WO2023051214A1 - Ceramic housing, preparation method therefor, and electronic device - Google Patents

Ceramic housing, preparation method therefor, and electronic device Download PDF

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Publication number
WO2023051214A1
WO2023051214A1 PCT/CN2022/117791 CN2022117791W WO2023051214A1 WO 2023051214 A1 WO2023051214 A1 WO 2023051214A1 CN 2022117791 W CN2022117791 W CN 2022117791W WO 2023051214 A1 WO2023051214 A1 WO 2023051214A1
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WIPO (PCT)
Prior art keywords
ceramic
ceramic layer
green body
pattern
layer
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PCT/CN2022/117791
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French (fr)
Chinese (zh)
Inventor
张文宇
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Oppo广东移动通信有限公司
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Publication of WO2023051214A1 publication Critical patent/WO2023051214A1/en

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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
    • 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
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F1/00—Details not covered by groups G06F3/00 - G06F13/00 and G06F21/00
    • G06F1/16—Constructional details or arrangements
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04M—TELEPHONIC COMMUNICATION
    • H04M1/00—Substation equipment, e.g. for use by subscribers
    • H04M1/02—Constructional features of telephone sets
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K5/00—Casings, cabinets or drawers for electric apparatus
    • H05K5/02—Details

Definitions

  • the application belongs to the technical field of electronic products, and in particular relates to a ceramic casing, a preparation method thereof, and electronic equipment.
  • Ceramic materials have a warm and jade-like texture and excellent wear resistance, and are very popular among consumers.
  • the mainstream ceramic shells are mainly black and white solid colors, and the colors are single. Therefore, it is particularly important to develop ceramic shells with rich colors and patterns and improve their appearance to meet more diverse needs.
  • the present application provides a ceramic shell, including a first ceramic layer, a second ceramic layer and a first pattern layer, the first pattern layer is located between the first ceramic layer and the second ceramic layer, and the first pattern layer is located between the first ceramic layer and the second ceramic layer.
  • the pattern of a pattern layer can be shown through the first ceramic layer.
  • the present application provides a method for preparing a ceramic shell, including providing a first ceramic layer green body and a second ceramic layer green body, and setting a first pattern on the second ceramic layer green body;
  • the first pattern is located between the first ceramic layer green body and the second ceramic layer green body;
  • the present application provides an electronic device, including a display device, a main board, and a ceramic housing.
  • the ceramic housing and the display device enclose an accommodating space
  • the main board is located in the accommodating space
  • the ceramic housing includes a first A ceramic layer, a second ceramic layer and a first pattern layer.
  • the first pattern layer is located between the first ceramic layer and the second ceramic layer. The pattern of the first pattern layer can be displayed through the first ceramic layer.
  • FIG. 1 is a schematic structural diagram of a ceramic housing provided in an embodiment of the present application.
  • FIG. 2 is a top view of the ceramic housing provided in FIG. 1 of the present application.
  • FIG. 3 is a schematic structural diagram of a ceramic housing provided in another embodiment of the present application.
  • FIG. 4 is a schematic structural diagram of a ceramic housing provided in yet another embodiment of the present application.
  • FIG. 5 is a top view of the ceramic housing provided in FIG. 4 of the present application.
  • FIG. 6 is a schematic structural diagram of a ceramic housing provided in yet another embodiment of the present application.
  • FIG. 7 is a top view of the ceramic housing provided in FIG. 6 of the present application.
  • FIG. 8 is a flowchart of a method for preparing a ceramic shell provided in an embodiment of the present application.
  • FIG. 9 is a schematic structural diagram of an electronic device provided by an embodiment of the present application.
  • FIG. 10 is a schematic diagram of the structure and composition of an electronic device provided in an embodiment of the present application.
  • the inventor has found through long-term research that in order to improve the appearance of the ceramic shell, it is possible to add toner to the ceramic raw material, use colored ions to impregnate the ceramic green body, or directly coat the ceramic shell, etc. Although these solutions can improve the appearance of the ceramic shell to a certain extent Ceramic appearance, but it is difficult to achieve a specific pattern on ceramic.
  • a colored glaze layer can be directly coated on the surface of the ceramic blank.
  • the glaze layer directly covers the surface of the ceramic shell, making the ceramic shell
  • the surface of the body loses its unique jade texture, and air bubbles often remain in the glaze layer, which affects the appearance of the shell.
  • FIG. 1 is a schematic structural diagram of a ceramic housing provided in an embodiment of the present application.
  • the ceramic shell 110 comprises a first ceramic layer 11, a second ceramic layer 12 and a first pattern layer 21, the first pattern layer 21 is located between the first ceramic layer 11 and the second ceramic layer 12, and the pattern of the first pattern layer 21 Visible through the first ceramic layer 11 .
  • the first pattern layer 21 covers a partial area of the second ceramic layer 12 , so that the finally obtained ceramic shell 110 presents a partial pattern effect.
  • the first pattern layer 21 completely covers the side of the second ceramic layer 12 close to the first ceramic layer 11 , so that the finally obtained ceramic shell 110 presents the effect of being covered with patterns.
  • the pattern of the first pattern layer 21 can be seen through the first ceramic layer 11 , wherein the total light transmittance of the first ceramic layer 11 is greater than that of the second ceramic layer 12 .
  • the total light transmittance of the first ceramic layer 11 is greater than or equal to 30%, such as but not limited to 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%. etc., to ensure that the pattern between the first ceramic layer 11 and the second ceramic layer 12 can be seen through the first ceramic layer 11, and can be observed by the user. Since the pattern is located in the stack, it can appear through the action of light. Stereoscopic and depth-of-field perception.
  • the linear light transmittance of the first ceramic layer 11 is greater than that of the second ceramic layer 12, and the linear light transmittance of the first ceramic layer 11 is greater than or equal to 0.5%, such as but not limited to 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, etc., ensuring the first pattern between the first ceramic layer 11 and the second ceramic layer 12
  • 0.5% such as but not limited to 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, etc.
  • FIG. 3 is a schematic structural diagram of a ceramic housing provided in another embodiment of the present application.
  • the ceramic housing 110 further includes a third ceramic layer 13 , and the third ceramic layer 13 is located on a side of the second ceramic layer 12 away from the first ceramic layer 11 .
  • a first pattern layer 21 is provided between the first ceramic layer 11 and the second ceramic layer 12, and a second pattern layer 21 is provided between the second ceramic layer 12 and the third ceramic layer 13.
  • Two pattern layers 22 are provided.
  • the total light transmittance of the first ceramic layer 11 is greater than that of the second ceramic layer 12
  • the total light transmittance of the second ceramic layer 12 is greater than that of the third ceramic layer 13 .
  • the total light transmittance of the first ceramic layer is greater than 30%
  • the total light transmittance of the second ceramic layer is greater than 10% but less than the total light transmittance of the first ceramic layer 11
  • the total light transmittance of the third ceramic layer Light transmittance is not required.
  • the high total light transmittance can ensure that the pattern of the pattern layer located between the ceramic layers can appear through the ceramic layer, specifically, the pattern of the first pattern layer 21 can appear on the surface of the ceramic housing 110 through the first ceramic layer 11,
  • the pattern of the second pattern layer 22 appears on the surface of the ceramic housing 110 through the first ceramic layer 11 and the second ceramic layer 12.
  • the patterns of the first pattern layer 21 and the second pattern layer 22 can be the same or different, and the finally obtained
  • the ceramic shell 110 presents a rich pattern effect.
  • the linear light transmittance of the first ceramic layer 11 is greater than that of the second ceramic layer 12
  • the linear light transmittance of the second ceramic layer 12 is greater than that of the third ceramic layer 13 .
  • the linear light transmittance of the first ceramic layer 11 is greater than 0.5%
  • the linear light transmittance of the second ceramic layer 12 is greater than 0.1% but less than the linear light transmittance of the first ceramic layer 11, and the third ceramic layer The linear light transmittance of 13 is not required.
  • the high linear light transmittance can ensure that the pattern of the pattern layer below the ceramic layer appears on the surface of the ceramic shell 110 through the ceramic layer, specifically, the pattern of the first pattern layer 21 appears on the ceramic shell through the first ceramic layer 11 On the surface of the body 110 , the pattern of the second pattern layer 22 appears on the surface of the ceramic shell 110 through the first ceramic layer 11 and the second ceramic layer 12 .
  • FIG. 5 is a top view of the ceramic housing provided in FIG. 4 of the present application.
  • the first pattern layer 21 and the second pattern layer 22 are respectively located in the middle of different ceramic layers, and can appear through the first ceramic layer 11 and the second ceramic layer 12 respectively.
  • the patterns of the first pattern layer 21 and the second pattern layer 22 are the same. Since the total light transmittance of the second ceramic layer 12 is lower than that of the first ceramic layer 11, the final second ceramic layer 110 appears on the ceramic shell 110.
  • the color of the pattern layer 22 is lighter than that of the first pattern layer 21 , so that the pattern on the ceramic housing 110 can be changed in depth or a gradient effect.
  • the patterns of the first pattern layer 21 and the second pattern layer 22 are different, so that the ceramic shell 110 finally presents various patterns with different shades.
  • FIG. 6 is a schematic structural diagram of a ceramic housing provided in yet another embodiment of the present application.
  • the first pattern layer 21 between the first ceramic layer 11 and the second ceramic layer 12 is multiple, such as 2, respectively 21a and 21b, the second pattern layer 21 between the second ceramic layer 12 and the third ceramic layer 13 Pattern layer is 1 and is 22.
  • the individual pattern layers are combined to form a specific pattern, such as a brand logo.
  • FIG. 7 is a top view of the ceramic housing in FIG. 6 , the letter O is obtained by combining the first pattern layers 21a and 21b with the second pattern layer 22 .
  • the third ceramic layer has a color, which can provide a base color for the first pattern layer 21 a and 21 b, and enrich the pattern effect on the surface of the ceramic housing 110 .
  • the ceramic shell 110 further includes a fourth ceramic layer and/or a fifth ceramic layer, the first ceramic layer 11 and the second ceramic layer 12, the second ceramic layer 12 and the third ceramic layer 13, the third ceramic layer At least one pattern layer is set between the ceramic layer 13 and the fourth ceramic layer, the fourth ceramic layer and the fifth ceramic layer, or multiple pattern layers are set between every two layers of ceramic layers, and the finally obtained ceramic shell 110 can present various patterns. Various patterns.
  • the thickness of the ceramic shell 110 is 0.4mm-0.6mm, and the thickness of the first ceramic layer 11 is greater than or equal to 0.01mm and less than 0.5mm.
  • the thickness of the first ceramic layer 11 is smaller than the thickness of the second ceramic layer 12 and the third ceramic layer 13, so that the first ceramic layer 11 has good light transmittance, and the pattern of the pattern layer can pass through the first ceramic layer. Ceramic layer 11 is shown.
  • the components of the first ceramic layer 11 and the second ceramic layer 12 include zirconia and yttrium oxide.
  • the components of the first ceramic layer 11 include 89%-97% zirconia (ZrO 2 ), 3%-7% yttrium oxide (Y 2 O 3 ), 0-0.5% aluminum oxide (Al 2 O 3 ), 0-3% hafnium oxide (HfO 2 ), 0-0.5% colorant.
  • the components of the second ceramic layer 12 include 80%-96.5% zirconia, 3%-7% yttrium oxide, 0-5% aluminum oxide, 0-3% hafnium oxide, and 0.5-5% colorant;
  • the composition of the third ceramic layer 13 includes 60%-92% zirconia, 3%-7% yttrium oxide, 0-20% aluminum oxide, 0-3% hafnium oxide, 5%-10% colorant .
  • the first pattern layer 21 and the second pattern layer 22 of the present application can be formed by ceramic slurry or ceramic ink, and the composition of the ceramic slurry or ceramic ink contains 60%-97% by weight. zirconia, 3%-7% yttrium oxide, 0-20% aluminum oxide, 0-3% hafnium oxide, 0.01-10% colorant.
  • Zirconia is the main component of ceramics. It is translucent white, with jade texture and high hardness.
  • Yttrium oxide is a stabilizer, the function is to inhibit the transformation of zirconia tetragonal phase to monoclinic phase, and ensure the crystal phase stability and mechanical strength of the ceramic shell. Too small yttrium oxide content is not conducive to the crystal phase stability of ceramics, which makes ceramics sintered and processed. It is easy to crack when the yttrium oxide content is too high, which will significantly reduce the mechanical strength and toughness of the ceramic shell.
  • the role of alumina is to reduce the light transmittance of zirconia ceramics and improve the whiteness.
  • hafnium oxide is a symbiosis of zirconia, and its physical and chemical properties are very similar to zirconia. Ceramic housings have little effect on performance.
  • the function of the coloring agent is to dye the original white zirconia into other colors, mainly transition metal oxides, rare earth element oxides or compounds composed of them, such as iron oxide, copper oxide, cobalt oxide, cerium oxide, Nickel oxide, zinc oxide, manganese oxide, chromium oxide, praseodymium oxide, neodymium oxide, strontium oxide, lanthanum oxide, erbium oxide, gallium oxide, cobalt aluminate, nickel ferrite, lanthanum manganate, etc.
  • the contents of zirconia, yttrium oxide, aluminum oxide and hafnium oxide in the second ceramic layer and/or the third ceramic layer are the same as those in the first ceramic layer except for the colorant content.
  • the first ceramic layer 11 does not contain a colorant
  • the second ceramic layer 12 and/or the third ceramic layer 13 contains a colorant but other components and contents are the same as those of the first ceramic layer 11, and the same components can be
  • the different ceramic layers have excellent bonding strength
  • the second ceramic layer 12 and/or the third ceramic layer 13 added with a colorant can add a background color to the pattern layer between the ceramic layers, so that the ceramic shell presents a richer color. Pattern, color and appearance.
  • Hardness characterizes the ability of the ceramic housing 110 to resist pressing hard objects into its surface.
  • the ceramic housing 110 is detected by a Vickers hardness tester.
  • the Vickers hardness Hv10 of the ceramic shell 110 is greater than 11 GPa, and has good deformation resistance.
  • the surface roughness of the ceramic housing 110 is less than 50 nm, and the reflectance of the surface of the ceramic housing is 10%-20% within the wavelength range of visible light.
  • the surface roughness of the ceramic shell is small and has a certain reflectivity, which can obtain a smooth surface and maintain a jade texture.
  • This application measures the porosity content of the ceramic shell 110 by adopting GB/T 25995-2010 "Test Method for Density and Apparent Porosity of Fine Ceramics".
  • the porosity content of the ceramic shell 110 is less than 0.5%, that is, the density of the ceramic shell 110 is greater than 99.5%.
  • the low pore content of the ceramic shell 110 ensures the bonding strength inside the ceramic shell 110 , which is beneficial to the improvement of the mechanical properties of the ceramic shell 110 .
  • the difference in thermal expansion coefficient between each ceramic layer is less than 0.1 ⁇ 10 -6 /°C; the suitable sintering temperature difference of each ceramic layer is less than 20°C, and the final ceramic shell 110
  • the four-point bending strength is greater than 1000MPa, and the four-point bending strength test method can be found in "GBT6569-2006-Fine Ceramic Bending Strength Test Method".
  • the bonding strength of the first ceramic layer 11 and the second ceramic layer 12 is greater than 800 MPa, and the porosity difference between the first ceramic layer 11 and the second ceramic layer 12 is Less than 0.1%, the obtained ceramic shell 110 has good mechanical properties.
  • FIG. 8 is a flow chart of a method for preparing a ceramic shell provided in an embodiment of the present application.
  • the preparation method prepares the ceramic shell 110 of any of the above-mentioned embodiments, including:
  • Step 101 providing a first ceramic layer green body and a second ceramic layer green body, and setting a first pattern on the second ceramic layer green body;
  • Step 102 laminate and press the first ceramic layer green body and the second ceramic layer green body, the first pattern is located between the first ceramic layer green body and the second ceramic layer green body;
  • Step 103 sintering the laminated and laminated ceramic layer green body to obtain a ceramic layer rough body
  • Step 104 Grinding and polishing the rough surface of the ceramic layer to obtain a ceramic shell.
  • the pattern in steps 101 and 102, can also be set only on the first ceramic layer green body, and the first ceramic layer green body and the second ceramic layer green body are laminated and pressed so that the pattern is located on the first ceramic layer green body. layer green body and the second ceramic layer green body.
  • providing the first ceramic layer green body includes preparing the first ceramic layer green body raw material, tape casting to obtain the first ceramic layer green body; the first ceramic layer green body raw material contains inorganic substances and organic additives, by weight percentage In total, the inorganic matter is 89%-97% zirconia, 3%-7% yttrium oxide, 0-0.5% aluminum oxide, 0-3% hafnium oxide, 0-0.5% colorant, organic additives The weight accounts for 10%-20% of the total weight of inorganic substances.
  • step 101 providing the second ceramic layer green body includes preparing the second ceramic layer green body raw material, and tape casting to obtain the second ceramic layer green body;
  • the second ceramic layer green body raw material contains inorganic substances and organic additives, by weight percentage
  • the inorganic matter is 80%-96.5% zirconia, 3%-7% yttrium oxide, 0-5% aluminum oxide, 0-3% hafnium oxide, 0.5%-5% colorant, organic auxiliary
  • the weight of the agent accounts for 10%-20% of the total weight of the inorganic matter.
  • step 101 and before step 103 it also includes providing a third ceramic layer green body, laminating and pressing the first ceramic layer green body, the second ceramic layer green body and the third ceramic layer green body, the third The ceramic layer is located on the side of the second ceramic layer away from the first ceramic layer.
  • the second pattern may be provided on the third ceramic layer green body, and the second pattern is located between the second ceramic layer green body and the third ceramic layer green body.
  • Providing the third ceramic layer green body includes preparing the third ceramic layer green body raw material, tape-casting to obtain the third ceramic layer green body; the third ceramic layer green body raw material contains inorganic substances and organic additives, by weight percentage, the inorganic substance 60%-92% of zirconia, 3%-7% of yttrium oxide, 0-20% of aluminum oxide, 0-3% of hafnium oxide, 5%-10% of coloring agent, the weight of organic additives accounts for the weight of inorganic 10%-20% of the total weight of the items.
  • the organic additives in the ceramic layer green body are mainly composed of one or more of binders, dispersants, defoamers, plasticizers, lubricants, and solvents.
  • the binder type includes but not limited to one or more of polymethylacrylate, polymethacrylic acid, polyvinyl butyral, ethyl cellulose;
  • the dispersant type includes but not limited to triolein, One or more in ethoxylate compound, phosphate ester;
  • Plasticizer type includes but not limited to one or more in polyethylene glycol, glycerol, dibutyl phthalate; Solvent can be Butanone, etc.; the role of organic additives is to assist production, promote the uniform dispersion of each component during mixing, and improve the plasticity and strength of ceramic blanks. In the subsequent sintering process, the organic additives will be completely burned off under high temperature operation.
  • Setting the first pattern in step 101 includes preparing raw materials for the first pattern, the raw material for the first pattern is ceramic slurry or ceramic ink;
  • the ceramic slurry components include inorganic substances and organic additives, and the inorganic substances are 60% by weight -97% zirconia, 3%-7% yttrium oxide, 0-20% aluminum oxide, 0-3% hafnium oxide, 0.01%-10% colorant, the weight of organic additives accounts for the total weight of inorganic substances
  • the viscosity of ceramic slurry is 5000mPa ⁇ s-20000mPa ⁇ s, the particle size of inorganic matter in ceramic slurry is ⁇ 10 ⁇ m;
  • the components of ceramic ink include inorganic matter and organic additives, by weight percentage, inorganic matter 60%-97% of zirconia, 3%-7% of yttrium oxide, 0-20% of aluminum oxide, 0-3% of hafnium oxide, 0.01%-10% of coloring agent, the weight of organic additives accounts for the weight of
  • the organic additives in the ceramic slurry or ceramic ink include solvents, binders, plasticizers, dispersants, defoamers, and the like.
  • Binders include but are not limited to one or more of polyvinyl alcohol, acrylic emulsion, polyvinyl ammonium salt, polyvinyl acetate;
  • dispersants include but are not limited to polyvinyl acid, polymethacrylic acid, methyl One or more of ammonium acrylate and triethanolamine;
  • the solvent can be a mixture of butanone and alcohol or water. In the subsequent sintering process, the organic additives will be completely burned off under high temperature operation.
  • the way of setting the first pattern or the second pattern can be specifically the way of printing or printing the pattern, and further, the ceramic slurry or ceramic ink can be printed or printed according to the designed pattern by silk screen printing, offset printing, pad printing or inkjet printing.
  • Silk screen printing refers to a screen printing plate with a pattern made by photosensitive plate-making method. The mesh of the pattern part can pass through the ceramic slurry, and the mesh of the non-pattern part cannot pass through the slurry.
  • the ceramic slurry passes through the mesh and The pattern is printed on the ceramic green body; offset printing is a flat printing technology, which transfers the ceramic slurry on the rubber surface to the ceramic green body through a roller-type rubber die, thereby printing the pattern on the green body; Pad printing refers to a curved surface pad printing head made of silicone rubber material. Dip the ceramic slurry on the gravure onto the surface of the pad printing head, and then press it on the surface of the ceramic green body to draw the pattern; inkjet printing refers to The most important thing is to make ceramic ink from ceramic powder, and print the ceramic ink onto the ceramic green body through a digital inkjet printer to obtain a pattern.
  • setting the first pattern or the second pattern also includes standing the patterned ceramic layer green body at room temperature or baking at a low temperature (temperature less than 150°C) for about 10min-120min, making the ceramic slurry or ceramic ink and ceramic The green body of the first layer is fully infiltrated, and the solvent in the organic auxiliary agent in the ceramic slurry or ceramic ink is further volatilized.
  • the lamination and pressing of the first ceramic layer green body and the second ceramic layer green body includes: after laminating the first ceramic layer green body and the second ceramic layer green body, further pressing by isostatic pressing, etc.
  • the static pressure is ⁇ 100MPa
  • the temperature is room temperature -100°C.
  • the purpose is to further compact the green bodies of each ceramic layer and prevent delamination during subsequent sintering.
  • the laminated billet can also be shaped as required, such as shaping the 2D billet into a 2.5D or 3D curved billet.
  • the pattern in the ceramic layer green body will be distorted and deformed during the lamination and pressing process. By adding a supporting fixture on the ceramic layer green body, the force direction of each surface of the ceramic layer green body Consistent to ensure that you get the pattern with the precision you need.
  • the ceramic layer green bodies are laminated and then sintered.
  • the sintering is divided into two stages.
  • the first stage is a low-temperature debinding stage with a temperature range from room temperature to 600°C.
  • the heating rate is required to be as slow as possible, not exceeding 0.5°C/min, preferably less than 0.2°C/min.
  • the slower the heating rate the more conducive to uniform debinding. Too fast heating will lead to delamination and cracking.
  • the second stage is a high-temperature sintering stage, the temperature rise range is 600°C-1500°C, and the temperature is kept at a maximum temperature of 1350°C-1500°C for 2h-4h.
  • the heating rate of this stage does not exceed 10°C/min, preferably less than 5°C/min.
  • the surface of the obtained rough ceramic layer is ground and polished to remove surface defects, reduce surface roughness, and increase light transmittance.
  • the rough ceramic layer includes a first surface and a second surface.
  • the first surface is used for displaying patterns, and can also be called a pattern display surface.
  • the roughness of the first surface is Ra ⁇ 50nm
  • the roughness of the second surface is The second surface is not required to be polished, and simple rough polishing can be performed, and the second surface roughness Ra ⁇ 1000nm can reduce the influence of machining knife lines on the strength of the ceramic shell 110 .
  • the finally obtained ceramic shell 110 includes a first ceramic layer 11 formed from a first ceramic layer green body, a second ceramic layer 12 formed from a second ceramic layer green body, and a ceramic layer formed from a first pattern.
  • the first pattern layer 21 , the first pattern layer 21 is located between the first ceramic layer 11 and the second ceramic layer 12 , the pattern of the first pattern layer 21 can be revealed through the first ceramic layer 11 .
  • the preparation method of the ceramic shell 110 provided in this application has simple operation steps, is easy to mass-produce, and can produce a ceramic shell 110 with rich appearance effects, which is beneficial to its application.
  • the present application also provides an electronic device 200 including the ceramic housing 110 of any one of the above-mentioned embodiments.
  • the electronic device 200 may be, but not limited to, a mobile phone, a tablet computer, a notebook computer, a watch, an MP3, an MP4, a GPS navigator, a digital camera, and the like.
  • the electronic device includes a display device 100 , a ceramic housing 110 and a main board.
  • the display device 100 may be a screen.
  • the ceramic housing and the display device define an accommodating space, and the main board is located in the accommodating space.
  • the ceramic housing includes the ceramic housing 110 of any one of the above embodiments.
  • the ceramic casing 110 can endow the electronic device with a rich pattern appearance and maintain a ceramic jade-like appearance, thereby improving the expressive force of the electronic device.
  • the ceramic housing 110 when the ceramic housing is applied to an electronic device, the ceramic housing 110 further contains an ink layer, and the ink layer is located on the opposite side of the ceramic housing to the pattern display surface, that is, the ink layer is located on the side of the ceramic housing close to the main board. one side.
  • the ink layer is formed of black ink, which can effectively cover electronic components in electronic equipment.
  • the ink layer thickness is 0.01mm-0.04mm.
  • the ceramic housing also includes an explosion-proof membrane, the explosion-proof membrane is made of polyethylene terephthalate (PET), the thickness of the explosion-proof membrane is 0.05mm-0.1mm, and the explosion-proof membrane can ensure that the ceramic housing is broken. Finally, the debris will not be generated to harm users, ensuring the safety of electronic equipment.
  • the structure of the electronic device 200 may include an RF circuit 210, a memory 220, an input unit 230, a display unit 240, a sensor 250, an audio circuit 260, a WiFi module 270, Processor 280 and power supply 290 and so on.
  • RF circuit 210 , memory 220 , input unit 230 , display unit 240 , sensor 250 , audio circuit 260 , and WiFi module 270 are respectively connected to processor 280 ; power supply 290 is used to provide electric energy for the entire electronic device 200 .
  • the RF circuit 210 is used for sending and receiving signals; the memory 220 is used for storing data instruction information; the input unit 230 is used for inputting information, and may specifically include other input devices such as a touch panel and operation buttons; the display unit 240 may include a display screen, etc.; sensor 250 includes an infrared sensor, a laser sensor, etc., and is used to detect user approach signals, distance signals, etc.; speaker 261 and microphone 262 are connected to processor 280 through audio circuit 260, and are used to receive and send sound signals; WiFi module 270 It is used to receive and transmit WiFi signals; the processor 280 is used to process data information of the electronic device 200 .
  • the ceramic housing prepared in the embodiment of the present application will be further described below through specific examples.
  • the raw materials of the first ceramic layer green body include inorganic substances: 93.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances.
  • the mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, the raw material of the green body of the second ceramic layer is the same as the raw material of the green body of the first ceramic layer,
  • the first pattern raw material includes inorganic substances: 86.5wt% zirconia, 4.2wt% yttrium oxide, 3.0wt% aluminum oxide, 2.3wt% hafnium oxide, 4.0wt% cobalt aluminate, the weight of organic additives accounts for the weight of inorganic substances 20% of the total, wherein the mass ratio of the binder polyvinyl alcohol to the dispersant polymethacrylic acid is 1:7.
  • the first ceramic layer green body and the second ceramic layer green body are obtained by tape casting, and the first pattern is printed on the second ceramic layer green body by silk screen printing.
  • the color of the first pattern is blue, and the silk screen of the silk screen is stainless steel.
  • the hole diameter is 450 mesh; the first ceramic layer and the second ceramic layer green body are laminated and pressed, the first pattern is located between the first ceramic layer and the second ceramic layer green body to form the first pattern layer, laminated and pressed, etc.
  • the static pressure is 150MPa and the temperature is 60°C; the first ceramic layer and the second ceramic layer green body obtained by sintering after lamination and pressing are obtained to obtain the rough body of the first ceramic layer and the second ceramic layer with a porosity content less than 0.5%, During sintering, the temperature rise rate of room temperature-600°C debinding section is 0.1°C/min, the temperature rise rate of 600°C-1450°C sintering section is 4°C/min, the highest temperature reaches 1450°C, and the temperature is kept for 3 hours.
  • the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10% ⁇ x ⁇ 20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each ceramic layer of the ceramic shell is less than 0.1 ⁇ 10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
  • test method for the light transmittance of each ceramic layer in each embodiment is: obtain a ceramic layer green body, such as the first ceramic layer green body, do not laminate with other layers, and put the single-layer first ceramic layer The green body is sintered under the same conditions as the multilayer ceramic shell containing the first ceramic layer, ground and polished to the required thickness (0.01mm-0.5mm), and then the light transmittance is tested with a light transmittance tester.
  • the obtained ceramic shell has higher light transmittance.
  • the components of the first ceramic layer and the second ceramic layer are consistent, and since the thickness of the first ceramic layer is smaller than that of the second ceramic layer, the total light transmittance of the first ceramic layer is greater than that of the second ceramic layer.
  • the ceramic shell is translucent on the side of the first ceramic layer away from the second ceramic layer as a whole, with a strong jade texture, and the blue first pattern layer between the layers can clearly appear on the surface of the ceramic shell through the first ceramic layer.
  • the surface roughness of the ceramic shell is less than 50nm.
  • the reflectance of the ceramic shell surface is x, 10% ⁇ x ⁇ 20%, that is, the obtained ceramic shell has a good jade texture;
  • the ceramic shell The Vickers hardness Hv10 is greater than 11Gpa, so the obtained ceramic shell has good wear resistance;
  • the difference in thermal expansion coefficient of each ceramic layer of the ceramic shell is less than 0.1 ⁇ 10 -6 /°C, so the ceramic layers can be better combined, and finally obtained
  • the four-point bending strength of the ceramic shell is greater than 1000MPa, that is, the ceramic shell has excellent mechanical properties.
  • the raw materials of the first ceramic layer green body include inorganic substances: 93.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein The mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the raw material of the green body of the second ceramic layer is the same as that of the green body of the first ceramic layer.
  • the raw materials of the three-layer ceramic layer green body include inorganic substances: 89.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 4.0wt% erbium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, of which The mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the first pattern raw material includes inorganic substances: 86.5wt% zirconia, 4.2wt% % of yttrium oxide, 3.0wt% of aluminum oxide, 2.3wt% of hafnium oxide, 4.0wt% of cobalt aluminate, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the binder polyvinyl alcohol and the dispersant polyformaldehyde The mass ratio of base acrylic acid is 1:7.
  • the first pattern is printed on the green body of the second ceramic layer by silk screen printing.
  • the color of the first pattern is blue.
  • the wire mesh is stainless steel, the mesh aperture is 450 meshes; the first ceramic layer, the second ceramic layer and the third ceramic layer green body are laminated, and the first pattern is located between the first ceramic layer and the second ceramic layer green body
  • the first pattern layer is formed between them, and the lamination pressure is 200MPa and the temperature is 30°C; the first ceramic layer, the second ceramic layer and the third ceramic layer green body after lamination and lamination obtained by sintering are obtained to obtain pores
  • the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10% ⁇ x ⁇ 20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each ceramic layer of the ceramic shell is less than 0.1 ⁇ 10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
  • the obtained ceramic shell Since the content of colorant and alumina in the first ceramic layer and the second ceramic layer components is 0, the obtained ceramic shell has a high total light transmittance, and the ceramic shell is far away from the second ceramic layer One side of the layer is translucent as a whole, with a strong jade texture.
  • the blue pattern layer between the layers can be clearly shown through the first ceramic layer and the second ceramic layer.
  • the third ceramic layer is pink, and can also be seen through the first ceramic layer.
  • the ceramic layer and the second ceramic layer are displayed on the ceramic shell to add background color to the pattern layer, so that the ceramic shell has richer patterns and colors.
  • the surface roughness of the ceramic shell is less than 50nm.
  • the reflectance of the ceramic shell surface is x, 10% ⁇ x ⁇ 20%, that is, the obtained ceramic shell has a good jade texture;
  • the ceramic shell The Vickers hardness Hv10 is greater than 11Gpa, so the obtained ceramic shell has good wear resistance;
  • the difference in thermal expansion coefficient of each ceramic layer of the ceramic shell is less than 0.1 ⁇ 10-6/°C, so the ceramic layers can be better combined, and finally obtained
  • the four-point bending strength of the ceramic shell is greater than 1000MPa, that is, the ceramic shell has excellent mechanical properties.
  • the first ceramic layer green body, the second ceramic layer green body, the third ceramic layer green body, the first pattern and the second pattern raw material are prepared.
  • the raw materials of the first ceramic layer green body include inorganic substances: 93.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein The mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the raw material of the green body of the second ceramic layer is the same as that of the green body of the first ceramic layer.
  • the raw materials of the three-layer ceramic layer green body include inorganic substances: 89.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 4.0wt% erbium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, of which The mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the first pattern raw material includes inorganic substances: 86.5wt% zirconia, 4.2wt% % of yttrium oxide, 3.0wt% of aluminum oxide, 2.3wt% of hafnium oxide, 4.0wt% of cobalt aluminate, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the binder polyvinyl alcohol and the dispersant polyformaldehyde The mass ratio of acrylic acid is 1:7, and the second pattern raw material includes inorganic
  • the first ceramic layer green body, the second ceramic layer green body, and the third ceramic layer green body are obtained by tape casting.
  • the first pattern is printed on the second ceramic layer green body by silk screen printing.
  • the color of the first pattern is blue.
  • the screen is made of stainless steel, the mesh aperture is 450 mesh, and the second pattern is printed on the green body of the third ceramic layer by inkjet printing, the color of the second pattern is black, the printing is 600dpi resolution, and the ink droplet volume is 6pl; laminate the first ceramic layer, the second ceramic layer and the third ceramic layer green body, the first pattern is located between the first ceramic layer and the second ceramic layer green body to form a first pattern layer, the second pattern is located in the second ceramic layer
  • the second pattern layer is formed between the green body of the layer and the third ceramic layer, and the lamination pressure is 200MPa and the temperature is 60°C; the first ceramic layer, the second ceramic layer and the third ceramic layer after sintering lamination Ceramic layer green body, obtain the first ceramic layer, the second ceramic layer and
  • the temperature rise rate of the debinding section at room temperature -600°C is 0.1°C/min, and at 600°C-
  • the heating rate of the sintering section at 1450°C is 3°C/min, the maximum temperature reaches 1450°C, and the temperature is kept for 2 hours.
  • the organic additives are completely volatilized; the surface of the rough ceramic layer is polished and polished, and finally a ceramic shell with a pattern is obtained. Specific parameters See Table 3.
  • the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10% ⁇ x ⁇ 20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each ceramic layer of the ceramic shell is less than 0.1 ⁇ 10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
  • the obtained ceramic shell has a high light transmittance, and the ceramic shell is far away from the first ceramic layer from the second ceramic layer.
  • One side is translucent as a whole, with a strong jade texture.
  • the blue first pattern layer and the black second pattern layer between the layers can be clearly shown through the first ceramic layer and the second ceramic layer, and the first pattern layer It has a different sense of hierarchy from the second pattern layer.
  • the third ceramic layer is pink, and can also be displayed on the ceramic shell through the first ceramic layer and the second ceramic layer, adding a base color to the first pattern layer and the second pattern layer, so that the ceramic shell has a richer pattern and color.
  • the surface roughness of the ceramic shell is less than 50nm.
  • the reflectance of the ceramic shell surface is x, 10% ⁇ x ⁇ 20%, that is, the obtained ceramic shell has a good jade texture;
  • the ceramic shell The Vickers hardness Hv10 is greater than 11Gpa, so the obtained ceramic shell has good wear resistance;
  • the difference in thermal expansion coefficient of each ceramic layer of the ceramic shell is less than 0.1 ⁇ 10 -6 /°C, so the ceramic layers can be better combined, and finally obtained
  • the four-point bending strength of the ceramic shell is greater than 1000MPa, that is, the ceramic shell has excellent mechanical properties.
  • the first ceramic layer green body, the second ceramic layer green body, the third ceramic layer green body, the first pattern and the second pattern raw material are prepared.
  • the raw materials of the first ceramic layer green body include inorganic substances: 93.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein The mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the raw material of the second ceramic layer includes inorganic substances: 89.5wt% zirconia , 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 4.0wt% erbium oxide, the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the binder polymethyl acrylate and dispersant triolein and The mass ratio of the plasticizer polyethylene glycol is 8:
  • the first ceramic layer green body, the second ceramic layer green body, and the third ceramic layer green body are obtained by tape casting.
  • the first pattern is printed on the second ceramic layer green body by silk screen printing.
  • the color of the first pattern is blue.
  • the screen is made of stainless steel, the mesh aperture is 450 mesh, and the second pattern is printed on the green body of the third ceramic layer by inkjet printing, the color of the second pattern is black, the printing is 600dpi resolution, and the ink droplet volume is 6pl;
  • the laminated ceramic layer green body, the first pattern is located between the first ceramic layer and the second ceramic layer green body to form the first pattern layer
  • the second pattern is located between the second ceramic layer and the third ceramic layer green body to form the second ceramic layer
  • the second pattern layer, laminated and pressed isostatic pressure is 150MPa, temperature is 60°C; the first ceramic layer, the second ceramic layer and the third ceramic layer green body after lamination and pressing are sintered to obtain a pore content of less than 0.5%.
  • the first ceramic layer, the second ceramic layer and the third ceramic layer rough body when sintering, the temperature rise rate is 0.1°C/min in the room temperature-600°C debinding section, and the temperature rise rate in the 600°C-1450°C sintering section is 4°C/min, The highest temperature reached 1450°C, and the temperature was kept for 2 hours. After sintering, the organic additives were completely volatilized; the surface of the rough ceramic layer was polished and polished, and finally a ceramic shell with a pattern was obtained.
  • the specific parameters are shown in Table 4.
  • the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10% ⁇ x ⁇ 20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each ceramic layer of the ceramic shell is less than 0.1 ⁇ 10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
  • the specific content of each substance in the colorant in the third ceramic layer is: zinc oxide 12.4wt% - chromium oxide 43.3wt% - cobalt oxide 5.9wt% - nickel oxide 38.4wt%.
  • the first ceramic layer does not contain colorants and alumina, so it has high total light transmittance, the second ceramic layer is semi-transparent pink, the third ceramic layer is green, and finally the ceramic shell is far away from the second ceramic layer.
  • One side of the ceramic layer is tea-green as a whole, with a strong jade texture.
  • the blue first pattern layer between the layers can clearly appear through the first ceramic layer, and the black second pattern layer can also pass through the first ceramic layer and the second ceramic layer.
  • the second ceramic layer is displayed on the ceramic shell, but the clarity is not as good as that of the first pattern layer, and the first pattern layer and the second pattern layer finally present different layers.
  • the ink-jet printed second pattern layer has a finer pattern texture than the silk-screened first pattern layer, and can ink-jet print a pattern with a more three-dimensional visual effect.
  • the surface roughness of the ceramic shell is less than 50nm.
  • the reflectance of the ceramic shell surface is x, 10% ⁇ x ⁇ 20%, that is, the obtained ceramic shell has a good jade texture;
  • the ceramic shell The Vickers hardness Hv10 is greater than 11Gpa, so the obtained ceramic shell has good wear resistance;
  • the difference in thermal expansion coefficient of each ceramic layer of the ceramic shell is less than 0.1 ⁇ 10 -6 /°C, so the ceramic layers can be better combined, and finally obtained
  • the four-point bending strength of the ceramic shell is greater than 1000MPa, that is, the ceramic shell has excellent mechanical properties.
  • the raw materials of the first ceramic layer green body include inorganic substances: 93.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein The mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6; the raw material of the second ceramic layer includes inorganic substances: 89.5wt% zirconia , 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 4.0wt% erbium oxide, the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the binder polymethyl acrylate and dispersant triolein and The mass ratio of the plasticizer poly
  • the first pattern is printed on the second ceramic layer green body by silk screen, the first The pattern color is blue, the screen printing screen is stainless steel, the mesh aperture is 450 mesh, the second pattern is printed on the green body of the fourth ceramic layer by inkjet printing, the color of the second pattern is black, and the printing resolution is 600dpi , the ink drop volume is 6pl; the laminated ceramic layer green bodies are laminated, the first pattern is located between the first ceramic layer and the second ceramic layer green body to form the first pattern layer, and the second pattern is located between the third ceramic layer and the fourth ceramic layer.
  • the second pattern layer is formed between the green bodies of the ceramic layers, and the isostatic pressing pressure of lamination is 150 MPa and the temperature is 60°C; the first ceramic layer, the second ceramic layer, the third ceramic layer and the first ceramic layer after lamination are sintered Four ceramic layers green body, obtain the first ceramic layer, the second ceramic layer, the third ceramic layer and the fourth ceramic layer rough body with the porosity content less than 0.5%, when sintering, the temperature rise rate of the debinding section at room temperature -600 °C is 0.1 °C /min, the heating rate of the sintering section at 600°C-1450°C is 4°C/min, the maximum temperature reaches 1450°C, and the temperature is kept for 2 hours. Ceramic shell, see Table 5 for specific parameters.
  • the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10% ⁇ x ⁇ 20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each ceramic layer of the ceramic shell is less than 0.1 ⁇ 10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
  • the specific content of each substance in the colorant in the fourth ceramic layer is: zinc oxide 12.4wt% - chromium oxide 43.3wt% - cobalt oxide 5.9wt% - nickel oxide 38.4wt%.
  • the first ceramic layer does not contain colorants and alumina, so it has a high total light transmittance, the second ceramic layer is translucent pink, the fourth ceramic layer is green, and the final ceramic shell is far away from the second ceramic layer.
  • One side of the ceramic layer is tea-green as a whole, with a strong jade texture.
  • the blue first pattern layer between the layers can clearly appear through the first ceramic layer, and the black second pattern layer can also pass through the first ceramic layer, the second ceramic layer
  • the second ceramic layer and the third ceramic layer are displayed on the ceramic shell, but the clarity is not as good as that of the first pattern layer, and the first pattern layer and the second pattern layer finally present different layers.
  • this implementation Example black second pattern layer for deeper depth and layering.
  • the ink-jet printed second pattern layer has a finer pattern texture than the silk-screened first pattern layer, and can ink-jet print a pattern with a more three-dimensional visual effect.
  • the surface roughness of the ceramic shell is less than 50nm.
  • the reflectance of the ceramic shell surface is x, 10% ⁇ x ⁇ 20%, that is, the obtained ceramic shell has a good jade texture;
  • the ceramic shell The Vickers hardness Hv10 is greater than 11Gpa, so the obtained ceramic shell has good wear resistance;
  • the difference in thermal expansion coefficient of each ceramic layer of the ceramic shell is less than 0.1 ⁇ 10 -6 /°C, so the ceramic layers can be better combined, and finally obtained
  • the four-point bending strength of the ceramic shell is greater than 1000MPa, that is, the ceramic shell has excellent mechanical properties.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • the raw materials of the first ceramic layer green body include inorganic substances: 93.2wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 0.1wt% aluminum oxide, 0.2% erbium oxide, and organic additives
  • the weight accounts for 20% of the total weight of the inorganic matter, wherein the mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the second ceramic layer is green
  • Raw materials include inorganic substances: 89.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 4.0wt% neodymium oxide, the weight of organic additives accounts for 20% of the total weight of inorganic substances, and the binder polyacrylic acid The mass ratio of methyl ester
  • the first pattern a and the first pattern b are printed on the second ceramic layer green body by pad printing, the color of the first pattern a is blue,
  • the first pattern b is white, using a silicone rubber head for pad printing, with a hardness of 15HS; laminated and laminated ceramic layer green bodies, the first pattern a and the first pattern b are at least partially non-overlapping and located on the first ceramic layer and the second ceramic layer
  • the first pattern layer a and the first pattern layer b are formed between the layers of green bodies, and the laminated isostatic pressure is 150 MPa and the temperature is 60°C; the laminated and laminated first ceramic layer and the second ceramic layer obtained by sintering Layer green body, to obtain the first ceramic layer and the second ceramic layer rough body with a porosity content of less than 0.5%.
  • the temperature rise rate of the room temperature-600°C debinding section is 0.1°C/min, and the temperature rise rate of the 600°C-1450°C sintering section The temperature is 4°C/min, the maximum temperature reaches 1450°C, and the temperature is kept for 2 hours.
  • the organic additives are completely volatilized; the surface of the rough ceramic layer is polished and polished, and finally a ceramic shell with a pattern is obtained.
  • Table 6 The specific parameters are shown in Table 6.
  • the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10% ⁇ x ⁇ 20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each layer of the ceramic shell is less than 0.1 ⁇ 10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
  • the ceramic shell includes a first ceramic layer and a second ceramic layer, and the blue first pattern a and the white first pattern b are printed on the middle of the two layers by means of pad printing, so that a shell with more abundant patterns can be obtained, and the manufacturing process is simple .
  • the first ceramic layer contains a small amount of coloring agent and alumina, which can still maintain a good total transmittance, the second ceramic layer is purple, and finally the ceramic shell on the side of the first ceramic layer away from the second ceramic layer as a whole appears as Pink-purple, with a strong jade texture, the blue first pattern layer a and the first white pattern layer b between the layers can clearly appear through the first ceramic layer.
  • the surface roughness of the ceramic shell is less than 50nm.
  • the reflectance of the ceramic shell surface is x, 10% ⁇ x ⁇ 20%, that is, the obtained ceramic shell has a good jade texture;
  • the ceramic shell The Vickers hardness Hv10 is greater than 11Gpa, so the obtained ceramic shell has good wear resistance;
  • the difference in thermal expansion coefficient of each ceramic layer of the ceramic shell is less than 0.1 ⁇ 10 -6 /°C, so the ceramic layers can be better combined, and finally obtained
  • the four-point bending strength of the ceramic shell is greater than 1000MPa, that is, the ceramic shell has excellent mechanical properties.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • the raw materials of the first ceramic layer green body include inorganic substances: 84.5wt% zirconia, 4.2wt% yttrium oxide, 5.0wt% aluminum oxide, 2.3wt% hafnium oxide, 4.0wt% neodymium oxide, organic
  • the auxiliary agent accounts for 20% of the total amount of inorganic substances, and the mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the second ceramic layer is green
  • the raw materials include inorganic substances: 93.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 4.0wt% cobalt aluminate, and the weight of organic additives accounts for 20% of the total weight of inorganic substances.
  • the mass ratio of methyl acrylate to dispersant triolein and plasticizer polyethylene glycol is 8:1:6;
  • the first pattern raw material includes inorganic substances: 86.5wt% zirconia, 4.2wt% yttrium oxide , 3.0wt% aluminum oxide, 2.3wt% hafnium oxide, 4.0wt% cobalt aluminate, the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the mass of binder polyvinyl alcohol and dispersant polymethacrylic acid The ratio is 1:7.
  • the first ceramic layer green body and the second ceramic layer green body are obtained by tape casting, and the first pattern is printed on the second ceramic layer green body by silk screen printing.
  • the color of the first pattern is blue, and the silk screen of the silk screen is stainless steel.
  • the hole diameter is 450 mesh; the first ceramic layer and the second ceramic layer green body are laminated and pressed, and the first pattern is located between the ceramic layer green body to form the first pattern layer. 60°C; sinter the first ceramic layer and the second ceramic layer green body after lamination and lamination to obtain the rough body of the first ceramic layer and the second ceramic layer with a porosity content less than 0.5%.
  • the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10% ⁇ x ⁇ 20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each ceramic layer of the ceramic shell is less than 0.1 ⁇ 10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
  • the first ceramic layer contains 4% purple colorant, the thickness is 0.1mm, and the total light transmittance is only 22.4%.
  • the second ceramic layer does not contain colorant and alumina, so it has a higher light transmittance.
  • the final ceramic shell is in The side of the first ceramic layer away from the second ceramic layer appears purple as a whole. Since the total light transmittance of the first ceramic layer is too low, less than 30%, the effect of the blue first pattern between the layers appearing on the surface of the ceramic shell through the first ceramic layer is poor.

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Abstract

The present application relates to a ceramic housing, a preparation method therefor, and an electronic device. The ceramic housing (110) comprises a first ceramic layer (11), a second ceramic layer (12) and a first pattern layer (21), wherein the first pattern layer (21) is located between the first ceramic layer (11) and the second ceramic layer (12). The preparation method for the ceramic housing (110) comprises: providing a first ceramic layer green body and a second ceramic layer green body; providing a first pattern on the second ceramic layer green body; stacking and pressing the first ceramic layer green body and the second ceramic layer green body, the first pattern being located between the first ceramic layer green body and the second ceramic layer green body; sintering the obtained laminated and pressed ceramic layer green body to obtain a ceramic layer rough body; and polishing a surface of the ceramic layer rough body to obtain the ceramic housing (110) .

Description

陶瓷壳体及其制备方法和电子设备Ceramic shell and its preparation method and electronic equipment
相关申请related application
本申请要求2021年9月29日申请的，申请号为2021111557540，名称为“陶瓷壳体及其制备方法和电子设备”的中国专利申请的优先权，在此将其全文引入作为参考。This application claims the priority of the Chinese patent application filed on September 29, 2021 with the application number 2021111557540 and titled "Ceramic Housing and Its Preparation Method and Electronic Equipment", which is hereby incorporated by reference in its entirety.
技术领域technical field
本申请属于电子产品技术领域，具体涉及陶瓷壳体及其制备方法和电子设备。The application belongs to the technical field of electronic products, and in particular relates to a ceramic casing, a preparation method thereof, and electronic equipment.
背景技术Background technique
陶瓷材料具有温润如玉的质感和优异的耐磨性能，备受消费者喜爱。目前主流的陶瓷壳体以黑、白纯色为主，颜色单一。因此，研发颜色、图案丰富的陶瓷壳体，改善其外观效果，以满足更加多样化的需求显得尤为重要。Ceramic materials have a warm and jade-like texture and excellent wear resistance, and are very popular among consumers. At present, the mainstream ceramic shells are mainly black and white solid colors, and the colors are single. Therefore, it is particularly important to develop ceramic shells with rich colors and patterns and improve their appearance to meet more diverse needs.
发明内容Contents of the invention
第一方面，本申请提供了一种陶瓷壳体，包括第一陶瓷层、第二陶瓷层和第一图案层，第一图案层位于第一陶瓷层和第二陶瓷层之间，所述第一图案层的图案可透过第一陶瓷层显现。In a first aspect, the present application provides a ceramic shell, including a first ceramic layer, a second ceramic layer and a first pattern layer, the first pattern layer is located between the first ceramic layer and the second ceramic layer, and the first pattern layer is located between the first ceramic layer and the second ceramic layer. The pattern of a pattern layer can be shown through the first ceramic layer.
第二方面，本申请提供了一种陶瓷壳体的制备方法，包括提供第一陶瓷层生坯和第二陶瓷层生坯，在第二陶瓷层生坯上设置第一图案；In a second aspect, the present application provides a method for preparing a ceramic shell, including providing a first ceramic layer green body and a second ceramic layer green body, and setting a first pattern on the second ceramic layer green body;
叠层压合第一陶瓷层生坯和第二陶瓷层生坯，第一图案位于第一陶瓷层生坯和第二陶瓷层生坯之间；Laminating and pressing the first ceramic layer green body and the second ceramic layer green body, the first pattern is located between the first ceramic layer green body and the second ceramic layer green body;
烧结获得的叠层压合后的陶瓷层生坯得到陶瓷层粗坯；Sintering the laminated and laminated ceramic layer green body to obtain a ceramic layer rough body;
打磨抛光陶瓷层粗坯表面，获得所述陶瓷壳体。Grinding and polishing the surface of the rough body of the ceramic layer to obtain the ceramic shell.
第三方面，本申请提供了一种电子设备，包括显示设备、主板及陶瓷壳体，陶瓷壳体与显示设备围设出容置空间，主板位于所述容置空间内，陶瓷壳体包括第一陶瓷层、第二陶瓷层和第一图案层，第一图案层位于第一陶瓷层和第二陶瓷层之间，第一图案层的图案可透过第一陶瓷层显现。In a third aspect, the present application provides an electronic device, including a display device, a main board, and a ceramic housing. The ceramic housing and the display device enclose an accommodating space, the main board is located in the accommodating space, and the ceramic housing includes a first A ceramic layer, a second ceramic layer and a first pattern layer. The first pattern layer is located between the first ceramic layer and the second ceramic layer. The pattern of the first pattern layer can be displayed through the first ceramic layer.
附图说明Description of drawings
为了更清楚地说明本申请实施例或传统技术中的技术方案，下面将对实施例或传统技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据公开的附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present application or the conventional technology, the following will briefly introduce the accompanying drawings that need to be used in the description of the embodiments or the traditional technology. Obviously, the accompanying drawings in the following description are only the present invention For the embodiments of the application, those skilled in the art can also obtain other drawings based on the disclosed drawings without creative effort.
图1为本申请一实施方式提供的陶瓷壳体的结构示意图。FIG. 1 is a schematic structural diagram of a ceramic housing provided in an embodiment of the present application.
图2为本申请图1提供的陶瓷壳体的俯视图。FIG. 2 is a top view of the ceramic housing provided in FIG. 1 of the present application.
图3为本申请另一实施方式提供的陶瓷壳体的结构示意图。FIG. 3 is a schematic structural diagram of a ceramic housing provided in another embodiment of the present application.
图4为本申请再一实施方式提供的陶瓷壳体的结构示意图。FIG. 4 is a schematic structural diagram of a ceramic housing provided in yet another embodiment of the present application.
图5为本申请图4提供的陶瓷壳体的俯视图。FIG. 5 is a top view of the ceramic housing provided in FIG. 4 of the present application.
图6为本申请再一实施方式提供的陶瓷壳体的结构示意图。FIG. 6 is a schematic structural diagram of a ceramic housing provided in yet another embodiment of the present application.
图7为本申请图6提供的陶瓷壳体的俯视图。FIG. 7 is a top view of the ceramic housing provided in FIG. 6 of the present application.
图8为本申请一实施方式提供的陶瓷壳体的制备方法流程图。FIG. 8 is a flowchart of a method for preparing a ceramic shell provided in an embodiment of the present application.
图9为本申请一实施方式提供的电子设备结构示意图。FIG. 9 is a schematic structural diagram of an electronic device provided by an embodiment of the present application.
图10为本申请一实施方式提供的电子设备的结构组成示意图。FIG. 10 is a schematic diagram of the structure and composition of an electronic device provided in an embodiment of the present application.
标号说明：Label description:
第一陶瓷层-11、第二陶瓷层-12、第一图案层-21、第三陶瓷层-13、第二图案层-22、显示设备-100、陶瓷壳体-110、电子设备-200、RF电路-210、存储器-220、输入单元-230、显示单元-240、传感器-250、音频电路-260、WiFi模块-270、处理器-280、电源-290First ceramic layer-11, second ceramic layer-12, first pattern layer-21, third ceramic layer-13, second pattern layer-22, display device-100, ceramic shell-110, electronic device-200 , RF circuit-210, memory-220, input unit-230, display unit-240, sensor-250, audio circuit-260, WiFi module-270, processor-280, power supply-290
具体实施方式Detailed ways
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the application with reference to the drawings in the embodiments of the application. Apparently, the described embodiments are only some of the embodiments of the application, not all of them. Based on the embodiments in this application, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the scope of protection of this application.
下文的公开提供了许多不同的实施方式或例子用来实现本申请的不同结构。为了简化本申请的公开，下文中对特定例子的部件和设置进行描述。当然，它们仅仅为示例，并且目的不在于限制本申请。此外，本申请可以在不同例子中重复参考数字和/或参考字母，这种重复是为了简化和清楚的目的，其本身不指示所讨论各种实施方式和/或设置之间的关系。此外，本申请提供了的各种特定的工艺和材料的例子，但是本领域普通技术人员可以意识到其他工艺的应用和/或其他材料的使用。The following disclosure provides many different implementations or examples for implementing different structures of the present application. To simplify the disclosure of the present application, components and arrangements of specific examples are described below. Of course, they are examples only and are not intended to limit the application. Furthermore, the present application may repeat reference numerals and/or reference letters in various instances, such repetition is for simplicity and clarity and does not in itself indicate a relationship between the various embodiments and/or arrangements discussed. In addition, various specific process and material examples are provided herein, but one of ordinary skill in the art may recognize the use of other processes and/or the use of other materials.
发明人经过长期研究发现，为了改善陶瓷壳体的外观，可以采用在陶瓷原料中添加色粉、使用着色离子浸渗陶瓷生坯或者直接在陶瓷壳体上镀膜等，这些方案虽然能一定程度改善陶瓷外观，但是难以在陶瓷上实现特定的图案。The inventor has found through long-term research that in order to improve the appearance of the ceramic shell, it is possible to add toner to the ceramic raw material, use colored ions to impregnate the ceramic green body, or directly coat the ceramic shell, etc. Although these solutions can improve the appearance of the ceramic shell to a certain extent Ceramic appearance, but it is difficult to achieve a specific pattern on ceramic.
为了在陶瓷壳体上实现特定的图案，可以直接在陶瓷坯料表面上涂覆彩色釉层，该方案虽然可以获得具有特定的图案的陶瓷，但由于釉层直接覆盖陶瓷壳体表面，使得陶瓷壳体表面失去特有的玉质感，且釉层中常会有气泡残留，影响壳体美观。In order to achieve a specific pattern on the ceramic shell, a colored glaze layer can be directly coated on the surface of the ceramic blank. Although this scheme can obtain ceramics with a specific pattern, the glaze layer directly covers the surface of the ceramic shell, making the ceramic shell The surface of the body loses its unique jade texture, and air bubbles often remain in the glaze layer, which affects the appearance of the shell.
基于此，本申请提供了一种陶瓷壳体。图1为本申请一实施方式提供的陶瓷壳体的结构示意图。陶瓷壳体110包括第一陶瓷层11、第二陶瓷层12和第一图案层21，第一图案层21位于第一陶瓷层11和第二陶瓷层12之间，第一图案层21的图案可透过第一陶瓷层11显现。在一个实施例中，第一图案层21覆盖第二陶瓷层12局部区域，使得最终获得的陶瓷壳体110呈现出局部图案效果。在另一个实施例中，第一图案层21完全覆盖第二陶瓷层12靠近第一陶瓷层11一侧，使得最终获得的陶瓷壳体110呈现出布满图案的效果。Based on this, the present application provides a ceramic housing. FIG. 1 is a schematic structural diagram of a ceramic housing provided in an embodiment of the present application. The ceramic shell 110 comprises a first ceramic layer 11, a second ceramic layer 12 and a first pattern layer 21, the first pattern layer 21 is located between the first ceramic layer 11 and the second ceramic layer 12, and the pattern of the first pattern layer 21 Visible through the first ceramic layer 11 . In one embodiment, the first pattern layer 21 covers a partial area of the second ceramic layer 12 , so that the finally obtained ceramic shell 110 presents a partial pattern effect. In another embodiment, the first pattern layer 21 completely covers the side of the second ceramic layer 12 close to the first ceramic layer 11 , so that the finally obtained ceramic shell 110 presents the effect of being covered with patterns.
图2为图1中陶瓷壳体的俯视图，第一图案层21的图案可以透过第一陶瓷层11显现，其中，第一陶瓷层11全透光率大于第二陶瓷层12。在一个实施例中，第一陶瓷层11全透光率大于等于30％，例如可以为但不限于为30％、35％、40％、45％、50％、55％、60％、65％等，确保位于第一陶瓷层11及第二陶瓷层12之间的图案能透过第一陶瓷层11显现，可被用户观察到，由于图案位于叠层中，经过光的作用，可呈现出立体感和景深感。在另一个实施例中，第一陶瓷层11直线透光率大于第二陶瓷层12，第一陶瓷层11直线透光率 大于等于0.5％，例如可以为但不限于为0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％、5.5％、6％等，确保位于第一陶瓷层11及第二陶瓷层12之间的第一图案层21的图案可透过第一陶瓷层11显现，可被用户观察到啊，并具有立体感和景深感。2 is a top view of the ceramic housing in FIG. 1 , the pattern of the first pattern layer 21 can be seen through the first ceramic layer 11 , wherein the total light transmittance of the first ceramic layer 11 is greater than that of the second ceramic layer 12 . In one embodiment, the total light transmittance of the first ceramic layer 11 is greater than or equal to 30%, such as but not limited to 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%. etc., to ensure that the pattern between the first ceramic layer 11 and the second ceramic layer 12 can be seen through the first ceramic layer 11, and can be observed by the user. Since the pattern is located in the stack, it can appear through the action of light. Stereoscopic and depth-of-field perception. In another embodiment, the linear light transmittance of the first ceramic layer 11 is greater than that of the second ceramic layer 12, and the linear light transmittance of the first ceramic layer 11 is greater than or equal to 0.5%, such as but not limited to 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, etc., ensuring the first pattern between the first ceramic layer 11 and the second ceramic layer 12 The pattern of the layer 21 can appear through the first ceramic layer 11, can be observed by the user, and has a sense of three-dimensionality and depth of field.
图3为本申请另一实施方式提供的陶瓷壳体的结构示意图。陶瓷壳体110进一步包括第三陶瓷层13，第三陶瓷层13位于第二陶瓷层12远离第一陶瓷层11一侧。在另一个实施例中，如图4所示，第一陶瓷层11和第二陶瓷层12之间设置有第一图案层21，第二陶瓷层12和第三陶瓷层13之间设置有第二图案层22。在一些实施例中，第一陶瓷层11的全透光率大于第二陶瓷层12，第二陶瓷层12的全透光率大于第三陶瓷层13。在一个实施例中，第一陶瓷层的全透光率大于30％，第二陶瓷层的全透光率大于10％但小于第一陶瓷层11的全透光率，第三陶瓷层的全透光率无要求。高的全透光率可以确保位于陶瓷层之间的图案层的图案能够透过陶瓷层显现，具体可以为第一图案层21的图案透过第一陶瓷层11显现于陶瓷壳体110表面，第二图案层22的图案透过第一陶瓷层11和第二陶瓷层12显现于陶瓷壳体110表面，第一图案层21与第二图案层22的图案可以相同也可以不同，最终获得的陶瓷壳体110呈现丰富图案效果。在另一些实施例中，第一陶瓷层11的直线透光率大于第二陶瓷层12，第二陶瓷层12的直线透光率大于第三陶瓷层13。在一个实施例中，第一陶瓷层11的直线透光率大于0.5％，第二陶瓷层12的直线透光率大于0.1％但小于第一陶瓷层11的直线透光率，第三陶瓷层13的直线透光率无要求。高的直线透光率可以确保位于陶瓷层下方的图案层的图案透过陶瓷层显现于陶瓷壳体110表面，具体可以为第一图案层21的图案透过第一陶瓷层11显现于陶瓷壳体110表面，第二图案层22的图案透过第一陶瓷层11和第二陶瓷层12显现于陶瓷壳体110表面。FIG. 3 is a schematic structural diagram of a ceramic housing provided in another embodiment of the present application. The ceramic housing 110 further includes a third ceramic layer 13 , and the third ceramic layer 13 is located on a side of the second ceramic layer 12 away from the first ceramic layer 11 . In another embodiment, as shown in FIG. 4 , a first pattern layer 21 is provided between the first ceramic layer 11 and the second ceramic layer 12, and a second pattern layer 21 is provided between the second ceramic layer 12 and the third ceramic layer 13. Two pattern layers 22 . In some embodiments, the total light transmittance of the first ceramic layer 11 is greater than that of the second ceramic layer 12 , and the total light transmittance of the second ceramic layer 12 is greater than that of the third ceramic layer 13 . In one embodiment, the total light transmittance of the first ceramic layer is greater than 30%, the total light transmittance of the second ceramic layer is greater than 10% but less than the total light transmittance of the first ceramic layer 11, and the total light transmittance of the third ceramic layer Light transmittance is not required. The high total light transmittance can ensure that the pattern of the pattern layer located between the ceramic layers can appear through the ceramic layer, specifically, the pattern of the first pattern layer 21 can appear on the surface of the ceramic housing 110 through the first ceramic layer 11, The pattern of the second pattern layer 22 appears on the surface of the ceramic housing 110 through the first ceramic layer 11 and the second ceramic layer 12. The patterns of the first pattern layer 21 and the second pattern layer 22 can be the same or different, and the finally obtained The ceramic shell 110 presents a rich pattern effect. In other embodiments, the linear light transmittance of the first ceramic layer 11 is greater than that of the second ceramic layer 12 , and the linear light transmittance of the second ceramic layer 12 is greater than that of the third ceramic layer 13 . In one embodiment, the linear light transmittance of the first ceramic layer 11 is greater than 0.5%, the linear light transmittance of the second ceramic layer 12 is greater than 0.1% but less than the linear light transmittance of the first ceramic layer 11, and the third ceramic layer The linear light transmittance of 13 is not required. The high linear light transmittance can ensure that the pattern of the pattern layer below the ceramic layer appears on the surface of the ceramic shell 110 through the ceramic layer, specifically, the pattern of the first pattern layer 21 appears on the ceramic shell through the first ceramic layer 11 On the surface of the body 110 , the pattern of the second pattern layer 22 appears on the surface of the ceramic shell 110 through the first ceramic layer 11 and the second ceramic layer 12 .
图5为本申请图4提供的陶瓷壳体的俯视图。第一图案层21和第二图案层22分别位于不同陶瓷层中间，可分别通过第一陶瓷层11与第二陶瓷层12显现。在一个实施例中，第一图案层21与第二图案层22的图案相同，由于第二陶瓷层12的全透光率低于第一陶瓷层11，最终陶瓷壳体110上呈现的第二图案层22的颜色比第一图案层21的颜色浅，可实现陶瓷壳体110上图案深浅变化或渐变效果。在另一个实施例中，第一图案层21与第二图案层22的图案不相同，最终使得陶瓷壳体110呈现各式各样、深浅不一的图案。FIG. 5 is a top view of the ceramic housing provided in FIG. 4 of the present application. The first pattern layer 21 and the second pattern layer 22 are respectively located in the middle of different ceramic layers, and can appear through the first ceramic layer 11 and the second ceramic layer 12 respectively. In one embodiment, the patterns of the first pattern layer 21 and the second pattern layer 22 are the same. Since the total light transmittance of the second ceramic layer 12 is lower than that of the first ceramic layer 11, the final second ceramic layer 110 appears on the ceramic shell 110. The color of the pattern layer 22 is lighter than that of the first pattern layer 21 , so that the pattern on the ceramic housing 110 can be changed in depth or a gradient effect. In another embodiment, the patterns of the first pattern layer 21 and the second pattern layer 22 are different, so that the ceramic shell 110 finally presents various patterns with different shades.
图6为本申请再一实施方式提供的陶瓷壳体的结构示意图。第一陶瓷层11和第二陶瓷层12之间的第一图案层21为多个，例如为2个，分别为21a和21b，第二陶瓷层12和第三陶瓷层13之间的第二图案层为1个，为22。各个图案层进行组合，可形成特定图案，例如品牌logo。FIG. 6 is a schematic structural diagram of a ceramic housing provided in yet another embodiment of the present application. The first pattern layer 21 between the first ceramic layer 11 and the second ceramic layer 12 is multiple, such as 2, respectively 21a and 21b, the second pattern layer 21 between the second ceramic layer 12 and the third ceramic layer 13 Pattern layer is 1 and is 22. The individual pattern layers are combined to form a specific pattern, such as a brand logo.
图7为图6中陶瓷壳体的俯视图，第一图案层21a、21b与第二图案层22组合获得字母O。在另一个实施例中，第一陶瓷层11和第二陶瓷层12中的第一图案层21为多个，例如为2个，分别为21a和21b，第二陶瓷层和第三陶瓷层中无图案层，第三陶瓷层具有颜色，可以为第一图案层21a和21b提供底色，丰富陶瓷壳体110表面上的图案效果。FIG. 7 is a top view of the ceramic housing in FIG. 6 , the letter O is obtained by combining the first pattern layers 21a and 21b with the second pattern layer 22 . In another embodiment, there are multiple first pattern layers 21 in the first ceramic layer 11 and the second ceramic layer 12, such as two, respectively 21a and 21b, and in the second ceramic layer and the third ceramic layer There is no pattern layer, and the third ceramic layer has a color, which can provide a base color for the first pattern layer 21 a and 21 b, and enrich the pattern effect on the surface of the ceramic housing 110 .
在一些实施例中，陶瓷壳体110进一步包含第四陶瓷层和/或第五陶瓷层，第一陶瓷层11与第二陶瓷层12、第二陶瓷层12与第三陶瓷层13、第三陶瓷层13与第四陶瓷层、第四陶瓷层与第五陶瓷层之间至少设置一个图案层，或者每两层陶瓷层之间设置多个图案层，最终获得的陶瓷壳体110可呈现各式各样的图案。In some embodiments, the ceramic shell 110 further includes a fourth ceramic layer and/or a fifth ceramic layer, the first ceramic layer 11 and the second ceramic layer 12, the second ceramic layer 12 and the third ceramic layer 13, the third ceramic layer At least one pattern layer is set between the ceramic layer 13 and the fourth ceramic layer, the fourth ceramic layer and the fifth ceramic layer, or multiple pattern layers are set between every two layers of ceramic layers, and the finally obtained ceramic shell 110 can present various patterns. Various patterns.
在一些实施例中，陶瓷壳体110厚度为0.4mm-0.6mm，第一陶瓷层11的厚度大于等 于0.01mm小于0.5mm。在一些实施例中，第一陶瓷层11的厚度与陶瓷壳体110的厚度比为n，0.01≤n≤0.4，例如可以为但不限于为n＝0.01、n＝0.05、n＝0.1、n＝0.15、n＝0.2、n＝0.25、n＝0.3、n＝0.35、n＝0.4等，此厚度范围内，第一陶瓷层11可以保持良好的全透过率，可以让图案更好的显示，并保持良好的加工性能，易于管控厚度公差，最终获得带有图案的玉质外观的陶瓷壳体110。在一个实施例中，第一陶瓷层11的厚度小于第二陶瓷层12及第三陶瓷层13的厚度，使得第一陶瓷层11具有良好的透光率，图案层的图案能够透过第一陶瓷层11显示。In some embodiments, the thickness of the ceramic shell 110 is 0.4mm-0.6mm, and the thickness of the first ceramic layer 11 is greater than or equal to 0.01mm and less than 0.5mm. In some embodiments, the ratio of the thickness of the first ceramic layer 11 to the thickness of the ceramic shell 110 is n, 0.01≤n≤0.4, such as but not limited to n=0.01, n=0.05, n=0.1, n = 0.15, n = 0.2, n = 0.25, n = 0.3, n = 0.35, n = 0.4, etc., within this thickness range, the first ceramic layer 11 can maintain a good total transmittance, allowing the pattern to be displayed better , and maintain good processing performance, easy to control the thickness tolerance, and finally obtain the ceramic shell 110 with a patterned jade appearance. In one embodiment, the thickness of the first ceramic layer 11 is smaller than the thickness of the second ceramic layer 12 and the third ceramic layer 13, so that the first ceramic layer 11 has good light transmittance, and the pattern of the pattern layer can pass through the first ceramic layer. Ceramic layer 11 is shown.
在本申请的一些实施例中，第一陶瓷层11和第二陶瓷层12组分包括氧化锆、氧化钇。In some embodiments of the present application, the components of the first ceramic layer 11 and the second ceramic layer 12 include zirconia and yttrium oxide.
在本申请的一些实施例中，按重量百分比计，第一陶瓷层11组分包含89％-97％的氧化锆(ZrO 2)，3％-7％的氧化钇(Y 2O 3)，0-0.5％的氧化铝(Al 2O 3)，0-3％的氧化铪(HfO 2)，0-0.5％的着色剂。第二陶瓷层12组分包含80％-96.5％的氧化锆，3％-7％的氧化钇，0-5％的氧化铝，0-3％的氧化铪，0.5-5％的着色剂；第三陶瓷层13组分包含60％-92％的氧化锆，3％-7％的氧化钇，0-20％的氧化铝，0-3％的氧化铪，5％-10％的着色剂。 In some embodiments of the present application, by weight percentage, the components of the first ceramic layer 11 include 89%-97% zirconia (ZrO 2 ), 3%-7% yttrium oxide (Y 2 O 3 ), 0-0.5% aluminum oxide (Al 2 O 3 ), 0-3% hafnium oxide (HfO 2 ), 0-0.5% colorant. The components of the second ceramic layer 12 include 80%-96.5% zirconia, 3%-7% yttrium oxide, 0-5% aluminum oxide, 0-3% hafnium oxide, and 0.5-5% colorant; The composition of the third ceramic layer 13 includes 60%-92% zirconia, 3%-7% yttrium oxide, 0-20% aluminum oxide, 0-3% hafnium oxide, 5%-10% colorant .
在一些实施例中，本申请的第一图案层21和第二图案层22可以由陶瓷浆料或者陶瓷墨水形成，按重量百分比计，陶瓷浆料或陶瓷墨水的组分包含60％-97％的氧化锆，3％-7％的氧化钇，0-20％的氧化铝，0-3％的氧化铪，0.01-10％的着色剂。In some embodiments, the first pattern layer 21 and the second pattern layer 22 of the present application can be formed by ceramic slurry or ceramic ink, and the composition of the ceramic slurry or ceramic ink contains 60%-97% by weight. zirconia, 3%-7% yttrium oxide, 0-20% aluminum oxide, 0-3% hafnium oxide, 0.01-10% colorant.
氧化锆是陶瓷主成分，本身为透白色，具有玉质感和高硬度。氧化钇是稳定剂，作用是抑制氧化锆四方相向单斜相转变，保证陶瓷壳体的晶相稳定性和机械强度，氧化钇含量过小不利于陶瓷晶相稳定性，使得陶瓷在烧结、加工时容易开裂，氧化钇含量过大会显著降低陶瓷壳体的机械强度和韧性。氧化铝作用是降低氧化锆陶瓷透光率，提高白度，其含量越高，陶瓷透光率越低；氧化铪是氧化锆的共生物，与氧化锆的物理化学性质非常相似，其含量对陶瓷壳体的性能影响不大。着色剂的作用是将原本透白色的氧化锆染成其他颜色，主要为过渡族金属元素氧化物、稀土元素氧化物或由它们组成的化合物，如氧化铁、氧化铜、氧化钴、氧化铈、氧化镍、氧化锌、氧化锰、氧化铬、氧化镨、氧化钕、氧化锶、氧化镧、氧化铒、氧化镓、铝酸钴、铁酸镍、锰酸镧等。Zirconia is the main component of ceramics. It is translucent white, with jade texture and high hardness. Yttrium oxide is a stabilizer, the function is to inhibit the transformation of zirconia tetragonal phase to monoclinic phase, and ensure the crystal phase stability and mechanical strength of the ceramic shell. Too small yttrium oxide content is not conducive to the crystal phase stability of ceramics, which makes ceramics sintered and processed. It is easy to crack when the yttrium oxide content is too high, which will significantly reduce the mechanical strength and toughness of the ceramic shell. The role of alumina is to reduce the light transmittance of zirconia ceramics and improve the whiteness. The higher the content, the lower the light transmittance of ceramics; hafnium oxide is a symbiosis of zirconia, and its physical and chemical properties are very similar to zirconia. Ceramic housings have little effect on performance. The function of the coloring agent is to dye the original white zirconia into other colors, mainly transition metal oxides, rare earth element oxides or compounds composed of them, such as iron oxide, copper oxide, cobalt oxide, cerium oxide, Nickel oxide, zinc oxide, manganese oxide, chromium oxide, praseodymium oxide, neodymium oxide, strontium oxide, lanthanum oxide, erbium oxide, gallium oxide, cobalt aluminate, nickel ferrite, lanthanum manganate, etc.
在一些实施例中，除了着色剂含量，第二陶瓷层和/或第三陶瓷层中的氧化锆、氧化钇、氧化铝、氧化铪含量与第一陶瓷层相同。在一个实施例中，第一陶瓷层11不含着色剂，第二陶瓷层12和/或第三陶瓷层13含有着色剂但其他组分和含量与第一陶瓷层11相同，相同组分可使得不同陶瓷层具有优异的结合强度，而添加有着色剂的第二陶瓷层12和/或第三陶瓷层13可以为陶瓷层之间的图案层添加底色，使得陶瓷壳体呈现更丰富的图案、色彩与外观。In some embodiments, the contents of zirconia, yttrium oxide, aluminum oxide and hafnium oxide in the second ceramic layer and/or the third ceramic layer are the same as those in the first ceramic layer except for the colorant content. In one embodiment, the first ceramic layer 11 does not contain a colorant, the second ceramic layer 12 and/or the third ceramic layer 13 contains a colorant but other components and contents are the same as those of the first ceramic layer 11, and the same components can be The different ceramic layers have excellent bonding strength, and the second ceramic layer 12 and/or the third ceramic layer 13 added with a colorant can add a background color to the pattern layer between the ceramic layers, so that the ceramic shell presents a richer color. Pattern, color and appearance.
硬度表征了陶瓷壳体110抵抗硬物压入其表面的能力。通过维氏硬度计对陶瓷壳体110进行检测。在本申请一实施方式中，陶瓷壳体110的维氏硬度Hv10大于11Gpa，抗形变能力佳。Hardness characterizes the ability of the ceramic housing 110 to resist pressing hard objects into its surface. The ceramic housing 110 is detected by a Vickers hardness tester. In an embodiment of the present application, the Vickers hardness Hv10 of the ceramic shell 110 is greater than 11 GPa, and has good deformation resistance.
在本申请一实施方式中，陶瓷壳体110的表面粗糙度小于50nm，在可见光波长范围内，陶瓷壳体表面的反射率为10％-20％。陶瓷壳体表面粗糙度小及具有一定反射率，可获得光滑的表面，并保持玉质感。In one embodiment of the present application, the surface roughness of the ceramic housing 110 is less than 50 nm, and the reflectance of the surface of the ceramic housing is 10%-20% within the wavelength range of visible light. The surface roughness of the ceramic shell is small and has a certain reflectivity, which can obtain a smooth surface and maintain a jade texture.
本申请通过采用GB/T 25995-2010《精细陶瓷密度和显气孔率试验方法》测量陶瓷壳体110的气孔含量。在本申请一实施方式中，陶瓷壳体110的气孔含量小于0.5％，即陶瓷 壳体110的致密度大于99.5％。陶瓷壳体110的低气孔含量保证了陶瓷壳体110内部的结合强度，有利于陶瓷壳体110机械性能的提升。This application measures the porosity content of the ceramic shell 110 by adopting GB/T 25995-2010 "Test Method for Density and Apparent Porosity of Fine Ceramics". In one embodiment of the present application, the porosity content of the ceramic shell 110 is less than 0.5%, that is, the density of the ceramic shell 110 is greater than 99.5%. The low pore content of the ceramic shell 110 ensures the bonding strength inside the ceramic shell 110 , which is beneficial to the improvement of the mechanical properties of the ceramic shell 110 .
本申请实施方式中，通过组分和工艺设计，各个陶瓷层之间热膨胀系数差小于0.1×10 -6/℃；各个陶瓷层适宜的烧结温度差小于20℃，最终获得的陶瓷壳体110的四点抗弯强度大于1000MPa，四点抗弯强度测试方法参见《GBT6569-2006-精细陶瓷弯曲强度试验方法》。 In the embodiment of the present application, through component and process design, the difference in thermal expansion coefficient between each ceramic layer is less than 0.1×10 -6 /°C; the suitable sintering temperature difference of each ceramic layer is less than 20°C, and the final ceramic shell 110 The four-point bending strength is greater than 1000MPa, and the four-point bending strength test method can be found in "GBT6569-2006-Fine Ceramic Bending Strength Test Method".
进一步的，在一个实施方式中，通过组分设计及工艺调整，第一陶瓷层11和第二陶瓷层12的结合强度大于800MPa，第一陶瓷层11和第二陶瓷层12的气孔率差值小于0.1％，获得的陶瓷壳体110具有良好的机械性能。Further, in one embodiment, through component design and process adjustment, the bonding strength of the first ceramic layer 11 and the second ceramic layer 12 is greater than 800 MPa, and the porosity difference between the first ceramic layer 11 and the second ceramic layer 12 is Less than 0.1%, the obtained ceramic shell 110 has good mechanical properties.
请参阅图8，为本申请一实施方式提供的陶瓷壳体的制备方法流程图，该制备方法制备上述任一实施例的陶瓷壳体110，包括：Please refer to FIG. 8 , which is a flow chart of a method for preparing a ceramic shell provided in an embodiment of the present application. The preparation method prepares the ceramic shell 110 of any of the above-mentioned embodiments, including:
步骤101：提供第一陶瓷层生坯和第二陶瓷层生坯，在第二陶瓷层生坯上设置第一图案；Step 101: providing a first ceramic layer green body and a second ceramic layer green body, and setting a first pattern on the second ceramic layer green body;
步骤102：叠层压合第一陶瓷层生坯和第二陶瓷层生坯，第一图案位于第一陶瓷层生坯和第二陶瓷层生坯之间；Step 102: laminate and press the first ceramic layer green body and the second ceramic layer green body, the first pattern is located between the first ceramic layer green body and the second ceramic layer green body;
步骤103：烧结获得的叠层压合后的陶瓷层生坯得到陶瓷层粗坯；Step 103: sintering the laminated and laminated ceramic layer green body to obtain a ceramic layer rough body;
步骤104：打磨抛光陶瓷层粗坯表面，获得陶瓷壳体。Step 104: Grinding and polishing the rough surface of the ceramic layer to obtain a ceramic shell.
在一个实施例中，步骤101和102中，也可以只在第一陶瓷层生坯上设置图案，叠层压合第一陶瓷层生坯和第二陶瓷层生坯，使得图案位于第一陶瓷层生坯和第二陶瓷层生坯之间。In one embodiment, in steps 101 and 102, the pattern can also be set only on the first ceramic layer green body, and the first ceramic layer green body and the second ceramic layer green body are laminated and pressed so that the pattern is located on the first ceramic layer green body. layer green body and the second ceramic layer green body.
步骤101中，提供第一陶瓷层生坯包括配制第一陶瓷层生坯原料，流延成型获得第一陶瓷层生坯；第一陶瓷层生坯原料包含无机物和有机助剂，按重量百分比计，无机物为89％-97％的氧化锆，3％-7％的氧化钇，0-0.5％的氧化铝，0-3％的氧化铪，0-0.5％的着色剂，有机助剂重量占无机物重量总和的10％-20％。In step 101, providing the first ceramic layer green body includes preparing the first ceramic layer green body raw material, tape casting to obtain the first ceramic layer green body; the first ceramic layer green body raw material contains inorganic substances and organic additives, by weight percentage In total, the inorganic matter is 89%-97% zirconia, 3%-7% yttrium oxide, 0-0.5% aluminum oxide, 0-3% hafnium oxide, 0-0.5% colorant, organic additives The weight accounts for 10%-20% of the total weight of inorganic substances.
步骤101中，提供第二陶瓷层生坯包括配制第二陶瓷层生坯原料，流延成型获得第二陶瓷层生坯；第二陶瓷层生坯原料包含无机物和有机助剂，按重量百分比计，无机物为80％-96.5％的氧化锆，3％-7％的氧化钇，0-5％的氧化铝，0-3％的氧化铪，0.5％-5％的着色剂，有机助剂重量占无机物重量总和的10％-20％。In step 101, providing the second ceramic layer green body includes preparing the second ceramic layer green body raw material, and tape casting to obtain the second ceramic layer green body; the second ceramic layer green body raw material contains inorganic substances and organic additives, by weight percentage In total, the inorganic matter is 80%-96.5% zirconia, 3%-7% yttrium oxide, 0-5% aluminum oxide, 0-3% hafnium oxide, 0.5%-5% colorant, organic auxiliary The weight of the agent accounts for 10%-20% of the total weight of the inorganic matter.
在一些实施例中，在步骤101之后，步骤103之前还包括提供第三陶瓷层生坯，叠层压合第一陶瓷生坯、第二陶瓷层生坯和第三陶瓷层生坯，第三陶瓷层位于第二陶瓷层远离第一陶瓷层一侧。在另一些实施例中，可以在第三陶瓷层生坯上设置第二图案，第二图案位于第二陶瓷层生坯和第三陶瓷层生坯之间。提供第三陶瓷层生坯包括配制第三陶瓷层生坯原料，流延成型获得第三陶瓷层生坯；第三陶瓷层生坯原料包含无机物和有机助剂，按重量百分比计，无机物为60％-92％的氧化锆，3％-7％的氧化钇，0-20％的氧化铝，0-3％的氧化铪，5％-10％的着色剂，有机助剂重量占无机物重量总和的10％-20％。In some embodiments, after step 101 and before step 103, it also includes providing a third ceramic layer green body, laminating and pressing the first ceramic layer green body, the second ceramic layer green body and the third ceramic layer green body, the third The ceramic layer is located on the side of the second ceramic layer away from the first ceramic layer. In some other embodiments, the second pattern may be provided on the third ceramic layer green body, and the second pattern is located between the second ceramic layer green body and the third ceramic layer green body. Providing the third ceramic layer green body includes preparing the third ceramic layer green body raw material, tape-casting to obtain the third ceramic layer green body; the third ceramic layer green body raw material contains inorganic substances and organic additives, by weight percentage, the inorganic substance 60%-92% of zirconia, 3%-7% of yttrium oxide, 0-20% of aluminum oxide, 0-3% of hafnium oxide, 5%-10% of coloring agent, the weight of organic additives accounts for the weight of inorganic 10%-20% of the total weight of the items.
陶瓷层生坯中的有机助剂主要由粘结剂、分散剂、消泡剂、增塑剂、润滑剂、溶剂中的一个或多个组成。粘结剂类型包括但不限于聚丙烯酸甲酯、聚甲基丙烯酸、聚乙烯醇缩丁醛、乙基纤维素中的一种或多种；分散剂类型包括但不限于三油酸甘油酯、乙氧基化合物、磷酸酯中的一种或多种；增塑剂类型包括但不限于聚乙二醇、丙三醇、邻苯二甲酸二 丁酯中的一种或多种；溶剂可以为丁酮等；有机助剂的作用是辅助生产，混料时促进各组分分散均匀、提高陶瓷坯料的塑性和强度等。在后续烧结过程中，有机助剂在高温作业下将被完全烧除。The organic additives in the ceramic layer green body are mainly composed of one or more of binders, dispersants, defoamers, plasticizers, lubricants, and solvents. The binder type includes but not limited to one or more of polymethylacrylate, polymethacrylic acid, polyvinyl butyral, ethyl cellulose; the dispersant type includes but not limited to triolein, One or more in ethoxylate compound, phosphate ester; Plasticizer type includes but not limited to one or more in polyethylene glycol, glycerol, dibutyl phthalate; Solvent can be Butanone, etc.; the role of organic additives is to assist production, promote the uniform dispersion of each component during mixing, and improve the plasticity and strength of ceramic blanks. In the subsequent sintering process, the organic additives will be completely burned off under high temperature operation.
步骤101中设置第一图案包括配制第一图案的原料，第一图案原料为陶瓷浆料或陶瓷墨水；陶瓷浆料组分包含无机物和有机助剂，按重量百分比计，无机物为60％-97％的氧化锆，3％-7％的氧化钇，0-20％的氧化铝，0-3％的氧化铪，0.01％-10％的着色剂，有机助剂重量占无机物重量总和的20％-100％；陶瓷浆料粘度为5000mPa·s-20000mPa·s，陶瓷浆料中无机物粒径＜10μm；陶瓷墨水组分包含无机物和有机助剂，按重量百分比计，无机物为60％-97％的氧化锆，3％-7％的氧化钇，0-20％的氧化铝，0-3％的氧化铪，0.01％-10％的着色剂，有机助剂重量占无机物重量总和的100％-200％；陶瓷墨水粘度为1mPa·s-100mPa·s，陶瓷浆料中无机物粒径＜1μm。在一些实施例中，陶瓷浆料或陶瓷墨水中的有机助剂包括溶剂、粘结剂、增塑剂、分散剂、消泡剂等。粘结剂包括但不限于聚乙烯醇、丙烯酸乳液、聚乙烯酸铵盐、聚醋酸乙烯酯中的一种或多种；分散剂包括但不限聚乙烯酸、聚甲基丙烯酸、基甲基丙烯酸铵盐、三乙醇胺中的一种或多种；溶剂可以为丁酮与酒精的混合物或者为水。在后续烧结过程中，有机助剂在高温作业下将被完全烧除。Setting the first pattern in step 101 includes preparing raw materials for the first pattern, the raw material for the first pattern is ceramic slurry or ceramic ink; the ceramic slurry components include inorganic substances and organic additives, and the inorganic substances are 60% by weight -97% zirconia, 3%-7% yttrium oxide, 0-20% aluminum oxide, 0-3% hafnium oxide, 0.01%-10% colorant, the weight of organic additives accounts for the total weight of inorganic substances The viscosity of ceramic slurry is 5000mPa·s-20000mPa·s, the particle size of inorganic matter in ceramic slurry is <10μm; the components of ceramic ink include inorganic matter and organic additives, by weight percentage, inorganic matter 60%-97% of zirconia, 3%-7% of yttrium oxide, 0-20% of aluminum oxide, 0-3% of hafnium oxide, 0.01%-10% of coloring agent, the weight of organic additives accounts for the weight of inorganic 100%-200% of the total weight of the material; the viscosity of the ceramic ink is 1mPa·s-100mPa·s, and the particle size of the inorganic matter in the ceramic slurry is <1μm. In some embodiments, the organic additives in the ceramic slurry or ceramic ink include solvents, binders, plasticizers, dispersants, defoamers, and the like. Binders include but are not limited to one or more of polyvinyl alcohol, acrylic emulsion, polyvinyl ammonium salt, polyvinyl acetate; dispersants include but are not limited to polyvinyl acid, polymethacrylic acid, methyl One or more of ammonium acrylate and triethanolamine; the solvent can be a mixture of butanone and alcohol or water. In the subsequent sintering process, the organic additives will be completely burned off under high temperature operation.
设置第一图案或第二图案的方式具体可以为印刷或打印图案的方式，更进一步的可以采用丝印、胶印、移印或喷墨打印的方式将陶瓷浆料或陶瓷墨水按设计的图案印刷或打印在陶瓷层生坯的表面上。丝印，指通过感光制版方法制成带有图案的丝网印版，图案部分的网孔可透过陶瓷浆料，非图案部分网孔不能透过浆料，陶瓷浆料透过网孔并在陶瓷生坯上印刷出图案；胶印，是一种平板印刷技术，通过滚筒式胶质印模把沾在胶面上的陶瓷浆料转印到陶瓷生坯上，从而在生坯印出图案；移印，指的是使用硅橡胶材料制成的曲面移印头，将凹版上的陶瓷浆料蘸到移印头的表面，然后在陶瓷生坯表面压一下从而引出图案；喷墨打印，指的是将陶瓷粉料制成陶瓷墨水，通过数码喷墨打印机将陶瓷墨水打印到陶瓷生坯上，从而得到图案。The way of setting the first pattern or the second pattern can be specifically the way of printing or printing the pattern, and further, the ceramic slurry or ceramic ink can be printed or printed according to the designed pattern by silk screen printing, offset printing, pad printing or inkjet printing. Printed on the surface of the ceramic layer green body. Silk screen printing refers to a screen printing plate with a pattern made by photosensitive plate-making method. The mesh of the pattern part can pass through the ceramic slurry, and the mesh of the non-pattern part cannot pass through the slurry. The ceramic slurry passes through the mesh and The pattern is printed on the ceramic green body; offset printing is a flat printing technology, which transfers the ceramic slurry on the rubber surface to the ceramic green body through a roller-type rubber die, thereby printing the pattern on the green body; Pad printing refers to a curved surface pad printing head made of silicone rubber material. Dip the ceramic slurry on the gravure onto the surface of the pad printing head, and then press it on the surface of the ceramic green body to draw the pattern; inkjet printing refers to The most important thing is to make ceramic ink from ceramic powder, and print the ceramic ink onto the ceramic green body through a digital inkjet printer to obtain a pattern.
进一步的，设置第一图案或第二图案，还包括将设置好图案的陶瓷层生坯常温静置或低温(温度小于150℃)烘烤约10min-120min，使陶瓷浆料或陶瓷墨水与陶瓷层生坯充分浸润，并进一步使陶瓷浆料或陶瓷墨水中的有机助剂中的溶剂充分挥发。Further, setting the first pattern or the second pattern also includes standing the patterned ceramic layer green body at room temperature or baking at a low temperature (temperature less than 150°C) for about 10min-120min, making the ceramic slurry or ceramic ink and ceramic The green body of the first layer is fully infiltrated, and the solvent in the organic auxiliary agent in the ceramic slurry or ceramic ink is further volatilized.
步骤102中，叠层压合第一陶瓷层生坯和第二陶瓷层生坯包括：叠层第一陶瓷层生坯和第二陶瓷层生坯后，再经等静压进一步压合，等静压压力≥100MPa，温度为室温-100℃，目的是进一步将各个陶瓷层生坯压合紧密，防止后续烧结出现分层。此外，等静压过程中还可以根据需要对叠层后的坯料进行塑形，如将2D坯料塑形成2.5D或者3D曲面坯料。在一些实施例中，陶瓷层生坯中的图案在叠层压合的过程中会出现扭曲变形，可以通过在陶瓷层生坯上增加支撑治具，使陶瓷层生坯每个面受力方向一致，确保获得所需精确度的图案。In step 102, the lamination and pressing of the first ceramic layer green body and the second ceramic layer green body includes: after laminating the first ceramic layer green body and the second ceramic layer green body, further pressing by isostatic pressing, etc. The static pressure is ≥100MPa, and the temperature is room temperature -100°C. The purpose is to further compact the green bodies of each ceramic layer and prevent delamination during subsequent sintering. In addition, during the isostatic pressing process, the laminated billet can also be shaped as required, such as shaping the 2D billet into a 2.5D or 3D curved billet. In some embodiments, the pattern in the ceramic layer green body will be distorted and deformed during the lamination and pressing process. By adding a supporting fixture on the ceramic layer green body, the force direction of each surface of the ceramic layer green body Consistent to ensure that you get the pattern with the precision you need.
步骤103中，将陶瓷层生坯叠层压合好后进行烧结。烧结分为两段，第一段为低温排胶段，温度范围为室温-600℃，该温度段要求升温速率尽可能慢，要求不超过0.5℃/min，优选小于0.2℃/min。升温速率越慢越有利于均匀排胶，升温过快会导致分层和开裂。第二段为高温烧结段，升温范围为600℃-1500℃，在最高温度1350℃-1500℃下保温2h-4h，该段升温速率不超过10℃/min，优选小于5℃/min。陶瓷层生坯烧结后获得气孔含量小于0.5％ 的陶瓷层粗坯。In step 103, the ceramic layer green bodies are laminated and then sintered. The sintering is divided into two stages. The first stage is a low-temperature debinding stage with a temperature range from room temperature to 600°C. In this temperature stage, the heating rate is required to be as slow as possible, not exceeding 0.5°C/min, preferably less than 0.2°C/min. The slower the heating rate, the more conducive to uniform debinding. Too fast heating will lead to delamination and cracking. The second stage is a high-temperature sintering stage, the temperature rise range is 600°C-1500°C, and the temperature is kept at a maximum temperature of 1350°C-1500°C for 2h-4h. The heating rate of this stage does not exceed 10°C/min, preferably less than 5°C/min. After the ceramic layer green body is sintered, a ceramic layer rough body with a pore content of less than 0.5% is obtained.
步骤104中，对获得的陶瓷层粗坯表面进行打磨抛光，可以去除表面缺陷、降低表面粗糙度、提高透光率。在一些实施例中，陶瓷层粗坯包括第一表面和第二表面，第一表面用于显示图案，也可称之为图案显示面，打磨抛光后，第一表面粗糙度Ra＜50nm，第二表面没有抛光要求，可进行简单的粗抛，第二表面粗糙度Ra＜1000nm，可减小加工刀纹对陶瓷壳体110强度的影响。In step 104, the surface of the obtained rough ceramic layer is ground and polished to remove surface defects, reduce surface roughness, and increase light transmittance. In some embodiments, the rough ceramic layer includes a first surface and a second surface. The first surface is used for displaying patterns, and can also be called a pattern display surface. After grinding and polishing, the roughness of the first surface is Ra<50nm, and the roughness of the second surface is The second surface is not required to be polished, and simple rough polishing can be performed, and the second surface roughness Ra<1000nm can reduce the influence of machining knife lines on the strength of the ceramic shell 110 .
在一个实施例中，最终获得的陶瓷壳体110包括由第一陶瓷层生坯形成的第一陶瓷层11、由第二陶瓷层生坯形成的第二陶瓷层12和由第一图案形成的第一图案层21，第一图案层21位于第一陶瓷层11和第二陶瓷层12之间，第一图案层21的图案可透过第一陶瓷层11显现。In one embodiment, the finally obtained ceramic shell 110 includes a first ceramic layer 11 formed from a first ceramic layer green body, a second ceramic layer 12 formed from a second ceramic layer green body, and a ceramic layer formed from a first pattern. The first pattern layer 21 , the first pattern layer 21 is located between the first ceramic layer 11 and the second ceramic layer 12 , the pattern of the first pattern layer 21 can be revealed through the first ceramic layer 11 .
在本申请提供的陶瓷壳体110的制备方法操作步骤简单，易于大规模生产，可以制得具有丰富外观效果的陶瓷壳体110，有利于其应用。The preparation method of the ceramic shell 110 provided in this application has simple operation steps, is easy to mass-produce, and can produce a ceramic shell 110 with rich appearance effects, which is beneficial to its application.
如图9，本申请还提供了一种电子设备200，包括上述任一实施例的陶瓷壳体110。可以理解的，电子设备200可以但不限于为手机、平板电脑、笔记本电脑、手表、MP3、MP4、GPS导航仪、数码相机等。在本申请一实施方式中，电子设备包括显示设备100、陶瓷壳体110和主板，显示设备100可以是屏幕，陶瓷壳体与显示设备围设出容置空间，主板位于容置空间内。陶瓷壳体包括上述任一实施例的陶瓷壳体110。该陶瓷壳体110可以赋予电子设备丰富图案的外观并保持陶瓷玉质感外观，提升电子设备的表现力。As shown in FIG. 9 , the present application also provides an electronic device 200 including the ceramic housing 110 of any one of the above-mentioned embodiments. It can be understood that the electronic device 200 may be, but not limited to, a mobile phone, a tablet computer, a notebook computer, a watch, an MP3, an MP4, a GPS navigator, a digital camera, and the like. In one embodiment of the present application, the electronic device includes a display device 100 , a ceramic housing 110 and a main board. The display device 100 may be a screen. The ceramic housing and the display device define an accommodating space, and the main board is located in the accommodating space. The ceramic housing includes the ceramic housing 110 of any one of the above embodiments. The ceramic casing 110 can endow the electronic device with a rich pattern appearance and maintain a ceramic jade-like appearance, thereby improving the expressive force of the electronic device.
在一些实施例中，当陶瓷壳体应用于电子设备时，陶瓷壳体110进一步含有油墨层，油墨层位于陶瓷壳体与图案显示面的相对的一面，即油墨层位于陶瓷壳体靠近主板的一面。油墨层由黑色油墨形成，可有效遮盖电子设备中电子元器件。油墨层厚度为0.01mm-0.04mm。在另一些实施例中，陶瓷壳体还包括防爆膜，防爆膜材质为聚对苯二甲酸乙二醇酯(PET)，防爆膜厚度0.05mm-0.1mm，防爆膜可确保陶瓷壳体摔裂后，不至于产生碎片伤害用户，确保电子设备使用的安全性。In some embodiments, when the ceramic housing is applied to an electronic device, the ceramic housing 110 further contains an ink layer, and the ink layer is located on the opposite side of the ceramic housing to the pattern display surface, that is, the ink layer is located on the side of the ceramic housing close to the main board. one side. The ink layer is formed of black ink, which can effectively cover electronic components in electronic equipment. The ink layer thickness is 0.01mm-0.04mm. In some other embodiments, the ceramic housing also includes an explosion-proof membrane, the explosion-proof membrane is made of polyethylene terephthalate (PET), the thickness of the explosion-proof membrane is 0.05mm-0.1mm, and the explosion-proof membrane can ensure that the ceramic housing is broken. Finally, the debris will not be generated to harm users, ensuring the safety of electronic equipment.
图10为本申请一实施方式提供的电子设备的结构组成示意图，电子设备200的结构可以包括RF电路210、存储器220、输入单元230、显示单元240、传感器250、音频电路260、WiFi模块270、处理器280以及电源290等。其中，RF电路210、存储器220、输入单元230、显示单元240、传感器250、音频电路260、WiFi模块270分别与处理器280连接；电源290用于为整个电子设备200提供电能。具体而言，RF电路210用于接发信号；存储器220用于存储数据指令信息；输入单元230用于输入信息，具体可以包括触控面板以及操作按键等其他输入设备；显示单元240可以包括显示屏等；传感器250包括红外传感器、激光传感器等，用于检测用户接近信号、距离信号等；扬声器261以及传声器262通过音频电路260与处理器280连接，用于接发声音信号；WiFi模块270则用于接收和发射WiFi信号；处理器280用于处理电子设备200的数据信息。10 is a schematic diagram of the structure and composition of an electronic device provided in an embodiment of the present application. The structure of the electronic device 200 may include an RF circuit 210, a memory 220, an input unit 230, a display unit 240, a sensor 250, an audio circuit 260, a WiFi module 270, Processor 280 and power supply 290 and so on. Wherein, RF circuit 210 , memory 220 , input unit 230 , display unit 240 , sensor 250 , audio circuit 260 , and WiFi module 270 are respectively connected to processor 280 ; power supply 290 is used to provide electric energy for the entire electronic device 200 . Specifically, the RF circuit 210 is used for sending and receiving signals; the memory 220 is used for storing data instruction information; the input unit 230 is used for inputting information, and may specifically include other input devices such as a touch panel and operation buttons; the display unit 240 may include a display screen, etc.; sensor 250 includes an infrared sensor, a laser sensor, etc., and is used to detect user approach signals, distance signals, etc.; speaker 261 and microphone 262 are connected to processor 280 through audio circuit 260, and are used to receive and send sound signals; WiFi module 270 It is used to receive and transmit WiFi signals; the processor 280 is used to process data information of the electronic device 200 .
以下通过具体实施例对本申请实施例制得的陶瓷壳体做进一步的说明。The ceramic housing prepared in the embodiment of the present application will be further described below through specific examples.
实施例1：Example 1:
配制第一陶瓷层生坯和第二陶瓷层生坯及第一图案原料。按照重量百分比计，第一陶瓷层生坯原料中包括无机物：93.5wt％的氧化锆、4.2wt％的氧化钇、2.3wt％氧化铪，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增 塑剂聚乙二醇的质量比例为8:1:6，第二陶瓷层生坯原料同第一陶瓷层生坯原料，第一图案原料包括无机物：86.5wt％的氧化锆、4.2wt％的氧化钇、3.0wt％的氧化铝、2.3wt％氧化铪、4.0wt％铝酸钴，有机助剂重量占无机物重量总和的20％，其中粘结剂聚乙烯醇与分散剂聚甲基丙烯酸的质量比例为1:7。Prepare the first ceramic layer green body, the second ceramic layer green body and the first pattern raw material. In terms of weight percentage, the raw materials of the first ceramic layer green body include inorganic substances: 93.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances. Wherein the mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, the raw material of the green body of the second ceramic layer is the same as the raw material of the green body of the first ceramic layer, The first pattern raw material includes inorganic substances: 86.5wt% zirconia, 4.2wt% yttrium oxide, 3.0wt% aluminum oxide, 2.3wt% hafnium oxide, 4.0wt% cobalt aluminate, the weight of organic additives accounts for the weight of inorganic substances 20% of the total, wherein the mass ratio of the binder polyvinyl alcohol to the dispersant polymethacrylic acid is 1:7.
流延成型获得第一陶瓷层生坯和第二陶瓷层生坯，第二陶瓷层生坯上通过丝印的方式印刷第一图案，第一图案颜色为蓝色，丝印的丝网为不锈钢，网孔孔径为450目；叠层压合第一陶瓷层和第二陶瓷层生坯，第一图案位于第一陶瓷层和第二陶瓷层生坯之间形成第一图案层，叠层压合等静压压力为150MPa、温度60℃；烧结获得的叠层压合后的第一陶瓷层和第二陶瓷层生坯，得到气孔含量小于0.5％的第一陶瓷层和第二陶瓷层粗坯，烧结时，室温-600℃排胶段升温速率为0.1℃/min，600℃-1450℃烧结段升温速率为4℃/min，最高温度达到1450℃，保温3h，烧结后，陶瓷层及图案原料中的有机助剂完全挥发；打磨抛光第一陶瓷层和第二陶瓷层粗坯表面，最终获得带有图案的陶瓷壳体，具体参数见表1。The first ceramic layer green body and the second ceramic layer green body are obtained by tape casting, and the first pattern is printed on the second ceramic layer green body by silk screen printing. The color of the first pattern is blue, and the silk screen of the silk screen is stainless steel. The hole diameter is 450 mesh; the first ceramic layer and the second ceramic layer green body are laminated and pressed, the first pattern is located between the first ceramic layer and the second ceramic layer green body to form the first pattern layer, laminated and pressed, etc. The static pressure is 150MPa and the temperature is 60°C; the first ceramic layer and the second ceramic layer green body obtained by sintering after lamination and pressing are obtained to obtain the rough body of the first ceramic layer and the second ceramic layer with a porosity content less than 0.5%, During sintering, the temperature rise rate of room temperature-600°C debinding section is 0.1°C/min, the temperature rise rate of 600°C-1450°C sintering section is 4°C/min, the highest temperature reaches 1450°C, and the temperature is kept for 3 hours. After sintering, the ceramic layer and pattern raw materials The organic additives in the method were completely volatilized; the surface of the rough body of the first ceramic layer and the second ceramic layer was ground and polished, and finally a ceramic shell with a pattern was obtained. The specific parameters are shown in Table 1.
此外，本实施例获得的陶瓷壳体的表面粗糙度小于50nm；在可见光波长范围内，陶瓷壳体表面的反射率为x，10％≤x≤20％；陶瓷壳体维氏硬度Hv10大于11Gpa；陶瓷壳体气孔含量小于0.5％；陶瓷壳体各个陶瓷层热膨胀系数差小于0.1×10 -6/℃；陶瓷壳体四点抗弯强度大于1000MPa。 In addition, the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10%≤x≤20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each ceramic layer of the ceramic shell is less than 0.1×10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
需要说明的是各个实施例中各个陶瓷层的透光率的测试方法为：获得陶瓷层生坯，例如第一陶瓷层生坯，不与其他层进行叠压，将单层的第一陶瓷层生坯进行与获得含有第一陶瓷层的多层陶瓷壳体同等条件的烧结、打磨抛光至所需厚度(0.01mm-0.5mm)，再使用透光率测试仪测试透光率。It should be noted that the test method for the light transmittance of each ceramic layer in each embodiment is: obtain a ceramic layer green body, such as the first ceramic layer green body, do not laminate with other layers, and put the single-layer first ceramic layer The green body is sintered under the same conditions as the multilayer ceramic shell containing the first ceramic layer, ground and polished to the required thickness (0.01mm-0.5mm), and then the light transmittance is tested with a light transmittance tester.
表1Table 1
Figure PCTCN2022117791-appb-000001
Figure PCTCN2022117791-appb-000001
由于第一陶瓷层和第二陶瓷层组分中着色剂和氧化铝的含量为0，因此获得的陶瓷壳体具有较高的透光率。第一陶瓷层和第二陶瓷层组分一致，由于第一陶瓷层的厚度小于第二陶瓷层，故第一陶瓷层的全透光率大于第二陶瓷层。陶瓷壳体在第一陶瓷层远离第二陶瓷层一侧整体呈半透明，有强烈玉质感，层间的蓝色第一图案层可以清晰的透过第一陶瓷层显现于陶瓷壳体表面。Since the contents of the coloring agent and alumina in the first ceramic layer and the second ceramic layer components are 0, the obtained ceramic shell has higher light transmittance. The components of the first ceramic layer and the second ceramic layer are consistent, and since the thickness of the first ceramic layer is smaller than that of the second ceramic layer, the total light transmittance of the first ceramic layer is greater than that of the second ceramic layer. The ceramic shell is translucent on the side of the first ceramic layer away from the second ceramic layer as a whole, with a strong jade texture, and the blue first pattern layer between the layers can clearly appear on the surface of the ceramic shell through the first ceramic layer.
陶瓷壳体的表面粗糙度小于50nm，在可见光波长范围内，陶瓷壳体表面的反射率为x，10％≤x≤20％，即获得的陶瓷壳体具有很好的玉质感；陶瓷壳体维氏硬度Hv10大于11Gpa，因此获得的陶瓷壳体具有良好的耐磨性能；陶瓷壳体各个陶瓷层热膨胀系数差小于0.1× 10 -6/℃，因此陶瓷各层能够更好的结合，最后获得的陶瓷壳体四点抗弯强度大于1000MPa，即陶瓷壳体具有优异的机械性能。 The surface roughness of the ceramic shell is less than 50nm. In the visible light wavelength range, the reflectance of the ceramic shell surface is x, 10%≤x≤20%, that is, the obtained ceramic shell has a good jade texture; the ceramic shell The Vickers hardness Hv10 is greater than 11Gpa, so the obtained ceramic shell has good wear resistance; the difference in thermal expansion coefficient of each ceramic layer of the ceramic shell is less than 0.1×10 -6 /°C, so the ceramic layers can be better combined, and finally obtained The four-point bending strength of the ceramic shell is greater than 1000MPa, that is, the ceramic shell has excellent mechanical properties.
实施例2：Example 2:
配制第一陶瓷层生坯、第二陶瓷层生坯、第三陶瓷层生坯及第一图案原料。按照重量百分比计，第一陶瓷层生坯原料包括无机物：93.5wt％的氧化锆、4.2wt％的氧化钇、2.3wt％氧化铪，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6，第二陶瓷层生坯原料同第一陶瓷层生坯原料，第三陶瓷层生坯原料包括无机物：89.5wt％的氧化锆、4.2wt％的氧化钇、2.3wt％氧化铪、4.0wt％氧化铒，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6，第一图案原料包括无机物：86.5wt％的氧化锆、4.2wt％的氧化钇、3.0wt％的氧化铝、2.3wt％氧化铪、4.0wt％铝酸钴，有机助剂重量占无机物重量总和的20％，其中粘结剂聚乙烯醇与分散剂聚甲基丙烯酸的质量比例为1:7。Prepare the first ceramic layer green body, the second ceramic layer green body, the third ceramic layer green body and the first pattern raw material. In terms of weight percentage, the raw materials of the first ceramic layer green body include inorganic substances: 93.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein The mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the raw material of the green body of the second ceramic layer is the same as that of the green body of the first ceramic layer. The raw materials of the three-layer ceramic layer green body include inorganic substances: 89.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 4.0wt% erbium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, of which The mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the first pattern raw material includes inorganic substances: 86.5wt% zirconia, 4.2wt% % of yttrium oxide, 3.0wt% of aluminum oxide, 2.3wt% of hafnium oxide, 4.0wt% of cobalt aluminate, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the binder polyvinyl alcohol and the dispersant polyformaldehyde The mass ratio of base acrylic acid is 1:7.
流延成型获得第一陶瓷层生坯、第二陶瓷层生坯、第三陶瓷层生坯，第二陶瓷层生坯上通过丝印的方式印刷第一图案，第一图案颜色为蓝色，丝印的丝网为不锈钢，网孔孔径为450目；叠层压合第一陶瓷层、第二陶瓷层和第三陶瓷层生坯，第一图案位于第一陶瓷层和第二陶瓷层生坯之间形成第一图案层，叠层压合等静压压力为200MPa、温度30℃；烧结获得的叠层压合后的第一陶瓷层、第二陶瓷层和第三陶瓷层生坯，得到气孔含量小于0.5％的第一陶瓷层、第二陶瓷层和第三陶瓷层粗坯，烧结时，室温-600℃排胶段升温速率为0.1℃/min，600℃-1450℃烧结段升温速率为4℃/min，最高温度达到1470℃，保温2h，烧结后，有机助剂完全挥发；打磨抛光陶瓷层粗坯表面，最终获得带有图案的陶瓷壳体，具体参数见表2。Tape casting to obtain the green body of the first ceramic layer, the green body of the second ceramic layer, and the green body of the third ceramic layer. The first pattern is printed on the green body of the second ceramic layer by silk screen printing. The color of the first pattern is blue. The wire mesh is stainless steel, the mesh aperture is 450 meshes; the first ceramic layer, the second ceramic layer and the third ceramic layer green body are laminated, and the first pattern is located between the first ceramic layer and the second ceramic layer green body The first pattern layer is formed between them, and the lamination pressure is 200MPa and the temperature is 30°C; the first ceramic layer, the second ceramic layer and the third ceramic layer green body after lamination and lamination obtained by sintering are obtained to obtain pores For the first ceramic layer, second ceramic layer and third ceramic layer green body with a content of less than 0.5%, when sintering, the temperature rise rate in the room temperature-600°C debinding section is 0.1°C/min, and the temperature rise rate in the 600°C-1450°C sintering section is 4°C/min, the highest temperature reached 1470°C, and held for 2 hours. After sintering, the organic additives were completely volatilized; the surface of the rough ceramic layer was polished and polished, and finally a ceramic shell with a pattern was obtained. The specific parameters are shown in Table 2.
此外，本实施例获得的陶瓷壳体的表面粗糙度小于50nm；在可见光波长范围内，陶瓷壳体表面的反射率为x，10％≤x≤20％；陶瓷壳体维氏硬度Hv10大于11Gpa；陶瓷壳体气孔含量小于0.5％；陶瓷壳体各个陶瓷层热膨胀系数差小于0.1×10 -6/℃；陶瓷壳体四点抗弯强度大于1000MPa。 In addition, the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10%≤x≤20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each ceramic layer of the ceramic shell is less than 0.1×10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
表2Table 2
Figure PCTCN2022117791-appb-000002
Figure PCTCN2022117791-appb-000002
Figure PCTCN2022117791-appb-000003
Figure PCTCN2022117791-appb-000003
由于第一陶瓷层和第二陶瓷层组分中着色剂和氧化铝的含量为0，因此获得的陶瓷壳体具有较高的全透光率，陶瓷壳体在第一陶瓷层远离第二陶瓷层一侧整体呈半透明，有强烈玉质感，层间的蓝色图案层可以清晰的透过第一陶瓷层和第二陶瓷层显现出来，第三陶瓷层为粉色，也可以透过第一陶瓷层和第二陶瓷层显示在陶瓷壳体上，为图案层添加底色，使得陶瓷壳体具有更丰富的图案及色彩。Since the content of colorant and alumina in the first ceramic layer and the second ceramic layer components is 0, the obtained ceramic shell has a high total light transmittance, and the ceramic shell is far away from the second ceramic layer One side of the layer is translucent as a whole, with a strong jade texture. The blue pattern layer between the layers can be clearly shown through the first ceramic layer and the second ceramic layer. The third ceramic layer is pink, and can also be seen through the first ceramic layer. The ceramic layer and the second ceramic layer are displayed on the ceramic shell to add background color to the pattern layer, so that the ceramic shell has richer patterns and colors.
陶瓷壳体的表面粗糙度小于50nm，在可见光波长范围内，陶瓷壳体表面的反射率为x，10％≤x≤20％，即获得的陶瓷壳体具有很好的玉质感；陶瓷壳体维氏硬度Hv10大于11Gpa，因此获得的陶瓷壳体具有良好的耐磨性能；陶瓷壳体各个陶瓷层热膨胀系数差小于0.1×10-6/℃，因此陶瓷各层能够更好的结合，最后获得的陶瓷壳体四点抗弯强度大于1000MPa，即陶瓷壳体具有优异的机械性能。The surface roughness of the ceramic shell is less than 50nm. In the visible light wavelength range, the reflectance of the ceramic shell surface is x, 10%≤x≤20%, that is, the obtained ceramic shell has a good jade texture; the ceramic shell The Vickers hardness Hv10 is greater than 11Gpa, so the obtained ceramic shell has good wear resistance; the difference in thermal expansion coefficient of each ceramic layer of the ceramic shell is less than 0.1×10-6/°C, so the ceramic layers can be better combined, and finally obtained The four-point bending strength of the ceramic shell is greater than 1000MPa, that is, the ceramic shell has excellent mechanical properties.
实施例3：Example 3:
配制第一陶瓷层生坯、第二陶瓷层生坯、第三陶瓷层生坯及第一图案和第二图案原料。按照重量百分比计，第一陶瓷层生坯原料包括无机物：93.5wt％的氧化锆、4.2wt％的氧化钇、2.3wt％氧化铪，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6，第二陶瓷层生坯原料同第一陶瓷层生坯原料，第三陶瓷层生坯原料包括无机物：89.5wt％的氧化锆、4.2wt％的氧化钇、2.3wt％氧化铪、4.0wt％氧化铒，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6，第一图案原料包括无机物：86.5wt％的氧化锆、4.2wt％的氧化钇、3.0wt％的氧化铝、2.3wt％氧化铪、4.0wt％铝酸钴，有机助剂重量占无机物重量总和的20％，其中粘结剂聚乙烯醇与分散剂聚甲基丙烯酸的质量比例为1:7，第二图案原料包括无机物：87.5wt％的氧化锆、4.2wt％的氧化钇、2.0wt％的氧化铝、2.3wt％氧化铪、4.0wt％氧化铁-氧化铬-氧化钴-氧化锰-氧化镍-氧化锌-氧化铝组成的复合物，有机助剂重量占无机物重量总和的100％，其中粘结剂聚乙烯醇与分散剂聚甲基丙烯酸的质量比例为1:7。The first ceramic layer green body, the second ceramic layer green body, the third ceramic layer green body, the first pattern and the second pattern raw material are prepared. In terms of weight percentage, the raw materials of the first ceramic layer green body include inorganic substances: 93.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein The mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the raw material of the green body of the second ceramic layer is the same as that of the green body of the first ceramic layer. The raw materials of the three-layer ceramic layer green body include inorganic substances: 89.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 4.0wt% erbium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, of which The mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the first pattern raw material includes inorganic substances: 86.5wt% zirconia, 4.2wt% % of yttrium oxide, 3.0wt% of aluminum oxide, 2.3wt% of hafnium oxide, 4.0wt% of cobalt aluminate, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the binder polyvinyl alcohol and the dispersant polyformaldehyde The mass ratio of acrylic acid is 1:7, and the second pattern raw material includes inorganic substances: 87.5wt% zirconia, 4.2wt% yttrium oxide, 2.0wt% aluminum oxide, 2.3wt% hafnium oxide, 4.0wt% iron oxide - a compound composed of chromium oxide-cobalt oxide-manganese oxide-nickel oxide-zinc oxide-alumina, the weight of organic additives accounts for 100% of the total weight of inorganic substances, wherein the binder polyvinyl alcohol and the dispersant polymethacrylic acid The mass ratio is 1:7.
流延成型获得第一陶瓷层生坯、第二陶瓷层生坯、第三陶瓷层生坯，第二陶瓷层生坯上通过丝印的方式印刷第一图案，第一图案颜色为蓝色,丝印的丝网为不锈钢，网孔孔径为450目，第三陶瓷层生坯上通过喷墨打印的方式印刷第二图案，第二图案颜色为黑色,打印为600dpi分辨率，墨滴体积6pl；叠层压合第一陶瓷层、第二陶瓷层和第三陶瓷层生坯，第一图案位于第一陶瓷层和第二陶瓷层生坯之间形成第一图案层,第二图案位于第二陶瓷层和第三陶瓷层生坯之间形成第二图案层,叠层压合等静压压力为200MPa、温度60℃；烧结叠层压合后的第一陶瓷层、第二陶瓷层和第三陶瓷层生坯，获得气孔含量小于0.5％的第一陶瓷层、第二陶瓷层和第三陶瓷层粗坯，烧结时，室温-600℃排胶段升温速率为0.1℃/min，600℃-1450℃烧结段升温速率为3℃/min，最高温度达到1450℃，保温2h，烧结后，有机助剂完全挥发；打磨抛光陶瓷层粗坯表面，最终获得带有图案的陶瓷壳体，具体参数见表3。The first ceramic layer green body, the second ceramic layer green body, and the third ceramic layer green body are obtained by tape casting. The first pattern is printed on the second ceramic layer green body by silk screen printing. The color of the first pattern is blue. The screen is made of stainless steel, the mesh aperture is 450 mesh, and the second pattern is printed on the green body of the third ceramic layer by inkjet printing, the color of the second pattern is black, the printing is 600dpi resolution, and the ink droplet volume is 6pl; laminate the first ceramic layer, the second ceramic layer and the third ceramic layer green body, the first pattern is located between the first ceramic layer and the second ceramic layer green body to form a first pattern layer, the second pattern is located in the second ceramic layer The second pattern layer is formed between the green body of the layer and the third ceramic layer, and the lamination pressure is 200MPa and the temperature is 60°C; the first ceramic layer, the second ceramic layer and the third ceramic layer after sintering lamination Ceramic layer green body, obtain the first ceramic layer, the second ceramic layer and the third ceramic layer rough body with a porosity content of less than 0.5%. During sintering, the temperature rise rate of the debinding section at room temperature -600°C is 0.1°C/min, and at 600°C- The heating rate of the sintering section at 1450°C is 3°C/min, the maximum temperature reaches 1450°C, and the temperature is kept for 2 hours. After sintering, the organic additives are completely volatilized; the surface of the rough ceramic layer is polished and polished, and finally a ceramic shell with a pattern is obtained. Specific parameters See Table 3.
此外，本实施例获得的陶瓷壳体的表面粗糙度小于50nm；在可见光波长范围内，陶 瓷壳体表面的反射率为x，10％≤x≤20％；陶瓷壳体维氏硬度Hv10大于11Gpa；陶瓷壳体气孔含量小于0.5％；陶瓷壳体各个陶瓷层热膨胀系数差小于0.1×10 -6/℃；陶瓷壳体四点抗弯强度大于1000MPa。 In addition, the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10%≤x≤20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each ceramic layer of the ceramic shell is less than 0.1×10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
表3table 3
Figure PCTCN2022117791-appb-000004
Figure PCTCN2022117791-appb-000004
备注：第二图案层中着色剂复合物中具体物质含量：氧化铁14.6wt％-氧化铬21.0wt％-氧化钴10.4wt％-氧化锰14.6wt％-氧化镍10.4wt％-氧化锌14.9wt％-氧化铝14.1wt％。Remarks: Specific substance content in the colorant compound in the second pattern layer: iron oxide 14.6wt% - chromium oxide 21.0wt% - cobalt oxide 10.4wt% - manganese oxide 14.6wt% - nickel oxide 10.4wt% - zinc oxide 14.9wt % - Alumina 14.1 wt%.
由于第一陶瓷层和第二陶瓷层组分中着色剂和氧化铝的含量为0，因此获得的陶瓷壳体具有较高的透光率，陶瓷壳体在第一陶瓷层远离第二陶瓷层一侧整体呈半透明，有强烈玉质感，层间的蓝色第一图案层和黑色第二图案层均可以清晰的透过第一陶瓷层和第二陶瓷层显现出来，且第一图案层和第二图案层具有不同层次感。第三陶瓷层为粉色，也可以透过第一陶瓷层和第二陶瓷层显示于陶瓷壳体上，为第一图案层和第二图案层添加底色，使得陶瓷壳体具有更丰富的图案及色彩。Since the content of colorant and alumina in the first ceramic layer and the second ceramic layer components is 0, the obtained ceramic shell has a high light transmittance, and the ceramic shell is far away from the first ceramic layer from the second ceramic layer. One side is translucent as a whole, with a strong jade texture. The blue first pattern layer and the black second pattern layer between the layers can be clearly shown through the first ceramic layer and the second ceramic layer, and the first pattern layer It has a different sense of hierarchy from the second pattern layer. The third ceramic layer is pink, and can also be displayed on the ceramic shell through the first ceramic layer and the second ceramic layer, adding a base color to the first pattern layer and the second pattern layer, so that the ceramic shell has a richer pattern and color.
陶瓷壳体的表面粗糙度小于50nm，在可见光波长范围内，陶瓷壳体表面的反射率为x，10％≤x≤20％，即获得的陶瓷壳体具有很好的玉质感；陶瓷壳体维氏硬度Hv10大于11Gpa，因此获得的陶瓷壳体具有良好的耐磨性能；陶瓷壳体各个陶瓷层热膨胀系数差小于0.1×10 -6/℃，因此陶瓷各层能够更好的结合，最后获得的陶瓷壳体四点抗弯强度大于1000MPa，即陶瓷壳体具有优异的机械性能。 The surface roughness of the ceramic shell is less than 50nm. In the visible light wavelength range, the reflectance of the ceramic shell surface is x, 10%≤x≤20%, that is, the obtained ceramic shell has a good jade texture; the ceramic shell The Vickers hardness Hv10 is greater than 11Gpa, so the obtained ceramic shell has good wear resistance; the difference in thermal expansion coefficient of each ceramic layer of the ceramic shell is less than 0.1×10 -6 /°C, so the ceramic layers can be better combined, and finally obtained The four-point bending strength of the ceramic shell is greater than 1000MPa, that is, the ceramic shell has excellent mechanical properties.
实施例4：Example 4:
配制第一陶瓷层生坯、第二陶瓷层生坯、第三陶瓷层生坯及第一图案、第二图案原料。按照重量百分比计，第一陶瓷层生坯原料包括无机物：93.5wt％的氧化锆、4.2wt％的氧化钇、2.3wt％氧化铪，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯 与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6，第二陶瓷层生坯原料包括无机物：89.5wt％的氧化锆、4.2wt％的氧化钇、2.3wt％氧化铪、4.0wt％氧化铒，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6，第三陶瓷层生坯原料包括无机物83.5wt％的氧化锆、4.2wt％的氧化钇、3.0wt％的氧化铝、2.3wt％氧化铪、7.0wt％氧化锌-氧化铬-氧化钴-氧化镍组成的复合物，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6，第一图案原料包括无机物86.5wt％的氧化锆、4.2wt％的氧化钇、3.0wt％的氧化铝、2.3wt％氧化铪、4.0wt％铝酸钴，有机助剂重量占无机物重量总和的20％，其中粘结剂聚乙烯醇与分散剂聚甲基丙烯酸的质量比例为1:7，第二图案原料包括无机物83.5wt％的氧化锆、4.2wt％的氧化钇、6.0wt％的氧化铝、2.3wt％氧化铪、4.0wt％铬酸锰铁，有机助剂重量占无机物重量总和的100％，其中粘结剂聚乙烯醇与分散剂聚甲基丙烯酸的质量比例为1:7。The first ceramic layer green body, the second ceramic layer green body, the third ceramic layer green body, the first pattern and the second pattern raw material are prepared. In terms of weight percentage, the raw materials of the first ceramic layer green body include inorganic substances: 93.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein The mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the raw material of the second ceramic layer includes inorganic substances: 89.5wt% zirconia , 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 4.0wt% erbium oxide, the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the binder polymethyl acrylate and dispersant triolein and The mass ratio of the plasticizer polyethylene glycol is 8:1:6, and the raw material of the green body of the third ceramic layer includes inorganic substances 83.5wt% zirconia, 4.2wt% yttrium oxide, 3.0wt% alumina, 2.3wt% % hafnium oxide, 7.0wt% zinc oxide-chromium oxide-cobalt oxide-nickel oxide compound, the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the binder polymethyl acrylate and dispersant trioleic acid The mass ratio of glyceride and plasticizer polyethylene glycol is 8:1:6, and the first pattern raw material includes inorganic substances 86.5wt% zirconia, 4.2wt% yttrium oxide, 3.0wt% aluminum oxide, 2.3wt% % hafnium oxide, 4.0wt% cobalt aluminate, the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the mass ratio of binder polyvinyl alcohol to dispersant polymethacrylic acid is 1:7, the second pattern raw material Including 83.5wt% zirconia, 4.2wt% yttrium oxide, 6.0wt% aluminum oxide, 2.3wt% hafnium oxide, 4.0wt% ferromanganese chromate, and the weight of organic additives accounts for 100% of the total weight of inorganic substances , wherein the mass ratio of the binder polyvinyl alcohol to the dispersant polymethacrylic acid is 1:7.
流延成型获得第一陶瓷层生坯、第二陶瓷层生坯、第三陶瓷层生坯，第二陶瓷层生坯上通过丝印的方式印刷第一图案，第一图案颜色为蓝色,丝印的丝网为不锈钢，网孔孔径为450目，第三陶瓷层生坯上通过喷墨打印的方式印刷第二图案，第二图案颜色为黑色,打印为600dpi分辨率，墨滴体积6pl；叠层压合陶瓷层生坯，第一图案位于第一陶瓷层和第二陶瓷层生坯之间形成第一图案层，第二图案位于第二陶瓷层和第三陶瓷层生坯之间形成第二图案层，叠层压合等静压压力为150MPa、温度60℃；烧结叠层压合后的第一陶瓷层、第二陶瓷层和第三陶瓷层生坯，获得气孔含量小于0.5％的第一陶瓷层、第二陶瓷层和第三陶瓷层粗坯，烧结时，室温-600℃排胶段升温速率为0.1℃/min，600℃-1450℃烧结段升温速率为4℃/min，最高温度达到1450℃，保温2h，烧结后，有机助剂完全挥发；打磨抛光陶瓷层粗坯表面，最终获得带有图案的陶瓷壳体，具体参数见表4。The first ceramic layer green body, the second ceramic layer green body, and the third ceramic layer green body are obtained by tape casting. The first pattern is printed on the second ceramic layer green body by silk screen printing. The color of the first pattern is blue. The screen is made of stainless steel, the mesh aperture is 450 mesh, and the second pattern is printed on the green body of the third ceramic layer by inkjet printing, the color of the second pattern is black, the printing is 600dpi resolution, and the ink droplet volume is 6pl; The laminated ceramic layer green body, the first pattern is located between the first ceramic layer and the second ceramic layer green body to form the first pattern layer, and the second pattern is located between the second ceramic layer and the third ceramic layer green body to form the second ceramic layer The second pattern layer, laminated and pressed isostatic pressure is 150MPa, temperature is 60°C; the first ceramic layer, the second ceramic layer and the third ceramic layer green body after lamination and pressing are sintered to obtain a pore content of less than 0.5%. The first ceramic layer, the second ceramic layer and the third ceramic layer rough body, when sintering, the temperature rise rate is 0.1°C/min in the room temperature-600°C debinding section, and the temperature rise rate in the 600°C-1450°C sintering section is 4°C/min, The highest temperature reached 1450°C, and the temperature was kept for 2 hours. After sintering, the organic additives were completely volatilized; the surface of the rough ceramic layer was polished and polished, and finally a ceramic shell with a pattern was obtained. The specific parameters are shown in Table 4.
此外，本实施例获得的陶瓷壳体的表面粗糙度小于50nm；在可见光波长范围内，陶瓷壳体表面的反射率为x，10％≤x≤20％；陶瓷壳体维氏硬度Hv10大于11Gpa；陶瓷壳体气孔含量小于0.5％；陶瓷壳体各个陶瓷层热膨胀系数差小于0.1×10 -6/℃；陶瓷壳体四点抗弯强度大于1000MPa。 In addition, the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10%≤x≤20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each ceramic layer of the ceramic shell is less than 0.1×10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
表4Table 4
Figure PCTCN2022117791-appb-000005
Figure PCTCN2022117791-appb-000005
Figure PCTCN2022117791-appb-000006
Figure PCTCN2022117791-appb-000006
备注：第三陶瓷层中着色剂中各物质具体含量为：氧化锌12.4wt％-氧化铬43.3wt％-氧化钴5.9wt％-氧化镍38.4wt％。Remarks: The specific content of each substance in the colorant in the third ceramic layer is: zinc oxide 12.4wt% - chromium oxide 43.3wt% - cobalt oxide 5.9wt% - nickel oxide 38.4wt%.
第一陶瓷层不含着色剂和氧化铝，因此具有高的全透光率，第二陶瓷层为半透的粉色，第三陶瓷层为绿色，最终陶瓷壳体在第一陶瓷层远离第二陶瓷层一侧整体呈现为茶绿色，有强烈玉质感，层间的蓝色第一图案层可以清晰的透过第一陶瓷层显现出来，黑色第二图案层也可通过第一陶瓷层和第二陶瓷层显示于陶瓷壳体上，但清晰度不如第一图案层，第一图案层和第二图案层最终呈现出不同的层次感。此外，喷墨打印的第二图案层相对于丝印的第一图案层具有更细腻的图案纹理，可喷墨打印更具有立体视觉效果的图案。The first ceramic layer does not contain colorants and alumina, so it has high total light transmittance, the second ceramic layer is semi-transparent pink, the third ceramic layer is green, and finally the ceramic shell is far away from the second ceramic layer. One side of the ceramic layer is tea-green as a whole, with a strong jade texture. The blue first pattern layer between the layers can clearly appear through the first ceramic layer, and the black second pattern layer can also pass through the first ceramic layer and the second ceramic layer. The second ceramic layer is displayed on the ceramic shell, but the clarity is not as good as that of the first pattern layer, and the first pattern layer and the second pattern layer finally present different layers. In addition, the ink-jet printed second pattern layer has a finer pattern texture than the silk-screened first pattern layer, and can ink-jet print a pattern with a more three-dimensional visual effect.
陶瓷壳体的表面粗糙度小于50nm，在可见光波长范围内，陶瓷壳体表面的反射率为x，10％≤x≤20％，即获得的陶瓷壳体具有很好的玉质感；陶瓷壳体维氏硬度Hv10大于11Gpa，因此获得的陶瓷壳体具有良好的耐磨性能；陶瓷壳体各个陶瓷层热膨胀系数差小于0.1×10 -6/℃，因此陶瓷各层能够更好的结合，最后获得的陶瓷壳体四点抗弯强度大于1000MPa，即陶瓷壳体具有优异的机械性能。 The surface roughness of the ceramic shell is less than 50nm. In the visible light wavelength range, the reflectance of the ceramic shell surface is x, 10%≤x≤20%, that is, the obtained ceramic shell has a good jade texture; the ceramic shell The Vickers hardness Hv10 is greater than 11Gpa, so the obtained ceramic shell has good wear resistance; the difference in thermal expansion coefficient of each ceramic layer of the ceramic shell is less than 0.1×10 -6 /°C, so the ceramic layers can be better combined, and finally obtained The four-point bending strength of the ceramic shell is greater than 1000MPa, that is, the ceramic shell has excellent mechanical properties.
实施例5：Example 5:
配制第一陶瓷层生坯、第二陶瓷层生坯、第三陶瓷层生坯、第四陶瓷层生坯及第一图案、第二图案原料。按照重量百分比计，第一陶瓷层生坯原料包括无机物：93.5wt％的氧化锆、4.2wt％的氧化钇、2.3wt％氧化铪，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6；第二陶瓷层生坯原料包括无机物：89.5wt％的氧化锆、4.2wt％的氧化钇、2.3wt％氧化铪、4.0wt％氧化铒，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6，第三陶瓷层生坯原料同第一陶瓷层生坯原料，第四陶瓷层生坯原料包括无机物83.5wt％的氧化锆、4.2wt％的氧化钇、3.0wt％的氧化铝、2.3wt％氧化铪、7.0wt％氧化锌-氧化铬-氧化钴-氧化镍组成的复合物，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6，第一图案原料包括无机物86.5wt％的氧化锆、4.2wt％的氧化钇、3.0wt％的氧化铝、2.3wt％氧化铪、4.0wt％铝酸钴，有机助剂重量占无机物重量总和的20％，其中粘结剂聚乙烯醇与分散剂聚甲基丙烯酸的质量比例为1:7，第二图案原料包括无机物83.5wt％的氧化锆、4.2wt％的氧化钇、6.0wt％的氧化铝、2.3wt％氧化铪、4.0wt％铬酸锰铁，有机助剂重量占无机物重量总和的100％，其中粘结剂聚乙烯醇与分散剂聚甲基丙烯酸的质量比例为1:7。Prepare the first ceramic layer green body, the second ceramic layer green body, the third ceramic layer green body, the fourth ceramic layer green body and the first pattern and the second pattern raw material. In terms of weight percentage, the raw materials of the first ceramic layer green body include inorganic substances: 93.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein The mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6; the raw material of the second ceramic layer includes inorganic substances: 89.5wt% zirconia , 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 4.0wt% erbium oxide, the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the binder polymethyl acrylate and dispersant triolein and The mass ratio of the plasticizer polyethylene glycol is 8:1:6, the raw material of the green body of the third ceramic layer is the same as that of the green body of the first ceramic layer, and the raw material of the green body of the fourth ceramic layer includes zirconia, 4.2wt% yttrium oxide, 3.0wt% aluminum oxide, 2.3wt% hafnium oxide, 7.0wt% zinc oxide-chromium oxide-cobalt oxide-nickel oxide composite, the weight of organic additives accounts for 20% of the total weight of inorganic substances %, wherein the mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the first pattern raw material includes zirconia of 86.5wt% inorganic matter, 4.2wt% yttrium oxide, 3.0wt% aluminum oxide, 2.3wt% hafnium oxide, 4.0wt% cobalt aluminate, the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the binder polyvinyl alcohol and dispersant The mass ratio of polymethacrylic acid is 1:7, and the second pattern raw material includes inorganic substances 83.5wt% zirconia, 4.2wt% yttrium oxide, 6.0wt% aluminum oxide, 2.3wt% hafnium oxide, 4.0wt% chromium Ferromanganese acid, the weight of the organic auxiliary agent accounts for 100% of the total weight of the inorganic matter, and the mass ratio of the binder polyvinyl alcohol to the dispersant polymethacrylic acid is 1:7.
流延成型获得第一陶瓷层生坯、第二陶瓷层生坯、第三陶瓷层生坯和第四陶瓷层生坯， 第二陶瓷层生坯上通过丝印的方式印刷第一图案，第一图案颜色为蓝色,丝印的丝网为不锈钢，网孔孔径为450目，第四陶瓷层生坯上通过喷墨打印的方式印刷第二图案，第二图案颜色为黑色,打印为600dpi分辨率，墨滴体积6pl；叠层压合各个陶瓷层生坯，第一图案位于第一陶瓷层和第二陶瓷层生坯之间形成第一图案层,第二图案位于第三陶瓷层和第四陶瓷层生坯之间形成第二图案层，叠层压合等静压压力为150MPa、温度60℃；烧结叠层压合后的第一陶瓷层、第二陶瓷层、第三陶瓷层和第四陶瓷层生坯，获得气孔含量小于0.5％的第一陶瓷层、第二陶瓷层、第三陶瓷层和第四陶瓷层粗坯，烧结时，室温-600℃排胶段升温速率为0.1℃/min，600℃-1450℃烧结段升温速率为4℃/min，最高温度达到1450℃，保温2h，烧结后，有机助剂完全挥发；打磨抛光陶瓷层粗坯表面，最终获得带有图案的陶瓷壳体，具体参数见表5。Tape casting to obtain the first ceramic layer green body, the second ceramic layer green body, the third ceramic layer green body and the fourth ceramic layer green body, the first pattern is printed on the second ceramic layer green body by silk screen, the first The pattern color is blue, the screen printing screen is stainless steel, the mesh aperture is 450 mesh, the second pattern is printed on the green body of the fourth ceramic layer by inkjet printing, the color of the second pattern is black, and the printing resolution is 600dpi , the ink drop volume is 6pl; the laminated ceramic layer green bodies are laminated, the first pattern is located between the first ceramic layer and the second ceramic layer green body to form the first pattern layer, and the second pattern is located between the third ceramic layer and the fourth ceramic layer. The second pattern layer is formed between the green bodies of the ceramic layers, and the isostatic pressing pressure of lamination is 150 MPa and the temperature is 60°C; the first ceramic layer, the second ceramic layer, the third ceramic layer and the first ceramic layer after lamination are sintered Four ceramic layers green body, obtain the first ceramic layer, the second ceramic layer, the third ceramic layer and the fourth ceramic layer rough body with the porosity content less than 0.5%, when sintering, the temperature rise rate of the debinding section at room temperature -600 °C is 0.1 °C /min, the heating rate of the sintering section at 600°C-1450°C is 4°C/min, the maximum temperature reaches 1450°C, and the temperature is kept for 2 hours. Ceramic shell, see Table 5 for specific parameters.
此外，本实施例获得的陶瓷壳体的表面粗糙度小于50nm；在可见光波长范围内，陶瓷壳体表面的反射率为x，10％≤x≤20％；陶瓷壳体维氏硬度Hv10大于11Gpa；陶瓷壳体气孔含量小于0.5％；陶瓷壳体各个陶瓷层热膨胀系数差小于0.1×10 -6/℃；陶瓷壳体四点抗弯强度大于1000MPa。 In addition, the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10%≤x≤20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each ceramic layer of the ceramic shell is less than 0.1×10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
表5table 5
Figure PCTCN2022117791-appb-000007
Figure PCTCN2022117791-appb-000007
备注：第四陶瓷层中着色剂中各物质具体含量为：氧化锌12.4wt％-氧化铬43.3wt％-氧化钴5.9wt％-氧化镍38.4wt％。Remarks: The specific content of each substance in the colorant in the fourth ceramic layer is: zinc oxide 12.4wt% - chromium oxide 43.3wt% - cobalt oxide 5.9wt% - nickel oxide 38.4wt%.
第一陶瓷层不含着色剂和氧化铝，因此具有较高的全透光率，第二陶瓷层为半透粉色，第四陶瓷层为绿色，最终陶瓷壳体在第一陶瓷层远离第二陶瓷层一侧整体呈现为茶绿色， 有强烈玉质感，层间的蓝色第一图案层可以清晰的透过第一陶瓷层显现出来，黑色第二图案层也可通过第一陶瓷层、第二陶瓷层和第三陶瓷层显示于陶瓷壳体上，但清晰度不如第一图案层，第一图案层和第二图案层最终呈现出不同的层次感，相比于实施例四，该实施例的黑色第二图案层具有更深的景深和层次感。此外，喷墨打印的第二图案层相对于丝印的第一图案层具有更细腻的图案纹理，可喷墨打印更具有立体视觉效果的图案。The first ceramic layer does not contain colorants and alumina, so it has a high total light transmittance, the second ceramic layer is translucent pink, the fourth ceramic layer is green, and the final ceramic shell is far away from the second ceramic layer. One side of the ceramic layer is tea-green as a whole, with a strong jade texture. The blue first pattern layer between the layers can clearly appear through the first ceramic layer, and the black second pattern layer can also pass through the first ceramic layer, the second ceramic layer The second ceramic layer and the third ceramic layer are displayed on the ceramic shell, but the clarity is not as good as that of the first pattern layer, and the first pattern layer and the second pattern layer finally present different layers. Compared with the fourth embodiment, this implementation Example black second pattern layer for deeper depth and layering. In addition, the ink-jet printed second pattern layer has a finer pattern texture than the silk-screened first pattern layer, and can ink-jet print a pattern with a more three-dimensional visual effect.
陶瓷壳体的表面粗糙度小于50nm，在可见光波长范围内，陶瓷壳体表面的反射率为x，10％≤x≤20％，即获得的陶瓷壳体具有很好的玉质感；陶瓷壳体维氏硬度Hv10大于11Gpa，因此获得的陶瓷壳体具有良好的耐磨性能；陶瓷壳体各个陶瓷层热膨胀系数差小于0.1×10 -6/℃，因此陶瓷各层能够更好的结合，最后获得的陶瓷壳体四点抗弯强度大于1000MPa，即陶瓷壳体具有优异的机械性能。 The surface roughness of the ceramic shell is less than 50nm. In the visible light wavelength range, the reflectance of the ceramic shell surface is x, 10%≤x≤20%, that is, the obtained ceramic shell has a good jade texture; the ceramic shell The Vickers hardness Hv10 is greater than 11Gpa, so the obtained ceramic shell has good wear resistance; the difference in thermal expansion coefficient of each ceramic layer of the ceramic shell is less than 0.1×10 -6 /°C, so the ceramic layers can be better combined, and finally obtained The four-point bending strength of the ceramic shell is greater than 1000MPa, that is, the ceramic shell has excellent mechanical properties.
实施例6：Embodiment 6:
配制第一陶瓷层生坯、第二陶瓷层生坯及第一图案a、第一图案b原料。按照重量百分比计，第一陶瓷层生坯原料包括无机物：93.2wt％的氧化锆、4.2wt％的氧化钇、2.3wt％氧化铪，0.1wt％氧化铝，氧化铒0.2％，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6，第二陶瓷层生坯原料包括无机物：89.5wt％的氧化锆、4.2wt％的氧化钇、2.3wt％氧化铪、4.0wt％氧化钕，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6，第一图案a原料包括无机物86.5wt％的氧化锆、4.2wt％的氧化钇、3.0wt％的氧化铝、2.3wt％氧化铪、4.0wt％铝酸钴，有机助剂重量占无机物重量总和的20％，其中粘结剂聚乙烯醇与分散剂聚甲基丙烯酸的质量比例为1:7，第一图案b原料包括无机物78.5wt％的氧化锆、4.2wt％的氧化钇、15wt％的氧化铝、2.3wt％氧化铪，有机助剂重量占无机物重量总和的20％，其中粘结剂聚乙烯醇与分散剂聚甲基丙烯酸的质量比例为1:7。Prepare the first ceramic layer green body, the second ceramic layer green body, and the raw materials for the first pattern a and the first pattern b. In terms of weight percentage, the raw materials of the first ceramic layer green body include inorganic substances: 93.2wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 0.1wt% aluminum oxide, 0.2% erbium oxide, and organic additives The weight accounts for 20% of the total weight of the inorganic matter, wherein the mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the second ceramic layer is green Raw materials include inorganic substances: 89.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 4.0wt% neodymium oxide, the weight of organic additives accounts for 20% of the total weight of inorganic substances, and the binder polyacrylic acid The mass ratio of methyl ester to dispersant glyceryl trioleate and plasticizer polyethylene glycol is 8:1:6, and the raw materials of the first pattern a include zirconia of 86.5wt% of inorganic substances, 4.2wt% of yttrium oxide, 3.0wt% aluminum oxide, 2.3wt% hafnium oxide, 4.0wt% cobalt aluminate, the weight of organic additives accounts for 20% of the total weight of inorganic substances, and the mass ratio of binder polyvinyl alcohol to dispersant polymethacrylic acid 1:7, the raw material of the first pattern b includes 78.5wt% zirconia, 4.2wt% yttrium oxide, 15wt% aluminum oxide, 2.3wt% hafnium oxide, and the weight of organic additives accounts for 20% of the total weight of inorganic substances. %, wherein the mass ratio of the binder polyvinyl alcohol to the dispersant polymethacrylic acid is 1:7.
流延成型获得第一陶瓷层生坯、第二陶瓷层生坯，第二陶瓷层生坯上通过移印的方式印刷第一图案a和第一图案b，第一图案a颜色为蓝色，第一图案b为白色，移印使用硅胶胶头，硬度为15HS；叠层压合陶瓷层生坯，第一图案a和第一图案b至少部分不重叠的位于第一陶瓷层和第二陶瓷层生坯之间形成第一图案层a、第一图案层b，叠层压合等静压压力为150MPa、温度60℃；烧结获得的叠层压合后的第一陶瓷层和第二陶瓷层生坯，得到气孔含量小于0.5％的第一陶瓷层和第二陶瓷层粗坯，烧结时，室温-600℃排胶段升温速率为0.1℃/min，600℃-1450℃烧结段升温速率为4℃/min，最高温度达到1450℃，保温2h，烧结后，有机助剂完全挥发；打磨抛光陶瓷层粗坯表面，最终获得带有图案的陶瓷壳体，具体参数见表6。Tape casting to obtain the first ceramic layer green body and the second ceramic layer green body, the first pattern a and the first pattern b are printed on the second ceramic layer green body by pad printing, the color of the first pattern a is blue, The first pattern b is white, using a silicone rubber head for pad printing, with a hardness of 15HS; laminated and laminated ceramic layer green bodies, the first pattern a and the first pattern b are at least partially non-overlapping and located on the first ceramic layer and the second ceramic layer The first pattern layer a and the first pattern layer b are formed between the layers of green bodies, and the laminated isostatic pressure is 150 MPa and the temperature is 60°C; the laminated and laminated first ceramic layer and the second ceramic layer obtained by sintering Layer green body, to obtain the first ceramic layer and the second ceramic layer rough body with a porosity content of less than 0.5%. During sintering, the temperature rise rate of the room temperature-600°C debinding section is 0.1°C/min, and the temperature rise rate of the 600°C-1450°C sintering section The temperature is 4°C/min, the maximum temperature reaches 1450°C, and the temperature is kept for 2 hours. After sintering, the organic additives are completely volatilized; the surface of the rough ceramic layer is polished and polished, and finally a ceramic shell with a pattern is obtained. The specific parameters are shown in Table 6.
此外，本实施例获得的陶瓷壳体的表面粗糙度小于50nm；在可见光波长范围内，陶瓷壳体表面的反射率为x，10％≤x≤20％；陶瓷壳体维氏硬度Hv10大于11Gpa；陶瓷壳体气孔含量小于0.5％；陶瓷壳体各层陶瓷层热膨胀系数差小于0.1×10 -6/℃；陶瓷壳体四点抗弯强度大于1000MPa。 In addition, the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10%≤x≤20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each layer of the ceramic shell is less than 0.1×10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
表6Table 6
Figure PCTCN2022117791-appb-000008
Figure PCTCN2022117791-appb-000008
陶瓷壳体包括第一陶瓷层和第二陶瓷层，两层中间通过移印的方式分别印刷蓝色第一图案a和白色第一图案b，可得到图案更丰富的壳体，且制作工艺简单。The ceramic shell includes a first ceramic layer and a second ceramic layer, and the blue first pattern a and the white first pattern b are printed on the middle of the two layers by means of pad printing, so that a shell with more abundant patterns can be obtained, and the manufacturing process is simple .
第一陶瓷层层含有少量着色剂和氧化铝，仍能保持较好的全透过率，第二陶瓷层为紫色，最终陶瓷壳体在第一陶瓷层远离第二陶瓷层一侧整体呈现为粉紫色，有强烈玉质感，层间的蓝色第一图案层a和第一白色图案层b可以清晰的透过第一陶瓷层显现出来。The first ceramic layer contains a small amount of coloring agent and alumina, which can still maintain a good total transmittance, the second ceramic layer is purple, and finally the ceramic shell on the side of the first ceramic layer away from the second ceramic layer as a whole appears as Pink-purple, with a strong jade texture, the blue first pattern layer a and the first white pattern layer b between the layers can clearly appear through the first ceramic layer.
陶瓷壳体的表面粗糙度小于50nm，在可见光波长范围内，陶瓷壳体表面的反射率为x，10％≤x≤20％，即获得的陶瓷壳体具有很好的玉质感；陶瓷壳体维氏硬度Hv10大于11Gpa，因此获得的陶瓷壳体具有良好的耐磨性能；陶瓷壳体各个陶瓷层热膨胀系数差小于0.1×10 -6/℃，因此陶瓷各层能够更好的结合，最后获得的陶瓷壳体四点抗弯强度大于1000MPa，即陶瓷壳体具有优异的机械性能。 The surface roughness of the ceramic shell is less than 50nm. In the visible light wavelength range, the reflectance of the ceramic shell surface is x, 10%≤x≤20%, that is, the obtained ceramic shell has a good jade texture; the ceramic shell The Vickers hardness Hv10 is greater than 11Gpa, so the obtained ceramic shell has good wear resistance; the difference in thermal expansion coefficient of each ceramic layer of the ceramic shell is less than 0.1×10 -6 /°C, so the ceramic layers can be better combined, and finally obtained The four-point bending strength of the ceramic shell is greater than 1000MPa, that is, the ceramic shell has excellent mechanical properties.
实施例7：Embodiment 7:
配制第一陶瓷层生坯和第二陶瓷层生坯及第一图案原料。按照重量百分比计，第一陶瓷层生坯原料中包括无机物：84.5wt％氧化锆、4.2wt％的氧化钇、5.0wt％的氧化铝、2.3wt％氧化铪、4.0wt％氧化钕，有机助剂占无机物总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6，第二陶瓷层生坯原料中包括无机物：93.5wt％氧化锆、4.2wt％的氧化钇、2.3wt％氧化铪、4.0wt％铝酸钴，有机助剂重量占无机物重量总和的20％，其中粘结剂聚丙烯酸甲酯与分散剂三油酸甘油酯及增塑剂聚乙二醇的质量比例为8:1:6；第一图案原料包括无机物：86.5wt％的氧化锆、4.2wt％的氧化钇、3.0wt％的氧化铝、2.3wt％氧化铪、4.0wt％铝酸钴，有机助剂重量占无机物重量总和的20％，其中粘结剂聚乙烯醇与分散剂聚甲基丙烯酸的质量比例为1:7。Prepare the first ceramic layer green body, the second ceramic layer green body and the first pattern raw material. In terms of weight percentage, the raw materials of the first ceramic layer green body include inorganic substances: 84.5wt% zirconia, 4.2wt% yttrium oxide, 5.0wt% aluminum oxide, 2.3wt% hafnium oxide, 4.0wt% neodymium oxide, organic The auxiliary agent accounts for 20% of the total amount of inorganic substances, and the mass ratio of the binder polymethyl acrylate to the dispersant triolein and the plasticizer polyethylene glycol is 8:1:6, and the second ceramic layer is green The raw materials include inorganic substances: 93.5wt% zirconia, 4.2wt% yttrium oxide, 2.3wt% hafnium oxide, 4.0wt% cobalt aluminate, and the weight of organic additives accounts for 20% of the total weight of inorganic substances. The mass ratio of methyl acrylate to dispersant triolein and plasticizer polyethylene glycol is 8:1:6; the first pattern raw material includes inorganic substances: 86.5wt% zirconia, 4.2wt% yttrium oxide , 3.0wt% aluminum oxide, 2.3wt% hafnium oxide, 4.0wt% cobalt aluminate, the weight of organic additives accounts for 20% of the total weight of inorganic substances, wherein the mass of binder polyvinyl alcohol and dispersant polymethacrylic acid The ratio is 1:7.
流延成型获得第一陶瓷层生坯和第二陶瓷层生坯，第二陶瓷层生坯上通过丝印的方式印刷第一图案，第一图案颜色为蓝色，丝印的丝网为不锈钢，网孔孔径为450目；叠层压合第一陶瓷层和第二陶瓷层生坯，第一图案位于陶瓷层生坯之间形成第一图案层，叠层压合等静压压力为150MPa、温度60℃；烧结叠层压合后的第一陶瓷层和第二陶瓷层生坯，获得气孔含量小于0.5％的第一陶瓷层和第二陶瓷层粗坯，烧结时，室温-600℃排胶段升温速率为0.1℃/min，600℃-1450℃烧结段升温速率为4℃/min，最高温度达到1450℃，保温 2h，烧结后，有机助剂完全挥发；打磨抛光陶瓷层粗坯表面，最终获得带有图案的陶瓷壳体，具体参数见表7。The first ceramic layer green body and the second ceramic layer green body are obtained by tape casting, and the first pattern is printed on the second ceramic layer green body by silk screen printing. The color of the first pattern is blue, and the silk screen of the silk screen is stainless steel. The hole diameter is 450 mesh; the first ceramic layer and the second ceramic layer green body are laminated and pressed, and the first pattern is located between the ceramic layer green body to form the first pattern layer. 60°C; sinter the first ceramic layer and the second ceramic layer green body after lamination and lamination to obtain the rough body of the first ceramic layer and the second ceramic layer with a porosity content less than 0.5%. During sintering, room temperature -600°C debinding The heating rate of the section is 0.1°C/min, the heating rate of the sintering section at 600°C-1450°C is 4°C/min, the maximum temperature reaches 1450°C, and the temperature is kept for 2 hours. After sintering, the organic additives are completely volatilized; the surface of the rough ceramic layer is polished, Finally, a patterned ceramic shell was obtained, and the specific parameters are shown in Table 7.
此外，本实施例获得的陶瓷壳体的表面粗糙度小于50nm；在可见光波长范围内，陶瓷壳体表面的反射率为x，10％≤x≤20％；陶瓷壳体维氏硬度Hv10大于11Gpa；陶瓷壳体气孔含量小于0.5％；陶瓷壳体各个陶瓷层热膨胀系数差小于0.1×10 -6/℃；陶瓷壳体四点抗弯强度大于1000MPa。 In addition, the surface roughness of the ceramic shell obtained in this embodiment is less than 50nm; in the visible light wavelength range, the reflectance of the surface of the ceramic shell is x, 10%≤x≤20%; the Vickers hardness Hv10 of the ceramic shell is greater than 11Gpa The pore content of the ceramic shell is less than 0.5%; the thermal expansion coefficient difference of each ceramic layer of the ceramic shell is less than 0.1×10 -6 /°C; the four-point bending strength of the ceramic shell is greater than 1000MPa.
表7Table 7
Figure PCTCN2022117791-appb-000009
Figure PCTCN2022117791-appb-000009
第一陶瓷层含有4％紫色着色剂，厚度0.1mm，全透光率仅有22.4％，第二陶瓷层不含着色剂和氧化铝，因此具有较高的透光率，最终陶瓷壳体在第一陶瓷层远离第二陶瓷层一侧整体呈现为紫色。由于第一陶瓷层全透光率太低，小于30％，层间的蓝色第一图案透过第一陶瓷层显现于陶瓷壳体表面的效果较差。The first ceramic layer contains 4% purple colorant, the thickness is 0.1mm, and the total light transmittance is only 22.4%. The second ceramic layer does not contain colorant and alumina, so it has a higher light transmittance. The final ceramic shell is in The side of the first ceramic layer away from the second ceramic layer appears purple as a whole. Since the total light transmittance of the first ceramic layer is too low, less than 30%, the effect of the blue first pattern between the layers appearing on the surface of the ceramic shell through the first ceramic layer is poor.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present application, and the description thereof is relatively specific and detailed, but should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the scope of protection of the patent application should be based on the appended claims.

Claims (20)

  1. 一种陶瓷壳体，用于电子设备，其特征在于，包括第一陶瓷层、第二陶瓷层和第一图案层，所述第一图案层位于第一陶瓷层和第二陶瓷层之间，所述第一图案层的图案可透过第一陶瓷层显现。A ceramic housing for electronic equipment, characterized in that it includes a first ceramic layer, a second ceramic layer and a first pattern layer, the first pattern layer is located between the first ceramic layer and the second ceramic layer, The pattern of the first pattern layer can appear through the first ceramic layer.
  2. 如权利要求1所述的陶瓷壳体，其特征在于，所述第一陶瓷层全透光率或直线透光率大于所述第二陶瓷层。The ceramic housing according to claim 1, wherein the total light transmittance or linear light transmittance of the first ceramic layer is greater than that of the second ceramic layer.
  3. 如权利要求1所述的陶瓷壳体，其特征在于，所述第一陶瓷层厚度与陶瓷壳体的厚度比为n，0.01≤n≤0.4。The ceramic shell according to claim 1, wherein the ratio of the thickness of the first ceramic layer to the thickness of the ceramic shell is n, 0.01≤n≤0.4.
  4. 如权利要求1所述的陶瓷壳体，其特征在于，所述陶瓷壳体还包括第三陶瓷层，第三陶瓷层位于第二陶瓷层远离第一陶瓷层一侧。The ceramic housing according to claim 1, wherein the ceramic housing further comprises a third ceramic layer, and the third ceramic layer is located on a side of the second ceramic layer away from the first ceramic layer.
  5. 如权利要求4所述的陶瓷壳体，其特征在于，所述陶瓷壳体还包括第二图案层，所述第二图案层位于第二陶瓷层和第三陶瓷层之间。The ceramic casing according to claim 4, wherein the ceramic casing further comprises a second pattern layer, and the second pattern layer is located between the second ceramic layer and the third ceramic layer.
  6. 如权利要求1所述的陶瓷壳体，其特征在于，所述第一陶瓷层和第二陶瓷层组分包括氧化锆、氧化钇。The ceramic housing according to claim 1, wherein the components of the first ceramic layer and the second ceramic layer include zirconia and yttrium oxide.
  7. 如权利要求1所述的陶瓷壳体，其特征在于，按重量百分比计，所述第一陶瓷层组分包含89％-97％的氧化锆，3％-7％的氧化钇，0-0.5％的氧化铝，0-3％的氧化铪，0-0.5％的着色剂。The ceramic casing according to claim 1, wherein, by weight percentage, the first ceramic layer component comprises 89%-97% zirconia, 3%-7% yttrium oxide, 0-0.5% % aluminum oxide, 0-3% hafnium oxide, 0-0.5% colorant.
  8. 如权利要求1所述的陶瓷壳体，其特征在于，按重量百分比计，所述第二陶瓷层组分包含80％-96.5％的氧化锆，3％-7％的氧化钇，0-5％的氧化铝，0-3％的氧化铪，0.5％-5％的着色剂。The ceramic casing according to claim 1, wherein, by weight percentage, the second ceramic layer component comprises 80%-96.5% zirconia, 3%-7% yttrium oxide, 0-5% % aluminum oxide, 0-3% hafnium oxide, 0.5%-5% colorant.
  9. 如权利要求4所述的陶瓷壳体，其特征在于，按重量百分比计，所述第三陶瓷层组分包含60％-92％的氧化锆，3％-7％的氧化钇，0-20％的氧化铝，0-3％的氧化铪，5％-10％的着色剂。The ceramic housing according to claim 4, wherein, by weight percentage, the third ceramic layer component comprises 60%-92% zirconia, 3%-7% yttrium oxide, 0-20% % aluminum oxide, 0-3% hafnium oxide, 5%-10% colorant.
  10. 如权利要求9所述的陶瓷壳体，其特征在于，除了着色剂含量，所述第二陶瓷层和/或所述第三陶瓷层中氧化锆、氧化钇、氧化铝、氧化铪的含量与第一陶瓷层相同。The ceramic casing according to claim 9, wherein, except for the colorant content, the content of zirconium oxide, yttrium oxide, aluminum oxide, and hafnium oxide in the second ceramic layer and/or the third ceramic layer is the same as The first ceramic layer is the same.
  11. 如权利要求5所述的陶瓷壳体，其特征在于，按重量百分比计，所述第一图案层和第二图案层由陶瓷浆料或者陶瓷墨水形成，所述陶瓷浆料或陶瓷墨水的组分包含60％-97％的氧化锆，3％-7％的氧化钇，0-20％的氧化铝，0-3％的氧化铪，0.01％-10％的着色剂。The ceramic casing according to claim 5, wherein, in terms of weight percentage, the first pattern layer and the second pattern layer are formed of ceramic slurry or ceramic ink, and the combination of ceramic slurry or ceramic ink is It contains 60%-97% zirconia, 3%-7% yttrium oxide, 0-20% aluminum oxide, 0-3% hafnium oxide, and 0.01%-10% colorant.
  12. 如权利要求1-11所述的陶瓷壳体，其特征在于，所述陶瓷壳体满足以下一个或多个特征：表面粗糙度小于50nm，在可见光波长范围内表面的反射率为10％-20％，维氏硬度Hv10大于11Gpa，气孔含量小于0.5％，各个陶瓷层热膨胀系数差小于0.1×10 -6/℃，四点抗弯强度大于1000MPa。 The ceramic housing according to claims 1-11, wherein the ceramic housing satisfies one or more of the following characteristics: the surface roughness is less than 50 nm, and the reflectance of the surface in the visible light wavelength range is 10%-20 %, the Vickers hardness Hv10 is greater than 11Gpa, the porosity content is less than 0.5%, the thermal expansion coefficient difference of each ceramic layer is less than 0.1×10 -6 /°C, and the four-point bending strength is greater than 1000MPa.
  13. 一种陶瓷壳体的制备方法，其特征在于，包括：A method for preparing a ceramic shell, characterized in that it comprises:
    提供第一陶瓷层生坯和第二陶瓷层生坯，在所述第二陶瓷层生坯上设置第一图案；providing a first ceramic layer green body and a second ceramic layer green body on which a first pattern is provided;
    叠层压合所述第一陶瓷层生坯和第二陶瓷层生坯，所述第一图案位于所述第一陶瓷层生坯和第二陶瓷层生坯之间；Laminating and pressing the first ceramic layer green body and the second ceramic layer green body, the first pattern is located between the first ceramic layer green body and the second ceramic layer green body;
    烧结获得的叠层压合后的陶瓷层生坯得到陶瓷层粗坯；Sintering the laminated and laminated ceramic layer green body to obtain a ceramic layer rough body;
    打磨抛光所述陶瓷层粗坯表面，获得所述陶瓷壳体。Grinding and polishing the surface of the rough ceramic layer to obtain the ceramic shell.
  14. 如权利要求13所述的制备方法，其特征在于，所述提供第一陶瓷层生坯和第二陶瓷层生坯，在所述第二陶瓷层生坯上设置第一图案之后，还包括提供第三陶瓷层生坯，叠层压合所述第一陶瓷生坯、第二陶瓷层生坯和第三陶瓷层生坯，所述第三陶瓷层位于第二陶瓷层远离第一陶瓷层一侧。The preparation method according to claim 13, characterized in that, providing the first ceramic layer green body and the second ceramic layer green body, after setting the first pattern on the second ceramic layer green body, further includes providing The third ceramic layer green body, laminated and pressed the first ceramic layer green body, the second ceramic layer green body and the third ceramic layer green body, the third ceramic layer is located on the second ceramic layer away from the first ceramic layer side.
  15. 如权利要求13所述的制备方法，其特征在于，提供第一陶瓷层生坯包括：The preparation method according to claim 13, wherein providing the green body of the first ceramic layer comprises:
    配制第一陶瓷层生坯原料，流延成型获得第一陶瓷层生坯；Preparing raw materials for the first ceramic layer green body, tape casting to obtain the first ceramic layer green body;
    所述第一陶瓷层生坯原料包含无机物和有机助剂，按重量百分比计，无机物为89％-97％的氧化锆，3％-7％的氧化钇，0-0.5％的氧化铝，0-3％的氧化铪，0-0.5％的着色剂，有机助剂重量占无机物重量总和的10％-20％。The raw material of the green body of the first ceramic layer includes inorganic substances and organic additives, and the inorganic substances are 89%-97% of zirconia, 3%-7% of yttrium oxide, and 0-0.5% of alumina , 0-3% of hafnium oxide, 0-0.5% of colorant, and the weight of organic additives accounts for 10%-20% of the total weight of inorganic substances.
  16. 如权利要求13所述的制备方法，其特征在于，提供第二陶瓷层生坯包括：The preparation method according to claim 13, wherein providing the second ceramic layer green body comprises:
    配制第二陶瓷层生坯原料，流延成型获得第二陶瓷层生坯；Preparing raw materials for the second ceramic layer green body, tape casting to obtain the second ceramic layer green body;
    所述第二陶瓷层生坯原料包含无机物和有机助剂，按重量百分比计，无机物为80％-96.5％的氧化锆，3％-7％的氧化钇，0-5％的氧化铝，0-3％的氧化铪，0.5％-5％的着色剂，有机助剂重量占无机物重量总和的10％-20％。The raw material of the second ceramic layer green body contains inorganic substances and organic additives, and the inorganic substances are 80%-96.5% zirconia, 3%-7% yttrium oxide, and 0-5% aluminum oxide , 0-3% of hafnium oxide, 0.5%-5% of colorant, and the weight of organic additives accounts for 10%-20% of the total weight of inorganic substances.
  17. 如权利要求14所述的制备方法，其特征在于，提供第三陶瓷层生坯包括：The preparation method according to claim 14, wherein providing the third ceramic layer green body comprises:
    配制第三陶瓷层生坯原料，流延成型获得第三陶瓷层生坯；Preparing raw materials for the third ceramic layer green body, tape casting to obtain the third ceramic layer green body;
    所述第三陶瓷层生坯原料包含无机物和有机助剂，按重量百分比计，无机物为60％-92％的氧化锆，3％-7％的氧化钇，0-20％的氧化铝，0-3％的氧化铪，5％-10％的着色剂，有机助剂重量占无机物重量总和的10％-20％。The raw material of the green body of the third ceramic layer includes inorganic substances and organic additives, and the inorganic substances are 60%-92% of zirconia, 3%-7% of yttrium oxide, and 0-20% of alumina , 0-3% of hafnium oxide, 5%-10% of colorant, and the weight of organic additives accounts for 10%-20% of the total weight of inorganic substances.
  18. 如权利要求13所述的制备方法，其特征在于，所述设置第一图案包括：The preparation method according to claim 13, wherein said setting the first pattern comprises:
    配制第一图案原料，所述第一图案原料为陶瓷浆料或陶瓷墨水；Prepare the first pattern raw material, the first pattern raw material is ceramic slurry or ceramic ink;
    所述陶瓷浆料组分包含无机物组分和有机助剂，按重量百分比计，无机物为60％-97％的氧化锆，3％-7％的氧化钇，0-20％的氧化铝，0-3％的氧化铪，0.01％-10％的着色剂，有机助剂重量占无机物重量总和的20％-100％；The ceramic slurry components include inorganic components and organic additives, and the inorganic substances are 60%-97% of zirconia, 3%-7% of yttrium oxide, and 0-20% of alumina , 0-3% hafnium oxide, 0.01%-10% coloring agent, the weight of organic additives accounts for 20%-100% of the total weight of inorganic substances;
    所述陶瓷墨水组分包含无机物组分和有机助剂，按重量百分比计，无机物为60％-97％的氧化锆，3％-7％的氧化钇，0-20％的氧化铝，0-3％的氧化铪，0.01％-10％的着色剂，有机助剂重量占无机物重量总和的100％-200％。The ceramic ink components include inorganic components and organic additives, and the inorganic substances are 60%-97% zirconia, 3%-7% yttrium oxide, 0-20% aluminum oxide, 0-3% of hafnium oxide, 0.01%-10% of coloring agent, and the weight of organic additives accounts for 100%-200% of the total weight of inorganic substances.
  19. 如权利要求13所述的制备方法，其特征在于，所述叠层压合所述第一陶瓷层生坯和第二陶瓷层生坯包括：叠层第一陶瓷层生坯和第二陶瓷层生坯后，经等静压进一步压合，等静压压力≥100MPa，温度为室温-100℃，并且在第一陶瓷层生坯和第二陶瓷层生坯上增加支撑治具。The preparation method according to claim 13, wherein the lamination and pressing of the first ceramic layer green body and the second ceramic layer green body comprises: laminating the first ceramic layer green body and the second ceramic layer After the green body, it is further pressed by isostatic pressing, the isostatic pressing pressure is ≥ 100 MPa, the temperature is room temperature - 100 ° C, and support fixtures are added on the first ceramic layer green body and the second ceramic layer green body.
  20. 一种电子设备，其特征在于，包括显示设备、主板及如权利要求1-12的陶瓷壳体，所述陶瓷壳体与显示设备围设出容置空间，所述主板位于所述容置空间内。An electronic device, characterized in that it comprises a display device, a main board, and the ceramic housing according to claims 1-12, the ceramic housing and the display device enclose an accommodating space, and the main board is located in the accommodating space Inside.
PCT/CN2022/117791 2021-09-29 2022-09-08 Ceramic housing, preparation method therefor, and electronic device WO2023051214A1 (en)

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