CN113862584A - Imitation gold alloy and preparation method and application thereof - Google Patents

Imitation gold alloy and preparation method and application thereof Download PDF

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Publication number
CN113862584A
CN113862584A CN202111456050.7A CN202111456050A CN113862584A CN 113862584 A CN113862584 A CN 113862584A CN 202111456050 A CN202111456050 A CN 202111456050A CN 113862584 A CN113862584 A CN 113862584A
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alloy
gold
equal
imitation
film
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CN113862584B (en
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谭志
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Vitalink Industry Shenzhen Co ltd
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Wuhan Zhongwei Chuangfa Industrial Research Institute Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/001—Amorphous alloys with Cu as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention relates to a gold-imitating alloy and a preparation method and application thereof. The chemical formula of the gold-imitating alloy is ZrxSiyNizCu1‑x‑y‑zX, y and z are atomic percentages, x is more than or equal to 0.05 and less than or equal to 0.13, y is more than or equal to 0.02 and less than or equal to 0.10, and z is more than or equal to 0.02 and less than or equal to 0.05, and the amorphous structure can form a four-phase alloy, which is mainly because the atomic radii of Zr, Si, Ni and Cu are very close to each other, and is beneficial to the alloying growth of the amorphous structure in the growth process. In addition, in the growth process, Zr and Cu, Ni and Cu, and Zr and Si are easy to form strong metal bonds, so that the powder structure is in an amorphous-like state, a compact internal structure is formed, and the corrosion resistance of the powder is improved. In addition, doping a small amount of Ni and Si is beneficial to improving the hardness of the alloyAnd structural stability, and then promoted the granule regularity of powder in ball-milling or sanding process.

Description

Imitation gold alloy and preparation method and application thereof
Technical Field
The invention relates to the technical field of alloy materials, in particular to a gold-imitating alloy and a preparation method and application thereof.
Background
The metal nano powder is an important processing material in the field of glass and plastic decoration due to excellent physical and chemical characteristics and metal color characterization. The gold-imitating decorative nanometer powder is similar to gold (Au) in color characterization and is always held by market pursuit, but because the gold powder is expensive in manufacturing cost and soft in texture, the gold powder is easy to adhere to ceramsite in the sanding process, the shape characterization consistency of the pure gold nanometer powder is poor, copper (Cu) nanometer powder is generally used in the industry to replace the pure gold nanometer powder, but because of the chemical characteristics of copper, the copper powder is easy to react with humid air, the corrosion resistance of the copper powder is poor, the hardness of the copper powder is poor, the shape consistency of the nanometer powder can be influenced, and the industrial and commercial application of the gold-imitating nanometer powder is greatly limited.
At present, a gold-like bonding alloy wire and a preparation method thereof are reported, wherein the gold-like bonding alloy wire comprises 65wt% -80wt% of silver (Ag), 17wt% -32wt% of copper, 0.5wt% -2wt% of indium (In) and 0.5wt% -1wt% of palladium (Pd), and the gold-like bonding alloy wire is obtained by adding a certain proportion of copper, palladium and indium based on silver. Because the raw material does not contain gold, the cost of the raw material can be greatly reduced relatively, which is about 1/20 of the traditional gold wire. The mechanical property is excellent, the welding technical requirement under the conventional condition can be met, the manufacturing cost of the LED and the IC package can be greatly reduced, and the gold wire can replace the traditional gold wire product to be applied to the packages of integrated circuits, large-scale integrated circuit miniaturization, discrete devices, LEDs and the like. Meanwhile, the bonding alloy wire can obtain perfect gold imitation and can meet the requirement of customers for the gold imitation of the color of the bonding alloy wire.
Therefore, the gold-imitating effect can be achieved through the alloy doping mode, and meanwhile, the mechanical property of the Cu alloy can be improved, for example, the gold-imitating bonding alloy wire is doped with metals such as Ag, In and Pd which are not easy to oxidize, so that the corrosion resistance of the copper alloy can be improved, but because Ag, In and Pd are all noble metals, the manufacturing cost of the alloy is still high, the hardness of the manufactured alloy is low, irregular deformation is easy to generate In the sanding process of manufacturing nano powder, and the process is not easy to apply to industrial mass production of the nano powder.
Therefore, how to reduce the cost of the imitation gold alloy and improve the comprehensive performance of the imitation gold alloy always troubles relevant researchers.
Disclosure of Invention
Based on the above, the invention provides the imitation gold alloy which has excellent imitation gold color, high hardness and excellent corrosion resistance and is low in manufacturing cost, and further provides a preparation method and application of the imitation gold alloy.
The technical scheme is as follows:
a gold-imitating alloy with a chemical formula of ZrxSiyNizCu1-x-y-zX, y and z satisfy: x, y and z are atomic percent, x is more than or equal to 0.05 and less than or equal to 0.13, y is more than or equal to 0.02 and less than or equal to 0.10, and z is more than or equal to 0.02 and less than or equal to 0.05.
In one embodiment, x, y, and z satisfy: x is more than or equal to 0.05 and less than or equal to 0.10, y is more than or equal to 0.02 and less than or equal to 0.05, and z is more than or equal to 0.02 and less than or equal to 0.05.
The invention also provides a preparation method of the imitation gold alloy, which is to prepare the imitation gold alloy in a physical vapor deposition mode;
the chemical formula of the gold-imitating alloy is ZrxSiyNizCu1-x-y-zX, y and z are atomic percentages, x, y and z satisfy: x is more than or equal to 0.05 and less than or equal to 0.13, y is more than or equal to 0.02 and less than or equal to 0.10, and z is more than or equal to 0.02 and less than or equal to 0.05.
In one embodiment, the physical vapor deposition is at least one of vacuum evaporation, magnetron sputtering, arc plasma, ion plating, and molecular beam epitaxy.
In one embodiment, the physical vapor deposition is magnetron sputtering coating, and the preparing the gold-imitation alloy by magnetron sputtering coating includes:
providing a substrate, a Zr source, a Si source, a Ni source and a Cu source, introducing working gas, and sputtering and depositing the imitation gold alloy on the substrate.
In one embodiment, the Zr source is a Zr target, the Si source is a Si target, the Ni source and the Cu source are Ni-Cu alloy targets, and the working gas is Ar.
In one embodiment, the process parameters for preparing the imitation gold alloy by magnetron sputtering coating comprise:
the sputtering temperature is 150-330 ℃, and the Ar gas pressure is 0.5-0.8 Pa; and/or
The power density of the Zr target is 0.5W/cm2-3W/cm2(ii) a And/or
The power density of the Si target is 0.1W/cm2-2W/cm2(ii) a And/or
The power density of the Ni-Cu alloy target is 4.5W/cm2-6.5W/cm2(ii) a And/or
The bias voltage of the substrate is-150V- (-50) V; and/or
The gas flow of Ar is 25sccm-45 sccm; and/or
The time of sputtering deposition is 10min-15 min.
In one embodiment, the vacuum chamber used for magnetron sputtering coating has a background vacuum degree of less than or equal to 5.0 x 10-4Pa。
In one embodiment, before the step of sputtering and depositing the imitation gold alloy on the substrate, the method further comprises the step of depositing a stripping layer on the substrate;
and a step of separating the gold-imitation alloy from the peeling layer to obtain a thin-film gold-imitation alloy after the step of sputtering and depositing the gold-imitation alloy on the substrate.
In one embodiment, the method further comprises a step of crushing the thin-film-like gold-imitating alloy to prepare a powdery gold-imitating alloy after the step of separating the gold-imitating alloy from the peeling layer to prepare the thin-film-like gold-imitating alloy.
In one embodiment, the thickness of the film-shaped imitation gold alloy is 150nm-3000nm, and the grain diameter of the powder-shaped imitation gold alloy is 0.1 μm-2.5 μm.
In one embodiment, the material of the substrate is polyethylene terephthalate (PET), polypropylene (PP), polymethyl methacrylate (PMMA) or glass.
The invention also provides ink which comprises resin and the imitation gold alloy, or the ink comprises the resin and the imitation gold alloy prepared according to the preparation method of the imitation gold alloy.
The invention also provides a coated product, which comprises a substrate and the gold-imitation alloy film covered on the surface of the substrate, wherein the gold-imitation alloy film comprises the gold-imitation alloy, or the gold-imitation alloy film comprises the gold-imitation alloy prepared by the preparation method of the gold-imitation alloy, or the gold-imitation alloy film is prepared from the printing ink.
In one embodiment, the coated article is an electronic device or an ornament.
In one embodiment, in the coated product, the substrate is made of glass, PMMA, PET or PP.
The invention has the following beneficial effects:
the invention provides a gold-imitating alloy with a chemical formula of ZrxSiyNizCu1-x-y-zX is more than or equal to 0.05 and less than or equal to 0.13, y is more than or equal to 0.02 and less than or equal to 0.10, and z is more than or equal to 0.02 and less than or equal to 0.05, and the alloy is of an amorphous structure and can form a four-phase alloy. Specifically, the atomic radius of Zr is 1.6 a, the atomic radius of Si is 1.17 a, the atomic radius of Ni is 1.24 a, the atomic radius of Cu is 1.28 a, which are very close in atomic size, favoring Zr during growthxSiyNizCu1-x-y-zThe alloy grows. And, in ZrxSiyNizCu1-x-y-zIn the growth process, Zr and Cu, Ni and Cu, and Zr and Si are easy to form stronger metal bonds, so that the powder structure is in an amorphous-like state, a compact internal structure is formed, and the corrosion resistance of the powder is further improved. In addition, the activity of Zr is highest and is higher than that of Cu, Zr reacts with oxygen in the air to form inert ZrO, the air is further prevented from contacting with copper, the hardness and the oxidation resistance of the material are improved, the ageing resistance of the material is further improved, the hardness and the structural stability of the alloy are improved by doping a small amount of Ni and Si, and the particle regularity of powder (particularly nano powder) in the ball milling or sanding process is further improved. Therefore, the amorphous hard gold-imitating alloy material which is compact, has gold-imitating color, high hardness and strong ageing resistance can be manufactured by optimizing the composition of the gold-imitating alloy material.
Through tests, compared with the traditional pure copper or pure gold material, the imitation gold alloy provided by the invention has more excellent hardness, and the hardness can reach more than 3 times of that of the pure copper or the pure gold. Meanwhile, compared with the traditional pure copper material, the imitation gold alloy provided by the invention has more excellent corrosion resistance and ageing resistance. In addition, compared with the traditional copper-containing alloy (such as Cr-Cu alloy), the imitation gold alloy disclosed by the invention has the advantages of more excellent corrosion resistance and ageing resistance, closer color to golden color, lower manufacturing cost, capability of meeting the application requirement of the imitation gold material in the field of decorative coating, and particular suitability for the field of cover plate decorative coating of 3C products.
In addition, the invention adopts a physical vapor deposition mode to prepare the imitation gold alloy, and has the advantages of high capacity, high efficiency, easy operation, good repeatability, environmental protection and suitability for industrial application.
Drawings
FIG. 1 is a schematic view of an apparatus for producing a gold-imitation alloy in an embodiment of the present invention;
fig. 2 is a flow chart of a method for preparing a gold-imitation alloy according to an embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
It should be noted that in the description of the present invention, for the terms of orientation, there are terms such as "central", "lateral", "longitudinal", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise" and the like indicating the orientation and positional relationship based on the orientation or positional relationship shown in the drawings, which are only for the convenience of describing the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and should not be construed as limiting the specific scope of the present invention.
In describing positional relationships, unless otherwise specified, when an element such as a layer, film or substrate is referred to as being "on" another layer, it can be directly on the other layer or intervening layers may also be present. Further, when a layer is referred to as being "under" another layer, it can be directly under, or one or more intervening layers may also be present. It will also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, as another element may be added, unless an explicit limitation is used, such as "only," "consisting of … …," etc.
In the present invention, at least one means any one, any two, or any two or more.
Unless mentioned to the contrary, terms in the singular may include the plural and are not to be construed as being one in number.
Furthermore, the drawings are not 1: 1 and the relative dimensions of the various elements in the figures are drawn for illustrative purposes only to facilitate understanding of the invention and are not necessarily drawn to scale, and are not to scale.
The technical scheme of the invention is as follows:
a gold-imitating alloy with a chemical formula of ZrxSiyNizCu1-x-y-zX, y and z are atomic percentages, x, y and z satisfy: x is more than or equal to 0.05 and less than or equal to 0.13, y is more than or equal to 0.02 and less than or equal to 0.10, and z is more than or equal to 0.02 and less than or equal to 0.05.
The invention provides a gold-imitating alloyIs amorphous structure, and can form four-phase alloy. Specifically, the atomic radius of Zr is 1.6 a, the atomic radius of Si is 1.17 a, the atomic radius of Ni is 1.24 a, and the atomic radius of Cu is 1.28 a, which are similar in atomic size and are conducive to their alloyed growth during growth. And, in ZrxSiyNizCu1-x-y-zIn the growth process, Zr and Cu, Ni and Cu, and Zr and Si are easy to form stronger metal bonds, so that the powder structure is in an amorphous-like state, a compact internal structure is formed, and the corrosion resistance of the powder is further improved. In addition, the activity of Zr is highest and is higher than that of Cu, Zr reacts with oxygen in the air to form inert ZrO, the air is further prevented from contacting with copper, the hardness and the oxidation resistance of the material are improved, the ageing resistance of the material is further improved, the hardness and the structural stability of the alloy are improved by doping a small amount of Ni and Si, and the particle regularity of powder (particularly nano powder) in the ball milling or sanding process is further improved.
In one embodiment, x, y, and z satisfy: x is more than or equal to 0.05 and less than or equal to 0.10, y is more than or equal to 0.02 and less than or equal to 0.05, and z is more than or equal to 0.02 and less than or equal to 0.05. And controlling x to be slightly larger than or equal to y and far larger than z is beneficial to further improving the hardness of the film.
In one embodiment, x is 0.13, y is 0.02, and z is 0.05.
In one embodiment, x is 0.05, y is 0.10, and z is 0.05.
In one embodiment, x is 0.10, y is 0.03, and z is 0.02.
In one embodiment, x is 0.05, y is 0.03, and z is 0.02.
The invention also provides a preparation method of the imitation gold alloy, which is to prepare the imitation gold alloy in a physical vapor deposition mode;
the chemical formula of the gold-imitating alloy is ZrxSiyNizCu1-x-y-zX, y and z are atomic percentages, x, y and z satisfy: x is more than or equal to 0.05 and less than or equal to 0.13, y is more than or equal to 0.02 and less than or equal to 0.10, and z is more than or equal to 0.02 and less than or equal to 0.05.
It is understood that the imitation gold alloy obtained by physical vapor deposition is a thin film.
In one embodiment, the physical vapor deposition is at least one of vacuum evaporation, magnetron sputtering, arc plasma, ion plating, and molecular beam epitaxy.
In one embodiment, the physical vapor deposition is magnetron sputtering coating, and the preparing the gold-imitation alloy by magnetron sputtering coating includes:
providing a substrate, a Zr source, a Si source, a Ni source and a Cu source, introducing working gas, and sputtering and depositing the imitation gold alloy on the substrate.
The invention adopts the magnetron sputtering coating mode to prepare the film-shaped gold-imitating alloy, has strong controllability, stable reaction, controllable gold color and high deposition rate, and has better film compactness and stronger controllability compared with the traditional evaporative alloy coating.
In one embodiment, the material of the substrate is polyethylene terephthalate (PET), polypropylene (PP), polymethyl methacrylate (PMMA) or glass.
In one embodiment, the Zr source is a Zr target, the Si source is a Si target, the Ni source and the Cu source are Ni-Cu alloy targets, and the working gas is Ar.
Controlling the power density of the Zr target, the Si target and the Ni-Cu alloy target and the gas amount of gas in the process of depositing the imitation gold alloy film to obtain the imitation gold alloys with different hardness.
In one embodiment, the process parameters for preparing the imitation gold alloy by magnetron sputtering coating comprise:
the sputtering temperature is 150-330 ℃, and the Ar gas pressure is 0.5-0.8 Pa; and/or
The power density of the Zr target is 0.5W/cm2-3W/cm2(ii) a And/or
The power density of the Si target is 0.1W/cm2-2W/cm2(ii) a And/or
The power density of the Ni-Cu alloy target is 4.5W/cm2-6.5W/cm2(ii) a And/or
The bias voltage of the substrate is-150V- (-50) V; and/or
The gas flow rate of Ar is 25sccm-45 sccm.
In one embodiment, the background vacuum of the vacuum chamber is ≦ 5.0 x 10-4Pa, the arrangement can ensure the collision of the sputtered particles and gas molecules, and can also reduce impurities entering the gas molecules in the deposition process, so as to improve the density, purity and bonding force of the gold-imitating alloy.
The thickness of the gold-like alloy in the form of a thin film can be controlled depending on the deposition time, and the thickness of the thin film becomes thicker as the deposition time becomes longer.
In one embodiment, the time for sputter deposition is 10min to 15 min.
In one embodiment, the thickness of the film-like gold-imitation alloy prepared by sputtering deposition is 150nm-300 nm.
In one embodiment, the step of performing a cleaning treatment on the substrate is further included before the step of sputtering and depositing the imitation gold alloy on the substrate.
In one embodiment, the substrate can be cleaned by a cleaning method conventional in the field of decorative coating. Such as washing with an organic solvent (alcohol, acetone, etc.) or washing with water.
In one embodiment, the cleaning process for the substrate comprises the steps of:
putting the substrate into deionized water (DI water) for ultrasonic cleaning for 10-15 minutes, finally putting the substrate into a vacuum baking oven for baking for 15-20 minutes, and putting the substrate onto a rotatable sample table in a vacuum cavity after drying.
In one embodiment, the step of depositing the imitation gold alloy on the substrate by sputtering further comprises the step of depositing a stripping layer on the substrate. The existence of the stripping layer is beneficial to the subsequent separation of the substrate and the imitation gold alloy, and is further beneficial to the subsequent pulverization of the thin-film imitation gold alloy.
In one embodiment, the material of the peeling layer is water-soluble material. Preferably, the material of the release layer is a water-soluble synthetic resin, such as water-based ink, and the main components of the release layer are water-based acrylic resin and water.
In one embodiment, the release layer has a thickness of 20nm to 100 nm.
In a more preferred embodiment of the present invention, the material of the release layer is an aqueous ink film material, that is, the release layer is a water-soluble release layer.
In one embodiment, depositing the aqueous ink release layer comprises:
placing the cleaned substrate on sample stage of resistance evaporation equipment, placing water-based ink (water-soluble synthetic resin) in evaporation boat, and evacuating to 5.0 × 10-5Pa, depositing a water-based ink stripping layer with the thickness of 20nm-100nm on the surface of the cleaned substrate, and taking out the substrate after the preparation is finished. Further, by controlling the film forming time, water-based ink release layers with different film thicknesses are prepared.
In one embodiment, the step of sputtering and depositing the imitation gold alloy on the substrate further includes a step of separating the imitation gold alloy from the peeling layer to obtain a thin-film imitation gold alloy.
In one embodiment, the separation process comprises:
immersing a substrate having a water-based ink release layer and a film-like gold-like alloy deposited on the surface thereof in water at room temperature, and dissolving the water-based ink release layer with water to obtain film-like ZrxSiyNizCu1-x-y-zAnd (4) simulating the gold alloy, filtering to remove filtrate, and collecting film-shaped gold alloy simulation filter residues.
In one embodiment, the method further comprises a step of crushing the thin-film gold-imitation alloy to prepare a powdery gold-imitation alloy after the step of separating the gold-imitation alloy from the peeling layer to obtain a thin-film gold-imitation alloy powder.
In one embodiment, the pulverization is performed by sand milling or ball milling.
In one embodiment, the attrition milling comprises:
and (3) putting the film-shaped gold-imitating alloy obtained after separation into a sand mill, performing sand milling by matching with sand milling particles with specific particle sizes and sand milling media (such as alcohol), filtering by a filter screen after completion, and naturally drying to obtain the gold-imitating alloy powder.
In one embodiment, the shredding process comprises:
collecting the completed Zr at room temperaturexSiyNizCu1-x-y-zPutting the gold-imitating alloy into a sand mill, selecting ZrO particles with the diameter of 1 mu m as ceramsite, wherein the solid-to-liquid ratio of the ZrO particles to alcohol is 1: 9, sanding for 1h, filtering by a filter screen, and naturally airing to obtain the imitation gold alloy powder.
In one embodiment, the thickness of the film-like gold-imitating alloy is 150nm-3000 nm. The grain diameter of the powdery gold-imitating alloy is 0.1-2.5 μm. Furthermore, the particle size of the powdery gold-imitating alloy is nano-scale.
FIG. 1 is a schematic diagram of an apparatus for preparing a gold-like alloy according to an embodiment of the present invention, which includes a vacuum chamber 1, a sample stage 2, a DC anode 3, a DC cathode-powered Zr target 4, a RF-assisted DC cathode-powered Ni-Cu alloy target 5, and a DC cathode-powered Si target 6, and the Zr of the present invention is formed by co-sputtering with Ar in the vacuum chamber 1xSiyNizCu1-x-y-zImitation gold alloy.
Fig. 2 is a flow chart of a preparation method of the imitation gold alloy according to an embodiment of the invention, which includes the following steps:
providing a substrate;
cleaning the substrate;
depositing a water-soluble release layer on the cleaned substrate;
sputtering and depositing a thin-film gold-imitating alloy on the water-soluble stripping layer;
immersing the substrate with the water-soluble stripping layer and the film-shaped gold-imitating alloy deposited on the surface into water, filtering, and collecting filter residues;
and (3) carrying out sand grinding treatment on the film-shaped gold-imitating alloy, and filtering to obtain gold-imitating alloy powder.
The invention also provides ink which comprises resin and the imitation gold alloy, or the ink comprises the resin and the imitation gold alloy prepared according to the preparation method of the imitation gold alloy.
In one embodiment, the resin is selected from synthetic resins, such as gloss oil;
the invention also provides a coated product, which comprises a substrate and the gold-imitation alloy film covered on the surface of the substrate, wherein the gold-imitation alloy film comprises the gold-imitation alloy, or the gold-imitation alloy film comprises the gold-imitation alloy prepared by the preparation method of the gold-imitation alloy, or the gold-imitation alloy film is prepared from the printing ink.
In one embodiment, the coated article is an electronic device or an ornament.
In one embodiment, in the coated product, the substrate is made of PET, polypropylene PP, PMMA or glass.
The specific embodiment is as follows:
the hardness testing method of the invention comprises the following steps: the hardness of each film was tested using an NHT3 nanoindenter model manufactured by Anton-Paar, Austria, equipped with a tetrahedral Berkvich indenter, set the indentation depth to 100nm, the load varied with indentation depth, and 5 matrix points were measured for each sample and averaged.
The invention relates to a composition test of a gold-imitating alloy, which utilizes an X-ray energy spectrometer (EDX) of an FEI Quanta TM 250 FEG to analyze the composition and the distribution of a coating. Selecting an area of not less than 30 mm for each sample2And area, the average value of its composition is measured.
The colorimetric value test method of the invention comprises the following steps: a bench type spectral test instrument which is produced by Nikkica in Japan and is of a model number CM-3700A-U is adopted to measure the colorimetric values of L, a and b of samples, an F2 light source is selected by a light receiving system, and each sample is averaged after 6 matrix points are tested.
The aging test of the invention adopts the ASTM G154-2006 standard, and the ultraviolet lamp box with the power of 20W is adopted for irradiation for 72h, and the manufacturing method of the printing ink comprises the steps of dissolving the gold-like alloy nano powder in the gloss oil according to the proportion that the solid content is 20%, uniformly stirring, and coating the printing ink on the surface of toughened glass in a screen printing mode to be used as a test sample.
The salt spray corrosion resistance test method comprises the following steps: the corrosion resistance is tested by adopting a program circulation type salt water sprayer, the laboratory temperature is 35 ℃ plus or minus 2 ℃, the temperature of a saturated bucket is 47 ℃ plus or minus 2 ℃, the pH value of the solution is 6.5-7.2, and the test period of each sample is 8 hours.
Example 1
The embodiment provides a gold-imitating alloy and a preparation method thereof.
Ni used in the present examplemCu1-mAn alloy target having m =0.10, m being atomic percent. The preparation method of the imitation gold alloy comprises the following steps:
1) pretreatment: putting a PET sample into DI water for ultrasonic cleaning for 15 minutes, drying the PET sample in a baking oven, putting the PET sample into a vacuum chamber of an evaporative film plating machine, and vacuumizing the vacuum chamber to 5 x 10-5Pa, heating to 80 ℃, and keeping the temperature for 15 minutes;
2) depositing a water-soluble release layer: in a vacuum chamber, a PET sample is placed on a sample table of a resistance type evaporation device, a water-soluble water-based ink film material is placed in an evaporation boat, and the evaporation boat is evacuated to 5.0 x 10-5Pa, depositing a water-based ink stripping layer with the thickness of 30nm on the surface of the PET sample, and taking out the sample after the preparation is finished;
3) depositing a gold-imitation alloy film: placing the PET sample into a vacuum chamber of a magnetic control type film plating machine shown in figure 1, and vacuumizing the vacuum chamber to 5 x 10-4Pa, heating to 120 ℃, keeping the temperature constant for 15 minutes, starting a sample table rotating frame, setting the rotating speed to be 6 circles per minute, adjusting the distance from the sample table to a target surface to be 8cm, adopting a direct current power supply to electrify Zr targets and Si targets, adopting a radio frequency power supply to electrify Ni-Cu targets, introducing Ar, keeping the pressure in a furnace body to be 0.5Pa, starting bias voltage to be-100V, and setting the power density of the Zr targets to be 2W/cm2The power density of the Si target was set to 0.2W/cm2Is prepared by reaction of NimCu1-mThe power density of the target was set to 5W/cm2Preparing a gold-imitation alloy thin film with the thickness of 200nm by controlling the film forming time;
4) soaking a PET sample with a water-based ink stripping layer and a gold-like alloy film deposited on the surface into water at room temperature, dissolving the water-based ink stripping layer by water to obtain a film-like gold-like alloy, filtering to remove filtrate, and collecting film-like gold-like alloy filter residue;
5) and (2) at room temperature, putting the collected film-shaped gold-like alloy filter residue into a sand mill, selecting ZrO particles with the diameter of 1 mu m as ceramsite, and mixing the ZrO particles with alcohol according to a solid-to-liquid ratio of 1: 9, sanding for 1h, filtering by a filter screen, and naturally airing to obtain imitation gold alloy powder with the particle size of 100 nm;
6) dissolving the gold-like alloy powder in varnish according to the proportion that the solid content is 20 percent, uniformly stirring, and coating the ink on the surface of toughened glass in a screen printing mode to obtain the gold-like alloy nano powder ink.
The composition of the gold-like alloy thin film obtained in this example was analyzed to determine that the component was Zr0.13Si0.02Ni0.05Cu0.80The ink has the advantages that the L value is 75.45, the a value is 5.49, the b value is 13.04, the ink has golden color and hardness value of 4.2GPa, and can pass the salt spray corrosion resistance test for 8h, and in addition, the nano powder ink of the embodiment can pass the aging test for 72 h.
Example 2
The embodiment provides a gold-imitating alloy and a preparation method thereof.
Ni used in the present examplemCu1-mAn alloy target having m =0.10, m being atomic percent. The preparation method of the imitation gold alloy comprises the following steps:
1) pretreatment: putting a PET sample into DI water for ultrasonic cleaning for 15 minutes, drying the PET sample in a baking oven, putting the PET sample into a vacuum chamber of an evaporative film plating machine, and vacuumizing the vacuum chamber to 5 x 10-5Pa, heating to 80 ℃, and keeping the temperature for 15 minutes;
2) depositing a water-soluble release layer: in a vacuum chamber, a PET sample is placed on a sample table of a resistance type evaporation device, a water-based ink film material is placed in an evaporation boat, and the evaporation boat is evacuated to 5.0 x 10-5Pa, depositing a water-based ink stripping layer with the thickness of 30nm on the surface of the PET sample, and taking out the sample after the preparation is finished;
3) depositing a gold-imitation alloy film: placing the PET sample into a vacuum chamber of a magnetic control type film plating machine shown in figure 1, and vacuumizing the vacuum chamber to 5 x 10-4Pa, heating to 120 ℃, keeping the temperature for 15 minutes, starting a sample table rotating frame, setting the rotating speed to be 6 circles per minute, adjusting the distance between the sample table and the target surface to be 8cm, and adjusting the Zr target and the S targetThe i target is electrified by a direct current power supply, the Ni-Cu target is electrified by a radio frequency power supply, Ar is introduced, the pressure in the furnace body is kept at 0.5Pa, the bias voltage is started and set to-100V, and the power density of the Zr target is set to 0.6W/cm2The power density of the Si target was set to 1W/cm2Is prepared by reaction of NimCu1-mThe power density of the target was set to 5W/cm2Preparing a gold-imitation alloy thin film with the thickness of 200nm by controlling the film forming time;
4) soaking a PET sample with a water-based ink stripping layer and a gold-like alloy film deposited on the surface into water at room temperature, dissolving the water-based ink stripping layer by water to obtain a film-like gold-like alloy, filtering to remove filtrate, and collecting film-like gold-like alloy filter residue;
5) and (2) at room temperature, putting the collected film-shaped gold-like alloy filter residue into a sand mill, selecting ZrO particles with the diameter of 1 mu m as ceramsite, and mixing the ZrO particles with alcohol according to a solid-to-liquid ratio of 1: 9, sanding for 1h, filtering by a filter screen, and naturally airing to obtain imitation gold alloy powder with the particle size of 100 nm;
6) dissolving the gold-like alloy powder in varnish according to the proportion that the solid content is 20 percent, uniformly stirring, and coating the ink on the surface of toughened glass in a screen printing mode to obtain the gold-like alloy nano powder ink.
The thin film obtained in this example was analyzed for its composition, and it was found that it contained Zr0.05Si0.10Ni0.05Cu0.80The L value is 74.32, the a value is 4.97, the b value is 13.52, the color is similar to golden, the hardness value is 3.5GPa, the ink can pass the salt spray corrosion resistance test for 8h, and in addition, the nano powder ink of the embodiment can pass the aging test for 72 h.
Example 3
The embodiment provides a gold-imitating alloy and a preparation method thereof.
Ni used in the present examplemCu1-mAn alloy target having m =0.05, m being atomic percent. The preparation method of the imitation gold alloy comprises the following steps:
1) pretreatment: putting a PET sample into DI water for ultrasonic cleaning for 15 minutes, drying the PET sample in a baking oven, putting the PET sample into a vacuum chamber of an evaporative film plating machine, and pumping the vacuum chamberVacuum to 5 x 10-5Pa, heating to 80 ℃, and keeping the temperature for 15 minutes;
2) depositing a water-soluble release layer: in a vacuum chamber, a PET sample is placed on a sample table of a resistance type evaporation device, a water-based ink film material is placed in an evaporation boat, and the evaporation boat is evacuated to 5.0 x 10-5Pa, depositing a water-based ink stripping layer with the thickness of 30nm on the surface of the PET sample, and taking out the sample after the preparation is finished;
3) depositing a gold-imitation alloy film: placing the PET sample into a vacuum chamber of a magnetic control type film plating machine shown in figure 1, and vacuumizing the vacuum chamber to 5 x 10-4Pa, heating to 120 ℃, keeping the temperature constant for 15 minutes, starting a sample table rotating frame, setting the rotating speed to be 6 circles per minute, adjusting the distance from the sample table to a target surface to be 8cm, adopting a direct current power supply to electrify Zr targets and Si targets, adopting a radio frequency power supply to electrify Ni-Cu targets, introducing Ar, keeping the pressure in a furnace body to be 0.5Pa, starting bias voltage to be-100V, and setting the power density of the Zr targets to be 1.7W/cm2The power density of the Si target was set to 0.3W/cm2Is prepared by reaction of NimCu1-mThe power density of the target was set to 4.5W/cm2Preparing a gold-imitation alloy thin film with the thickness of 200nm by controlling the film forming time;
4) soaking a PET sample with a water-based ink stripping layer and a gold-like alloy film deposited on the surface into water at room temperature, dissolving the water-based ink stripping layer by water to obtain a film-like gold-like alloy, filtering to remove filtrate, and collecting film-like gold-like alloy filter residue;
5) and (2) at room temperature, putting the collected film-shaped gold-like alloy filter residue into a sand mill, selecting ZrO particles with the diameter of 1 mu m as ceramsite, and mixing the ZrO particles with alcohol according to a solid-to-liquid ratio of 1: 9, sanding for 1h, filtering by a filter screen, and naturally airing to obtain imitation gold alloy powder with the particle size of 100 nm;
6) dissolving the gold-like alloy powder in varnish according to the proportion that the solid content is 20 percent, uniformly stirring, and coating the ink on the surface of toughened glass in a screen printing mode to obtain the gold-like alloy nano powder ink.
The thin film obtained in this example was analyzed for its composition, and it was found that the composition was Zr0.10Si0.03N0.02Cu0.85The ink has the advantages that the L value is 76.72, the a value is 5.67, the b value is 14.71, the ink is in golden color, the hardness value is 3.5GPa, and the ink can pass the salt spray corrosion resistance test for 8h, and in addition, the nano powder ink of the embodiment can pass the aging test for 72 h.
Example 4
The embodiment provides a gold-imitating alloy and a preparation method thereof.
Ni used in the present examplemCu1-mAn alloy target having m =0.05, m being atomic percent. The preparation method of the imitation gold alloy comprises the following steps:
1) pretreatment: putting a PET sample into DI water for ultrasonic cleaning for 15 minutes, drying the PET sample in a baking oven, putting the PET sample into a vacuum chamber of an evaporative film plating machine, and vacuumizing the vacuum chamber to 5 x 10-5Pa, heating to 80 ℃, and keeping the temperature for 15 minutes;
2) depositing a water-soluble release layer: in a vacuum chamber, a PET sample is placed on a sample table of a resistance type evaporation device, a water-based ink film material is placed in an evaporation boat, and the evaporation boat is evacuated to 5.0 x 10-5Pa, depositing a water-based ink stripping layer with the thickness of 30nm on the surface of the PET sample, and taking out the sample after the preparation is finished;
3) depositing a gold-imitation alloy film: placing the PET sample into a vacuum chamber of a magnetic control type film plating machine shown in figure 1, and vacuumizing the vacuum chamber to 5 x 10-4Pa, heating to 120 ℃, keeping the temperature constant for 15 minutes, starting a sample table rotating frame, setting the rotating speed to be 6 circles per minute, adjusting the distance from the sample table to a target surface to be 8cm, adopting a direct current power supply to electrify Zr targets and Si targets, adopting a radio frequency power supply to electrify Ni-Cu targets, introducing Ar, keeping the pressure in a furnace body to be 0.5Pa, starting bias voltage to be-100V, and setting the power density of the Zr targets to be 0.6W/cm2The power density of the Si target was set to 0.3W/cm2Is prepared by reaction of NimCu1-mThe power density of the target was set to 5W/cm2Preparing a gold-imitation alloy thin film with the thickness of 200nm by controlling the film forming time;
4) soaking a PET sample with a water-based ink stripping layer and a gold-like alloy film deposited on the surface into water at room temperature, dissolving the water-based ink stripping layer by water to obtain a film-like gold-like alloy, filtering to remove filtrate, and collecting film-like gold-like alloy filter residue;
5) and (2) at room temperature, putting the collected film-shaped gold-like alloy filter residue into a sand mill, selecting ZrO particles with the diameter of 1 mu m as ceramsite, and mixing the ZrO particles with alcohol according to a solid-to-liquid ratio of 1: 9, sanding for 1h, filtering by a filter screen, and naturally airing to obtain imitation gold alloy powder with the particle size of 100 nm;
6) dissolving the gold-like alloy powder in varnish according to the proportion that the solid content is 20 percent, uniformly stirring, and coating the ink on the surface of toughened glass in a screen printing mode to obtain the gold-like alloy nano powder ink.
The thin film obtained in this example was analyzed for its composition, and it was found that the composition was Zr0.05Si0.03N0.02Cu0.90The L value is 77.45, the a value is 5.79, the b value is 15.04, the color is similar to golden, the hardness value is 3.0GPa, the ink can pass the salt spray corrosion resistance test for 8h, and in addition, the nano powder ink of the embodiment can pass the aging test for 72 h.
Comparative example 1
This comparative example provides an alloy and a method of making the same.
In this comparative example, a Cr target having a purity of 99.8% was installed at 4 targets shown in fig. 1, and direct current cathode charging was used, and a Cu target having a purity of 99.8% was installed at 5 targets shown in fig. 1, and radio frequency-assisted direct current charging was used.
1) Pretreatment: putting a PET sample into DI water for ultrasonic cleaning for 15 minutes, drying the PET sample in a baking oven, putting the PET sample into a vacuum chamber of an evaporative film plating machine, and vacuumizing the vacuum chamber to 5 x 10-5Pa, heating to 80 ℃, and keeping the temperature for 15 minutes;
2) depositing a water-soluble release layer: in a vacuum chamber, a PET sample is placed on a sample table of a resistance type evaporation device, a water-based ink film material is placed in an evaporation boat, and the evaporation boat is evacuated to 5.0 x 10-5Pa, depositing a water-based ink stripping layer with the thickness of 30nm on the surface of the PET sample, and taking out the sample after the preparation is finished;
3) depositing a Cr-Cu alloy film: placing the PET sample into a vacuum chamber of a magnetic control type film plating machine shown in figure 1, and vacuumizing the vacuum chamber to 5 x 10-4Pa, heating to 120 ℃, keeping the temperature for 15 minutes, starting a sample table rotating frame, setting the rotating speed to be 6 circles per minute, and adjusting the distance from the sample table to the target surfaceThe distance is 8cm, the Cr target is electrified by a direct current power supply, the Cu target is electrified by a radio frequency power supply, Ar is introduced, the pressure in the furnace body is kept to be 0.5Pa, the bias voltage is started and set to be-100V, and the power density of the Cr target is set to be 2.5W/cm2The power density of the Cu target was set to 6W/cm2Controlling the film forming time to prepare an alloy film with the film thickness of 200 nm;
4) soaking a PET sample with a water-based ink stripping layer and an alloy film deposited on the surface into water at room temperature, dissolving the water-based ink stripping layer by water to obtain a film-like gold-imitating alloy, filtering to remove filtrate, and collecting film-like alloy filter residue;
5) and (2) at room temperature, putting the collected film-shaped alloy filter residue into a sand mill, selecting ZrO particles with the diameter of 1 mu m as ceramsite, and mixing the ZrO particles with alcohol according to a solid-to-liquid ratio of 1: 9, sanding for 1h, filtering by a filter screen, and naturally airing to obtain alloy powder with the particle size of 100 nm;
6) dissolving alloy powder in varnish at a solid content of 20%, uniformly stirring, and coating the ink on the surface of toughened glass by a screen printing mode to obtain the alloy nano powder ink.
The alloy thin film prepared in the comparative example was subjected to composition analysis, and it was found that the composition thereof was Cr0.3Cu0.7The ink has an L value of 71.05, an a value of 1.99 and a b value of 6.51, is in a faint yellow color, has a hardness value of 2.5GPa, and cannot pass an 8-hour salt spray corrosion resistance test, and the nano powder ink of the comparative example cannot pass a 72-hour aging test.
Comparative example 2
This comparative example provides copper and a method of making the same.
In this comparative example, a Cu target having a purity of 99.8% was mounted on the 5-target site shown in fig. 1, and radio frequency-assisted direct current was used for charging.
1) Pretreatment: putting a PET sample into DI water for ultrasonic cleaning for 15 minutes, drying the PET sample in a baking oven, putting the PET sample into a vacuum chamber of an evaporative film plating machine, and vacuumizing the vacuum chamber to 5 x 10-5Pa, heating to 80 ℃, and keeping the temperature for 15 minutes;
2) depositing a water-soluble release layer: in a vacuum chamber, a PET sample is placed in a resistorPutting the water-based ink film material in an evaporation boat on a sample table of the evaporation equipment, and evacuating to 5.0 multiplied by 10-5Pa, depositing a water-based ink stripping layer with the thickness of 30nm on the surface of the PET sample, and taking out the sample after the preparation is finished;
3) depositing a Cu film: placing the PET sample into a vacuum chamber of a magnetic control type film plating machine shown in figure 1, and vacuumizing the vacuum chamber to 5 x 10-4Pa, heating to 120 ℃, keeping the temperature for 15 minutes, starting a sample table rotating frame, setting the rotating speed to be 6 circles per minute, adjusting the distance from the sample table to a target surface to be 8cm, leading the Cu target by adopting a radio frequency power supply, introducing Ar, keeping the pressure in a furnace body to be 0.5Pa, starting bias voltage to be-100V, and setting the power density of the Cu target to be 6W/cm2Controlling the film forming time to prepare a Cu thin film with the film thickness of 200 nm;
4) soaking a PET sample with a water-based ink stripping layer and a Cu film deposited on the surface into water at room temperature, dissolving the water-based ink stripping layer by water to obtain film-shaped Cu, filtering to remove filtrate, and collecting film-shaped Cu filter residue;
5) and (3) at room temperature, putting the collected Cu filter residue into a sand mill, selecting ZrO particles with the diameter of 1 mu m as ceramsite, and mixing the ZrO particles with alcohol according to a solid-to-liquid ratio of 1: 9, sanding for 1h, filtering by a filter screen, and naturally airing to obtain Cu powder with the particle size of 100 nm;
6) dissolving Cu powder in varnish at a solid content of 20%, uniformly stirring, and coating the ink on the surface of toughened glass by a screen printing mode to obtain the Cu nano powder ink.
The composition of the film obtained in this comparative example was analyzed to find that the composition was pure Cu, L was 77.82, a was 7.81, b was 15.94, had a rose gold color and a hardness of 1.0GPa, and failed the salt spray corrosion resistance test for 8 hours, and further, the Cu nano-powder ink failed the aging test for 72 hours.
Comparative example 3
This comparative example provides gold and a method of making the same.
In this comparative example, an Au target having a purity of 97.8% was mounted on the 5 th target shown in fig. 1, and radio frequency-assisted direct current was used for the electrification.
1) Front sideAnd (3) treatment: putting a PET sample into DI water for ultrasonic cleaning for 15 minutes, drying the PET sample in a baking oven, putting the PET sample into a vacuum chamber of an evaporative film plating machine, and vacuumizing the vacuum chamber to 5 x 10-5Pa, heating to 80 ℃, and keeping the temperature for 15 minutes;
2) depositing a water-soluble release layer: in a vacuum chamber, a PET sample is placed on a sample table of a resistance type evaporation device, a water-based ink film material is placed in an evaporation boat, and the evaporation boat is evacuated to 5.0 x 10-5Pa, depositing a water-based ink stripping layer with the thickness of 30nm on the surface of the PET sample, and taking out the sample after the preparation is finished;
3) and (3) depositing an Au film: placing the PET sample into a vacuum chamber of a magnetic control type film plating machine shown in figure 1, and vacuumizing the vacuum chamber to 5 x 10-4Pa, heating to 120 ℃, keeping the temperature for 15 minutes, starting a sample table rotating frame, setting the rotating speed to be 6 circles per minute, adjusting the distance from the sample table to a target surface to be 8cm, leading the Au target by adopting a radio frequency power supply, introducing Ar, keeping the pressure in a furnace body to be 0.5Pa, starting bias voltage to be-100V, and setting the power density of the Au target to be 6W/cm2Preparing an Au thin film with the thickness of 200nm by controlling the film forming time;
4) at room temperature, soaking a PET sample with a water-based ink stripping layer and an Au film deposited on the surface into water, dissolving the water-based ink stripping layer by water to obtain film-shaped Au, filtering to remove filtrate, and collecting film-shaped Au filter residue;
5) and (2) at room temperature, putting the collected film-shaped Au filter residue into a sand mill, selecting ZrO particles with the diameter of 1 mu m as ceramsite, and mixing the ZrO particles with alcohol according to a solid-to-liquid ratio of 1: 9, sanding for 1h, filtering by using a filter screen, and naturally airing to obtain Au powder with the particle size of 100 nm;
6) and dissolving the Au powder into the varnish according to the solid content of 20%, uniformly stirring, and coating the ink on the surface of toughened glass in a screen printing mode to obtain the Au nano-powder ink.
The Au thin film prepared in the comparative example was analyzed for the composition of pure Au0.97Pd0.03The ink has the advantages that the L value is 79.81, the a value is 5.82, the b value is 22.41, the ink is golden in color and luster, the hardness value is 1.0GPa, the ink can pass the salt spray corrosion resistance test for 8h, and in addition, the Au nano powder ink can pass the aging test for 72h。
Comparative example 4
This comparative example provides an alloy and a method of making the same.
Ni used in this comparative examplemCu1-mAn alloy target having m =0.10, m being atomic percent. The preparation method of the alloy comprises the following steps:
1) pretreatment: putting a PET sample into DI water for ultrasonic cleaning for 15 minutes, drying the PET sample in a baking oven, putting the PET sample into a vacuum chamber of an evaporative film plating machine, and vacuumizing the vacuum chamber to 5 x 10-5Pa, heating to 80 ℃, and keeping the temperature for 15 minutes;
2) depositing a water-soluble release layer: in a vacuum chamber, a PET sample is placed on a sample table of a resistance type evaporation device, a water-based ink film material is placed in an evaporation boat, and the evaporation boat is evacuated to 5.0 x 10-5Pa, depositing a water-based ink stripping layer with the thickness of 30nm on the surface of the PET sample, and taking out the sample after the preparation is finished;
3) depositing a gold-imitation alloy film: placing the PET sample into a vacuum chamber of a magnetic control type film plating machine shown in figure 1, and vacuumizing the vacuum chamber to 5 x 10-4Pa, heating to 120 ℃, keeping the temperature constant for 15 minutes, starting a sample table rotating frame, setting the rotating speed to be 6 circles per minute, adjusting the distance from the sample table to a target surface to be 8cm, adopting a direct current power supply to electrify Zr targets and Si targets, adopting a radio frequency power supply to electrify Ni-Cu targets, introducing Ar, keeping the pressure in a furnace body to be 0.5Pa, starting bias voltage to be-100V, and setting the power density of the Zr targets to be 6W/cm2The power density of the Si target was set to 0.3W/cm2Is prepared by reaction of NimCu1-mThe power density of the target was set to 3.5W/cm2Controlling the film forming time to prepare an alloy film with the film thickness of 200 nm;
4) at room temperature, immersing a PET sample with a water-based ink stripping layer and an alloy film deposited on the surface into water, dissolving the water-based ink stripping layer by water to obtain a film-shaped alloy, filtering to remove filtrate, and collecting film-shaped alloy filter residue;
5) and (2) at room temperature, putting the collected film-shaped alloy filter residue into a sand mill, selecting ZrO particles with the diameter of 1 mu m as ceramsite, and mixing the ZrO particles with alcohol according to a solid-to-liquid ratio of 1: 9, sanding for 1h, filtering by a filter screen, and naturally airing to obtain alloy powder with the particle size of 100 nm;
6) dissolving alloy powder in varnish at a solid content of 20%, uniformly stirring, and coating the ink on the surface of toughened glass by a screen printing mode to obtain the alloy nano powder ink.
The alloy thin film obtained in this comparative example was subjected to composition analysis, and it was found that the composition thereof was Zr0.40Si0.03Ni0.02Cu0.55The L value is 68.05, the a value is 1.69, the b value is 5.3, the ink is in faint yellow color, the hardness value is 5.3GPa, the ink can pass the salt spray corrosion resistance test for 8h, and in addition, the nano powder ink of the comparative example can pass the aging test for 72 h.
Comparative example 5
This comparative example provides an alloy and a method of making the same.
Ni used in this comparative examplemCu1-mAn alloy target having m =0.10, m being atomic percent. The preparation method of the alloy comprises the following steps:
1) pretreatment: putting a PET sample into DI water for ultrasonic cleaning for 15 minutes, drying the PET sample in a baking oven, putting the PET sample into a vacuum chamber of an evaporative film plating machine, and vacuumizing the vacuum chamber to 5 x 10-5Pa, heating to 80 ℃, and keeping the temperature for 15 minutes;
2) depositing a water-soluble release layer: in a vacuum chamber, a PET sample is placed on a sample table of a resistance type evaporation device, a water-based ink film material is placed in an evaporation boat, and the evaporation boat is evacuated to 5.0 x 10-5Pa, depositing a water-based ink stripping layer with the thickness of 30nm on the surface of the PET sample, and taking out the sample after the preparation is finished;
3) depositing an alloy film: placing the PET sample into a vacuum chamber of a magnetic control type film plating machine shown in figure 1, and vacuumizing the vacuum chamber to 5 x 10-4Pa, heating to 120 ℃, keeping the temperature constant for 15 minutes, starting a sample table rotating frame, setting the rotating speed to be 6 circles per minute, adjusting the distance from the sample table to a target surface to be 8cm, adopting a direct current power supply to electrify Zr targets and Si targets, adopting a radio frequency power supply to electrify Ni-Cu targets, introducing Ar, keeping the pressure in a furnace body to be 0.5Pa, starting bias voltage to be-100V, and setting the power density of the Zr targets to be 0.6W/cm2The power density of the Si target was set to 3W/cm2Is prepared by reaction of NimCu1-mPower density of targetSet to be 3W/cm2Controlling the film forming time to prepare an alloy film with the film thickness of 200 nm;
4) at room temperature, immersing a PET sample with a water-based ink stripping layer and an alloy film deposited on the surface into water, dissolving the water-based ink stripping layer by water to obtain a film-shaped alloy, filtering to remove filtrate, and collecting film-shaped alloy filter residue;
5) and (2) at room temperature, putting the collected film-shaped alloy filter residue into a sand mill, selecting ZrO particles with the diameter of 1 mu m as ceramsite, and mixing the ZrO particles with alcohol according to a solid-to-liquid ratio of 1: 9, sanding for 1h, filtering by a filter screen, and naturally airing to obtain alloy powder with the particle size of 100 nm;
6) dissolving alloy powder in varnish at a solid content of 20%, uniformly stirring, and coating the ink on the surface of toughened glass by a screen printing mode to obtain the alloy nano powder ink.
The alloy thin film obtained in this comparative example was subjected to composition analysis, and it was found that the composition thereof was Zr0.06Si0.37Ni0.02Cu0.55The ink has an L value of 67.91, an a value of 1.62, a b value of 5.1, a light yellow color and a hardness value of 5.0GPa, and can pass a salt spray corrosion resistance test for 8h, and in addition, the nano powder ink of the comparative example can pass a 72h aging test.
And (3) data analysis:
by comparison, in examples 1 to 4 of the present invention, Zr in the chemical formula of the present invention was changedxSiyNizCu1-x-y-zThe atomic ratio of each element obtains the imitation gold alloy film with the color and luster of imitation gold and high hardness, excellent corrosion resistance and excellent aging resistance. In particular, the color value of the gold-like alloy prepared in example 4 is relatively close to that of a pure gold plating layer, the corrosion resistance test of the gold-like alloy can pass the 8-hour test, and the nano powder ink can pass the 72-hour aging test, and thus, the gold-like alloy can be used as a preferred embodiment scheme of the invention.
The Cr-Cu alloy is adopted in the comparative examples 1-3 respectively, pure Cu and Au are designed as gold-imitating films, and tests prove that the comparative examples 1 and 2 cannot pass corrosion resistance and ageing resistance tests, and the analysis reason is that Cu in the Cr-Cu alloy films and the pure Cu films in the comparative examples 1-2 is easy to contact with oxygen in humid air to generate chemical reaction. Comparative example 3 adopts an Au thin film as a reference system to further verify the golden-like color of example 4, and in comparative examples 4-5, after Zr or Si exceeds the design range of the components of the invention, the thin film integrally presents a faint yellow color instead of golden-like color, and the decorative effect of the 3C product cannot be achieved.
The above results fully illustrate the composition of the alloy as ZrxSiyNizCu1-x-y-zX, y and z are atomic percentages, and x, y and z satisfy: x is more than or equal to 0.05 and less than or equal to 0.13, y is more than or equal to 0.02 and less than or equal to 0.10, and z is more than or equal to 0.02 and less than or equal to 0.05, so that the gold-like alloy film which has golden color and luster, high hardness, excellent corrosion resistance and excellent aging resistance can be manufactured.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the patent of the present invention shall be subject to the content of the appended claims, and the description and the attached drawings can be used for explaining the content of the claims.

Claims (12)

1. A gold-imitating alloy is characterized in that the chemical formula is ZrxSiyNizCu1-x-y-zX, y and z are atomic percentages, x, y and z satisfy: x is more than or equal to 0.05 and less than or equal to 0.13, y is more than or equal to 0.02 and less than or equal to 0.10, and z is more than or equal to 0.02 and less than or equal to 0.05.
2. The imitation gold alloy of claim 1, wherein x, y, and z satisfy: x is more than or equal to 0.05 and less than or equal to 0.10, y is more than or equal to 0.02 and less than or equal to 0.05, and z is more than or equal to 0.02 and less than or equal to 0.05.
3. The preparation method of the imitation gold alloy is characterized in that the imitation gold alloy is prepared by a physical vapor deposition mode;
the chemical formula of the gold-imitating alloy is ZrxSiyNizCu1-x-y-zX, y and z are atomic percentages, x, y and z satisfy: x is more than or equal to 0.05 and less than or equal to 0.13, y is more than or equal to 0.02 and less than or equal to 0.10, and z is more than or equal to 0.02 and less than or equal to 0.05.
4. The method for preparing the imitation gold alloy according to claim 3, wherein the physical vapor deposition is magnetron sputtering coating, and the preparing the imitation gold alloy by magnetron sputtering coating comprises:
providing a substrate, a Zr source, a Si source, a Ni source and a Cu source, introducing working gas, and sputtering and depositing the imitation gold alloy on the substrate.
5. The method of claim 4, wherein the Zr source is a Zr target, the Si source is a Si target, the Ni source and the Cu source are Ni-Cu alloy targets, and the working gas is Ar.
6. The method for preparing the imitation gold alloy according to claim 5, wherein the process parameters for preparing the imitation gold alloy by magnetron sputtering coating comprise:
the sputtering temperature is 150-330 ℃, and the Ar gas pressure is 0.5-0.8 Pa; and/or
The power density of the Zr target is 0.5W/cm2-3W/cm2(ii) a And/or
The power density of the Si target is 0.1W/cm2-2W/cm2(ii) a And &Or
The power density of the Ni-Cu alloy target is 4.5W/cm2-6.5W/cm2(ii) a And/or
The bias voltage of the substrate is-150V- (-50) V; and/or
The gas flow of Ar is 25sccm-45 sccm; and/or
The time of sputtering deposition is 10min-15 min.
7. The method for producing an imitation gold alloy according to any one of claims 3 to 6, further comprising a step of depositing a peeling layer on the base, before the step of sputter-depositing the imitation gold alloy on the base;
and a step of separating the gold-imitation alloy from the peeling layer to obtain a thin-film gold-imitation alloy after the step of sputtering and depositing the gold-imitation alloy on the substrate.
8. The method according to claim 7, further comprising a step of pulverizing the thin-film gold-imitating alloy to prepare a powdery gold-imitating alloy after the step of separating the gold-imitating alloy from the peeling layer to prepare the thin-film gold-imitating alloy.
9. The method of claim 8, wherein the thickness of the gold-imitation alloy in the form of a thin film is 150nm to 3000nm, and the particle size of the powdered gold-imitation alloy is 0.1 μm to 2.5 μm.
10. An ink comprising a resin and the imitation gold alloy of any one of claims 1 to 2, or an ink comprising a resin and an imitation gold alloy obtained by the method for producing an imitation gold alloy of any one of claims 3 to 9.
11. A plated article comprising a substrate and a gold-like alloy thin film covering a surface of the substrate, wherein the gold-like alloy thin film comprises the gold-like alloy according to any one of claims 1 to 2, or the gold-like alloy thin film comprises the gold-like alloy produced by the method for producing the gold-like alloy according to any one of claims 3 to 9, or the gold-like alloy thin film is made from the ink according to claim 10.
12. The coated article according to claim 11, wherein the coated article is an electronic device or a decorative article; and/or
In the film-coated product, the substrate is made of glass, PMMA, PET or PP.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0515730A1 (en) * 1991-05-29 1992-12-02 Mitsui Engineering and Shipbuilding Co, Ltd. Antibacterial amorphous alloy highly resistant to oxidation, discoloration, and corrosion, fabric coated with amorphous alloy, and insole
EP1548143A1 (en) * 2002-08-30 2005-06-29 Japan Science and Technology Agency Cu-BASE AMORPHOUS ALLOY
CN1710138A (en) * 2005-06-07 2005-12-21 山东大学 Copper-base amorphous alloy and its preparing proess
CN109158587A (en) * 2018-10-24 2019-01-08 华南理工大学 A kind of spherical shape suitable for 3D printing imitates billon powder and preparation method thereof
CN111250871A (en) * 2020-03-10 2020-06-09 中国科学院物理研究所 Amorphous alloy coloring method, amorphous alloy and application thereof
CN113564411A (en) * 2021-07-29 2021-10-29 沈阳造币有限公司 Novel high-corrosion-resistance anti-tarnishing imitation gold copper alloy and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0515730A1 (en) * 1991-05-29 1992-12-02 Mitsui Engineering and Shipbuilding Co, Ltd. Antibacterial amorphous alloy highly resistant to oxidation, discoloration, and corrosion, fabric coated with amorphous alloy, and insole
EP1548143A1 (en) * 2002-08-30 2005-06-29 Japan Science and Technology Agency Cu-BASE AMORPHOUS ALLOY
CN1710138A (en) * 2005-06-07 2005-12-21 山东大学 Copper-base amorphous alloy and its preparing proess
CN109158587A (en) * 2018-10-24 2019-01-08 华南理工大学 A kind of spherical shape suitable for 3D printing imitates billon powder and preparation method thereof
CN111250871A (en) * 2020-03-10 2020-06-09 中国科学院物理研究所 Amorphous alloy coloring method, amorphous alloy and application thereof
CN113564411A (en) * 2021-07-29 2021-10-29 沈阳造币有限公司 Novel high-corrosion-resistance anti-tarnishing imitation gold copper alloy and preparation method thereof

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