer is reduced to below 30, and the color is not easy to generate heterochrosis when the chromium carbide composite film layer is attached to the surface of a product. The rubber does not discolor and rust for 96 hours in neutral salt spray, can bear 350g for 500 times in an eraser wear-resisting experiment, and has better wear resistance and corrosion resistance.
Referring to fig. 4, the preparation method of the chromium carbide composite film includes the following steps S110 to S150.
S110, placing the substrate in a vacuum coating machine, and glow cleaning the surface of the substrate.
The substrate may be, for example, the housing of various types of terminals, such as a cell phone housing, a computer housing, the housing of a smart watch, and the like.
Specifically, the substrate may be subjected to degreasing treatment, spraying treatment, dewaxing treatment, spraying treatment, acid washing treatment, pure water treatment, slow lifting treatment, baking treatment, and the like in advance in sequence, so that the surface of the substrate is clean, and the adhesion of the plated film layer is strong.
After the substrate is placed in a vacuum coating machine, the surface of the substrate is treated by glow cleaningAnd (3) enhancing the surface activity of the substrate. The degree of vacuum of the coating film may be 3.0-1～5.0-1Pa, e.g. 4.0-1Pa。
S120, adopting a metal chromium target as a target material, controlling the coating bias voltage to be 80V-120V and the target current to be 20A-30A, and introducing C at a first air flow rate2H2As a reaction gas, and gradually increasing C at a first rate2H2To a second gas flow rate, thereby plating a first chromium carbide layer on the surface of the substrate obtained in S110.
Specifically, the purity of the metal chromium target is 99.9%, and the metal chromium target is sputtered under the coating conditions that the coating bias voltage is 80V-120V and the target current is 20A-30A to form a uniform first chromium carbide layer.
Specifically, the first gas flow rate is 80sccm to 100sccm, such as 80sccm, 85sccm, 90sccm, 95sccm, or 100 sccm. The first rate is 8sccm/min to 12sccm/min, i.e. increasing C gradually at a rate of 8sccm to 12sccm every 1min2H2To a second airflow rate. The second flow rate can be between 180sccm and 200sccm, such as 180sccm, 185sccm, 190sccm, 195sccm, or 200sccm, and so on.
Specifically, C2H2The gas flow rate is increased at a constant speed from the first gas flow rate to the second gas flow rate, so that the mass content of carbon in the first chromium carbide layer is gradually increased.
S130, gradually increasing C at a second speed on the basis of the second air flow2H2To a third air flow rate, the second rate being less than the first rate, thereby plating a second chromium carbide layer on the surface of the first chromium carbide layer obtained in S120.
Specifically, the metal chromium target used for plating the second chromium carbide layer is the same as the metal chromium target used for plating the first chromium carbide layer.
Specifically, the second flow rate can be 180sccm to 200sccm, such as 180sccm, 185sccm, 190sccm, 195sccm, or 200sccm, etc. The second rate is 6 sccm/min-10 sccm/min, i.e. gradually increasing C at a rate of 6 sccm-10 sccm every 1min2H2To a third airflow rate. First, theThe three gas flow rate can be 260sccm to 280sccm, such as 260sccm, 265sccm, 270sccm, 275sccm, or 280sccm, and so on. The second rate is less than the first rate, based on the second amount of airflow, C2H2The gas flow is larger, and the increasing speed (second speed) is relatively smaller on the basis, so that the transition between the second chromium carbide layer and the first chromium carbide layer is mild, and the influence of glossiness and the like caused by too fast change of the carbon content is eliminated.
Specifically, C2H2The gas flow rate is increased at a constant speed from the second gas flow rate to the third gas flow rate, so that the mass content of carbon in the second chromium carbide layer is gradually increased.
S140, gradually increasing C at a third speed on the basis of the third air flow2H2To a fourth gas flow rate, the third rate being less than the second rate, thereby plating a third chromium carbide layer on the surface of the second chromium carbide layer obtained in S130.
Specifically, the metallic chromium target used for plating the third chromium carbide layer is the same as the metallic chromium target used for plating the first chromium carbide layer.
Specifically, the third flow rate can be 260sccm to 280sccm, such as 260sccm, 265sccm, 270sccm, 275sccm, or 280sccm, and so on. The third rate is 4 sccm/min-8 sccm/min, i.e. gradually increasing C at a rate of increasing 4 sccm-8 ccm every 1min2H2Until a fourth airflow is reached. The fourth gas flow rate can be 320sccm to 340sccm, such as 320sccm, 325sccm, 330sccm, 335sccm, or 340sccm, and so on. A third rate less than the second rate, based on a third amount of airflow, C2H2The gas flow is larger, the increasing speed (third speed) is relatively smaller than the second speed, so that the transition between the third chromium carbide layer and the second chromium carbide layer is mild, and the influence of the glossiness and the like caused by too fast change of the carbon content is eliminated.
Specifically, C2H2The gas flow rate is increased at a constant speed from the third gas flow rate to the fourth gas flow rate, so that the mass content of carbon in the third chromium carbide layer is gradually increased.
S150, gradually increasing C at a fourth rate on the basis of the fourth air flow2H2To a fifth gas flow, and the fourth rate is lower than the third rate, so that a fourth chromium carbide layer is plated on the surface of the third chromium carbide layer obtained in S140, to obtain a chromium carbide composite film layer.
Specifically, the metallic chromium target used for plating the fourth chromium carbide layer is the same as the metallic chromium target used for plating the first chromium carbide layer.
Specifically, the fourth gas flow rate can be 320sccm to 340sccm, such as 320sccm, 325sccm, 330sccm, 335sccm, or 340sccm, and so on. The fourth rate is 3 sccm/min-6 sccm/min, i.e. gradually increasing C at a rate of increasing 3 sccm-6 ccm every 1min2H2To a fifth airflow. The fifth flow rate can be 370sccm to 390sccm, such as 370sccm, 375sccm, 380sccm, 385sccm, or 390sccm, and so on. The fourth rate is less than the third rate, based on the third amount of airflow, C2H2The gas flow is larger, the increasing speed (fourth speed) is relatively smaller than the third speed, so that the transition between the fourth chromium carbide layer and the third chromium carbide layer is mild, and the influence of the glossiness and the like caused by too fast change of the carbon content is eliminated.
Specifically, C2H2The gas flow rate is increased at a constant speed from the fourth gas flow rate to the fifth gas flow rate, so that the mass content of carbon in the fourth chromium carbide layer is gradually increased.
The chromium carbide composite film prepared by the method is adjusted by at least four times of different rates, and C is gradually increased2H2The mass content of carbon in the first chromium carbide layer, the second chromium carbide layer, the third chromium carbide layer and the fourth chromium carbide layer gradually increases from the surface of the substrate to the outside through the gas flow, and the mass content of carbon in each layer gradually increases, so that the change is uniform, and the generation of different colors is difficult when the composite film is attached to the surface of a product.
The thicknesses of the first chromium carbide layer, the second chromium carbide layer, the third chromium carbide layer and the fourth chromium carbide layer are controlled by controlling the coating time. In one embodiment, the first, second, third and fourth chromium carbide layers are all 50nm thick, as tested, the first carbonThe average carbon content in the chromium carbide layer, the second chromium carbide layer, the third chromium carbide layer and the fourth chromium carbide layer is 10%, 15%, 20% and 25% in sequence. Can be adjusted by C2H2The first, second, third and fourth chromium carbide layers of different carbon contents are obtained from the starting gas flow.
In one embodiment, the step of applying a fourth chromium carbide layer to the surface of the third chromium carbide layer further comprises gradually increasing C at a fifth rate based on a fifth amount of airflow2H2To a sixth gas flow rate, the fifth rate being less than the fourth rate, thereby plating a fifth chromium carbide layer on the surface of the fourth chromium carbide layer. Then gradually increasing C at a sixth rate based on a sixth airflow2H2To a seventh air flow rate, the sixth rate being less than the fifth rate, thereby plating a sixth chromium carbide layer on the surface of the fifth chromium carbide layer. Gradually increasing C at a seventh rate based on a seventh airflow2H2To an eighth gas flow rate, the seventh rate being less than the sixth rate, thereby plating a seventh chromium carbide layer on the surface of the sixth chromium carbide layer. Increasing C gradually at eighth rate based on eighth airflow2H2To a ninth air flow rate, the eighth rate being less than the seventh rate, thereby plating an eighth chromium carbide layer on a surface of the seventh chromium carbide layer. And gradually increasing C at a ninth rate based on the ninth amount of airflow2H2Is less than the eighth rate, thereby plating a ninth chromium carbide layer on the surface of the eighth chromium carbide layer. Gradually increasing C by adjusting different rates for a plurality of times2H2The mass contents of carbon in the fifth chromium carbide layer, the sixth chromium carbide layer, the seventh chromium carbide layer and the eighth chromium carbide layer gradually increase from the surface of the substrate to the outside through the gas flow, and the mass contents of carbon in each layer gradually increase, so that the change is uniform, and the generation of different colors is difficult when the composite film is attached to the surface of a product.
Specifically, the fifth flow rate is 370sccm to 390sccm, and the fifth rate is 3sccm/min to 5 sccm/min. The sixth gas flow rate is 410 sccm-430 sccm, and the sixth rate is 2 sccm/min-4 sccm/min. The seventh flow rate is 440sccm to 460sccm, and the seventh rate is 1sccm/min to 3 sccm/min. The eighth flow rate is 460sccm to 480sccm, and the eighth rate is 0.5sccm/min to 1.5 sccm/min. The ninth flow rate is 470sccm to 490sccm, and the ninth rate is 0.25sccm/min to 0.75 sccm/min. The tenth gas flow rate is 480sccm to 500 sccm.
In this embodiment, C2H2Referring to FIG. 5, the first flow rate is 90sccm, the first rate is 10sccm/min, the second flow rate is 190sccm, the second rate is 8sccm/min, the third flow rate is 270sccm, the third rate is 6sccm/min, the fourth flow rate is 330sccm, the fourth rate is 5sccm/min, and the fifth flow rate is 380 sccm. The fifth flow rate was 380sccm and the fifth rate was 4 sccm/min. The sixth gas flow rate is 4200sccm, and the sixth rate is 3 sccm/min. The seventh flow rate is 450sccm and the seventh rate is 2 sccm/min. The eighth flow rate is 480sccm and the eighth rate is 1 sccm/min. The ninth flow rate is 480sccm and the ninth rate is 0.5 sccm/min. The tenth gas flow rate was 490 sccm. The flow rate is gradually increased according to a certain slope, the mass content of carbon in each layer is gradually increased, and the change is uniform.
Specifically, more than three metal chromium targets are arranged in the vacuum coating machine, at least two metal chromium targets operate simultaneously in the process of coating the chromium carbide composite film, and the substrate is arranged in the area defined by the metal chromium targets, so that the chromium carbide sputtered on the substrate is more uniform.
In one embodiment, after the glow cleaning process is performed on the surface of the substrate, the method further comprises plating a transition layer on the surface of the substrate, wherein the transition layer comprises a metal titanium layer, a metal chromium layer, a titanium chromium mixed layer and a titanium chromium mixed nitride layer which are sequentially stacked, and the step of plating the transition layer comprises the following steps: a metallic titanium target is used as a target material, the coating bias voltage is controlled to be 250V-350V, the target current is controlled to be 60A-100A, Ar is introduced to be used as reaction gas, and therefore a metallic titanium layer is coated on the surface of the substrate. Adopting a chromium metal target as a target material, controlling the coating bias voltage to be 250-350V, controlling the target current to be 60-100A, and introducing Ar as a reaction gas, thereby coating a chromium metal layer on the surface of the titanium metal layer. MiningUsing a metal titanium target and a metal chromium target as target materials, controlling the coating bias voltage of the metal titanium target and the coating bias voltage of the metal chromium target to be 110V-130V, controlling the target current to be 60A-100A, and introducing Ar as a reaction gas, so as to coat a titanium-chromium mixed layer on the surface of the metal chromium layer; and adopting a metal titanium target and a metal chromium target as target materials, controlling the coating bias voltage of the metal titanium target and the coating bias voltage of the metal chromium target to be 110V-130V, controlling the target current to be 60A-100A, and introducing N2As a reaction gas, a titanium-chromium mixed nitride layer is plated on the surface of the titanium-chromium mixed layer.
Specifically, the metal chromium target used in plating the transition layer is different from the metal chromium target used in plating the first chromium carbide layer. The target voltage, current and other parameters during plating can be conveniently adjusted.
The transition layer is plated on the substrate in advance, the metal titanium layer has strong adhesive force and is easy to be formed by sputtering coating, so that the chromium carbide composite film layer can be plated on various substrates of different types, and the application range is wide. And the metal titanium layer, the metal chromium layer, the titanium-chromium mixed layer and the titanium-chromium mixed nitride layer are sequentially laminated, the titanium-containing material layer is gradually transited to the chromium-containing material layer and then to the chromium mixed layer and the titanium-chromium mixed nitride layer, the change of each layer is mild, the first chromium carbide layer is directly contacted with the titanium-chromium mixed nitride layer, and the overall glossiness is good.
The preparation method of the chromium carbide composite film layer gradually increases C through at least four times of adjustment of different rates2H2The mass content of carbon in the first chromium carbide layer, the second chromium carbide layer, the third chromium carbide layer and the fourth chromium carbide layer gradually increases from the surface of the substrate to the outside through the gas flow, and the mass content of carbon in each layer gradually increases, so that the change is uniform, and the generation of different colors is difficult when the composite film is attached to the surface of a product. Experimental results show that the chromium carbide composite film prepared by the method is good in overall glossiness and very uniform in color, the L value of the chromium carbide composite film is reduced to be below 30, and different colors are not easy to generate when the chromium carbide composite film is attached to the surface of a product. The rubber does not discolor and rust for 96 hours in neutral salt spray, can bear 350g for 500 times in an eraser wear-resisting experiment, and has better wear resistance and corrosion resistance.
The following are specific examples.
The following examples are experimental methods in which specific conditions are not specified, and general conditions are generally followed. In the following examples, the vacuum coater was an SP1912AS coater, and the target distribution was as shown in fig. 6. Metal chromium targets are placed at the positions of the cylindrical targets, and the included angle of 3 cylindrical targets is 120 degrees. Wherein, metal titanium targets are arranged at the positions of 4 multi-arc targets on one side, and metal chromium targets are arranged at the positions of 4 multi-arc targets on the other side.
Example 1
(1) Glow cleaning the surface of a substrate
Firstly, the substrate is placed in the center of a film coating machine, and is vacuumized by a vacuumizing process until the vacuum degree is 5.0 multiplied by 10- 2Heating is started at Pa. After keeping the temperature at 250 ℃ for 15 minutes, the temperature is reduced to 150 ℃. Vacuum pumping to 5.0 × 10-3Pa starts the glow wash. Argon gas of 2000sccm was fed according to the process parameter table. The coating bias is gradually increased from 200V to 700V in an increasing mode, and the duty ratio is 50%. Turning on a bias power supply and starting, timing for 8 minutes, observing whether the furnace is bright or not, and turning off argon after the process is finished. The bias duty cycle is zeroed, and the bias is stopped and turned off.
(2) Plating the transition layer
After glow cleaning, the display vacuum degree of the ionization gauge (H) unit is higher than 5.0X 10-3Introducing argon gas at Pa, and adjusting the flow rate of the argon gas to ensure that the vacuum degree is 3.0 multiplied by 10-1Pa, filling argon to the vacuum degree of 0.3-1Pa. And 4 multi-arc titanium targets on the left vacuum chamber are subjected to ion bombardment simultaneously, the bias voltage is 300v, the duty ratio is 65%, the target current is 80A, the bombardment time is 30s, and a metal titanium layer is plated on the surface of the substrate. The vacuum degree is maintained at 0.3-1Pa is unchanged, 4 multi-arc chromium targets on the vacuum chamber on the right side are subjected to ion bombardment simultaneously, the bias voltage is 300v, the duty ratio is 65%, the target current is 80A, and the bombardment time is 30 s. And plating a metal chromium layer on the surface of the metal titanium layer. The vacuum degree is maintained at 0.3-1Pa is unchanged, 8 multi-arc targets on the left and right vacuum chambers are subjected to ion bombardment simultaneously, the bias voltage is 200v, the duty ratio is 50 percent, the target current is 80A, the bombardment time is 120s, and the vacuum degree is kept at 0.3-1Pa is not changed, and more than 8 vacuum chambers on the left and right sidesAnd (3) carrying out ion bombardment on the arc targets simultaneously, wherein the bias voltage is 120v, the duty ratio is 50%, the target current is 80A, and the bombardment time is 180 s. And plating a titanium-chromium mixed layer on the surface of the metal chromium layer. Filling argon to the vacuum degree of 4.0-1Without changing, the N at 700sccm is flushed2And simultaneously carrying out ion bombardment on 8 multi-arc targets on the left and right vacuum chambers, wherein the bias voltage is 120v, the duty ratio is 50%, the target current is 80A, and the bombardment time is 240s, so that the titanium-chromium mixed nitride layer is plated on the surface of the titanium-chromium mixed layer.
(3) Plating chromium carbide composite film layer
Vacuum degree is maintained at 4.0-1Pa is unchanged, four arc target power supplies are closed, 3 pairs of cylindrical targets are uniformly opened, the bias voltage is 100V, the duty ratio is 50 percent, the cylindrical target current is 25A, and C of 90sccm is charged2H2Air entrainment was performed in a ramp fashion with 10sccm every 60s until 190sccm was added. Time 600s, bias 100V duty cycle 50%, cylindrical target current 22A, to plate the first chromium carbide layer on the titanium chromium mixed nitride layer.
Vacuum degree is maintained at 4.0-1Pa unchanged, C2H2And adding 8sccm for every 60s on the basis of the previous step in a slope manner until 270sccm is added and the time is 600 s. A bias of 100V, a duty cycle of 50%, a cylindrical target current 22A, to plate a second chromium carbide layer on the surface of the first chromium carbide layer.
Vacuum degree is maintained at 4.0-1Pa unchanged, C2H2And (3) continuously adding 6sccm to gas in a slope manner every 60s on the basis of the previous step until 330sccm is added, the time is 600s, the bias voltage is 100V, the duty ratio is 50%, and the cylindrical target current is 22A, so that a third chromium carbide layer is plated on the surface of the second chromium carbide layer.
Vacuum degree is maintained at 4.0-1Pa unchanged, C2H2And (3) continuously adding 5sccm to gas in a slope manner every 60s on the basis of the previous step until 380sccm is added, the time is 600s, the bias voltage is 100V, the duty ratio is 50%, and the cylindrical target current is 22A. Thereby plating a fourth chromium carbide layer on the surface of the third chromium carbide layer.
Vacuum degree is maintained at 4.0-1Pa unchanged, C2H2On the basis of the previous step with a slopeThe gas filling is continued to add 4sccm every 60s until 420sccm is added, the time is 600s, the bias voltage is 100V, the duty ratio is 50%, and the cylindrical target current is 22A. Thereby plating a fifth chromium carbide layer on the surface of the fourth chromium carbide layer.
Vacuum degree is maintained at 4.0-1Pa unchanged, C2H2And (3) sccm is added to gas filling for every 60s in a slope mode on the basis of the previous step until 450sccm is added, the time is 600s, the bias voltage is 80V, the duty ratio is 30%, and the cylindrical target current is 22A. Thereby plating a sixth chromium carbide layer on the surface of the fifth chromium carbide layer.
Vacuum degree is maintained at 4.0-1Pa unchanged, C2H2And (3) continuously adding 2sccm for every 60s in a slope mode on the basis of the previous step until 470sccm is added, the time is 600s, the bias voltage is 80V, the duty ratio is 30%, and the cylindrical target current is 22A. Thereby plating a seventh chromium carbide layer on the surface of the sixth chromium carbide layer.
Vacuum degree is maintained at 4.0-1Pa unchanged, C2H2And continuing to add 1sccm for every 60s in a slope manner on the basis of the previous step until 480sccm is added, the time is 600s, the bias voltage is 80V, the duty ratio is 30 percent, and the cylindrical target current is 22A, so that the eighth chromium carbide layer is plated on the surface of the seventh chromium carbide layer.
Vacuum degree is maintained at 4.0-1Pa unchanged, C2H2And continuously adding 1sccm to gas in a slope manner every 120s on the basis of the previous step until 490sccm is added, the time is 1200s, the bias voltage is 80V, the duty ratio is 30 percent, and the cylindrical target current is 22A, so that the ninth chromium carbide layer is plated on the surface of the eighth chromium carbide layer. And (4) closing the cylindrical target power supply/bias power supply/Ar and the like in sequence, and discharging when the furnace temperature is reduced to 80 ℃. Plating a chromium carbide composite film layer on the surface of the substrate. Wherein in the coating process C2H2Please refer to fig. 5. Tests show that the average mass content of carbon in the first chromium carbide layer, the second chromium carbide layer, the third chromium carbide layer and the fourth chromium carbide layer is 10%, 15%, 20% and 25% in sequence.
The preparation methods of the chromium carbide composite film layers of the following embodiments 2 to 5 are similar to those of embodiment 1, except that the parameters of the coating film are adjusted, and are specifically shown in the following table 1. "/" indicates that the plating process is finished without introducing gas, for example, after plating a fourth chromium carbide layer on the surface of the third chromium carbide layer.
Table 1: coating parameters of examples 1 to 5
Example 6
In this embodiment, after the surface of the substrate was glow-cleaned, the surface of the substrate was directly plated with the chromium carbide composite film. The remaining coating process was the same as in example 1.
Example 7
In this embodiment, after the titanium-chromium mixed nitride layer is plated on the surface of the titanium-chromium mixed layer, and before the chromium carbide composite film layer is plated, an intermediate transition layer is plated. The method comprises the following steps: the vacuum degree is kept unchanged, and N is closed2And 8 arc targets, 3 pairs of cylindrical targets are switched on simultaneously, the target current is 25A, the bias voltage is 200A, and the time is 300SDuty ratio of 50% to plate a metallic chromium layer on the surface of the titanium chromium mixed nitride layer.
Vacuum degree is maintained at 4.0-1Constant charging of 100sccm C2H2Gas filling is carried out in a slope mode, 10sccm is added every 60s until 200sccm is added, the time is 600s, and the duty cycle of the target current 25A of the bias voltage 120V is 50%. Vacuum degree is maintained at 4.0-1And (4) continuously adding 7sccm to gas in a slope mode on the basis of the previous step until the gas is added to 270sccm, the time is 600s, the bias voltage is 120V, the duty ratio is 50%, and the target current is 25A. Vacuum degree is maintained at 4.0-1Invariable, C2H2The flux of the metal chromium layer is kept to be 270sccm, the plating is continuously carried out for 600s, the duty ratio is 50 percent under the condition of 120V, and the target current is 25A, so that the chromium carbide layer is plated on the surface of the metal chromium layer.
The degree of hollowness is kept at 4.0-1Unchanged, close C2H2All things in one stateClosing 3 pairs of cylindrical target power supplies, opening 4 multi-arc chromium targets on the left vacuum chamber to continuously bombard for 180s, biasing for 120V, duty ratio for 50 percent, arc target current for 80A, time: 180s, thereby plating a metallic chromium layer on the surface of the chromium carbide layer. And then plating a first chromium carbide layer to a ninth chromium carbide layer on the metal chromium layer, wherein the plating parameters are the same as those in the embodiment 1. In the embodiment, the intermediate transition layer is added, so that the overall glossiness of the chromium carbide composite film layer is further improved.
Example 8
In this embodiment, a chromium target is used as the target material, the coating bias is controlled to be 100V, the target current is controlled to be 25A, and C is introduced at a constant gas flow of 420sccm2H2As a reaction gas, thereby plating a chromium carbide layer on the surface of the substrate.
Performance test one
50 pieces of the substrates coated with the film layers prepared in examples 1 to 8 were taken, wiped back and forth with an eraser under a pressure of 350g over the coated substrate, and the average number of times that the substrates could withstand was counted. The average data are shown in table 2:
table 2: data for abrasion resistance test of films of examples 1 to 8
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Number of times | 590 | 570 | 580 | 530 | 500 | 510 | 600 | 200 |
As can be seen from Table 2, the carbon content of the chromium carbide composite film layer which is gradually increased layer by layer can bear 350g for at least 500 times in the rubber wear resistance test. The wear resistance of the chromium carbide composite film layer is far higher than that of the chromium carbide composite film layer for 200 times in example 8.
Performance test 2
100 substrates coated with the film layers prepared in examples 1 to 8 were placed in neutral salt spray for testing, and the number of hours after which rust began was counted and observed every 4 hours. The average data are shown in Table 3.
Table 3: data for testing corrosion resistance of films of examples 1 to 8
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Rusting time (h) | 104 | 100 | 96 | 104 | 100 | 96 | 108 | 72 |
As can be seen from table 3, the chromium carbide composite film layer in which the mass content of carbon is gradually increased layer by layer has rusting for at least 96 hours in neutral salt spray. The corrosion resistance of the chromium carbide composite film layer is better than that of the chromium carbide composite film layer in 72 hours in example 8.
Performance test three
The L value, a value and b value of the film layer were measured using a color difference meter using 100 film-coated substrates prepared in each of examples 1 and 8, and the average data is shown in table 4.
Table 4: gloss test data for film layers of examples 1 and 8
| Parameter(s) | L | a | b | Gloss | △L | △a | △b | △E |
| Example 1 | 29.08 | -0.12 | -0.59 | 3.10 | <2.29 | <0.25 | <0.60 | <2.36 |
| Example 8 | 40 | -0.10 | -0.49 | 2.10 | <3.15 | <0.5 | <0.7 | <3.26 |
As can be seen from table 3, the chromium carbide composite film layer prepared in example 1, in which the carbon content is gradually increased layer by layer, has an L value of 29.08, which is much smaller than that of example 8. The L value is smaller, and the color is darker. The total color difference Δ E was smaller than that of example 8, and color difference was not easily generated when the color difference Δ E was attached to the surface of the product.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A chromium carbide composite film layer coated on the surface of a substrate is characterized in that the chromium carbide composite film layer sequentially comprises a first chromium carbide layer, a second chromium carbide layer, a third chromium carbide layer and a fourth chromium carbide layer from the surface of the substrate to the outside, the mass contents of carbon in the first chromium carbide layer, the second chromium carbide layer, the third chromium carbide layer and the fourth chromium carbide layer are sequentially increased layer by layer, and the mass contents of carbon in the first chromium carbide layer, the second chromium carbide layer, the third chromium carbide layer and the fourth chromium carbide layer are gradually increased, wherein the thicknesses of the first chromium carbide layer, the second chromium carbide layer, the third chromium carbide layer and the fourth chromium carbide layer are all 40-60 nm, the mass content of carbon in the first chromium carbide layer is 10-15%, the mass content of carbon in the second chromium carbide layer is 15-20%, the mass content of carbon in the third chromium carbide layer is 20-25%, and the mass content of carbon in the fourth chromium carbide layer is 25-30%;
the composite chromium carbide layer further comprises a transition layer, wherein the transition layer comprises a metal titanium layer, a metal chromium layer, a titanium-chromium mixed layer and a titanium-chromium mixed nitride layer which are sequentially stacked, the metal titanium layer is in direct contact with the substrate, the first chromium carbide layer is in direct contact with the titanium-chromium mixed nitride layer, the thickness of the metal titanium layer is 1 nm-2 nm, the thickness of the metal chromium layer is 1 nm-2 nm, the thickness of the titanium-chromium mixed layer is 5 nm-10 nm, and the thickness of the titanium-chromium mixed nitride layer is 10 nm-20 nm.
2. The chromium carbide composite film according to claim 1, wherein a fifth chromium carbide layer, a sixth chromium carbide layer, a seventh chromium carbide layer, an eighth chromium carbide layer and a ninth chromium carbide layer are further sequentially stacked on the fourth chromium carbide layer, the mass contents of carbon in the fourth chromium carbide layer, the fifth chromium carbide layer, the sixth chromium carbide layer, the seventh chromium carbide layer, the eighth chromium carbide layer and the ninth chromium carbide layer sequentially increase from layer to layer, and the mass contents of carbon in the fifth chromium carbide layer, the sixth chromium carbide layer, the seventh chromium carbide layer, the eighth chromium carbide layer and the ninth chromium carbide layer gradually increase from layer to layer.
3. The preparation method of the chromium carbide composite film according to any one of claims 1 to 2, comprising the steps of:
placing a substrate in a vacuum coating machine, and performing glow cleaning treatment on the surface of the substrate;
plating a transition layer on the surface of the substrate, wherein the transition layer comprises a metal titanium layer, a metal chromium layer, a titanium-chromium mixed layer and a titanium-chromium mixed nitride layer which are sequentially stacked;
adopting a metal chromium target as a target material, controlling the coating bias voltage to be 80V-120V, controlling the target current to be 20A-30A, and introducing C at a first air flow rate2H2As a reaction gas, and gradually increasing the C at a first rate2H2To a second gas flow, thereby plating a first chromium carbide layer on the surface of the substrate;
gradually increasing C at a second rate based on the second airflow2H2To a third gas flow, the second rate being less than the first rate, thereby plating a second chromium carbide layer on a surface of the first chromium carbide layer;
gradually increasing the C at a third rate based on the third airflow2H2To a fourth gas flow rate, the third rate being less than the second rate, thereby plating a third chromium carbide layer on a surface of the second chromium carbide layer; and
gradually increasing C at a fourth rate based on the fourth airflow2H2To a fifth gas flow, the fourth rate being less than the third rate, thereby plating a fourth chromium carbide layer on a surface of the third chromium carbide layer to obtain the chromium carbide composite film layer.
4. The method for preparing a chromium carbide composite film according to claim 3, wherein three or more of the chromium metal targets are provided in the vacuum coater, at least two of the chromium metal targets are simultaneously operated during the process of coating the chromium carbide composite film, and the substrate is placed in an area surrounded by the chromium metal targets.
5. The method for preparing a chromium carbide composite film according to claim 3, wherein the first gas flow rate is 80sccm to 100sccm, the first rate is 8sccm to 12sccm/min, the second gas flow rate is 180sccm to 200sccm, the second rate is 6sccm to 10sccm/min, the third gas flow rate is 260sccm to 280sccm, the third rate is 4sccm to 8sccm/min, the fourth gas flow rate is 320sccm to 340sccm, the fourth rate is 3sccm to 6sccm/min, and the fifth gas flow rate is 370sccm to 390 sccm.
6. The method for preparing a chromium carbide composite film according to claim 3, wherein the step of plating a fourth chromium carbide layer on the surface of the third chromium carbide layer further comprises:
gradually increasing said C at a fifth rate based on said fifth airflow rate2H2To a sixth air flow rate, the fifth rate being less than the fourth rate, thereby to be at the third ratePlating a fifth chromium carbide layer on the surface of the four chromium carbide layers;
gradually increasing said C at a sixth rate based on said sixth airflow2H2To a seventh air flow rate, the sixth rate being less than the fifth rate, thereby plating a sixth chromium carbide layer on a surface of the fifth chromium carbide layer;
gradually increasing said C at a seventh rate based on said seventh airflow rate2H2To an eighth gas flow, the seventh rate being less than the sixth rate, thereby plating a seventh chromium carbide layer on a surface of the sixth chromium carbide layer;
gradually increasing C at an eighth rate based on the eighth airflow2H2To a ninth gas flow, the eighth rate being less than the seventh rate, thereby plating an eighth chromium carbide layer on a surface of the seventh chromium carbide layer; and
gradually increasing the C at a ninth rate based on the ninth airflow2H2To a tenth air flow rate, the ninth rate being less than the eighth rate, thereby plating a ninth chromium carbide layer on a surface of the eighth chromium carbide layer.
7. The method for preparing a chromium carbide composite film according to claim 6, wherein the fifth gas flow is 370sccm to 390sccm, the fifth rate is 3sccm to 5sccm/min, the sixth gas flow is 410sccm to 430sccm, the sixth rate is 2sccm to 4sccm/min, the seventh gas flow is 440sccm to 460sccm, the seventh rate is 1sccm to 3sccm/min, the eighth gas flow is 460sccm to 480sccm, the eighth rate is 0.5sccm to 1.5sccm/min, the ninth rate is 470sccm to 490sccm, the ninth rate is 0.25sccm to 0.75sccm/min, and the tenth gas flow is 480sccm to 500 sccm.
8. The method of claim 3, wherein the step of plating the transition layer comprises:
adopting a metallic titanium target as a target material, controlling the coating bias voltage to be 250-350V, controlling the target current to be 60-100A, and introducing Ar as a reaction gas so as to coat a metallic titanium layer on the surface of the substrate;
adopting a metal chromium target as a target material, controlling the coating bias voltage to be 250-350V and the target current to be 60-100A, and introducing Ar as a reaction gas, thereby coating a metal chromium layer on the surface of the metal titanium layer;
adopting a metal titanium target and a metal chromium target as target materials, controlling the coating bias voltage of the metal titanium target and the coating bias voltage of the metal chromium target to be 110V-130V, controlling the target current to be 60A-100A, and introducing Ar as a reaction gas, thereby coating a titanium-chromium mixed layer on the surface of the metal chromium layer; and
adopting a metal titanium target and a metal chromium target as target materials, controlling the coating bias voltage of the metal titanium target and the coating bias voltage of the metal chromium target to be 110V-130V, controlling the target current to be 60A-100A, and introducing N2As a reaction gas, thereby plating a titanium-chromium mixed nitride layer on the surface of the titanium-chromium mixed layer.
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