CN114657503B - Coating material, preparation method thereof and electronic product shell - Google Patents

Coating material, preparation method thereof and electronic product shell Download PDF

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Publication number
CN114657503B
CN114657503B CN202011529041.1A CN202011529041A CN114657503B CN 114657503 B CN114657503 B CN 114657503B CN 202011529041 A CN202011529041 A CN 202011529041A CN 114657503 B CN114657503 B CN 114657503B
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layer
color
coating material
transition
thickness
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CN114657503A (en
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许金宝
禹跃斌
刘晨岑
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BYD Co Ltd
Shaoguan BYD Electronics Co Ltd
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BYD Co Ltd
Shaoguan BYD Electronics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • 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
    • C23C14/0635—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
    • C23C14/22—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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K5/00—Casings, cabinets or drawers for electric apparatus
    • H05K5/04—Metal casings

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

A coating material, a preparation method thereof and an electronic product shell. The application relates to a coating material, which comprises a base material and a film layer positioned on the surface of the base material, wherein the film layer comprises a basic layer, a transition layer and a color layer which are sequentially laminated, the basic layer is positioned on the surface of the base material, and the basic layer comprises an X1 element; the transition layer comprises X2, si, Y1 and C elements; the color layer comprises Ti, si, Y2 and C elements, and the molar ratio of the Ti, the Si, the Y2 to the C is 5: (1-3): (1-3): (10-18); wherein the X1 element comprises Cr and/or Ti element, the X2 element comprises Cr and/or Ti element, the Y1 comprises at least one of Zr, W and Nb, and the Y2 comprises at least one of Zr, W and Nb. The film layer of the coating material can show uniform blue effect, and has good wear resistance and corrosion resistance.

Description

Coating material, preparation method thereof and electronic product shell
Technical Field
The application relates to the field of coating, in particular to a coating material, a preparation method thereof and an electronic product shell.
Background
Because the competition of electronic products is increasingly strong, consumers have higher requirements on quality and appearance, and the blue film prepared by adopting a physical vapor deposition method can lead the products to obtain appearance surfaces with more metallic luster, and have more excellent wear resistance and the like.
The prior art has a method for preparing a blue decorative film on the surface of a metal substrate by utilizing a TiAlN film layer, but the method has higher requirement on the film forming time of a color layer and has general process stability; the TiAlN film layer has limited wear resistance and corrosion resistance, and has difficulty in meeting the requirements of the surface performance of the decorative film; in addition, when the shape of the substrate is complex, uneven color and color are likely to occur at the position of abrupt shape change.
Disclosure of Invention
The application aims to overcome the problems in the prior art and provide a coating material, a preparation method thereof and an electronic product shell.
The first aspect of the application provides a coating material, which comprises a substrate and a film layer positioned on the surface of the substrate, wherein the film layer comprises a basic layer, a transition layer and a color layer which are sequentially laminated, the basic layer is positioned on the surface of the substrate, and the basic layer comprises an X1 element; the transition layer comprises X2, si, Y1 and C elements; the color layer comprises Ti, si, Y2 and C elements, and the molar ratio of the Ti, the Si, the Y2 to the C is 5: (1-3): (1-3): (10-18); wherein the X1 element comprises Cr and/or Ti element, the X2 element comprises Cr and/or Ti element, the Y1 comprises at least one of Zr, W and Nb, and the Y2 comprises at least one of Zr, W and Nb.
Preferably, the base layer comprises Cr and Ti elements, and the molar ratio of Ti to Cr is 2: (1-5).
Preferably, the molar ratio of X2, si, Y1 to C in the transition layer is 3: (1-2): (1-2): (6-12).
Preferably, the color layer further contains Cr element, wherein the molar ratio of Ti, cr, si, Y2 to C is 5: (1-2): (1-3): (1-3): (10-18).
Preferably, the thickness of the basic layer is 100-1000nm, the thickness of the transition layer is 300-3000nm, and the thickness of the color layer is 100-1000nm.
Preferably, the thickness of the base layer is 200-500nm, the thickness of the transition layer is 500-1500nm, and the thickness of the color layer is 100-500nm.
Preferably, the substrate comprises at least one of metal, ceramic, glass and plastic.
Preferably, the color value range of the film layer is: l is 30-50, a is-1 to-10, and b is-1 to-18.
In a second aspect, the present application provides a method for preparing a coating material as described above, which includes sequentially depositing a base layer, a transition layer, and a color layer on a surface of the substrate.
A third aspect of the present application provides an electronic product housing, including the foregoing coating material.
The coating material provided by the application comprises a substrate and a film layer positioned on the surface of the substrate, wherein the film layer comprises a basic layer, a transition layer and a color layer which are sequentially laminated, the transition layer and the color layer contain at least one element of Zr, W and Nb, so that the wear resistance and corrosion resistance of the film layer are improved, and the film layer can also show a blue effect; in addition, ti, si and C elements in the color layer can ensure that the film layer presents a uniform blue effect. The base layer, the transition layer and the color layer cooperate to enable the film layer on the surface of the base material to show a uniform blue effect, and the wear-resistant and corrosion-resistant performances are good.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The application provides a coating material, which comprises a substrate and a film layer positioned on the surface of the substrate, wherein the film layer comprises a basic layer, a transition layer and a color layer which are sequentially laminated, the basic layer is positioned on the surface of the substrate, and the basic layer comprises an X1 element; the transition layer comprises X2, si, Y1 and C elements; the color layer comprises Ti, si, Y2 and C elements, and the molar ratio of the Ti, the Si, the Y2 to the C is 5: (1-3): (1-3): (10-18); wherein the X1 element comprises Cr and/or Ti element, the X2 element comprises Cr and/or Ti element, the Y1 comprises at least one of Zr, W and Nb, and the Y2 comprises at least one of Zr, W and Nb.
The coating material provided by the application comprises a substrate and a film layer positioned on the surface of the substrate, wherein the film layer comprises a basic layer, a transition layer and a color layer which are sequentially laminated, the transition layer and the color layer contain at least one element of Zr, W and Nb, so that the wear resistance and corrosion resistance of the film layer are improved, and the film layer can also show a blue effect; in addition, ti, si and C elements in the color layer can ensure that the film layer presents a uniform blue effect. The base layer, the transition layer and the color layer cooperate to enable the film layer on the surface of the base material to show a uniform blue effect, and the wear-resistant and corrosion-resistant performances are good.
In some embodiments, the X1 element in the base layer may be the same or different from the X2 element in the transition layer, e.g., when the X1 element in the base layer selects Cr element, the X2 element in the transition layer may select Cr and/or Ti element. Preferably, the X1 element in the base layer is selected to be the same as the X2 element in the transition layer, for example, when the X1 element in the base layer is selected to be Cr element, the X2 element in the transition layer is selected to be Cr element.
In some embodiments, the Y1 element in the transition layer may be the same or different from the Y2 element in the color layer, e.g., when the Y1 element in the transition layer selects Zr element, the Y2 element in the color layer may select at least one of Zr, W, and Nb. Preferably, the Y1 element in the transition layer is selected to be the same as the Y2 element in the color layer, for example, when the Y1 element in the transition layer is selected to be Zr element, the Y2 element in the color layer is selected to be Zr element.
The base layer of the present application can improve adhesion between the film layer and the substrate, and in some embodiments, the base layer includes Cr and/or Ti elements. Specifically, the base layer may be a Cr layer or a Ti layer or a CrTi layer. In the case where the base layer includes Cr and Ti elements, in order to further increase the adhesion between the film layer and the substrate, the molar ratio of Ti to Cr is 2: (1-5).
In some embodiments, the transition layer comprises X2, si, Y1, and C elements, wherein the X2 element comprises Cr and/or Ti element and the Y1 comprises at least one of Zr, W, and Nb. The transition layer has good adhesive force with the base layer, can reach color transition with the color layer, and presents even blue effect. In order to further improve the transition effect, preferably, the molar ratio of X2, si, Y1 to C in the transition layer is 3: (1-2): (1-2): (6-12). Preferably, Y1 is one of Zr, W and Nb in view of cost reduction and process simplicity.
Specifically, the transition layer may be one of a CrSiZrC layer, a CrSiWC layer, a CrSiNbC layer, a tiszrc layer, a TiSiWC layer, a tisimbc layer, a crtiszrc layer, a crtisimbc layer, a crsizrbc layer, a CrSiZrWNbC layer, a tiszrbc layer, a tiszrnbc layer, a tiszrwnbc layer, a crtiszrbc layer, and a crtiszrwnbc layer. In view of cost reduction and process simplicity, the transition layer is preferably one of a CrSiZrC layer, a CrSiWC layer, a CrSiNbC layer, a tiszrc layer, a TiSiWC layer, a tisimbc layer, a crtiszrc layer, a CrTiSiWC layer, and a crtisimbc layer.
In some embodiments, the color layer includes Ti, si, Y2, and C elements, the molar ratio of Ti, si, Y2 to C being 5: (1-3): (1-3): (10-18), wherein the Y2 comprises at least one of Zr, W and Nb. The Ti, si and C elements in the color layer regulate and control the color of the product, so that the color change range of the product is smaller, the process stability is improved, the color regulation difficulty is reduced, and the color uniformity is improved; zr or W or Nb element in the color layer improves the surface abrasion resistance and corrosion resistance of the product, and prolongs the service life of the product. The molar ratio of Ti, si, Y2 and C in the color layer is controlled at 5: (1-3): (1-3): in the range of (10-18), the final product can show uniform blue effect, and has good wear resistance and corrosion resistance.
In some embodiments, cr element may be further included in the color layer to further increase adhesion between film layers. Preferably, the molar ratio of Ti, cr, si, Y2 to C in the color layer is 5: (1-2): (1-3): (1-3): (10-18).
In some embodiments, it is preferable that the Y2 is one of Zr, W, and Nb, based on cost reduction and process simplicity.
Specifically, the color layer may be one of a TiSiZrC layer, a TiSiWC layer, a TiSiNbC layer, a tisizrbc layer, a TiSiZrNbC layer, a TiSiZrWNbC layer, a TiCrSiZrC layer, a TiCrSiWC layer, a TiCrSiNbC layer, a ticrsizrbc layer, a TiCrSiZrNbC layer, and a TiCrSiZrWNbC layer. The color layer may preferably be one of tisiczrc layer, tisicwc layer, tisicb layer, tiCrSiZrC layer, tiCrSiWC layer, and TiCrSiNbC layer in view of cost reduction and process simplicity.
In some embodiments, to further promote the synergistic effect of the base layer, the transition layer and the color layer, the film layer on the surface of the substrate can exhibit a uniform blue effect, and has good wear and corrosion resistance, the thickness of the base layer is 100-1000nm, the thickness of the transition layer is 300-3000nm, and the thickness of the color layer is 100-1000nm. From the viewpoint of cost reduction, it is preferable that the thickness of the base layer is 200 to 500nm, the thickness of the transition layer is 500 to 1500nm, and the thickness of the color layer is 100 to 500nm.
In some embodiments, the substrate can be a variety of materials, preferably the substrate comprises at least one of metal, ceramic, glass, and plastic.
In some embodiments, the color value range of the film layer of the coating material is: the L value is 30-50, the a value is-1 to-10, the b value is-1 to-18, and the blue effect is shown.
The application also provides a preparation method of the coating material, which comprises the step of sequentially depositing a base layer, a transition layer and a color layer on the surface of the base material.
In some embodiments, the deposition mode adopts a magnetron sputtering mode for deposition, and the film layer prepared by the magnetron sputtering has better binding force, wear resistance and corrosion resistance, namely, the preparation method of the film coating material sequentially comprises the following steps:
s1, performing deposition of a base layer on the surface of a substrate by adopting magnetron sputtering;
s2, performing deposition transition layer on the surface of the base layer by adopting magnetron sputtering;
and S3, performing deposition of a color layer on the surface of the transition layer by adopting magnetron sputtering.
In one embodiment, the preparation method of the coating material sequentially comprises the following steps:
(1) Ion source bombardment cleaning of the substrate: placing a substrate in a vacuum furnace, vacuumizing, filling argon into a machine table, opening a rotating frame, opening an ion source after gas is stabilized, and performing ion cleaning on the surface of the substrate and the surface of a target;
(2) Argon is introduced into the vacuum furnace, a sputtering power supply of an X1 target (one or two of a Cr target and a Ti target) is started, a base layer is deposited on the surface of a substrate, and the thickness of the base layer is preferably in the range of 100-1000 nm;
(3) Acetylene and argon are introduced, a sputtering power supply of an X2 target (one or two of a Cr target and a Ti target), a Si target and a Y1 target (at least one of a Zr target, a W target and a Nb target) is started, a transition layer is deposited on the surface of the base layer, and the thickness of the transition layer is preferably in the range of 300-3000 nm;
(4) Acetylene and argon are introduced, a sputtering power supply of a Ti target, a Si target and a Y2 target (at least one of a Zr target, a W target and a Nb target) is started, a color layer is deposited on the surface of the transition layer, and the thickness of the color layer is preferably in the range of 100-1000 nm;
(5) Argon is introduced into the vacuum furnace, and the vacuum furnace is cooled to below 50 ℃ and discharged, so as to obtain the coating material.
In some embodiments, to further better deposit a film layer on the surface of the substrate, the surface of the substrate may be pretreated before depositing the film layer on the surface of the substrate, to remove dirt on the surface of the substrate, for example, the wax removal and oil removal treatments may be sequentially performed.
A third aspect of the present application provides an electronic product housing, including the foregoing coating material.
The present application will be described in detail by way of examples, but the present application is not limited to the following examples.
Example 1
The substrate used in this example was a stainless steel watch case,
(1) Placing the substrate in wax-removing water at 50 ℃ for ultrasonic cleaning for 5 minutes, then soaking in oil-removing water at 50 ℃ for 3 minutes, then placing in deionized water for ultrasonic cleaning for 5 minutes, baking the cleaned product for 20 minutes at 120 ℃, taking out, and naturally cooling to room temperature;
(2) Putting the substrate into a vacuum coating machine, heating when the vacuum degree in the furnace reaches 0.9Pa, heating to 130deg.C, and evacuating to 6X10 -3 Argon is introduced after Pa, medium-frequency ion bombardment is carried out on the base material for 20 minutes, and the heating device is closed;
(3) And (3) magnetron sputtering deposition of a base layer: continuously supplying an argon gas source, starting an intermediate frequency sputtering power supply of the Cr target, and sputtering for 20 minutes to finish depositing a base layer (Cr layer) on the surface of the substrate, wherein the thickness of the Cr layer is 200nm;
(4) And (3) magnetron sputtering deposition of a transition layer: acetylene and argon are introduced, an intermediate-frequency sputtering power supply of the Cr target, the Si target and the Zr target is started, the sputtering time is 150 minutes, and a transition layer (CrSiZrC layer) is deposited on the surface of the base layer, wherein the thickness of the CrSiZrC layer is 1000nm, and the molar ratio of Cr, si, zr, C in the CrSiZrC layer is 3:1:1:8, 8;
(5) And (3) magnetron sputtering deposition of a color layer: acetylene and argon are introduced, an intermediate-frequency sputtering power supply of the Ti target, the Si target and the Zr target is started, the sputtering time is 15 minutes, and a color layer (TiSiZrC layer) is deposited on the surface of the transition layer, the thickness of the TiSiZrC layer is 200nm, and the molar ratio of Ti, si, zr, C in the TiSiZrC layer is 5:2:3:16;
(6) And (3) introducing argon for passivation for 10 minutes, opening an inflation valve when the temperature in the furnace is lower than 50 ℃ to take out the product, and obtaining the stainless steel watch case, and marking as S1.
Example 2
The substrate used in this example was a stainless steel watch case,
(1) Placing the substrate in wax-removing water at 50 ℃ for ultrasonic cleaning for 5 minutes, then soaking in oil-removing water at 50 ℃ for 3 minutes, then placing in deionized water for ultrasonic cleaning for 5 minutes, baking the cleaned product for 20 minutes at 120 ℃, taking out, and naturally cooling to room temperature;
(2) Putting the substrate into a vacuum coating machine, heating when the vacuum degree in the furnace reaches 0.9Pa, heating to 130deg.C, and evacuating to 6X10 -3 Argon is introduced after Pa, and medium frequency is carried out on the base material for 20 minutesBombarding the seeds and turning off the heating device;
(3) And (3) magnetron sputtering deposition of a base layer: continuously supplying an argon gas source, starting an intermediate frequency sputtering power supply of the Ti target material, and sputtering for 20 minutes to finish depositing a base layer (Ti layer) on the surface of the substrate, wherein the thickness of the Ti layer is 200nm;
(4) And (3) magnetron sputtering deposition of a transition layer: acetylene and argon are introduced, an intermediate-frequency sputtering power supply of the Ti target, the Si target and the W target is started, the sputtering time is 150 minutes, a transition layer (TiSiWC layer) is deposited on the surface of the base layer, the thickness of the TiSiWC layer is 1000nm, and the molar ratio of Ti, si, W, C in the TiSiWC layer is 3:2:1:10;
(5) And (3) magnetron sputtering deposition of a color layer: acetylene and argon are introduced, an intermediate-frequency sputtering power supply of the Ti target, the Si target and the W target is started, the sputtering time is 15 minutes, a color layer (TiSiWC layer) is deposited on the surface of the transition layer, the thickness of the TiSiWC layer is 200nm, and the molar ratio of Ti, si, zr, C in the TiSiZrC layer is 5:2:2:16;
(6) And (3) introducing argon for passivation for 10 minutes, opening an inflation valve when the temperature in the furnace is lower than 50 ℃ to take out the product, and obtaining the stainless steel watch case, and marking as S2.
Example 3
The substrate used in this example was a stainless steel watch case,
(1) Placing the substrate in wax-removing water at 50 ℃ for ultrasonic cleaning for 5 minutes, then soaking in oil-removing water at 50 ℃ for 3 minutes, then placing in deionized water for ultrasonic cleaning for 5 minutes, baking the cleaned product for 20 minutes at 120 ℃, taking out, and naturally cooling to room temperature;
(2) Putting the substrate into a vacuum coating machine, heating when the vacuum degree in the furnace reaches 0.9Pa, heating to 130deg.C, and evacuating to 6X10 -3 Argon is introduced after Pa, medium-frequency ion bombardment is carried out on the base material for 20 minutes, and the heating device is closed;
(3) And (3) magnetron sputtering deposition of a base layer: the argon gas source is continuously supplied, an intermediate frequency sputtering power supply of the Cr target and the Ti target is started, the sputtering time is 20 minutes, the deposition of a base layer (CrTi layer) on the surface of a substrate is completed, the thickness of the CrTi layer is 300nm, and the molar ratio of Ti to Cr in the CrTi layer is 2:3, a step of;
(4) And (3) magnetron sputtering deposition of a transition layer: acetylene and argon are introduced, an intermediate-frequency sputtering power supply of a Cr target, a Ti target, a Si target and a Nb target is started, the sputtering time is 150 minutes, a transition layer (CrTiSiNbC layer) is deposited on the surface of a base layer, the thickness of the CrTiSiNbC layer is 1500nm, and the molar ratio of CrTi, si, nb to C in the CrTiSiNbC layer is 3:1:1:7, preparing a base material;
(5) And (3) magnetron sputtering deposition of a color layer: acetylene and argon are introduced, an intermediate-frequency sputtering power supply of the Ti target, the Si target and the W target is started, the sputtering time is 15 minutes, a color layer (TiCrSiWC layer) is deposited on the surface of the transition layer, the thickness of the TiCrSiWC layer is 200nm, and the molar ratio of Ti, cr, si, W to C in the TiCrSiWC layer is 5: :1:1:2:14;
(6) And (3) introducing argon for passivation for 10 minutes, opening an inflation valve when the temperature in the furnace is lower than 50 ℃ to take out the product, and obtaining the stainless steel watch case, and marking as S3.
Example 4
The substrate used in this example was a stainless steel watch case,
the preparation method of this example is the same as that of example 1, except that: the molar ratio of Cr, si, zr, C in the CrSiZrC layer in the step (4) is 3:4:4:9. a stainless steel watch case is obtained, marked S4.
Example 5
The substrate used in this example was a stainless steel watch case,
the preparation method of this example is the same as that of example 1, except that:
in step (3), the base layer: the thickness of the Cr layer is 300nm;
in step (4), the transition layer: the thickness of the CrSiZrC layer is 600nm;
in step (5), the color layer: the TiSiZrC layer has a thickness of 400nm.
A stainless steel watch case was obtained, marked S5.
Example 6
The substrate used in this example was a stainless steel watch case,
the preparation method of this example is the same as that of example 1, except that: in step (4), the transition layer: the CrSiZrC layer had a thickness of 400nm.
A stainless steel watch case is obtained, marked S6.
Example 7
The substrate used in this example was a stainless steel watch case,
the preparation method of this example is the same as that of example 1, except that: in step (4), the transition layer: the CrSiZrC layer had a thickness of 3000nm.
A stainless steel watch case was obtained, marked S7.
Example 8
The substrate used in this example was a stainless steel watch case,
the preparation method of this example is the same as that of example 1, except that: in step (4), the transition layer: the CrSiZrC layer had a thickness of 200nm.
A stainless steel watch case was obtained, marked S8.
Comparative example 1
The substrate used in this comparative example was a stainless steel watch case,
the preparation method of this comparative example is the same as in example 1, except that: step (3) is not performed, i.e. no base layer (Cr layer) is deposited. A stainless steel watch case was obtained, designated D1.
Comparative example 2
The substrate used in this comparative example was a stainless steel watch case,
the preparation method of this comparative example is the same as in example 1, except that: step (4) was not performed, i.e. no transition layer (CrSiZrC layer) was deposited. A stainless steel watch case was obtained, marked D2.
Comparative example 3
The substrate used in this comparative example was a stainless steel watch case,
the preparation method of this comparative example is the same as in example 1, except that: step (5) is not performed, i.e. no color layer (TiSiZrC layer) is deposited. A stainless steel watch case was obtained, marked D3.
Comparative example 4
The substrate used in this comparative example was a stainless steel watch case,
the preparation method of this comparative example is the same as in example 1, except that:
in the step (5), a color layer is deposited by magnetron sputtering: and (3) introducing acetylene and argon, starting an intermediate-frequency sputtering power supply of the Ti target and the Zr target, and sputtering for 15 minutes to finish depositing a color layer (TiZrC layer) on the surface of the transition layer, wherein the thickness of the TiZrC layer is 200nm.
A stainless steel watch case was obtained, marked D4.
Comparative example 5
The substrate used in this comparative example was a stainless steel watch case,
the preparation method of this comparative example is the same as in example 1, except that:
in the step (5), a color layer is deposited by magnetron sputtering: and (3) introducing acetylene and argon, starting an intermediate-frequency sputtering power supply of the Si target and the Zr target, and sputtering for 15 minutes to finish depositing a color layer (SiZrC layer) on the surface of the transition layer, wherein the thickness of the SiZrC layer is 200nm.
A stainless steel watch case was obtained, marked D5.
Comparative example 6
The substrate used in this example was a stainless steel watch case,
the preparation method of this example is the same as that of example 1, except that: the molar ratio of Ti, si, zr, C in the TiSiZrC layer in the step (5) is 5:4:4:14. a stainless steel watch case was obtained, marked D6.
Comparative example 7
The substrate used in this comparative example was a stainless steel watch case,
the preparation method of this comparative example is the same as in example 1, except that:
in the step (4), a transition layer is deposited by magnetron sputtering: argon is introduced, an intermediate-frequency sputtering power supply of the Cr target and the TiAl target is started, the sputtering time is 180 minutes, and a transition layer (CrAlN layer) is deposited on the surface of the base layer, wherein the thickness of the CrAlN layer is 1200nm;
in the step (5), a color layer is deposited by magnetron sputtering: and (3) introducing argon, starting an intermediate-frequency sputtering power supply of the TiAl target, and sputtering for 15 minutes to finish depositing a color layer (TiAlN layer) on the surface of the transition layer, wherein the thickness of the TiAlN layer is 200nm.
A stainless steel watch case was obtained, marked D7.
Performance testing
(1) Lab value test: lab values for the Meinada CM-700D test product.
(2) Hundred cell adhesion test: using a cutting tool, cutting to form 10×10 continuous square lattices of 1mm×1mm in the cross-cut direction at an angle of 45 degrees with the sample, then attaching an adhesive tape, standing for 90s, holding one end of the adhesive tape in the air, rapidly pulling down the adhesive tape at an angle of approximately 60 degrees within 0.5-1.0s, and checking the falling state of the film layer. Wherein, the liquid crystal display device comprises a liquid crystal display device,
5B: the cutting edge is completely smooth, and no cutting edge falls off;
4B: a small amount of coating is dropped at the intersection of the incisions, and the affected intersection cutting area is not more than 5%;
3B: coating is peeled off at the intersection of the incisions and/or along the edges of the incisions, the affected intersection cut area being greater than 5% but not greater than 15%;
2B: the film layer is partially or completely fallen off in large fragments along the cutting edge and/or partially or completely fallen off on different parts of the grid, and the affected cross cutting area is more than 15 percent but not more than 35 percent;
1B: the coating flakes off along the large fragments of the cut edge and/or some or all of the squares are peeled off, the affected cross-cut area being greater than 35%, but not greater than 65%;
0B: the degree of exfoliation exceeded 1B.
(3) Wear resistance:
(a) Preparing 3 parts of RKF 10K (yellow cone) and 1 part of RKK P (green pyramid) which are 15L in total, adding into a grinding groove of a vibrating friction device (ROSLER, model R180/530 TE-30, frequency 50+/-0.5 Hz and amplitude 1.65+/-0.1 mm);
(b) Sucking FC120 ml with a pipette, adding water to 500ml, and adding into a grinding tank;
(c) Adding 0.5L of water into the grinding tank, and adding 0.5L of water and 120 ml of FC120 every 30min in the test process;
(d) The samples are mounted on a complete machine, put into vibration friction testing equipment for testing, and each sample is checked every 0.5 hour, and the longest time meeting the standard (continuous sawtooth abrasion is not more than 10mm (sawtooth definition: more than two positions in a linear abrasion area are between 1 and 1.5mm wide and are not accepted by the width more than 1.5 mm), point abrasion is not more than 1.5mm by 1.5mm, 1mm by 1.5mm is not more than 2, and 1mm by less than 1mm is not counted).
(4) Salt spray test: continuously spraying salt water on the surface of the substrate with NaCl solution with pH value of 6.8 and 5 wt% in a closed environment with temperature of 35 ℃ and humidity of 90%; taking out the sample at intervals, then gently flushing with warm water at 38 ℃, wiping with dust-free cloth, standing at normal temperature for 2 hours, checking the sample, and continuously putting the sample back into the salt water spray test for continuous test, wherein the film layer of the sample has no abnormal appearance and no obvious change in appearance (such as rust, color change, peeling of surface treatment layer and the like); the appearance of the samples was checked at intervals and the longest time was recorded without any abnormality in the appearance of the film layer and without any significant change in the appearance.
TABLE 1
As can be seen from the examples and the comparative examples, the coating material provided by the application can exhibit a uniform blue effect and has good wear resistance and corrosion resistance. As can be seen from the results of example 1 and comparative examples 1 to 6, the coating material lacks one of the base layer, the transition layer and the color layer, and lacks the element protected by the present application in the coating layer, and the ratio of the element in the color layer is not within the scope of the present application, so that the coating material cannot have both uniform blue appearance and wear and corrosion resistance; compared with the blue film layer structure in the prior art, the embodiment of the application and the comparative example 7 can show that the protection scheme of the application can show uniform blue effect and has good wear resistance and corrosion resistance.
The preferred embodiments of the present application have been described in detail above, but the present application is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present application within the scope of the technical concept of the present application, and all the simple modifications belong to the protection scope of the present application.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the application can be made without departing from the spirit of the application, which should also be considered as disclosed herein.

Claims (10)

1. The coating material is characterized by comprising a base material and a film layer positioned on the surface of the base material, wherein the film layer presents a uniform blue effect; the film layer comprises a basic layer, a transition layer and a color layer which are sequentially laminated, wherein the basic layer is positioned on the surface of the base material, and the basic layer comprises an X1 element; the transition layer comprises X2, si, Y1 and C elements; the color layer comprises Ti, si, Y2 and C elements, and the molar ratio of the Ti, the Si, the Y2 to the C is 5: (1-3): (1-3): (10-18); wherein the X1 element comprises Cr and/or Ti element, the X2 element comprises Cr and/or Ti element, the Y1 comprises at least one of Zr, W and Nb, and the Y2 comprises at least one of Zr and W.
2. The plating material according to claim 1, wherein the base layer includes Cr and Ti elements, and a molar ratio of Ti to Cr is 2: (1-5).
3. The coating material according to claim 1, wherein the molar ratio of X2, si, Y1 to C in the transition layer is 3: (1-2): (1-2): (6-12).
4. The plating material according to claim 1, wherein the color layer further contains Cr element, and wherein a molar ratio of Ti, cr, si, Y to C is 5: (1-2): (1-3): (1-3): (10-18).
5. The coating material according to claim 1, wherein the thickness of the base layer is 100-1000nm, the thickness of the transition layer is 300-3000nm, and the thickness of the color layer is 100-1000nm.
6. The coating material according to claim 5, wherein the thickness of the base layer is 200-500nm, the thickness of the transition layer is 500-1500nm, and the thickness of the color layer is 100-500nm.
7. The coating material of claim 1, wherein the substrate comprises at least one of metal, ceramic, glass, and plastic.
8. The coating material according to any one of claims 1 to 7, wherein the range of color values of the film layer is: l is 30-50, a is-1 to-10, and b is-1 to-18.
9. The method for producing a plating material according to any one of claims 1 to 8, comprising depositing a base layer, a transition layer and a color layer in this order on the surface of the substrate.
10. An electronic product housing comprising the coating material according to any one of claims 1 to 8.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101468538A (en) * 2007-12-24 2009-07-01 比亚迪股份有限公司 Coating material and preparation method thereof
RU2414530C1 (en) * 2009-11-03 2011-03-20 Государственное образовательное учреждение высшего профессионального образования "Ульяновский государственный технический университет" Procedure for cutting tool multi-layer coating
JP2012036506A (en) * 2011-11-08 2012-02-23 Tungaloy Corp Coating member
CN107254662A (en) * 2017-06-28 2017-10-17 维达力实业(深圳)有限公司 Blue laminated film and preparation method thereof
CN206791844U (en) * 2016-03-16 2017-12-26 斯沃奇集团研究和开发有限公司 The part of jewellery or clock and watch
CN208362448U (en) * 2018-07-09 2019-01-11 深圳市正和忠信股份有限公司 A kind of stiffened deep space grey PVD film
CN110577369A (en) * 2018-08-13 2019-12-17 蓝思科技股份有限公司 Multilayer metal coating Logo, preparation method thereof, glass substrate and electronic equipment

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101468538A (en) * 2007-12-24 2009-07-01 比亚迪股份有限公司 Coating material and preparation method thereof
RU2414530C1 (en) * 2009-11-03 2011-03-20 Государственное образовательное учреждение высшего профессионального образования "Ульяновский государственный технический университет" Procedure for cutting tool multi-layer coating
JP2012036506A (en) * 2011-11-08 2012-02-23 Tungaloy Corp Coating member
CN206791844U (en) * 2016-03-16 2017-12-26 斯沃奇集团研究和开发有限公司 The part of jewellery or clock and watch
CN107254662A (en) * 2017-06-28 2017-10-17 维达力实业(深圳)有限公司 Blue laminated film and preparation method thereof
CN208362448U (en) * 2018-07-09 2019-01-11 深圳市正和忠信股份有限公司 A kind of stiffened deep space grey PVD film
CN110577369A (en) * 2018-08-13 2019-12-17 蓝思科技股份有限公司 Multilayer metal coating Logo, preparation method thereof, glass substrate and electronic equipment

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