CN114249608A - Gradient color ceramic part, processing method thereof and terminal equipment - Google Patents
Gradient color ceramic part, processing method thereof and terminal equipment Download PDFInfo
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- CN114249608A CN114249608A CN202011023006.2A CN202011023006A CN114249608A CN 114249608 A CN114249608 A CN 114249608A CN 202011023006 A CN202011023006 A CN 202011023006A CN 114249608 A CN114249608 A CN 114249608A
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
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Abstract
The application provides a gradient ceramic piece, includes: the ceramic substrate comprises a ceramic substrate, and a priming layer, an intermediate layer and a gradient layer which are sequentially formed on the surface of the ceramic substrate; the material of the gradual change layer is one or more of silicon, silicon dioxide and titanium dioxide, and the thicknesses of the gradual change layer at least two positions are different, so that the gradual change layer at least two positions shows gradual change. Also provides a processing method of the gradient color ceramic piece and terminal equipment.
Description
Technical Field
The application relates to the technical field of electronics, in particular to a gradient-color ceramic part, a processing method thereof and terminal equipment.
Background
The ceramic has the properties of high strength, high gloss, high fracture toughness, excellent heat insulation performance, high temperature resistance and the like, is widely applied to structural members such as a rear cover, a middle frame, a key, a camera support and the like of terminal equipment, and is popular with consumers; in addition, the ceramic has low dielectric constant, is not used for shielding signals, is a structural material with good 5G communication, and has good application prospect. However, how to form a gradual color effect on the surface of the ceramic to improve the appearance of the ceramic is a problem to be solved at present.
Disclosure of Invention
In order to solve the problems, the application provides a gradient color ceramic part, a processing method thereof and a terminal device, wherein the gradient color ceramic part has a gradient color effect and provides different visual experiences for users, and the gradient color ceramic part is non-conductive and very suitable for being used as a structural part of the terminal device.
The application provides a gradient ceramic part, which comprises a ceramic substrate, and a priming layer, an intermediate layer and a gradient layer which are sequentially formed on the surface of the ceramic substrate; the material of the gradual change layer is one or more of silicon, silicon dioxide and titanium dioxide, and the thicknesses of the gradual change layer at least two positions are different, so that the gradual change layer at least two positions shows gradual change.
The application also provides a processing method of the gradient color ceramic part, which comprises the following steps: preparing a ceramic matrix; sequentially depositing on the surface of the ceramic substrate to form a bottom layer, an intermediate layer and a gradient layer; the material of the gradual change layer is one or more of silicon, silicon dioxide and titanium dioxide, and the thicknesses of the gradual change layer at least two positions are different, so that the gradual change layer at least two positions shows gradual change.
The application also provides a terminal device comprising the gradient-color ceramic piece.
According to the gradient ceramic part, the processing method thereof and the terminal equipment provided by the embodiment of the application, the thickness of the gradient layer at least two positions is different, so that the at least two positions of the gradient layer present a gradient effect; and a base layer and an intermediate layer are formed between the ceramic substrate and the graded layer, so that the bonding force between the graded layer and the ceramic substrate is better.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic cross-sectional view of a gradient color ceramic article according to a first embodiment of the present application.
Fig. 2 is a schematic flow chart of a method for processing a gradient color ceramic part according to a second embodiment of the present application.
Fig. 3 is a schematic top-view structural diagram of a terminal device according to a third embodiment of the present application.
Detailed Description
In order to make the technical solutions of the present application better understood, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The terms "first," "second," and the like in the description and claims of the present application and in the above-described drawings are used for distinguishing between different objects and not for describing a particular order. Furthermore, the terms "include" and "have," as well as any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
The technical solutions in the embodiments of the present application will be described below with reference to the accompanying drawings.
It should be noted that, for convenience of description, like reference numerals denote like parts in the embodiments of the present application, and a detailed description of the like parts is omitted in different embodiments for the sake of brevity.
The application provides a gradient ceramic part, which comprises a ceramic substrate, and a priming layer, an intermediate layer and a gradient layer which are sequentially formed on the surface of the ceramic substrate; the material of the gradual change layer is one or more of silicon, silicon dioxide and titanium dioxide, and the thicknesses of the gradual change layer at least two positions are different.
According to the gradient ceramic part, the thicknesses of the gradient layers at least two positions are different, so that the at least two positions of the gradient layers have gradient effects; and a base layer and an intermediate layer are formed between the ceramic substrate and the graded layer, so that the bonding force between the graded layer and the ceramic substrate is better.
Referring to fig. 1, a ceramic part 100 with a gradient color according to a first embodiment of the present application includes a ceramic substrate 10, and a primer layer 20, an intermediate layer 30 and a gradient layer 40 sequentially formed on a surface of the ceramic substrate 10.
The main material of the ceramic substrate 10 may be alumina, zirconia, titania, or the like, that is, the ceramic substrate 10 may be alumina ceramic, zirconia ceramic, titania ceramic, or the like.
In some embodiments, the ceramic substrate 10 is formed by sintering a ceramic raw material including:
70-99 parts by mass of powder;
1 to 30 parts by mass of a binder; and
0 to 10 parts by mass of a coloring material;
wherein the powder is at least one of alumina powder, zirconia powder and titanium oxide powder.
The binder can be one or more of paraffin, polyethylene glycol, stearic acid, dioctyl phthalate, polyethylene, polypropylene, polymethyl methacrylate and polyformaldehyde.
In some embodiments, the colorant may be a metal oxide, such as an oxide of a metal such as iron, manganese, chromium, cobalt, nickel, titanium, tin, aluminum, cerium, and the like; the addition of the coloring material may make the ceramic substrate 10 show a predetermined color, for example, the addition of an oxide of metal manganese or metal chromium may make the ceramic substrate 10 show a black color, the addition of an oxide of metal cerium may make the ceramic substrate 10 show a red color, and the addition of an oxide of metal cobalt may make the ceramic substrate 10 show a blue color.
In a preferred embodiment, the ceramic substrate 10 is black in color, and the colorant is an oxide of metal manganese or metal chromium; among them, the black ceramic substrate 10 can make the color change of the graded layer 40 more remarkable, and has a better appearance effect.
In some embodiments, the material of the primer layer 20 is alumina, zirconia, titania, or the like.
In a preferred embodiment, the material of the primer layer 20 is consistent with the main material of the ceramic substrate 10, so that the adhesion of the primer layer 20 on the surface of the ceramic substrate 10 and the consistency with the ceramic substrate 10 are better; for example, when the ceramic substrate 10 is zirconia ceramic, the material of the primer layer 20 is preferably zirconia, and when the ceramic substrate 10 is alumina ceramic, the material of the primer layer 20 is preferably alumina.
In some embodiments, the thickness of the primer layer is 20 nm to 40 nm, which may make the mechanical properties of the primer layer 20 better and make the adhesion of the primer layer 20 on the surface of the ceramic substrate 10 better.
In some embodiments, the material of the intermediate layer 30 is silicon dioxide, aluminum oxide or titanium oxide; the intermediate layer 30 is used to reduce the surface stress of the ceramic substrate 10 to improve the adhesion of the graded layer 40 on the surface of the ceramic substrate 10, that is, the intermediate layer 30 plays a role of transition, so that the graded layer 40 can be better adhered to the surface of the ceramic substrate 10.
In some embodiments, the intermediate layer 30 has a thickness of 10 nm to 40 nm, and is too thin to function to reduce stress, and too thick to risk adhesion reduction.
In this application, the material of the graded layer 40 may be one or more of silicon, silicon dioxide and titanium dioxide; the thickness of the graded layer 40 is different at least two locations, wherein the graded layer 40 of the present application is formed such that the graded layer at least two locations exhibits a graded color.
In some embodiments, the thickness of the graded layer 40 is different for at least two locations and the thicker regions smoothly transition with the thinner regions; in other embodiments, the thickness of the thinner region may be 0, that is, at least one region does not form the graded layer 40, so that the graded layer 40 is hollowed out, and at this time, the thicker region and the thinner region do not have a smooth transition.
In some embodiments, the material of the graded layer 40 is silicon, wherein the thicknesses of the silicon of the graded layer 40 at least at two positions are different, so that the graded layer 40 at least two positions exhibits a graded effect, specifically, the graded layer 40 in the area with the larger thickness exhibits a silver color, the graded layer 40 in the area with the smaller thickness exhibits a gray color, and the boundary of the graded layer 40 at least at two positions exhibits a gradual silver color to gray color.
In a preferred embodiment, the difference between the thinnest area and the thickest area of the graded layer 40 in at least two locations is greater than or equal to 15 nm, and more preferably, the difference between the thinnest area and the thickest area of the graded layer 40 in at least two locations is greater than or equal to 20 nm; the thickness of the thinner region in the graded layer 40 is 0 to 15 nm, and the thickness of the thicker region in the graded layer 40 is 15 nm to 30 nm.
In other embodiments, the graded layer 40 includes alternating silicon dioxide layers and titanium dioxide layers, and at least one of the silicon dioxide layers and the titanium dioxide layers has a different thickness at least two locations, so that the graded layer 40 at least two locations exhibits a graded effect.
In a specific embodiment, when the graded layer 40 includes alternating silicon dioxide layers and titanium dioxide layers, the thickness of each silicon dioxide layer and the thickness of each titanium dioxide layer both exhibit a uniform gradient change, that is, in the same direction, the thickness of each oxide layer and the thickness of each nitride layer both gradually decrease or both gradually increase, and the silicon dioxide layers and the titanium dioxide layers make the graded layer 40 gradually change in rainbow color as a whole under the interference of light.
In some embodiments, the color-graded ceramic piece 100 further includes a transparent protective layer 50, the transparent protective layer 50 is formed on the surface of the graded layer 40, and the transparent protective layer 50 is used for protecting the graded layer 40, preventing the graded layer 40 from being scratched or worn, and the like; preferably, the surface hardness of the transparent protective layer 50 is greater than the surface hardness of the gradation layer 40.
In some embodiments, the material of the transparent protection layer 50 is silicon dioxide, aluminum oxide, zirconium oxide, or titanium oxide, which can have a good bonding force with the graded layer 40.
In some embodiments, the transparent protective layer has a thickness of 20 to 40 nanometers.
In some embodiments, a cover-bottom ink layer 60 is formed on a side of the ceramic substrate 10 of the graded color ceramic part 100 away from the base layer 20, the middle layer 30 and the graded layer 40, and the cover-bottom ink layer 60 is used for shielding the cover bottom and preventing the graded color ceramic part 100 from transmitting light.
In some embodiments, the thickness of the capping ink layer 60 is 10 to 15 microns.
Wherein, the bottom ink layer 60 can be one or more layers, and is arranged as required; for example, when the ceramic substrate 10 is a light-colored ceramic substrate, more layers of the bottom-covering ink layer 60 may be provided, and when the ceramic substrate 10 is a dark-colored ceramic substrate, fewer layers of the bottom-covering ink layer 60, such as one or two layers, may be provided.
In one embodiment of the present application, the powder in the ceramic raw material forming the ceramic substrate 10 may be zirconia powder; the primer layer 20 may be a zirconia film layer; the intermediate layer 30 may be a silicon dioxide film layer; the graded layer 40 may be a silicon layer; a transparent protective layer 50 is further formed on the surface of the graded layer 40, and the transparent protective layer 50 is a zirconia layer. The base layer 20 is made of the same material as the main material of the ceramic substrate 10, so that the bonding force between the base layer 20 and the ceramic substrate 10 is good, the middle layer 30 is made of silicon dioxide, the base layer 20 and the silicon dioxide are both oxides, the surface stress of a zirconia layer can be reduced by the silicon dioxide, the surface mechanical property of the ceramic substrate 10 is better, the gradual change layer 40 is made of silicon, the middle layer 30 and the gradual change layer 40 both contain silicon, so that the bonding force between the gradual change layer and the middle layer is better, in addition, the traditional medium film layer is easy to generate a color change phenomenon, when the gradual change layer 40 is a silicon layer, the gradual change layer 40 has the color of silver gray, so that the color change phenomenon can be weakened, and the gradual change ceramic part has a better appearance.
In some embodiments, the base layer 20, the middle layer 30, the gradient layer 40 and the transparent protective layer 50 of the gradient color ceramic part 100 can be deposited by a physical vapor deposition process.
In some embodiments, the color-graded ceramic part 100 is a battery back cover of a terminal device, the graded layer 40 is located on an outer side of the battery back cover, and an inner side of the battery back cover, that is, a side of the ceramic substrate 10 away from the graded layer 40, is used for accommodating a battery.
In other embodiments, the color-changing ceramic part 100 may also be a middle frame, a key, a camera bracket, or other structural parts of a terminal device.
The application also provides a processing method of the gradient color ceramic part, which comprises the following steps: preparing a ceramic matrix; and
sequentially depositing on the surface of the ceramic substrate to form a bottom layer, an intermediate layer and a gradient layer; the material of the gradual change layer is one or more of silicon, silicon dioxide and titanium dioxide, and the thicknesses of the gradual change layer at least two positions are different, so that the gradual change layer at least two positions shows gradual change.
As shown in fig. 2, a method for processing a gradient color ceramic part in a second embodiment of the present application includes:
s201, preparing a ceramic matrix;
s203, sequentially depositing and forming a priming layer, an intermediate layer and a gradient layer on the surface of the ceramic substrate; the material of the gradual change layer is one or more of silicon, silicon dioxide and titanium dioxide, and the thicknesses of the gradual change layer at least two positions are different, so that the gradual change layer at least two positions shows gradual change.
The main material of the ceramic matrix may be alumina, zirconia, titania, or the like, that is, the ceramic matrix may be alumina ceramic, zirconia ceramic, titania ceramic, or the like.
In some embodiments, the ceramic matrix is formed by sintering a ceramic raw material comprising:
70-99 parts by mass of powder;
1 to 30 parts by mass of a binder; and
0 to 10 parts by mass of a coloring material;
wherein the powder is at least one of alumina powder, zirconia powder and titanium oxide powder.
The binder can be one or more of paraffin, polyethylene glycol, stearic acid, dioctyl phthalate, polyethylene, polypropylene, polymethyl methacrylate and polyformaldehyde.
In some embodiments, the colorant may be a metal oxide, such as an oxide of a metal such as iron, manganese, chromium, cobalt, nickel, titanium, tin, aluminum, cerium, and the like; the addition of the pigment can make the ceramic matrix present a predetermined color, for example, the addition of oxides of metal manganese or metal chromium can make the ceramic matrix present a black color, the addition of oxides of metal cerium can make the ceramic matrix present a red color, and the addition of oxides of metal cobalt can make the ceramic matrix present a blue color.
In a preferred embodiment, the ceramic matrix is black in color, and the colorant is an oxide of metal manganese or metal chromium, for example; the black ceramic matrix can make the color change of the gradient layer more obvious and has better appearance effect.
In a specific embodiment, the method for preparing the ceramic matrix may include: preparing a ceramic blank, for example, the ceramic raw material may be subjected to injection molding, casting, or dry pressing to obtain a ceramic blank; performing gel discharging or degreasing, namely performing gel discharging or degreasing on the ceramic green body at a high temperature, wherein the temperature of the gel discharging or degreasing can be below 400 ℃, and the time can be 0.5 to 4 hours; sintering, namely sintering the ceramic blank in reducing gas, oxidizing gas or inert gas, wherein the sintering temperature can be higher than 1200 ℃, and the sintering time can be 0.5 to 10 hours; and (3) processing the appearance, namely preparing the ceramic matrix by CNC (computer numerical control) processing, grinding and polishing and the like.
In some embodiments, before the ceramic substrate surface is deposited in sequence to form the primer layer, the intermediate layer and the graded layer, the method further comprises the following steps:
s202, performing pre-plating treatment on the ceramic substrate.
The pre-plating treatment may include cleaning, preheating, and the like.
Cleaning may include degreasing, organic solvents, ultrasonic deionized water cleaning, and the like.
The preheating can be preheating in a vacuum furnace body: heating to 80-100 deg.C for 10-20 min; preheating can make the gaseous release of impurity on ceramic substrate surface to discharge through the evacuation, thereby can avoid other releases of impurity and influence the purity of coating film layer in the coating film process, and then influence rete cohesion and wearability.
In some embodiments, the primer layer, the intermediate layer and the graded layer may be sequentially deposited on the surface of the ceramic substrate by physical vapor deposition.
In some embodiments, when the priming layer, the intermediate layer and the gradient layer are sequentially deposited on the surface of the ceramic substrate by physical vapor deposition, the coating chamber may be evacuated, then argon gas is introduced, the pulse bias power supply is turned on, and the ceramic substrate is glow-cleaned; after glow cleaning is finished, introducing a small amount of argon, opening the metal target, closing the target shielding cover, and performing decontamination treatment on the surface of the target to remove a metal oxide thin layer on the surface of the target and reduce pollution to a film layer; after that, the sample surface was cleaned by ion beam: closing the magnetic control target material, starting an arc target power supply, closing a shielding cover, starting an anode power supply, cleaning the surface of the substrate and activating surface chemical bonds by high-strength plasma for 5-10 minutes; and then opening the magnetic control target material, and opening a magnetic control target material shielding case for film coating.
In some embodiments, when the priming layer, the intermediate layer and the gradient layer are sequentially deposited on the surface of the ceramic substrate by physical vapor deposition, the deposition time and the thickness of the film thickness measuring device can be controlled to realize accurate deposition of the film layer; after the deposition of the bottom layer is finished, the target deposition middle layer can be replaced; after the intermediate layer is deposited, the gradient layer can be deposited by shielding the jig, wherein the distance between the jig and the ceramic substrate can be changed, for example, 0-3 cm, and the distance between the jig and the ceramic edge is 0-10 cm.
If the distance between the jig and the ceramic substrate is greater than 0, that is, the jig and the ceramic substrate are not completely attached to form a gap, a thinner gradient layer is formed on the surface of the ceramic substrate in the region corresponding to the jig due to the movement of the particles, and the thicker region and the thinner region are in smooth transition; if the tool with the distance of ceramic base member is 0, that is to say the tool with ceramic base member laminates completely, thereby, with the ceramic base member surface in the region that the tool corresponds will not form the gradual change layer, also promptly, the thickness on the gradual change layer in thinner region is 0, thereby the gradual change layer is the fretwork form, and at this moment, thicker region is not smooth transition with thinner region.
In some embodiments, the material of the primer layer is alumina, zirconia, titania, or the like.
In a preferred embodiment, the material of the primer layer is consistent with the main material of the ceramic substrate, so that the adhesion of the primer layer on the surface of the ceramic substrate and the consistency with the ceramic substrate are better; for example, when the ceramic substrate is zirconia ceramic, the material of the primer layer is preferably zirconia, and when the ceramic substrate is alumina ceramic, the material of the primer layer is preferably alumina.
In some embodiments, the thickness of the primer layer is 20 nm to 40 nm, which can make the primer layer have better mechanical properties and better adhesion on the surface of the ceramic substrate.
In some embodiments, the intermediate layer is made of silicon dioxide, aluminum oxide or titanium oxide; the intermediate layer is used for reducing the surface stress of the ceramic matrix so as to improve the adhesive force of the gradual change layer on the surface of the ceramic matrix, namely, the intermediate layer plays a role in transition and enables the gradual change layer to be better attached to the surface of the ceramic matrix.
In some embodiments, the intermediate layer has a thickness of 10 nm to 40 nm, too thin to function to reduce stress, and too thick to risk adhesion reduction.
In the application, the material of the gradient layer may be one or more of silicon, silicon dioxide and titanium dioxide; the thickness of the gradient layer at least two positions is different, wherein the gradient layer of the application is passed through so that the gradient layer at least two positions presents gradient.
In some embodiments, the graded layer is made of silicon, wherein the thicknesses of the silicon of the graded layer at least at two positions are different, so that the graded layer at least at two positions exhibits a graded effect, specifically, the graded layer in an area with a larger thickness exhibits a silver color, the graded layer in an area with a smaller thickness exhibits a gray color, and a boundary of at least two positions of the graded layer exhibits a gradual change from the silver color to the gray color.
In a preferred embodiment, the difference between the thinnest area and the thickest area in the graded layer in at least two locations is greater than or equal to 15 nm, and more preferably, the difference between the thinnest area and the thickest area in the graded layer 40 in at least two locations is greater than or equal to 20 nm; the thickness of the thinner area in the gradual change layer is 0 to 15 nanometers, and the thickness of the thicker area in the gradual change layer is 15 to 30 nanometers.
In other embodiments, the graded layer comprises a silicon dioxide layer and a titanium dioxide layer arranged alternately, wherein the silicon dioxide layer and the titanium dioxide layer arranged alternately can be deposited by alternating targets; the thickness of the silicon dioxide layer is different from that of at least one layer of the titanium dioxide layer at least two positions, so that the gradient layer at least two positions has gradient effect.
In a specific embodiment, when the graded layer includes silicon dioxide layers and titanium dioxide layers which are alternately arranged, the thickness of each silicon dioxide layer and the thickness of each titanium dioxide layer both present a uniform gradient change, that is, in the same direction, the thickness of each oxide layer and the thickness of each nitride layer both gradually decrease or both gradually increase, and the silicon dioxide layers and the titanium dioxide layers make the graded layer gradually change in an iridescent color as a whole under the interference of light.
In some embodiments, after the ceramic substrate surface is sequentially deposited to form the primer layer, the intermediate layer and the graded layer, the method further comprises the following steps:
and S204, forming a transparent protective layer on the surface of the gradient layer.
In some embodiments, the transparent protective layer may be formed on the surface of the graded layer of the ceramic matrix by physical vapor deposition; and after the gradient layer is formed, the target material is replaced to continue depositing and forming the transparent protective layer.
The transparent protective layer is used for protecting the gradual change layer and preventing the gradual change layer from being scratched or worn and the like; preferably, the surface hardness of the transparent protective layer is greater than the surface hardness of the graded layer.
In some embodiments, the material of the transparent protection layer is silicon dioxide, aluminum oxide, zirconium oxide, titanium oxide, or the like, and such material may have a better bonding force with the graded layer.
In some embodiments, the transparent protective layer has a thickness of 20 to 40 nanometers.
In some embodiments, after the transparent protective layer is formed on the surface of the ceramic substrate by sequential deposition, the method further comprises the steps of:
and S205, forming a bottom covering ink layer on one side of the ceramic substrate, which is far away from the bottom coating layer, the middle layer and the gradual change layer.
In some embodiments, the capping ink layer may be formed by spraying, and the ratio of the spraying liquid may be: the weight ratio of the printing ink, the curing agent and the diluent is 50-60: 15 to 40: 10 to 30, the viscosity of the spraying liquid is 8 to 12 Pa second (Pa.s), the distance between a spray gun and a sprayed sample is 10 cm, the sample self-conveying speed is 10 to 60 degrees per second (DEG/s), the spraying speed during spraying is 600 millimeters per second (mm/s), the ink supply pressure is 200Pa, the atomization pressure is 300Pa, and the ejection pressure is 350 Pa; the bottom covering ink layer can be formed by baking and curing after spraying, the baking temperature is 80-90 ℃, and the baking time is 50-60 min.
The cover bottom ink layer is used for shielding the cover bottom and preventing the gradient color ceramic piece from transmitting light.
In some embodiments, the thickness of the capping ink layer is 10 to 15 microns.
The bottom ink layer can be one or more layers and is arranged as required; for example, when the ceramic base is a light-colored ceramic base, more layers of the bottom-covering ink layer may be provided, and when the ceramic base is a dark-colored ceramic base, fewer layers of the bottom-covering ink layer may be provided, for example, one layer or two layers.
In one embodiment of the present application, the powder in the ceramic raw material forming the ceramic matrix may be zirconia powder; the priming layer can be a zirconium oxide film layer; the intermediate layer may be a silicon dioxide film layer; the graded layer may be a silicon layer; and a transparent protective layer is also formed on the surface of the gradient layer, and the transparent protective layer is a zirconium oxide layer. The material of the priming layer is the same as the main material component of the ceramic substrate, so that the binding force of the priming layer and the ceramic substrate is better, the material of the middle layer is silicon dioxide, the priming layer is oxide, the silicon dioxide can reduce the surface stress of the zirconia layer, the surface mechanical property of the ceramic substrate is better, and the material of the gradual change layer is silicon, the middle layer and the gradual change layer both contain silicon, so that the binding force between the layers is better, in addition, the traditional medium film layer easily generates a heterochrosis phenomenon, when the gradual change layer is a silicon layer, the gradual change layer has a color to be silver gray, so that the heterochrosis phenomenon can be weakened, and the gradual change ceramic part has better appearance.
The third embodiment of the present application further provides a terminal device 300, as shown in fig. 3, wherein the terminal device 300 includes the gradient color ceramic piece 100 according to the first embodiment of the present application.
In some embodiments, the color-graded ceramic part 100 is a rear battery cover of the terminal device 300, the graded layer 40 is located on an outer side of the rear battery cover, and an inner side of the rear battery cover, that is, a side of the ceramic substrate 10 away from the graded layer 40, is used for accommodating a battery.
In other embodiments, the color-changing ceramic part 100 may also be a middle frame, a button, a camera bracket, or other structural parts of the terminal device 300.
The present invention will be described with reference to specific embodiments.
Example 1
Preparing a ceramic matrix; sequentially depositing and forming a priming layer, a middle layer, a gradient layer and a transparent protective layer on the surface of the ceramic substrate to obtain a gradient-color ceramic part; wherein the middle position of the gradient layer is thicker and the two sides are thinner.
Wherein, the powder in the ceramic raw material forming the ceramic matrix is zirconia powder; the bottom layer is a zirconium oxide film layer; the middle layer is a silicon dioxide film layer; the gradient layer is a silicon layer; the transparent protective layer is a zirconia layer.
In this embodiment, the thickness of the primer layer is 25 nm; the thickness of the intermediate layer is 20 nanometers; the thickness of the thinner area in the gradual change layer is 10 nanometers, and the thickness of the thicker area in the gradual change layer is 25 nanometers; the thickness of the transparent protective layer is 30 nanometers.
The adhesion of the film layer on the surface of the ceramic substrate in example 1 was tested, and the surface condition and color of the graded-color ceramic part were observed.
Example 2
Preparing a ceramic matrix; and sequentially depositing and forming a priming layer, a middle layer, a gradient layer and a transparent protective layer on the surface of the ceramic substrate to obtain the gradient-color ceramic part.
Wherein, the powder in the ceramic raw material forming the ceramic matrix is zirconia powder; the bottom layer is a zirconium oxide film layer; the middle layer is a silicon dioxide film layer; the gradient layers are alternately arranged silicon dioxide layers and titanium dioxide layers; the transparent protective layer is a zirconia layer.
In this embodiment, the thickness of the primer layer is 25 nm; the thickness of the intermediate layer is 20 nanometers; the thickness of the silicon dioxide layer and the titanium dioxide layer is gradually reduced in one area along the same direction, the thickness of the thinner area in each layer of the silicon dioxide layer and the titanium dioxide layer is 10 nanometers, and the thickness of the thicker area is 25 nanometers; the thickness of the transparent protective layer is 30 nanometers.
The adhesion of the film layer on the surface of the ceramic substrate in example 2 was tested, and the surface condition and color of the gradient-colored ceramic article were observed.
Comparative example 1
Preparing a ceramic matrix; depositing an intermediate layer, a gradient layer and a transparent protective layer on the surface of the ceramic substrate in sequence to obtain a gradient-color ceramic part; wherein the middle position of the gradient layer is thicker and the two sides are thinner.
Wherein, the powder in the ceramic raw material forming the ceramic matrix is zirconia powder; the middle layer is a silicon dioxide film layer; the gradient layer is a silicon layer; the transparent protective layer is a zirconia layer.
In this embodiment, the thickness of the intermediate layer is 20 nm; the thickness of the thinner area in the gradual change layer is 10 nanometers, and the thickness of the thicker area in the gradual change layer is 25 nanometers; the thickness of the transparent protective layer is 30 nanometers.
And (3) testing the adhesion of the film layer on the surface of the ceramic substrate in the comparative example 1, and observing the surface condition and the color of the gradient-color ceramic piece.
Comparative example 2
Preparing a ceramic matrix; sequentially depositing on the surface of the ceramic substrate to form a priming layer, a gradient layer and a transparent protective layer to obtain a gradient-color ceramic part; wherein the middle position of the gradient layer is thicker and the two sides are thinner.
Wherein, the powder in the ceramic raw material forming the ceramic matrix is zirconia powder; the bottom layer is a zirconium oxide film layer; the gradient layer is a silicon layer; the transparent protective layer is a zirconia layer.
In this embodiment, the thickness of the primer layer is 25 nm; the thickness of the thinner area in the gradual change layer is 10 nanometers, and the thickness of the thicker area in the gradual change layer is 25 nanometers; the thickness of the transparent protective layer is 30 nanometers.
And (3) testing the adhesion of the film layer on the surface of the ceramic substrate in the comparative example 2, and observing the surface condition and the color of the gradient-color ceramic piece.
Comparative example 3
Preparing a ceramic matrix; sequentially depositing and forming a priming layer, an intermediate layer, a silicon layer and a transparent protective layer on the surface of the ceramic substrate to obtain a gradient-color ceramic part; wherein the silicon layer has a uniform thickness.
Wherein, the powder in the ceramic raw material forming the ceramic matrix is zirconia powder; the bottom layer is a zirconium oxide film layer; the middle layer is a silicon dioxide film layer; the transparent protective layer is a zirconia layer.
In this embodiment, the thickness of the primer layer is 25 nm; the thickness of the intermediate layer is 20 nanometers; the thickness of the silicon layer is 20 nanometers; the thickness of the transparent protective layer is 30 nanometers.
And (3) testing the adhesion of the film layer on the surface of the ceramic substrate in the comparative example 3, and observing the surface condition and the color of the gradient-color ceramic piece.
Comparative example 4
Preparing a ceramic matrix; and sequentially depositing and forming a priming layer, a middle layer, a gradient layer and a transparent protective layer on the surface of the ceramic substrate to obtain the gradient-color ceramic part.
Wherein, the powder in the ceramic raw material forming the ceramic matrix is zirconia powder; the bottom layer is a zirconium oxide film layer; the middle layer is a silicon dioxide film layer; the gradient layers are alternately arranged silicon dioxide layers and titanium dioxide layers; the transparent protective layer is a zirconia layer.
In this embodiment, the thickness of the primer layer is 25 nm; the thickness of the intermediate layer is 20 nanometers; the thickness of each layer of the silicon dioxide layer and the titanium dioxide layer is uniform and is 20 nanometers; the thickness of the transparent protective layer is 30 nanometers.
And (3) testing the adhesion of the film layer on the surface of the ceramic substrate in the comparative example 4, and observing the surface condition and the color of the gradient-color ceramic piece.
It should be noted that, for the convenience of the test and the comparison of the test results, the specifications and other parameters of the samples tested in the above examples and comparative examples are the same.
The method for testing the adhesive force comprises the following steps: GB9286-98 hundred grids test, no shedding is passed, otherwise, no shedding is passed.
The test results are shown in the following table:
TABLE 1
As can be seen from comparison of examples 1 and 2 and comparative examples 1 to 3, the film layers of comparative example 1 and comparative example 2, which were not provided with the primer layer or the intermediate layer, were easily peeled off and had poor adhesion, and the film layers of examples 1 and 2 and comparative example 3, which were provided with the primer layer and the intermediate layer, had good adhesion; comparing examples 1 and 2 and comparative example 3, it can be seen that the thickness of the gradient layer is different, the surface of the sample can show gradient, and the gradient color thickness is the same, and the surface of the sample has no gradient color.
Reference herein to "an embodiment" or "an implementation" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present application and not for limiting, and although the present application is described in detail with reference to the above preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application.
Claims (14)
1. A gradient ceramic part is characterized by comprising a ceramic substrate, and a priming layer, an intermediate layer and a gradient layer which are sequentially formed on the surface of the ceramic substrate; the material of the gradual change layer is one or more of silicon, silicon dioxide and titanium dioxide, and the thicknesses of the gradual change layer at least two positions are different, so that the gradual change layer at least two positions shows gradual change.
2. The graded ceramic article of claim 1, wherein thicker regions of the graded layer smoothly transition with thinner regions.
3. The graded ceramic article of claim 1 wherein the graded layer is a silicon layer; wherein the thickness difference between the thinnest area and the thickest area in the gradient layers at least two positions is greater than or equal to 15 nanometers; the thickness of the thinner area in the gradual change layer is 0 to 15 nanometers, and the thickness of the thicker area in the gradual change layer is 15 to 30 nanometers; the thinner area of the gradual change layer is gray, the thicker area of the gradual change layer is silver, and the gradual change layer is silver gray.
4. The graded ceramic article of claim 1 wherein the graded layer comprises alternating layers of silica and titania, at least one of the silica and titania layers having a thickness that is different in at least two locations.
5. The graded ceramic article of claim 1 wherein the thickness of each of the silica layers and the thickness of each of the titania layers exhibit a uniform gradient, the thickness of the oxide layer and the thickness of the nitride layer both decrease or increase in the same direction, and the graded layers are graded iridescently throughout.
6. The gradient-color ceramic part according to claim 1, wherein the primer layer is made of alumina, zirconia or titania, and the primer layer is made of the same material as the main component of the ceramic substrate; the thickness of the bottom layer is 20 to 40 nanometers; the intermediate layer is made of silicon dioxide, aluminum oxide or titanium oxide; the thickness of the intermediate layer is 10 to 40 nm.
7. The gradient-color ceramic part according to claim 1 or 3, wherein a transparent protective layer is further formed on the surface of the gradient layer, and the transparent protective layer is made of silicon dioxide, aluminum oxide, zirconium oxide or titanium oxide; the thickness of the transparent protective layer is 20 to 40 nanometers.
8. A graded colour ceramic article as claimed in any one of claims 1 to 7, characterised in that the ceramic substrate is formed by sintering a ceramic raw material comprising:
70-99 parts by mass of powder;
1 to 30 parts by mass of a binder; and
0 to 10 parts by mass of a coloring material;
wherein the powder is at least one of alumina powder, zirconia powder and titanium oxide powder.
9. The graded ceramic article according to any one of claims 1 to 7, wherein a capping ink layer is formed on a side of the ceramic substrate away from the primer layer, the intermediate layer and the graded layer; the thickness of the bottom ink covering layer is 10-15 microns.
10. The graded ceramic article of claim 1 wherein the powder in the ceramic raw material forming the ceramic substrate is zirconia powder; the bottom layer is a zirconium oxide film layer; the middle layer is a silicon dioxide film layer; the gradient layer is a silicon layer; and a transparent protective layer is also formed on the surface of the gradient layer, and the transparent protective layer is a zirconium oxide layer.
11. A method for processing a gradient color ceramic part is characterized by comprising the following steps:
preparing a ceramic matrix; and
sequentially depositing on the surface of the ceramic substrate to form a bottom layer, an intermediate layer and a gradient layer; the material of the gradual change layer is one or more of silicon, silicon dioxide and titanium dioxide, and the thicknesses of the gradual change layer at least two positions are different, so that the gradual change layer at least two positions shows gradual change.
12. The method of manufacturing a graded ceramic article according to claim 11, wherein the step of depositing the graded layer comprises:
providing a shielding jig;
arranging the shielding jig on the ceramic substrate after the intermediate layer is deposited, wherein the distance between the shielding jig and the surface of the intermediate layer is adjustable; and
depositing the graded layer on the surface of the intermediate layer by a physical vapor deposition process; the thickness of the gradual change layer on the surface of the intermediate layer provided with the shielding jig is smaller than that of the gradual change layer on the surface of the intermediate layer not provided with the shielding jig.
13. The method of manufacturing a gradient color ceramic article according to claim 11, wherein the powder in the ceramic raw material forming the ceramic base is zirconia powder; the bottom layer is a zirconium oxide film layer; the middle layer is a silicon dioxide film layer; the gradient layer is a silicon layer; and a transparent protective layer is also formed on the surface of the gradient layer, and the transparent protective layer is a zirconium oxide layer.
14. A terminal device, characterized in that it comprises a gradient-colour ceramic piece according to any one of claims 1 to 10.
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