WO2020048215A1 - Article en métal précieux ayant un revêtement sur sa surface et procédé de préparation associé - Google Patents

Article en métal précieux ayant un revêtement sur sa surface et procédé de préparation associé Download PDF

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WO2020048215A1
WO2020048215A1 PCT/CN2019/094842 CN2019094842W WO2020048215A1 WO 2020048215 A1 WO2020048215 A1 WO 2020048215A1 CN 2019094842 W CN2019094842 W CN 2019094842W WO 2020048215 A1 WO2020048215 A1 WO 2020048215A1
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precious metal
vacuum
metal substrate
noble metal
film layer
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PCT/CN2019/094842
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English (en)
Chinese (zh)
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王彤
唐双喜
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深圳市联合蓝海科技开发有限公司
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Priority to SG11202101923RA priority Critical patent/SG11202101923RA/en
Publication of WO2020048215A1 publication Critical patent/WO2020048215A1/fr

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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
    • C23C14/0694—Halides
    • 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
    • C23C14/24—Vacuum evaporation
    • 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
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • 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
    • 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

Definitions

  • the invention relates to the field of noble metal surface coatings, in particular to a noble metal product with a coating on its surface and a preparation method thereof.
  • Gold products have bright colors and good stability. They are often used as jewelry and are popular with consumers. At present, the production process of gold products mainly includes casting wax, inverted mold, and surface trimming. In order to improve the gloss of the surface of gold products, the surface of gold products is usually treated by electroplating.
  • CN106521594A discloses a manufacturing method and equipment for processing K gold into a natural color of gold, pre-preparing a semi-finished product of jewelry; electroplating the semi-finished product of jewelry to restore the external color to the natural color of gold; and surface treating the semi-finished product of electroplating after plating To form finished jewelry.
  • the plating method is applied to the surface of the gold product, the film layer on the surface of the gold product is unstable and easily peeled off.
  • CN107675136A discloses a method for physical vapor deposition (PVD) coating on the surface of a workpiece.
  • the workpiece to be plated is put into a coating chamber to be evacuated and heated, and then argon is passed, and the workpiece to be plated is subjected to ion bombardment, and then a working gas is passed to be plated.
  • the workpiece is biased to deposit a coating of the corresponding material on the workpiece to be plated.
  • CN105803412A discloses a PVD coating layer on the surface of an airspeed tube and a preparation method thereof. A single metal plating layer is plated on the polished surface of the airspeed tube substrate by a physical vapor deposition method.
  • PVD a PVD method is used to coat the surface of the workpiece to improve the binding ability between the coating and the workpiece to be plated.
  • PVD is only suitable for coating on the surface of materials with higher hardness.
  • the bonding force between the film layer and the substrate is still weak.
  • the object of the present invention is to overcome the problems of unstable plating and low gloss of the coating on the surface of the precious metal in the prior art, and provide a precious metal product with a coating on the surface and a preparation method thereof.
  • the transparent film layer is formed, and the formed transparent film layer has a stable structure, strong abrasion resistance, and can make the color of precious metal products persistent and not fade.
  • the first aspect of the present invention provides a precious metal product, wherein the precious metal product includes a precious metal substrate and a transparent film layer attached to the precious metal substrate, and the precious metal is gold or silver.
  • the second aspect of the present invention provides the aforementioned method for preparing a precious metal product, wherein the method includes: depositing a transparent film layer on a surface of the precious metal substrate.
  • the color of the obtained precious metal product is durable and does not fade.
  • the precious metal substrate is surface-treated in advance to improve the surface roughness of the precious metal substrate. Then, PVD is more easily used to form a transparent film layer on the surface of the precious metal substrate, which can make the formed film layer more stable and wear-resistant. Stronger, and can make the color of precious metal products last longer and do not fade.
  • FIG. 1 is a schematic structural diagram of a precious metal product prepared in Example 1 of the present invention.
  • the first aspect of the present invention provides a noble metal product, as shown in FIG. 1, the noble metal product includes a noble metal substrate 1 and a transparent film layer 2 (preferably composed of the noble metal substrate 1 and The transparent film layer 2 on the noble metal substrate 1 is composed of gold or silver.
  • the content of the noble metal in the noble metal substrate 1 may be 33-99.99% by weight, preferably 75-99.99% by weight (or 99-99.99% by weight); for example, in the present invention, the noble metal substrate 1 may be It is K gold, but it can also be gold.
  • the K gold refers to the precious metal matrix 1 formed by mixing and smelting gold with silver, zinc, copper, palladium, or nickel; the pure gold refers to the precious metal matrix 1 with a gold content of not less than 99% by weight;
  • the solid gold includes 3D hard gold.
  • the content of silver in the silver may be 92.5-99% by weight.
  • the surface roughness of the noble metal substrate 1 is preferably 0.001-50 ⁇ m, and more preferably 0.005-0.1 ⁇ m.
  • the surface roughness is Ra, that is, the small pitch of the processed surface and the unevenness of the small peaks and valleys can be directly tested by a surface roughness measuring instrument.
  • the subsequent steps may be directly performed. If the raw material of the noble metal substrate 1 does not satisfy the above-mentioned surface roughness limitation, the noble metal substrate 1 may be treated by a chemical or mechanical method, and the method is not particularly limited as long as the above roughness can be satisfied.
  • the surface roughness of the noble metal substrate 1 satisfies the above conditions, and it is easier to plate a film on the surface of the noble metal substrate. If the surface roughness is too low, the firmness of the bonding between the film layer and the precious metal substrate is reduced; if the surface roughness is too large, the color of the final precious metal product is affected.
  • the thickness of the transparent film layer 2 may be 0.0001-10 ⁇ m (such as 0.0001 ⁇ m, 0.0002 ⁇ m, 0.001 ⁇ m, 0.006 ⁇ m, 0.01 ⁇ m, 0.09 ⁇ m, 0.1 ⁇ m, 0.2 ⁇ m, 1 ⁇ m, 10 ⁇ m, or any of the above values.
  • the material of the transparent film layer 2 may be a fluoride; for example, the fluoride may be It is an AF pill; in the present invention, the AF pill can be obtained commercially, for example, the AF pill can be purchased from the manufacturer Huizhou Memet Electronic Technology Co., Ltd. and the model is TS-2AB.
  • the thickness and material of the transparent film layer 2 are limited to the above range. One is to prevent the formed film layer from being oxidized to make it more stable, and the other is to increase the abrasion resistance and make the The resulting color is more durable and does not fade. In the present invention, especially when the formed film layer is rose gold, since the target used contains copper and is easily oxidized, coating the AF film on it can prevent oxidation and play a protective role.
  • the gloss is measured using an angle of 60 degrees, and the gloss of the precious metal product 1 may be 880-950Gu, preferably 880-900Gu.
  • Gu means English gloss unit
  • 1 gloss unit 1Gu.
  • the second aspect of the present invention provides the aforementioned method for preparing a precious metal product, wherein the method includes: depositing a transparent film layer 2 on the surface of the precious metal substrate 1 by physical vapor deposition.
  • the physical vapor deposition method may be a vacuum evaporation coating, a vacuum sputtering coating, or a vacuum ion coating.
  • the physical vapor deposition method is vacuum ion plating.
  • the manner of the vacuum evaporation coating includes: turning on an evaporation source current, evaporating fluoride, and forming a transparent film layer 2.
  • the method of the vacuum evaporation coating includes: evaporating 170-190s under the condition that the current of the evaporation source is 700-750A; then evaporating 170-190s under the condition that the current of the evaporation source is 750-800A; and then Evaporate 410-430s at 800-900A.
  • the vacuum evaporation coating method includes: adjusting the vacuum degree to 1.8 ⁇ 10 -2 -2.2 ⁇ 10 -2 Pa, making the environment in the furnace suitable for electroplating, injecting argon, and argon flow rate of 55-65sccm, adjusting Vacuum degree is 1.3 ⁇ 10 ° -1.7 ⁇ 10 ° Pa, glow cleaning is 170-190s, oxygen is injected, oxygen flow rate is 75-85sccm, vacuum degree is adjusted to 3.8 ⁇ 10 -1 -4.2 ⁇ 10 -1 Pa, start separately Aluminum target 80-100s, silicon target 170-190s, then turn off the power of the aluminum target and silicon target, start the power of the evaporation source, the silicon target current is 2.8-3.2A; evaporate 170-190s under the condition of the evaporation source current 700-740A ; Then evaporate for 170-190s under the condition of evaporation source current of 750-800A; then evaporate for 410-430s under the condition of evaporation source
  • the vacuum evaporation coating was performed at normal temperature, with a vacuum degree of 3 ⁇ 10 -1 Pa to 6 ⁇ 10 -1 Pa, an argon flow rate of 50-60 sccm, an oxygen flow rate of 70-80 sccm, and a loading bias of 30-40V.
  • the duty cycle is 30-40% and the time is 20-30min.
  • the targets are aluminum target and silicon target. When aluminum target is used, the current is 2-3A. When silicon target is used, the current is 2-3A.
  • the principle of vacuum evaporation coating is used, that is, a solid material is placed in a vacuum chamber, and the solid material is heated and evaporated under a vacuum condition, and the evaporated atoms or molecules can be freely spread on the wall of the container.
  • the noble metal substrate 1 when the noble metal substrate 1 is placed therein, the evaporated atoms or molecules will be adsorbed on the noble metal substrate 1 to gradually form a thin film.
  • a vacuum evaporation coating method is used, and the fluoride is heated and evaporated in a vacuum to deposit it on the surface of the metal substrate 1.
  • the step of vacuum ion plating includes: heating the noble metal substrate 1 under vacuum, starting a metal target, injecting a gas, applying a bias voltage, and placing the noble metal substrate 1 on the noble metal substrate 1. Coating on the surface;
  • the heating temperature is 50-260 ° C, and the temperature will affect the binding force and color of the plating layer and the precious metal substrate 1, especially in When producing rose gold, the heating temperature in the furnace is generally 100-250 ° C, preferably 200 ° C.
  • the coating time is 2-2000min.
  • the deposition time is different according to the target material and the coated color, and the coating time will be different.
  • the target material is divided into three types: arc target, column target, flat target, and arc target ion.
  • the particles are the thickest, followed by the flat target, and the column target ion particles are the thinnest, so the arc target is colored fast, followed by the flat target, the column target is colored slowly, taking rose gold as an example, the coating time of the arc target is about 10min, and the coating time of the column target.
  • the magic color coating time is about 10min
  • the purple coating time is the shortest, which is 2-3min, so the color difference of the plating purple is large and the color is unstable.
  • the metal used in the metal target is selected from the group consisting of nickel, zinc, magnesium, tin, iron, chromium, silicon, copper, titanium, zirconium, molybdenum, tungsten, aluminum, niobium, indium, tantalum, germanium, silver, At least one of gold, cobalt, thallium, lanthanum, yttrium, cerium, thallium, tungsten, stainless steel and alloys or oxides, nitrides, carbides, fluorides, sulfides, gold-copper alloys, and borides; preferably Gold copper alloy.
  • the gas includes a protective gas and a toning gas
  • the protective gas is an inert gas
  • the toning gas is selected from one or more of nitrogen, acetylene, methane, and oxygen; in the present invention, it is preferred
  • argon is used as a protective gas
  • argon is used to adjust the degree of vacuum.
  • the gas flow of the protective gas is 20-200 sccm, preferably 20-150 sccm.
  • nitrogen, acetylene, methane or oxygen is preferred.
  • the gas flow used to adjust the color is 50-500 sccm.
  • the loading bias voltage is 10-150V, and the duty ratio is 10-80%.
  • the "duty cycle” refers to the ratio of the time occupied by the pulse to the total time during a period of continuous working time.
  • the higher the bias voltage the greater the brightness, but beyond a certain value, the edge of the precious metal product will turn yellow; therefore, it is best to limit the loading bias voltage to the above range.
  • the target current of the metal target is: column target 3-120A, preferably 10-120A, more preferably 20-120A, and arc target 50-200A; in the present invention, the larger the current, the more ionic particles will be.
  • the gloss of the coating is very important. Therefore, it is best to limit the target current to the above range.
  • the noble metal substrate 1 is heated at a temperature of 1 ⁇ 10 -2 Pa to 7 ⁇ 10 -3 Pa at 100-250 ° C., and the surface oxide film is removed from the target to be plated.
  • the sputtering voltage was selected from 300-700V, and a thin film was formed on the surface of the precious metal substrate.
  • the metal target and gas can be selected according to the color displayed by the final precious metal product.
  • the metal target may be a gold copper target or a TiAl column target
  • the gas may be nitrogen. Specifically, it can be specifically explained in the embodiments.
  • the method further comprises depositing a noble metal on the surface of a transparent film substrate 1 is performed prior to evacuation process 2, wherein the coating color according to the requirements and the target degree of vacuum during the evacuation of 1 ⁇ 10 - 2 Pa to 7 ⁇ 10 -3 Pa.
  • the vacuum degree in the furnace is different, and the vacuum time Usually in 0.5-2 hours.
  • the glow cleaning is performed before the physical vapor deposition, wherein the conditions of the glow cleaning include: an argon flow rate of 100-320 sccm, preferably 280-320 sccm, and a loading bias of 380-1000 V, preferably It is 380-420V, the duty ratio is 10-80%, preferably 48-52%, and the time is 160-720s, preferably 160-200s.
  • the method further comprises first cleaning the surface of the precious metal substrate 1.
  • different cleaning methods are selected according to the surface structure, area, and cleaning degree of the precious metal substrate 1.
  • the first type ultrasonically wash the precious metal substrate 1 under the condition of 20-30kHz for 1-15min; in the present invention, it should be noted that in special cases, the ultrasonic cleaning time can be extended. After the ultrasonic cleaning is completed, the water is washed 6 times. In the above, the residue of the surface cleaning agent is removed. After the cleaning is completed, a drying treatment is required to dehydrate and bake.
  • the second type the surface of the precious metal substrate 1 is clean and has no oxide layer.
  • the surface can be cleaned by using a dust-free cloth dipped in 95-98% by weight alcohol without ultrasonic cleaning.
  • the cleaning method may be the first or the second method.
  • the cleaning method may be the first method or the second method.
  • the noble metal substrate 1 is subjected to ultrasonic treatment and / or alcohol cleaning under the above conditions, which can further improve the binding force between the transparent film layer 2 and the noble metal substrate 1; and in a short time, it can be used on the surface of the noble metal substrate 1.
  • a film layer having a thickness of 10 nm-50 ⁇ m is formed, and the formed film layer is more stable.
  • the method may further include a step of drying the ultrasonic-treated noble metal substrate 1, the drying temperature is 100-150 ° C, and the drying time is 5-30 minutes.
  • the surface treatment method of the noble metal substrate 1 is not particularly limited, and a physical grinding or chemical etching method can be adopted, as long as the surface roughness of the noble metal substrate 1 is 0.001-50 ⁇ m, and preferably 0.005-0.1 ⁇ m.
  • Gloss LS192 gloss instrument is used to test the gloss of precious metal products at 60 degrees.
  • Abrasion resistance The WS-97 coating adhesion scratch tester developed by Zhongke Kaihua Technology Development Co., Ltd. is used to perform a scratch test on precious metal products.
  • the scratch test uses a stylus with a smooth conical tip to characterize the coating surface under gradually increasing load until the coating is damaged.
  • the load applied when the coating is broken is the critical load, and this is used as the adhesion strength of the coating and the substrate. measure. Set the loading rate to 10 N / min, the loading load to 30 N, the scratch speed to 2 mm / min, and the scratch length to 5 mm.
  • This embodiment is to use the method of the present invention to prepare a pure gold product coated with a transparent film layer.
  • Select noble metal substrate 1 pure gold is selected as the noble metal substrate 1, and its surface roughness is 0.02 ⁇ m;
  • Vacuum in the furnace Put the dried gold in a vacuum furnace and adjust the vacuum to 3 ⁇ 10 -3 Pa to ensure that the vacuum environment in the furnace is clean and the environment in the furnace is suitable for electroplating;
  • Adjust the vacuum degree For 4.0 ⁇ 10 -1 Pa start the aluminum target for 90s and the silicon target for 180s, then turn off the power of the aluminum target and the silicon target, start the power of the evaporation source to evaporate the fluoride AF pills; evaporate for 180s under the condition of the current of the evaporation source being 720A; Then, it is evaporated for 180s under the condition that the current of the evaporation source is 780A; then it is evaporated for 420s under the condition that the current of the evaporation source is 850A; a transparent film layer 2 having a thickness of 0.05 ⁇ m is formed.
  • the prepared precious metal product is referred to as S1 (the structure is shown in FIG. 1), and the performance test is performed on it, and the results are shown in Table 1.
  • This embodiment is to use the method of the present invention to prepare a pure gold product coated with a transparent film layer.
  • Select noble metal substrate 1 Select pure gold as the noble metal substrate 1 with a surface roughness of 0.05 ⁇ m;
  • Vacuum in the furnace Put the dried gold in a vacuum furnace, adjust the vacuum to 3 ⁇ 10 -3 Pa, and adjust the temperature in the furnace to 200 ° C;
  • the fluoride AF pill is evaporated by turning on the power of the evaporation source. Evaporate for 175s at a current of 720A; then evaporate for 175s at a current of 760A; then evaporate for 410s at a current of 840A; and form a transparent film layer 2 with a thickness of 0.001 ⁇ m.
  • This embodiment is to use the method of the present invention to prepare a pure gold product coated with a transparent film layer.
  • Select precious metal substrate 1 Pure gold is selected as precious metal substrate 1, and its surface roughness is 0.2 ⁇ m;
  • Vacuum in the furnace Put the dried gold in a vacuum furnace and adjust the vacuum to 3 ⁇ 10 -3 Pa to ensure that the vacuum environment in the furnace is clean and the environment in the furnace is suitable for electroplating;
  • the fluoride AF pill is evaporated by turning on the power of the evaporation source. 170s at a current of 720A; 170s at a current of 770A; 410s at a current of 850A; and a transparent film layer 2 having a thickness of 0.01 ⁇ m.
  • This embodiment is to use the method of the present invention to prepare a pure gold product coated with a transparent film layer.
  • Select noble metal substrate 1 Select pure gold as the noble metal substrate 1 with a surface roughness of 0.03 ⁇ m;
  • Vacuum in the furnace Put the dried gold in a vacuum furnace and adjust the vacuum to 3 ⁇ 10 -3 Pa to ensure that the vacuum environment in the furnace is clean and the environment in the furnace is suitable for electroplating;
  • the fluoride AF pill is evaporated by turning on the power of the evaporation source. 170s at a current of 700A; 170s at a current of 750A; 410s at a current of 800A; and a transparent film layer 2 having a thickness of 0.01 ⁇ m.
  • This embodiment is to prepare a 18k gold precious metal product coated with a transparent film layer by using the method of the present invention.
  • the surface of the gold was plated in the same manner as in Example 1, except that the gold was replaced with 18k gold.
  • the prepared noble metal product is recorded as S5, and the performance test is performed on it, and the results are shown in Table 1.
  • This embodiment is to use the method of the present invention to prepare a pure gold product coated with a transparent film layer.
  • Select noble metal substrate 1 pure gold is selected as the noble metal substrate 1, and its surface roughness is 0.02 ⁇ m;
  • Vacuum in the furnace Put the dried gold in a vacuum furnace and adjust the vacuum to 3 ⁇ 10 -3 Pa to ensure that the vacuum environment in the furnace is clean and the environment in the furnace is suitable for electroplating;
  • the fluoride AF pill is evaporated by turning on the power of the evaporation source. Evaporate for 190s at a current of 750A; then evaporate for 190s at a current of 800A at the source; then evaporate for 430s at a current of 900A at the source; and form a transparent film layer 2 with a thickness of 0.01 ⁇ m.
  • the prepared noble metal product is recorded as S6, and the performance test is performed, and the results are shown in Table 1.
  • This embodiment is to use the method of the present invention to prepare a pure gold product coated with a transparent film layer.
  • the surface of the gold was plated, except that the fluoride AF pellet was evaporated by activating the power source of the evaporation source, and the evaporation was performed for 170s under the condition that the current of the evaporation source was 730A; and the current of the evaporation source was Evaporate for 180s under the condition of 770A; then evaporate for 420s under the condition of an evaporation source current of 820A; and form a transparent film layer 2 with a thickness of 0.0005 ⁇ m.
  • the prepared noble metal products were recorded as S7, and performance tests were performed on them. The results are shown in Table 1.
  • This embodiment is to use the method of the present invention to prepare a pure gold product coated with a transparent film layer.
  • Example 6 The same method as in Example 6 was used to coat the surface of the pure gold, except that the fluoride AF pellet was evaporated by activating the power source of the evaporation source, and evaporated for 190s under the condition that the current of the evaporation source was 720A; and the current of the evaporation source was Evaporate for 190s under the condition of 780A; then evaporate for 420s under the condition of an evaporation source current of 860A; and form a transparent film layer 2 with a thickness of 0.1 ⁇ m.
  • the fluoride AF pellet was evaporated by activating the power source of the evaporation source, and evaporated for 190s under the condition that the current of the evaporation source was 720A; and the current of the evaporation source was Evaporate for 190s under the condition of 780A; then evaporate for 420s under the condition of an evaporation source current of 860A; and form a transparent film layer 2 with a thickness of 0.1 ⁇
  • the prepared noble metal product is recorded as S8, and the performance test is performed on it, and the results are shown in Table 1.
  • the surface of the pure gold was plated in the same manner as in Example 1, except that the surface roughness of the pure gold was 10 ⁇ m.
  • the prepared noble metal product is recorded as S9, and performance test is performed on it, and the results are shown in Table 1.
  • the surface of the pure gold was plated in the same manner as in Example 1, except that the surface roughness of the pure gold was 1 ⁇ m.
  • the prepared precious metal product is referred to as S10, and the performance test is performed on it, and the results are shown in Table 1.
  • the surface of the gold was plated in the same manner as in Example 1, except that the gold was ultrasonically cleaned at 5 kHz for 10 minutes.
  • the prepared noble metal product was recorded as S11, and the performance test was performed on it. The results are shown in Table 1.
  • the surface of the pure gold was plated in the same manner as in Example 1, except that the pure gold was ultrasonically cleaned at 50 kHz for 10 minutes.
  • the prepared noble metal product is recorded as S12, and the performance test is performed on it, and the results are shown in Table 1.
  • the surface of the pure gold was plated in the same manner as in Example 1, except that the cleaned pure gold was not dried.
  • the prepared precious metal product is recorded as S13, and the performance test is performed, and the results are shown in Table 1.
  • the surface of the pure gold was plated in the same manner as in Example 1, except that the thickness of the formed transparent film layer was 0.15 ⁇ m.
  • the prepared noble metal product is recorded as S14, and the performance test is performed. The results are shown in Table 1.
  • step (2) a transparent fluoride film layer 2 having a thickness of 0.002 ⁇ m was formed.
  • the prepared noble metal product is recorded as S15, and the performance test is performed, and the results are shown in Table 1.
  • step (2) the evaporation was performed for 200s under the condition of an evaporation source current of 600A; and the evaporation was performed for 200s under the condition of an evaporation source current of 700A. ; Then evaporate for 300s under the condition that the current of the evaporation source is 750A.
  • the prepared noble metal product is recorded as S16, and the performance test is performed on it.
  • the surface of the pure gold is plated, except that in step (2), the pure gold is subjected to a copper plating treatment, the pH of the copper-containing plating solution is 0.1, and the plating temperature is 25 ° C.
  • the cathode current density was 4A / dm 2 , and the plating was performed for 1 hour to form a copper layer with a thickness of 800 micrometers on the surface of the gold.
  • the prepared noble metal products were recorded as DS1, and performance tests were performed on them.
  • the surface of pure gold was plated in the same manner as in Example 1, except that an aluminum alloy was used as a precious metal substrate.
  • the precious metal substrate is surface-treated in advance to improve the surface roughness of the precious metal substrate.
  • PVD is easier to deposit a transparent film layer on the surface coating of the precious metal substrate, which can make The formed film layer is more stable, more resistant to abrasion, and can make the color of precious metal products last longer and not fade.
  • Precious metal products were prepared according to the methods of Examples 1-16 and Comparative Examples 1-2. The difference was that S17-S32, DS3 and DS4 were prepared by using silver (92.5% by weight of silver) instead of precious metal. See Table 2.

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Abstract

L'invention concerne un article en métal précieux ayant un revêtement sur sa surface et un procédé de préparation associé. L'article en métal précieux comprend : une base de métal précieux (1) et une couche de film transparent (2) fixée sur la base de métal précieux. Le métal précieux est l'or ou l'argent. Le procédé de préparation de l'article en métal précieux comprend : le dépôt d'une couche de film transparent (2) sur une surface de la base de métal précieux (1) à l'aide d'un dépôt physique en phase vapeur. La couche de film transparent formée sur la surface de l'article en métal précieux obtenu est stable et hautement résistante à l'usure et peut faire durer la couleur de l'article en métal précieux sans décoloration.
PCT/CN2019/094842 2018-09-06 2019-07-05 Article en métal précieux ayant un revêtement sur sa surface et procédé de préparation associé WO2020048215A1 (fr)

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CN102766845A (zh) * 2012-07-09 2012-11-07 珠海承鸥卫浴用品有限公司 一种金属表面pvd装饰性镀膜方法
CN109097736A (zh) * 2018-09-06 2018-12-28 深圳市联合蓝海科技开发有限公司 表面带有镀层的贵金属制品及其制备方法

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