CN110527959A - A kind of protective layer and preparation method thereof for the coat of metal - Google Patents
A kind of protective layer and preparation method thereof for the coat of metal Download PDFInfo
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- CN110527959A CN110527959A CN201910881696.6A CN201910881696A CN110527959A CN 110527959 A CN110527959 A CN 110527959A CN 201910881696 A CN201910881696 A CN 201910881696A CN 110527959 A CN110527959 A CN 110527959A
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- metal
- protective layer
- coat
- layer
- sulfide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
- C23C14/0611—Diamond
-
- 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
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
-
- 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
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present invention provides a kind of protective layer for the coat of metal, the material of the protective layer is selected from at least one of Nano diamond powder, metal oxide, metal sulfide；Wherein, the metal oxide is selected from at least one of the oxide containing aluminium, the oxide containing niobium, the oxide containing zirconium, and the metal sulfide is selected from at least one of the sulfide containing aluminium, the sulfide containing niobium, the sulfide containing zirconium.The material is the higher hard particulate material of hardness; add the hard particulate material; the material of protective layer can be made to be dispersed in metal coating surface; reunion will not be generated; disperse uniform enough; above-mentioned material property is stablized; it will not react with metal coating material; simultaneously; it can guarantee the coat of metal and air exclusion that are added to above-mentioned protective layer raw material; oxidation reaction will not occur, the material of the coat of metal is protected, the coat of metal antioxygenic property enhancing that makes that treated, wear resistance improve.
Description
Technical field
The present invention relates to Material Field more particularly to a kind of protective layers and preparation method thereof for the coat of metal.
Background technique
Currently, the ornament of the metal materials such as the ornaments of some high values, wrist-watch, it will usually at one layer of its electroplating surface
Decorative coating, material of coating such as gold, silver, copper, rose gold, black chromium, black nickel etc.；It, can by the way that these coating are electroplated
Increase the style of these high value metals material ornaments, keep style more diversified, more gets consumer reception.
But the high value metals material ornament by plating, since warehouse storage is improper, or have one in transit
A little uncontrollable conditions such as gaseous environment, empty gas and water drink the destruction of general corrosion, are easy to cause the high value metals material of plating
The coating surface of material ornament occurs aoxidizing and wear, and affects the quality of coating, and then causes to occur not meeting in terms of aesthetics
The problem of quality standard, causes the loss of high added value ornament.
Summary of the invention
The protective layer and preparation method thereof that the purpose of the present invention is to provide a kind of for the coat of metal, it is intended to solve existing
Oxidizable, the easy to wear problem of electrodeposited material in number.
For achieving the above object, The technical solution adopted by the invention is as follows:
The material of a kind of protective layer for the coat of metal, the protective layer is selected from Nano diamond, metal oxide, gold
Belong at least one of sulfide；Wherein, the metal oxide is selected from the oxide containing aluminium, the oxide containing niobium, the oxygen containing zirconium
At least one of compound, the metal sulfide are selected from the sulfide containing aluminium, the sulfide containing niobium, the sulfide containing zirconium at least
It is a kind of.
And a kind of preparation method of the protective layer for the coat of metal, the protective layer use physical vaporous deposition
It prepares, the specific method of the physical vaporous deposition includes the following steps:
Ion vacuum coating machine is provided, selects the material of above-mentioned at least one protective layer as target；
Surface clean is carried out to the sample containing the coat of metal, the sample is fixedly placed in the ion vacuum plated film
Inside machine；
In inert ambient environment, when improving pressure inside the ion vacuum coating machine and temperature and preheated one-section
Between, high velocity bombardment, then cooling decompression are carried out, the protective layer for the coat of metal is obtained.
And a kind of wristwatch case, comprising: the coat of metal of the watchcase body surface is arranged in watchcase ontology, and
It is incorporated in the protective layer on the coat of metal at least partly surface, the protective layer is the protection for the coat of metal
Layer.
And a kind of wrist-watch, the wrist-watch include the wristwatch case.
The material of protective layer of the present invention is selected from at least one of Nano diamond, metal oxide, metal sulfide；
The nano-diamond layer, metal oxide layer, metal sulfide layer are the higher hard particulate material of hardness, described in addition
Hard particulate material can make the material of protective layer be dispersed in metal coating surface, will not generate reunion, disperse equal enough
It is even, it can be improved the hardness of the coat of metal, scratch the coat of metal will not easily；Wherein, the metal oxide is selected from and contains
At least one of the oxide of aluminium, the oxide containing niobium, the oxide containing zirconium, the metal sulfide are selected from the vulcanization containing aluminium
At least one of object, the sulfide containing niobium, the sulfide containing zirconium, above-mentioned protective layer property are stablized, will not be with coat of metal material
Material reacts, meanwhile, it is capable to which guarantee that treated the coat of metal and air exclusion, will not occur oxidation reaction, to metal-plated
The material of layer is protected；Selected above-mentioned protective layer material strong adsorption, with the adhesive property of the coat of metal it is good, be not easy to take off
It falls, makes that treated and cover the coat of metal antioxygenic property enhancing of protective layer, wear resistance improves.
The preparation method of protective layer of the present invention for the coat of metal is physical vaporous deposition, and this method is to use object
The method of reason makes the material of protective layer gasify such as sputtering, in the method for the surface of coat of metal deposition film forming, Coating Materials particle
Reactivity is high, and obtained protective layer is high-quality, and this method is simple and pollution-free, is conducive to environmental protection.
Wristwatch case provided by the present invention, on the coat of metal at least partly surface of the watchcase body surface, there are institutes
Protective layer is stated, can be improved the inoxidizability and wear resistance of the wristwatch case coat of metal.
Wrist-watch provided by the invention, the wristwatch case including the above-mentioned protective layer existing for coat of metal part of the surface should
The inoxidizability and wear resistance of the wristwatch case of wrist-watch are preferable.
Specific embodiment
To keep the purpose, technical solution and technical effect of the embodiment of the present invention clearer, the present invention will be implemented below
Technical solution in example is clearly and completely described, it is clear that and described embodiments are some of the embodiments of the present invention, and
The embodiment being not all of.In conjunction with the embodiment in the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
Present example provides a kind of protective layer for the coat of metal, and the material of the protective layer is selected from nanometer Buddha's warrior attendant
At least one of stone, metal oxide, metal sulfide；Wherein, the metal oxide is selected from oxide containing aluminium, containing niobium
At least one of oxide, oxide containing zirconium, the metal sulfide are selected from the sulfide containing aluminium, the sulfide containing niobium, contain
At least one of the sulfide of zirconium.
The material of protective layer of the present invention is selected from at least one of Nano diamond, metal oxide, metal sulfide；
The nano-diamond layer, metal oxide layer, metal sulfide layer are the higher hard particulate material of hardness, described in addition
Hard particulate material can make the material of protective layer be dispersed in metal coating surface, will not generate reunion, disperse equal enough
It is even, it can be improved the hardness of the coat of metal, scratch the coat of metal will not easily；Wherein, the metal oxide is selected from and contains
At least one of the oxide of aluminium, the oxide containing niobium, the oxide containing zirconium, the metal sulfide are selected from the vulcanization containing aluminium
At least one of object, the sulfide containing niobium, the sulfide containing zirconium, above-mentioned protective layer property are stablized, will not be with coat of metal material
Material reacts, meanwhile, it is capable to which guarantee that treated the coat of metal and air exclusion, will not occur oxidation reaction, to metal-plated
The material of layer is protected；Selected above-mentioned protective layer material strong adsorption, with the adhesive property of the coat of metal it is good, be not easy to take off
It falls, makes that treated and cover the coat of metal antioxygenic property enhancing of protective layer, wear resistance improves.In some embodiments
In, the material of the protective layer is selected from nano-diamond layer, and diamond is the material of the stable structure of pure carbon composition, nanometer Buddha's warrior attendant
Stone powder is nanoscale material；The hardness of Nano diamond powder is higher, mohs hardness 10, microhardness 10000kg/
mm2.On the one hand material using Nano diamond as protective layer can be improved the hardness of the coat of metal, improve its surface
Wear-resistant degree, makes the coat of metal during transport or use, and the material of the coat of metal is made to be not easy to be scratched；Another party
Face, the Nano diamond property are stablized, will not both react with the material of the coat of metal, at the same can also completely cut off air and
Moisture, guarantees that the coat of metal will not be oxidized, and plays the role of protection to metal coating material.
In some embodiments, the protective layer is selected from metal oxide materials or metal sulfide material；Wherein, described
Metal oxide materials are selected from at least one of the oxide containing aluminium, the oxide containing niobium, the oxide containing zirconium, the metal sulphur
Compound material is selected from at least one of the sulfide containing aluminium, the sulfide containing niobium, the sulfide containing zirconium.Above-mentioned oxide material and
Sulfide material hardness is higher, when above-mentioned granular materials Dispersed precipitate is in the coat of metal, can effectively improve the coat of metal
Hardness therefore using above-mentioned metal oxide or metal sulfide as when the material of protective layer, can be improved the coat of metal
Hardness improves the wear-resistant degree of metal coating surface.On the other hand, above-mentioned metal oxide or metal sulfide property are steady
It is fixed, it will not both react with the material of the coat of metal, while air and moisture can also be completely cut off, and guarantee that the coat of metal will not be by
Oxidation, plays the role of protection to metal coating material.
Preferably, the metal oxide is selected from Al2O3、ZrO2、Nb2O5At least one.Aluminium oxide (Al2O3) it is a kind of
The compound of high rigidity, the raw material as protective layer can be improved the hardness on metal coating material surface, make the coat of metal
Wear-resisting property is improved；Meanwhile aluminium oxide structure is stablized, and performance is stablized, and it is not soluble in water, but water imbibition is very strong, has stronger
Adsorption capacity can forcefully be adsorbed on metal coating surface as the raw material of protective layer, be that protective layer material is not easy
It is detached from, and then enhances the abrasion resistance properties and oxidation resistent susceptibility of the coat of metal.Zirconium dioxide (ZrO2) be a kind of high rigidity change
Object is closed, chemical property is stablized, has the characteristics that high-melting-point, is insoluble in water, hydrochloric acid and dilute sulfuric acid, using the material as protective layer
Raw material, the stability of metal coating surface can be further increased, enhance the abrasion resistance properties and oxidative resistance of the coat of metal
Energy.Niobium oxide (Nb2O5) hardness is higher, it is not soluble in water, it is insoluble in acid, it, can be further using the material as the raw material of protective layer
The stability for improving metal coating surface, enhances the abrasion resistance properties and oxidation resistent susceptibility of the coat of metal.
Preferably, the metal oxide is Al2O3、ZrO2、Nb2O5Mixture.When the metal oxide is
Al2O3、ZrO2、Nb2O5Mixture when, for very strong translucency the advantages of the protective layer being prepared, higher hardness,
Wearability, caking property and corrosion resistance.
Preferably, the protective layer is the nano-diamond layer or metal oxide layer or metal sulfide of single-layer or multi-layer
Layer.In some embodiments, the single layer structure is nano-diamond layer；Preferably, the nano-diamond layer with a thickness of
50nm。
In some embodiments, the single layer structure is metal oxide layer.Preferably, the metal oxide layer is single
The material layer that one substance is formed, in a preferred embodiment of the invention, the material for the material layer that the single substance is formed, which is selected from, to be contained
Any one of the oxide of aluminium, the oxide containing niobium, the oxide containing zirconium.Preferably, the metal oxide layer is two kinds
Or the mixed material layer that two or more metal oxides are formed, in a preferred embodiment of the invention, the material of the mixed material layer
Material selected from the oxide containing aluminium, the oxide containing niobium, the oxide containing zirconium at least two.
In some embodiments, the single layer structure is metal sulfide layer.Preferably, the metal sulfide layer is single
The material layer that one substance is formed, in a preferred embodiment of the invention, the material for the material layer that the single substance is formed, which is selected from, to be contained
Any one of the sulfide of aluminium, the sulfide containing niobium, the sulfide containing zirconium.Preferably, the metal sulfide layer is two kinds
Or the mixed material layer that two or more metal sulfides are formed, in a preferred embodiment of the invention, the material of the mixed material layer
Material selected from the sulfide containing aluminium, the sulfide containing niobium, the sulfide containing zirconium at least two.
In some embodiments, the single layer structure be metal oxide, metal sulfide, in Nano diamond at least
The mixed material layer of two kinds of formation.Preferably, the protective layer is single layer structure, and contains metal simultaneously in the single layer structure
Oxide, metal sulfide.Wherein, the metal oxide is selected from the oxide containing aluminium, the oxide containing niobium, the oxidation containing zirconium
At least one of object, the metal sulfide be selected from the sulfide containing aluminium, the sulfide containing niobium, the sulfide containing zirconium at least one
Kind.Preferably, in the mixed material layer, the mass ratio of various mixing materials is 1:1.
In some embodiments, the multilayered structure is nano-diamond layer, it is preferred that the thickness of the multilayered structure
For 50~100nm.
In some embodiments, the multilayered structure is metal oxide layer.Preferably, the metal oxide layer is
The material layer that single substance is formed, in a preferred embodiment of the invention, the material for the material layer that the single substance is formed are selected from
Any one of oxide containing aluminium, the oxide containing niobium, the oxide containing zirconium.Preferably, the metal oxide layer is two
The mixed material layer that kind or two or more metal oxides are formed, in a preferred embodiment of the invention, the mixed material layer
Material be selected from the oxide containing aluminium, the oxide containing niobium, the oxide containing zirconium at least two.
In some embodiments, the multilayered structure is metal sulfide layer.Preferably, the metal sulfide layer is
The material layer that single substance is formed, in a preferred embodiment of the invention, the material for the material layer that the single substance is formed are selected from
Any one of sulfide containing aluminium, the sulfide containing niobium, the sulfide containing zirconium.Preferably, the metal sulfide layer is two
The mixed material layer that kind or two or more metal sulfides are formed, in a preferred embodiment of the invention, the mixed material layer
Material be selected from the sulfide containing aluminium, the sulfide containing niobium, the sulfide containing zirconium at least two.
Preferably, the protective layer is multilayered structure, and is nano-diamond layer, metal oxide layer, metal sulfide
The composite layer of at least two layers formation in layer；Preferably, the metal oxide layer is the material layer or two that single substance is formed
The mixed material layer that kind or two or more metal oxides are formed；Preferably, the material for the material layer that the single substance is formed
Selected from any one of the oxide containing aluminium, the oxide containing niobium, the oxide containing zirconium；The material of the mixed material layer is selected from
Oxide containing aluminium, the oxide containing niobium, the oxide containing zirconium at least two.It is further preferred that the metal sulfide
Layer is the material layer that single substance is formed or the mixed material layer that two or more metal sulfide is formed；Preferably, institute
State single substance formation material layer material be selected from the sulfide containing aluminium, the sulfide containing niobium, the sulfide containing zirconium it is any
It is a kind of；The material of the mixed material layer be selected from the sulfide containing aluminium, the sulfide containing niobium, the sulfide containing zirconium at least two
Kind.
Preferably, the multilayered structure that the protective layer is two layers or two layers or more, and in at least one layer in multilayered structure
Contain metal oxide, metal sulfide simultaneously.Wherein, the metal oxide is selected from the oxide containing aluminium, the oxidation containing niobium
At least one of object, oxide containing zirconium, the metal sulfide are selected from the sulfide containing aluminium, the sulfide containing niobium, containing zirconium
At least one of sulfide.Preferably, in the mixed material layer, the mass ratio of various mixing materials is 1:1.
Preferably, the coat of metal is rose gold plate.Increase a protective layer on rose gold plate, it can be ensured that
Rose gold plate is wear-resistant, resistance to oxidation, it is protected to keep rose gold color.
Preferably, 0.1 μm of the roughness < of the protective layer.The protective layer material of selection smaller particle is handled, energy
The protective layer that enough guarantees are handled is finer and smoother, and roughness is 0.1 μm of <；It is seen by the naked eye protective layer material not, Bu Huiying
Ring the cosmetic variation of the coat of metal.
After being added to protective layer material, the color of metal coating surface is caused to form variation, it is preferred that institute
State the thickness with a thickness of at least one atomic monolayer of protective layer, it is further preferred that if the protective layer with a thickness of one
The thickness of atomic monolayer, then the thickness of the protective layer is at least 50nm.Preferably, the protective layer with a thickness of 50~100nm.
If protective layer thickness is too thin, the material that not can guarantee processing is uniform, poor to the protecting effect of the coat of metal, can not improve gold
Belong to coating resistance to oxidation, anti abrasive performance；If protective layer thickness is too thick, it will affect the color of metal coating surface, influence beauty
See, at the same will not greatly improvement, cause unnecessary waste.
Further, after in order to avoid being added to protective layer material, the color of metal coating surface is caused to form variation,
Preferably, the color change Δ ELab numerical value between the coat of metal and protective layer is 0.1~0.8.If color change Δ ELab number
Value is higher, then light transmittance is lower, will affect visual effect, and the color that will lead to metal coating surface forms variation, is unfavorable for making
With.It is further preferred that the color change between the coat of metal of untreated protective layer and the coat of metal for having handled protective layer
Δ ELab numerical value is 0.1~0.2, and when color change Δ ELab numerical value is between 0.1~0.2, function and effect are best, protective layer
The coat of metal can be completely secured to be protected, while the light transmittance of protective layer is higher, face will not be formed on the surface of the coat of metal
Color change.
Preferably, bond strength >=200MPa of the protective layer and the coat of metal.Improve protective layer and the coat of metal
Bond strength, the combination effect both enhanced, improve with the adhesive property of the coat of metal, keep protection materials not easily to fall off, make to locate
The coat of metal antioxygenic property enhancing of protective layer raw material is managed, wear resistance improves.If protective layer and the coat of metal
Bond strength is lower, then the adhesive effect of the two is poor, and protective layer material is easy to fall off, and it is anti-can not preferably to improve the coat of metal
Oxidation susceptibility and wear resistance.
The raw material of protective layer of the present invention for the coat of metal include Nano diamond powder, metal oxide,
At least one of metal sulfide；The raw material are the higher hard particulate material of hardness, add the hard particles material
Material, can make the material of protective layer be dispersed in metal coating surface, will not generate reunion, disperse uniform enough, Neng Gouti
The hardness of high metal coating scratch the coat of metal will not easily；The raw material are Nano diamond powder, the oxygen containing aluminium
Compound, the sulfide containing aluminium；Oxide containing niobium, the sulfide containing niobium；Oxide containing zirconium, the sulfide containing zirconium, above-mentioned material
Expect that property is stablized, will not react with metal coating material, meanwhile, it is capable to guarantee to have handled above-mentioned protective layer raw material
Oxidation reaction will not occur for the coat of metal and air exclusion, protect to the material of the coat of metal；Selected above-mentioned protective layer
Material strong adsorption, it is good, not easily to fall off with the adhesive property of the coat of metal, keep the coat of metal for having handled protective layer raw material anti-
Oxidation susceptibility enhancing, wear resistance improve.
The above-mentioned protective layer for the coat of metal by being prepared following preparation method
Correspondingly, the embodiment of the invention also provides a kind of preparation method of protective layer for the coat of metal, the use
In the coat of metal protective layer preparation method be physical vaporous deposition.Using physical vaporous deposition, this method is to use object
The method of reason makes the material of protective layer gasify such as sputtering, in the method for the surface of coat of metal deposition film forming, Coating Materials particle
Reactivity is high, and obtained protective layer is high-quality, and this method is simple and pollution-free, is conducive to environmental protection.
Specifically, the specific method of the physical vaporous deposition includes the following steps:
S01., ion vacuum coating machine is provided, the raw material of at least one protective layer described in the claims 1 are selected
As target；
S02. surface clean is carried out to the sample containing the coat of metal, the sample is fixedly placed in the ion vacuum
Inside coating machine；
S03. in inert ambient environment, pressure inside the ion vacuum coating machine and temperature and preheated one-section are improved
Time carries out high velocity bombardment, then cooling decompression, obtains the protective layer for the coat of metal.
Specifically, providing ion vacuum coating machine in above-mentioned steps S01, above-mentioned at least one protective layer is selected
Raw material are as target；The optional Nano diamond powder of the target, the oxide containing aluminium, the sulfide containing aluminium；Oxygen containing niobium
Compound, the sulfide containing niobium；At least one of oxide containing zirconium, the sulfide containing zirconium；Preferably, the purity of the target >=
98%, select the target material of high-purity, it is ensured that be prepared that Protective coatings are good, and compactness is strong.It is further preferred that
If using two or more mixing materials as target simultaneously, the addition quality of each material mixed is 1:1.
Specifically, carrying out surface clean in above-mentioned steps S02 to the sample containing the coat of metal, the sample being consolidated
Surely it is placed in inside the ion vacuum coating machine；Preferably, the described pair of sample containing the coat of metal carries out surface clean
In step, organic solvent is provided, the coat of metal is cleaned, is dried, the coat of metal cleaned using organic solvent, mesh
Be the substances such as impurity, grease for removing metal coating surface, keep metal coating surface clean, be conducive to protective layer material
Deposition processes.Preferably, the organic solvent is selected from at least one such as ethyl alcohol, methanol.
Preferably, the sample is fixedly placed in the step inside the ion vacuum coating machine, by the sample
It is fixedly placed on the shelf inside the ion vacuum coating machine.
Specifically, in inert ambient environment, being improved inside the ion vacuum coating machine in above-mentioned steps S03
Pressure and temperature and preheated one-section time carry out high velocity bombardment, then cooling decompression, obtain the protective layer for the coat of metal.
Preferably, the inert atmosphere is selected from argon gas, it is further preferred that in the inert atmosphere, gas it is dense
Degree >=99.99%., under the gas condition of above-mentioned concentration, guarantee that inside ion vacuum coating machine be rare gas, without oxygen
Other gas dopings such as gas, the purity for improving the material for the protective layer being prepared are higher.
Preferably, in above-mentioned steps, pressure inside the ion vacuum coating machine and temperature and preheated one-section are improved
Time, the pressure are 1.0 × 10-3Pa~2.0 × 10-3Pa, the temperature are 700~800 DEG C, the preheated one-section time
It is 20~30 minutes；It preheats coating machine under conditions of high temperature and pressure, is conducive to subsequent reactions and goes on smoothly.
Preferably, in the step of carrying out high velocity bombardment, the high pressure is 1300~1500V, the time object 10 of the bombardment
~15 minutes.It is handled under above-mentioned condition of high voltage, the protective layer for the coat of metal can be obtained in processing.Preferably, high
Pressure bombardment processing terminates and then cools down decompression, is passed through 99.99% nitrogen, pressure is down to 1-5Pa, be cooled to room temperature~
100 DEG C are come out of the stove again.
With the film plating process, the binding strength of the coat of metal after plated film, protective layer and the coat of metal is strong, protection
Layer is visually invisible, and the coat of metal can be made not oxidized and worn, gold is maintained.Obtained protective layer is high-quality, this method letter
It is single and pollution-free, be conducive to environmental protection.
Correspondingly, the present invention also provides a kind of wristwatch cases, comprising: watchcase ontology is arranged in the watchcase body surface
The coat of metal, and be incorporated in the protective layer on the coat of metal at least partly surface, the protective layer is described is used for
The protective layer of the coat of metal.Wristwatch case provided by the present invention, the watchcase body surface the coat of metal at least partly
There are the protective layers on surface, can be improved the inoxidizability and wear resistance of the wristwatch case coat of metal
Correspondingly, the wrist-watch includes a kind of wristwatch case the present invention also provides a kind of wrist-watch.The present invention provides
Wrist-watch, the wristwatch case including the above-mentioned protective layer existing for coat of metal part of the surface, the wristwatch case of the wrist-watch it is anti-
Oxidisability and wear resistance are preferable.
The content that specific embodiment is provided below further illustrates.
Embodiment 1
With ion vacuum coating machine, the purity of target need to reach 98% or more, and target is Nano diamond powder；With organic
Solvent cleans the surface of the plated coat of metal, is dried, and is sent into vacuum ion membrane plating room and is fixed with special fixture
On frame；Coating chamber door is shut, is evacuated to 1.0 × 10-3Pa；Heater switch is opened, is heated to 800 DEG C, keeps 20min；Xiang Zhen
It is passed through 99.99% argon gas in empty ion plating equipment, opens voltage arc switch, discharges the voltage arc of 1500V, bombard 10 minutes；
It is passed through 99.99% N2, pressure is down to 1Pa, is cooled to room temperature and comes out of the stove, the Nano diamond for the coat of metal can be obtained
Protective layer.
Embodiment 2
With ion vacuum coating machine, the purity of target need to reach 98% or more, target Al2O3Mixture, mixed matter
Amount ratio is 1:1；It cleaned, dried with surface of the organic solvent to the coat of metal, and be sent into vacuum ionic with special fixture
On coating chamber inner fixed stand；Coating chamber door is shut, is evacuated to 1.5 × 10-3Pa；Heater switch is opened, is heated to 750 DEG C, is protected
Hold 25min；It is passed through 99.99% argon gas into vaccum ion coater, opens voltage arc switch, discharges the voltage arc of 1400V,
Bombardment 12 minutes or so；It is passed through 99.99% N2, pressure is down to 2Pa, 50 DEG C is cooled to and comes out of the stove, can be obtained for metal
The protective layer of alumina of coating.
Embodiment 3
With ion vacuum coating machine, the purity of target need to reach 98% or more, target ZrO2Mixture, mixed matter
Amount ratio is 1:1；It cleaned, dried with surface of the organic solvent to the coat of metal, and be sent into vacuum ionic with special fixture
On coating chamber inner fixed stand；Coating chamber door is shut, is evacuated to 1.5 × 10-3Pa；Heater switch is opened, is heated to 750 DEG C, is protected
Hold 25min；It is passed through 99.99% argon gas into vaccum ion coater, opens voltage arc switch, discharges the voltage arc of 1400V,
Bombardment 12 minutes or so；It is passed through 99.99% N2, pressure is down to 2Pa, 50 DEG C is cooled to and comes out of the stove, can be obtained for metal
The zirconium dioxide protective layer of coating.
Embodiment 4
With ion vacuum coating machine, the purity of target need to reach 98% or more, target Nb2O5Mixture, mixed matter
Amount ratio is 1:1；It cleaned, dried with surface of the organic solvent to the coat of metal, and be sent into vacuum ionic with special fixture
On coating chamber inner fixed stand；Coating chamber door is shut, is evacuated to 2.0 × 10-3Pa；Heater switch is opened, is heated to 700 DEG C, is protected
Hold 30min；It is passed through 99.99% argon gas into vaccum ion coater, opens voltage arc switch, discharges the voltage arc of 1300V,
Bombardment 15 minutes；It is passed through 99.99% N2, pressure is down to 5Pa, 90 DEG C is cooled to and comes out of the stove, can be obtained for the coat of metal
Niobium oxide protective layer.
Embodiment 5
With ion vacuum coating machine, the purity of target need to reach 98% or more, target Al2O3And ZrO2Mixture, mix
The mass ratio of conjunction is 1:1；It cleaned, dried with surface of the organic solvent to the coat of metal, and be sent into very with special fixture
In empty ion film plating room on fixed frame；Coating chamber door is shut, is evacuated to 1.5 × 10-3Pa；Heater switch is opened, is heated to 750
DEG C, keep 25min；It is passed through 99.99% argon gas into vaccum ion coater, opens voltage arc switch, discharges the electricity of 1400V
Arc is pressed, is bombarded 12 minutes or so；It is passed through 99.99% N2, pressure is down to 2Pa, 50 DEG C is cooled to and comes out of the stove, can be obtained and be used for
The aluminium oxide of the coat of metal and the protective layer of zirconium dioxide composite material.
Embodiment 6
With ion vacuum coating machine, the purity of target need to reach 98% or more, target ZrO2And Nb2O5Mixture, mix
The mass ratio of conjunction is 1:1；It cleaned, dried with surface of the organic solvent to the coat of metal, and be sent into very with special fixture
In empty ion film plating room on fixed frame；Coating chamber door is shut, is evacuated to 2.0 × 10-3Pa；Heater switch is opened, is heated to 700
DEG C, keep 30min；It is passed through 99.99% argon gas into vaccum ion coater, opens voltage arc switch, discharges the electricity of 1300V
Arc is pressed, is bombarded 15 minutes；It is passed through 99.99% N2, pressure is down to 5Pa, 90 DEG C is cooled to and comes out of the stove, can be obtained for metal
The zirconium dioxide of coating and the protective layer of niobium oxide composite material.
Neutral salt examination in 24 hours is successively carried out to the protective layer for the coat of metal that above-described embodiment 1~6 is prepared
Test with 24 hours Sweat Tests, test result such as the following table 1:
Table 1
Above-mentioned table 1 the results show that the protective layer in the coat of metal that is prepared of Examples 1 to 6 in 24 hours neutrality
Under the processing of salt test and 24 hours Sweat Tests, without any influence, show the coat of metal being prepared
Protective layer has preferable inoxidizability.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of protective layer for the coat of metal, which is characterized in that the material of the protective layer is selected from Nano diamond, metal
At least one of oxide, metal sulfide；Wherein, the metal oxide be selected from the oxide containing aluminium, the oxide containing niobium,
At least one of oxide containing zirconium, the metal sulfide are selected from the sulfide containing aluminium, the sulfide containing niobium, the vulcanization containing zirconium
At least one of object.
2. the protective layer according to claim 1 for the coat of metal, which is characterized in that the metal oxide is selected from
Al2O3、ZrO2、Nb2O5At least one.
3. the protective layer according to claim 1 for the coat of metal, which is characterized in that the metal oxide is
Al2O3、ZrO2、Nb2O5Mixture.
4. any protective layer for the coat of metal according to claim 1~3, which is characterized in that
The protective layer is the nano-diamond layer or metal oxide layer or metal sulfide layer of single-layer or multi-layer；And/or
The protective layer is single layer structure, and contains metal oxide, metal sulfide in the single layer structure simultaneously；And/or
The protective layer is multilayered structure, and is at least two in nano-diamond layer, metal oxide layer, metal sulfide layer
The composite layer that layer is formed；And/or
The protective layer is two layers or two layers or more of multilayered structure, and contains metal simultaneously in at least one layer in multilayered structure
Oxide, metal sulfide.
5. any protective layer for the coat of metal according to claim 1~3, which is characterized in that the coat of metal
For rose gold plate.
6. any protective layer for the coat of metal according to claim 1~3, which is characterized in that the protective layer
With a thickness of 50~100nm.
7. a kind of preparation method of the protective layer for the coat of metal, which is characterized in that the protective layer is heavy using physical vapor
Area method prepares, and the specific method of the physical vaporous deposition includes the following steps:
Ion vacuum coating machine is provided, selects the material of at least one protective layer described in the claims 1 as target；
Surface clean is carried out to the sample containing the coat of metal, the sample is fixedly placed in the ion vacuum coating machine
Portion；In inert ambient environment, pressure inside the ion vacuum coating machine and temperature and preheated one-section time are improved, is carried out
High velocity bombardment, then cooling decompression, obtain the protective layer for the coat of metal.
8. the preparation method of the protective layer according to claim 7 for the coat of metal, which is characterized in that
The step of improving pressure inside the ion vacuum coating machine and temperature and preheated one-section time, carrying out high velocity bombardment
In,
The pressure is 1.0 × 10-3Pa~2.0 × 10-3Pa, the temperature are 700~800 DEG C, and the preheated one-section time is
20~30 minutes；And/or
The high pressure is 1300~1500V, the time object of the bombardment 10~15 minutes.
9. a kind of wristwatch case characterized by comprising the coat of metal of the watchcase body surface is arranged in watchcase ontology,
And it is incorporated in the protective layer on the coat of metal at least partly surface, the protective layer is as described in claim 1-6 is any
The protective layer for the coat of metal.
10. a kind of wrist-watch, which is characterized in that the wrist-watch includes wristwatch case described in the claims 9.
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Application publication date: 20191203 |