WO2023279800A1

WO2023279800A1 - Housing, preparation method therefor, and electronic device

Info

Publication number: WO2023279800A1
Application number: PCT/CN2022/087305
Authority: WO
Inventors: 陈奕君; 胡梦; 李聪
Original assignee: Oppo广东移动通信有限公司
Priority date: 2021-07-09
Filing date: 2022-04-18
Publication date: 2023-01-12
Also published as: CN115604943A

Abstract

Provided in the present application is a housing. The housing comprises a polymer ceramic layer. The polymer ceramic layer comprises a ceramic composite structure and a polymer. The ceramic composite structure comprises ceramic particles and a coating layer disposed on the surfaces of the ceramic particles. The material of the coating layer comprises a layered material. The ceramic composite structure in the housing has a core-shell structure. The material of the coating layer in the ceramic composite structure comprises a layered material. The inter-layer acting force inside of the layered material is weak, and relative sliding can be generated, which further generates a lubricating effect, thereby increasing the fluidity of the ceramic composite structure in the polymer, and being helpful in increasing the solid content of the housing. The mechanical properties and ceramic texture of the housing are enhanced, which is beneficial for the application of the housing. Further provided in the present application are a method for preparing a housing, and an electronic device.

Description

Shell and its preparation method and electronic equipment

technical field

The application belongs to the technical field of electronic products, and in particular relates to a casing, a preparation method thereof, and electronic equipment.

Background technique

With the improvement of consumption level, consumers not only pursue the diversification of functions of electronic products, but also have higher and higher requirements for their appearance and texture. In recent years, ceramic materials have become a hot spot in the research of electronic equipment casings due to their warm and moist texture. In the related art, products are prepared by composite materials formed by resin and ceramic materials, but compared with real ceramic products, the products are quite different in terms of hardness, luster and moist touch, and it is difficult to obtain real ceramic texture. Therefore, the current ceramic shell and its preparation method still need to be improved.

Contents of the invention

In view of this, the present application provides a casing, a preparation method thereof, and an electronic device.

In a first aspect, the present application provides a casing, the casing includes a polymer ceramic layer, the polymer ceramic layer includes a ceramic composite structure and a polymer, the ceramic composite structure includes ceramic particles and is disposed on the A coating layer on the surface of the ceramic particle, the material of the coating layer includes a layered material.

In a second aspect, the present application provides a method for preparing a shell, including:

Forming a coating layer on the surface of the ceramic particles to obtain a ceramic composite structure, the material of the coating layer includes a layered material;

The ceramic composite structure is blended with a polymer, banburyed and granulated to form an injection molding feed;

The injection molding feed is injected to obtain a polymer ceramic sheet, and the polymer ceramic sheet is pressed to obtain a polymer ceramic layer to obtain a casing.

In a third aspect, the present application provides an electronic device, including a casing, the casing includes a polymer ceramic layer, the polymer ceramic layer includes a ceramic composite structure and a polymer, and the ceramic composite structure includes ceramic particles and The coating layer is arranged on the surface of the ceramic particle, and the material of the coating layer includes a layered material.

Description of drawings

In order to more clearly describe the technical solutions in the embodiments of the present application, the following will describe the drawings that need to be used in the embodiments of the present application.

FIG. 1 is a schematic structural diagram of a casing provided by an embodiment of the present application.

Fig. 2 is a schematic structural view of a ceramic composite structure provided by an embodiment of the present application.

Figure 3 is a schematic diagram of the structure of graphite.

Fig. 4 is a schematic structural diagram of a housing provided in another embodiment of the present application.

FIG. 5 is a flowchart of a method for preparing a housing provided in an embodiment of the present application.

Fig. 6 is an internal schematic diagram of a ceramic composite structure and a polymer blended according to an embodiment of the present application.

Fig. 7 is an internal schematic diagram of the blending of ceramic particles and polymers provided by the embodiment of the present application before improvement.

FIG. 8 is a flowchart of a method for preparing a housing provided in another embodiment of the present application.

FIG. 9 is a flow chart of a method for preparing a casing provided in another embodiment of the present application.

FIG. 10 is a schematic structural diagram of an electronic device provided by an embodiment of the present application.

FIG. 11 is a schematic diagram of the structure and composition of an electronic device provided by an embodiment of the present application.

detailed description

The following are preferred embodiments of the application. It should be pointed out that for those skilled in the art, without departing from the principle of the application, some improvements and modifications can also be made, and these improvements and modifications are also considered as the present invention. The scope of protection applied for.

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.

An embodiment of the present application provides a casing, the casing includes a polymer ceramic layer, the polymer ceramic layer includes a ceramic composite structure and a polymer, the ceramic composite structure includes ceramic particles and The cladding layer on the surface, the material of the cladding layer includes a layered material.

Wherein, the mass ratio of the ceramic particles to the coating layer in the ceramic composite structure is 2.5-20.

Wherein, the mass proportion of the ceramic particles in the ceramic composite structure is 70%-95%, and the mass proportion of the coating layer is 5%-30%.

Wherein, the layered material includes a two-dimensional material, the number of layers of the two-dimensional material is at least two layers, and the two-dimensional material includes at least one of graphene, graphene oxide, transition metal group compounds and black phosphorus kind.

Wherein, the layered material includes at least one of graphite and graphite oxide.

Wherein, the coverage rate of the coating layer on the surface of the ceramic particles is greater than or equal to 70%.

Wherein, the particle size of the ceramic particles is 0.5 μm-2 μm, and the thickness of the coating layer is 20 nm-150 nm.

Wherein, the mass proportion of the ceramic composite structure in the polymer ceramic layer is 50%-95%, and the mass proportion of the polymer is 5%-50%.

Wherein, the ceramic particles include at least one of Al ₂ O ₃ , ZrO ₂ , Si ₃ N ₄ , SiO ₂ , TiO ₂ , AlN, SiC and Si, and the polymer includes polyphenylene sulfide, polycarbonate , polyamide, polybutylene terephthalate and polymethyl methacrylate at least one.

Wherein, the particle size of the ceramic particles is 0.5 μm-2 μm.

Wherein, the glossiness of the surface of the polymer ceramic layer is greater than or equal to 120; the pencil hardness of the surface of the polymer ceramic layer is greater than or equal to 2H.

Wherein, the housing further includes a protective layer, and the protective layer is arranged on the surface of the polymer ceramic layer.

The embodiment of the present application provides a method for preparing a shell, including: forming a coating layer on the surface of ceramic particles to obtain a ceramic composite structure, the material of the coating layer includes a layered material; the ceramic composite structure and polymer Blending, banburying and granulation to form injection molding feed; the injection molding feed is injection molded to obtain polymer ceramic sheets, and the polymer ceramic sheets are pressed to obtain a polymer ceramic layer to obtain a shell.

Wherein, forming the coating layer on the surface of the ceramic particles includes: forming the coating layer on the surface of the ceramic particles by at least one of a solid phase coating method and a liquid phase coating method.

Wherein, the ceramic particles are dispersed in the graphite precursor solution, and the coating layer is formed on the surface of the ceramic particles by heating and annealing to form the ceramic composite structure.

Wherein, the solute of the graphite precursor solution includes at least one of glucose, fructose, sucrose, and polyvinylpyrrolidone; the concentration of the graphite precursor solution is 50mg/ml-200mg/ml; the heating temperature is 140 °C-200°C, the time is 5h-20h; the annealing temperature is 700°C-1000°C, and the time is 2h-5h.

Wherein, before the ceramic composite structure is blended with the polymer, it also includes: mixing the ceramic composite structure with a surface modifier and drying, and the mass of the surface modifier accounts for 0.5%- 3%.

Wherein, pressing the polymer ceramic sheet includes: subjecting the polymer ceramic sheet to warm isostatic pressing, the temperature of the warm isostatic pressing is 80°C-300°C, and the temperature of the warm isostatic pressing is as high as At the glass transition temperature of the polymer, the pressure of the warm isostatic pressing is 50MPa-500MPa, and the time of the warm isostatic pressing is 0.5h-2h.

Wherein, the melt index of the injection molding feedstock is greater than or equal to 10g/10min.

An embodiment of the present application provides an electronic device, including a casing, the casing includes a polymer ceramic layer, the polymer ceramic layer includes a ceramic composite structure and a polymer, the ceramic composite structure includes ceramic particles and is disposed on The coating layer on the surface of the ceramic particles, the material of the coating layer includes a layered material.

Please refer to FIG. 1 , which is a schematic structural view of a housing provided in an embodiment of the present application. The housing 100 includes a polymer ceramic layer 10. The polymer ceramic layer 10 includes a ceramic composite structure 11 and a polymer. The ceramic composite structure 11 includes ceramic particles. 111 and a coating layer 112 disposed on the surface of the ceramic particle 111, the material of the coating layer 112 includes a layered material.

In this application, the ceramic composite structure 11 is a core-shell structure, and the cladding layer 112 is made of a layered material. The layered material has a layered crystal structure, and the interlayer force inside the layered material is weak, which can produce relative Sliding produces a lubricating effect, which can reduce the viscosity between the ceramic composite structure 11 and the polymer, which is beneficial to increase the solid content of the shell 100 and enhance the mechanical properties and ceramic texture of the shell 100 . Compared with plastic shells, the shell 100 provided by this application has ceramic particles 111, thereby improving the hardness, wear resistance and glossiness of the shell 100, and has a high-grade texture of ceramics, which improves product competitiveness. At the same time, the shell of this application The ceramic composite structure 11 in the body 100 has lubricating properties and can be better mixed with polymers to improve the performance of the shell 100; Toughness and dielectric properties, while reducing the quality of the casing 100, meeting the need for thinner and lighter.

Please refer to FIG. 2 , which is a schematic structural view of a ceramic composite structure provided by an embodiment of the present application. The ceramic composite structure 11 includes ceramic particles 111 and a coating layer 112 disposed on the surface of the ceramic particles 111 . By setting the ceramic composite structure 11 of the core-shell structure, the viscosity of the ceramic particles 111 in the polymer is reduced, the fluidity of the ceramic particles 111 in the polymer is improved, and the toughness, hardness and Gloss.

In the embodiment of the present application, the ceramic particles 111 include at least one of Al ₂ O ₃ , ZrO ₂ , Si ₃ N ₄ , SiO ₂ , TiO ₂ , AlN, SiC and Si. The above-mentioned ceramic powder is resistant to high temperature, high in hardness and good in strength, which is conducive to improving the performance of the housing 100 . It can be understood that the ceramic particles 111 can also be selected from other materials not listed above that are suitable for manufacturing the casing 100 .

In the embodiment of the present application, the particle size of the ceramic particles 111 is 0.5 μm-2 μm. The ceramic particles 111 with the above particle size are beneficial to improve the delicate texture, strength and hardness of the casing 100 . Further, the particle diameter D50 of the ceramic particles 111 is 0.8 μm-1.8 μm. Furthermore, the particle size D50 of the ceramic particles 111 is 1 μm-1.5 μm. Specifically, the particle size of ceramic particles 111 can be, but not limited to, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm μm, 1.8μm, 1.9μm or 2μm etc.

In this application, the material of the coating layer 112 includes a layered material, the layered material has a layered crystal structure, and the interlayer force inside the layered material is weak, so that the coating layer 112 can produce a lubricating effect and improve fluidity , the viscosity between the ceramic composite structure 11 and the polymer is reduced, which is beneficial to increase the content of the ceramic composite structure 11 , thereby increasing the solid content of the shell 100 and improving the performance of the shell 100 . In one embodiment of the present application, the layered material includes a two-dimensional material. In another embodiment of the present application, the layered material includes at least one of graphite and graphite oxide. In yet another embodiment of the present application, the layered material includes at least one of two-dimensional materials, graphite and graphite oxide. The interlayer force inside the above-mentioned layered material is van der Waals force, and the interlayer force is weak, which further improves the lubricating effect of the cladding layer 112 and the fluidity of the ceramic composite structure 11, thereby helping to increase the solid content of the shell 100 and the shell. The performance of the body 100. Please refer to Figure 3, which is a schematic diagram of the structure of graphite. Graphite has a layered structure, and there is Van der Waals force between adjacent layers. As shown by the vertical dotted line in the figure, the van der Waals force is weak, making it easy for relative sliding between layers, as shown in the horizontal direction in the figure. As shown by the lines, graphite has a lubricating effect. In an embodiment of the present application, the two-dimensional material includes at least one of graphene, graphene oxide, transition metal compounds and black phosphorus. Specifically, the transition metal group compound can be, but not limited to, molybdenum disulfide, tungsten disulfide, zirconium disulfide, titanium disulfide, molybdenum diselenide, tungsten diselenide, zirconium diselenide and titanium diselenide at least one. In another embodiment of the present application, the number of layers of the two-dimensional material is at least two, so that the two-dimensional material has an interlayer force, which can improve the lubricating effect of the cladding layer 112 . In a specific embodiment, the cladding layer 112 includes at least one of a graphite layer, a graphite oxide layer and a two-dimensional material layer.

In the embodiment of the present application, the thickness of the cladding layer 112 is 20nm-150nm. Further, the thickness of the cladding layer 112 is 40nm-130nm. Furthermore, the thickness of the cladding layer 112 is 50nm-110nm. Specifically, the thickness of the cladding layer 112 may be, but not limited to, 30nm, 60nm, 80nm, 100nm, 120nm, 140nm or 150nm. In this application, the thickness of the coating layer 112 is relatively thin, which can increase the solid content in the housing 100 without excessively increasing the weight of the housing 100, and also ensure the content of the ceramic particles 111 in the housing 100, The performance of the casing 100 is guaranteed.

In the embodiment of the present application, the coating rate of the coating layer 112 on the surface of the ceramic particle 111 is greater than or equal to 70%. Further, the coating rate of the coating layer 112 on the surface of the ceramic particles 111 is greater than or equal to 80%. Specifically, the coverage rate of the coating layer 112 on the surface of the ceramic particles 111 may be, but not limited to, 70%, 75%, 80%, 85%, 90%, 95% or 100%. Having the above coating ratio can improve the fluidity of the ceramic composite structure 11 in the polymer during the preparation process of the shell 100 , which is beneficial to increase the solid content of the shell 100 , thereby improving the performance of the shell 100 .

In the embodiment of the present application, the mass ratio of the ceramic particles 111 to the coating layer 112 in the ceramic composite structure 11 is 2.5-20. Further, the mass ratio of the ceramic particles 111 to the cladding layer 112 in the ceramic composite structure 11 is 4-18. Furthermore, the mass ratio of the ceramic particles 111 to the coating layer 112 in the ceramic composite structure 11 is 8-15. Specifically, the mass ratio of the ceramic particles 111 and the cladding layer 112 in the ceramic composite structure 11 can be, but not limited to, 3, 5, 5.5, 6, 7, 9, 10, 11, 11.5, 12, 13, 14, 15, 16, 17, 18, 19 or 20 etc. Within this range, it is beneficial to improve the fluidity of the ceramic composite structure 11 in the polymer during the preparation of the shell 100, ensure the solid content of the shell 100, and also ensure the quality of the ceramic particles 111 in the shell 100, and further The ceramic texture and mechanical properties of the casing 100 are guaranteed. In the embodiment of the present application, the mass proportion of the ceramic particles 111 in the ceramic composite structure 11 is 70%-95%, and the mass proportion of the cladding layer 112 is 5%-30%. Further, the mass proportion of the ceramic particles 111 in the ceramic composite structure 11 is 75%-92%, and the mass proportion of the cladding layer 112 is 8%-25%. Furthermore, the mass proportion of the ceramic particles 111 in the ceramic composite structure 11 is 85%-90%, and the mass proportion of the cladding layer 112 is 10%-15%. Specifically, the mass proportion of the ceramic particles 111 in the ceramic composite structure 11 may be, but not limited to, 72%, 76%, 80%, 83%, 85%, 88%, 90%, 93% or 94%.

In the embodiment of the present application, the mass proportion of the ceramic composite structure 11 in the polymer ceramic layer 10 is 50%-95%. Further, the mass proportion of the ceramic composite structure 11 in the polymer ceramic layer 10 is 55%-90%. Furthermore, the mass proportion of the ceramic composite structure 11 in the polymer ceramic layer 10 is 70%-85%. Specifically, the mass proportion of the ceramic composite structure 11 in the polymer ceramic layer 10 may be, but not limited to, 58%, 62%, 67%, 70%, 73%, 75%, 84%, 86% or 91%. The lubricating properties of the coating layer 112 help to increase the solid content in the housing 100 and improve the mechanical properties of the housing 100 .

In the present application, the polymer in the polymer ceramic layer 10 is cross-linked to form a three-dimensional network structure, which improves the internal bonding force and toughness of the housing 100 . In the embodiment of the present application, the polymer includes at least one of polyphenylene sulfide, polycarbonate, polyamide, polybutylene terephthalate and polymethyl methacrylate. The physical and chemical properties of the above-mentioned polymer can match the preparation process of the housing 100 , and will not decompose during the preparation process, and will not increase the difficulty of the preparation process, which is beneficial to reduce production costs. It can be understood that the material of the polymer can also be selected from other materials not listed above that are suitable for manufacturing the casing 100 . In the embodiment of the present application, the mass proportion of the polymer in the polymer ceramic layer 10 is 5%-50%. Further, the mass proportion of the polymer in the polymer ceramic layer 10 is 10%-40%. Furthermore, the mass proportion of the polymer in the polymer ceramic layer 10 is 15%-35%. Specifically, the mass proportion of the polymer in the polymer ceramic layer 10 may be, but not limited to, 7%, 10%, 15%, 20%, 25%, 35%, 40%, 45% or 50%. Using the polymer in the above content can not only improve the toughness inside the casing 100 , reduce the weight of the casing 100 , but also not affect the ceramic texture of the casing 100 .

In the embodiment of the present application, the polymer ceramic layer 10 may also have a colorant, so that the casing 100 has different color appearances and improves the visual effect. Specifically, the coloring agent can be, but not limited to, at least one selected from iron oxide, cobalt oxide, cerium oxide, nickel oxide, bismuth oxide, zinc oxide, manganese oxide, chromium oxide, copper oxide, vanadium oxide and tin oxide. . In one embodiment, the mass content of the colorant in the polymer ceramic layer 10 is less than or equal to 10%, so as to improve the color of the polymer ceramic layer 10 without affecting the content of the ceramic composite structure 11 and polymer. Further, the mass content of the colorant in the polymer ceramic layer 10 is 0.5%-10%.

The present application uses a gloss meter to detect the gloss of the surface of the polymer ceramic layer 10 according to the GB/T 8807-1988 standard, wherein the angle of the gloss meter is 60°. In the embodiment of the present application, the glossiness of the surface of the polymer ceramic layer 10 is greater than or equal to 120. Further, the glossiness of the surface of the polymer ceramic layer 10 is 120-140. Specifically, the glossiness of the surface of the polymer ceramic layer 10 may be, but not limited to, 125, 128, 130, 133, 135, 137 or 140.

The present application detects the hardness of the surface of the polymer ceramic layer 10 by adopting the GB/T 6739-1996 standard. In the embodiment of the present application, the pencil hardness of the surface of the polymer ceramic layer 10 is greater than or equal to 2H. Further, the pencil hardness of the surface of the polymer ceramic layer 10 is 2H-5H, thereby greatly improving the hardness of the casing 100 and enhancing the strength of the casing 100 . Furthermore, the pencil hardness of the surface of the polymer ceramic layer 10 is 2H-4H. Specifically, the pencil hardness of the surface of the polymer ceramic layer 10 may be, but not limited to, 2H, 3H, 4H or 5H.

In the present application, the performance of the polymer ceramic layer 10 is detected by using a falling ball impact test, wherein the falling ball is a 32 g stainless steel ball, and the thickness of the polymer ceramic layer 10 is 0.8 mm. In one embodiment, the polymer ceramic layer 10 is supported on the jig, wherein the surrounding edges of the polymer ceramic layer 10 are supported by 3 mm, and the middle part is suspended; 32 g of stainless steel balls are freely dropped from a certain height to the polymer to be tested. For the point to be detected on the surface of the ceramic layer 10, record the height at which the polymer ceramic layer 10 is broken as the falling ball height. Further, a 32g stainless steel ball was freely dropped from a certain height to five detection points at the four corners and the center of the surface of the polymer ceramic layer 10 to be tested, and the height at which the polymer ceramic layer 10 was broken was recorded as the falling ball height. In the embodiment of the present application, the falling ball height of the polymer ceramic layer 10 is greater than or equal to 40 cm. Further, the falling ball height of the polymer ceramic layer 10 is 40cm-100cm. Furthermore, the falling ball height of the polymer ceramic layer 10 is 60cm-75cm.

Please refer to FIG. 4 , which is a schematic structural diagram of a housing provided in another embodiment of the present application. The housing 100 may further include a protective layer 20 disposed on the surface of the polymer ceramic layer 10 . The casing 100 has an inner surface and an outer surface oppositely disposed during use, and the protective layer 20 is located on one side of the outer surface, so as to play a protective role in the use of the casing 100 . Specifically, the protective layer 20 may be, but not limited to, an anti-fingerprint layer, a hardened layer, and the like. Specifically, the thickness of the protection layer 20 may be, but not limited to, 5nm-20nm. In one embodiment, the protection layer 20 includes an anti-fingerprint layer. Optionally, the contact angle of the anti-fingerprint layer is greater than 105°. The contact angle is an important parameter to measure the wettability of the liquid on the surface of the material. The contact angle of the anti-fingerprint layer is greater than 105°, indicating that the liquid is easy to move on the anti-fingerprint layer, thereby avoiding pollution to its surface, and has excellent anti-fingerprint properties. performance. Optionally, the anti-fingerprint layer includes fluorine-containing compounds. Specifically, the fluorine-containing compound may be, but not limited to, fluorosilicone resin, perfluoropolyether, fluorine-containing acrylate, and the like. Further, the anti-fingerprint layer also includes silicon dioxide, and the friction resistance of the anti-fingerprint layer is further improved by adding silicon dioxide. In another embodiment, the protective layer 20 includes a hardened layer. The surface hardness of the casing 100 is further improved by providing a hardened layer. Further, the material of the hardening layer includes at least one of polyurethane acrylate, silicone resin, and perfluoropolyether acrylate.

In the present application, the thickness of the housing 100 can be selected according to the requirements of its application scenarios, which is not limited. In one embodiment, the casing 100 can be used as a casing, a middle frame, a decoration, etc. of an electronic device, such as a casing of a mobile phone, a tablet computer, a notebook computer, a watch, MP3, MP4, GPS navigator, or a digital camera. The casing 100 in the embodiment of the present application may have a 2D structure, a 2.5D structure, a 3D structure, etc., which may be selected according to needs. In one embodiment, when the casing 100 is used as a mobile phone back cover, the thickness of the casing 100 is 0.6mm-1.2mm. Specifically, the thickness of the housing 100 may be, but not limited to, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm or 1.2mm. In another embodiment, when the case 100 is used as the back cover of a mobile phone, the case 100 includes a main body and an extension portion disposed on the edge of the main body, and the extension is bent toward the main body; at this time, the case 100 is curved.

In this application, the porosity of the casing 100 is detected by adopting the GB/T 25995-2010 standard. In the embodiment of the present application, the porosity of the casing 100 is less than 1%. That is, the density of the casing 100 is greater than or equal to 99%. The low porosity of the casing 100 ensures the bonding strength inside the casing 100 , which is beneficial to the improvement of the mechanical properties of the casing 100 . Further, the porosity of the casing 100 is less than 0.5%. The compactness of the casing 100 is further improved.

In the embodiment of the present application, the surface roughness of the casing 100 is less than 0.1 μm. By providing the housing 100 with a small surface roughness, it is beneficial to enhance its ceramic texture, improve the appearance effect, and facilitate the use of the housing 100 . Further, the surface roughness of the casing 100 is 0.02 μm-0.08 μm.

Please refer to FIG. 5 , which is a flowchart of a method for preparing a housing provided in an embodiment of the present application. The method is used to prepare the housing 100 in any of the above embodiments, including:

S101: forming a coating layer on the surface of the ceramic particles to obtain a ceramic composite structure, and the material of the coating layer includes a layered material.

S102: Blend the ceramic composite structure with the polymer, banbury and granulate to form injection molding feed.

S103: The injection molding feed is injected to obtain a polymer ceramic sheet, and the polymer ceramic sheet is pressed to obtain a polymer ceramic layer to obtain a casing.

The preparation method of the shell 100 provided in the present application is simple to operate, easy to produce on a large scale, and can produce the shell 100 with excellent performance, which is beneficial to its application.

In S101 , forming the coating layer 112 on the surface of the ceramic particle 111 helps to reduce the viscosity after mixing with the polymer, and at the same time increases the solid content of the mixed liquid formed by mixing with the polymer.

In S102, the injection molding feed is formed by blending the ceramic composite structure 11 and the polymer, banburying and granulating, which facilitates subsequent injection molding. In the related art, when the ceramic particles 111 are mixed with the polymer, the resulting mixed liquid has high viscosity and low fluidity, which tends to increase the resistance during the injection molding process, and even make the flow marks of the polymer ceramic sheet obvious, reducing the shell size. The mechanical properties of 100; in this application, the ceramic composite structure 11 is blended with the polymer, and the self-lubricating effect of the ceramic composite structure 11 is conducive to improving the solid content in the formed mixed solution, and can also reduce the viscosity of the formed mixed solution. The hysteresis improves the fluidity, which is beneficial to the injection molding process, improves the quality of the injection molding, and further helps to improve the mechanical properties of the housing 100 .

It can be understood that when the ceramic composite structure 11 and the polymer are blended, the mixing ratio of the ceramic composite structure 11 and the polymer can be selected according to the content of each substance in the polymer ceramic layer 10 , which is not limited. In one embodiment, the mass ratio of the ceramic composite structure 11 to the polymer is 1-20, which is conducive to making the polymer ceramic layer 10 with high hardness, good toughness, high gloss and strong ceramic texture. In the embodiment of the present application, the blending includes dry grinding or wet grinding, such as ball mill or sand mill. In one embodiment, the blending is carried out by a dry method, which is beneficial to improve the blending efficiency. In a specific embodiment, the ceramic composite structure 11, the polymer and the ball milling beads are placed together in a dry ball mill for grinding for 2h-10h. In this application, banburying and granulation is beneficial to the injection molding process, for example, the blended mixture can be placed in a banburying and granulating integrated machine for banburying and granulation. In one embodiment, the temperature of the mixer granulation is higher than the melting point of the selected polymer and lower than the decomposition temperature of the selected polymer. Specifically, the temperature of banburying and granulation can be but not limited to 200°C-350°C, and the time of banburying and granulation can be but not limited to 1h-12h. Furthermore, the banburying process is in a negative pressure state, and the absolute value of the pressure is less than 0.01MPa, so as to effectively prevent the selected polymer from being oxidized, and can effectively promote the elimination of gases generated by side reactions.

Please refer to Figure 6, which is the internal schematic diagram of the ceramic composite structure and polymer blended in one embodiment of the present application; please refer to Figure 7, the ceramic particle and polymer blended in the embodiment before the improvement of the present application. Internal schematic. It can be seen from Figures 6 and 7 that the friction between the ceramic particles 111 and the polymer is large, and the viscosity of the mixed liquid after blending is high and the fluidity is low; , so that the friction between the ceramic composite structure 11 and the polymer is reduced, the viscosity of the mixed solution after blending is reduced, the fluidity of the mixed solution is improved, and the injection molding is more conducive to improving the Glossiness and mechanical properties of the housing 100 .

This application passes the melt index that detects injection molding feedstock according to GB/T 3682-2000 standard. In the embodiment of the present application, the melt index of the injection molding feedstock is greater than or equal to 10 g/10 min. Further, the melt index of the injection molding feed is 10g/10min-25g/10min. Furthermore, the melt index of the injection molding feed is 12g/10min-20g/10min. The injection molding feedstock provided by the application has a high melt index and excellent fluidity, which is beneficial to the improvement of injection molding quality.

In S103 , the polymer ceramic layer 10 is obtained by injecting and pressing the injection molding material, and the shell 100 is manufactured.

In this application, the injection molding temperature can be selected according to the properties of the selected polymer. For example, the injection molding temperature can be but not limited to 200°C-350°C; 330°C. The thickness of the polymer ceramic sheet obtained by injection molding can be selected according to needs, and the thickness of the polymer ceramic sheet will be reduced during the subsequent pressing and processing, so the thickness of the polymer ceramic sheet can be increased during injection molding. In this application, the method of injection molding is simpler to operate. Compared with tape casting, there is no need to consider the compatibility between solvents and polymers, and the preparation cost is low. At the same time, the ceramic composite structure 11 and polymer The contact between the two improves the adhesion between the two; at the same time, the surface of the polymer ceramic sheet mentioned in the injection molding of this application is smooth without obvious scratches, which ensures the performance of the housing 100 . It can be understood that other molding methods such as tape casting can also be used to prepare polymer ceramic sheets.

In the embodiment of the present application, pressing the polymer ceramic sheet includes performing warm isostatic pressing on the polymer ceramic sheet. The porosity inside the polymer ceramic sheet is reduced by warm isostatic pressing, and the internal bonding force is improved. Isostatic pressing technology is a technology that uses the products in the closed high-pressure container to form under the uniform ultra-high pressure state in all directions. Isostatic pressing technology is divided into three different types: cold isostatic pressing, warm isostatic pressing, and hot isostatic pressing according to the temperature during forming and consolidation. In this application, the temperature of warm isostatic pressing is higher than the glass transition temperature of the polymer, so that the polymer in the polymer ceramic sheet can be softened, and at the same time, the density is better under pressure, thereby eliminating the polymer ceramic sheet The internal pores improve the bonding force between the ceramic composite structure 11 and the polymer. In one embodiment, the pressure of warm isostatic pressing is 50MPa-500MPa, which is conducive to fully compacting the polymer ceramic sheet, and the process has low requirements for equipment, good safety, and is more conducive to practical operation and application . Further, the pressure of warm isostatic pressing is 100MPa-400MPa. In this application, the time of warm isostatic pressing can be selected according to the thickness of the polymer ceramic sheet. In one embodiment, the temperature of warm isostatic pressing is 80°C-300°C, the time of warm isostatic pressing is 0.5h-2h, and the pressure of warm isostatic pressing is 50MPa-500MPa, which can further reduce the Porosity, improve the internal bonding force. In a specific embodiment, the polymer ceramic sheet can be packed into the package, the gas adsorbed on the surface of the green body and the internal space and the package can be sucked out, and then vacuum-sealed and then placed in a pressure vessel with a heating furnace for heating. Isostatic pressing.

Please refer to FIG. 8 , which is a flow chart of a method for preparing a housing provided in another embodiment of the present application. The preparation method prepares the housing 100 of any of the above embodiments, including:

S201: Form the coating layer on the surface of the ceramic particles by at least one of a solid phase coating method and a liquid phase coating method to obtain a ceramic composite structure, and the material of the coating layer includes a layered material.

S202: Blending the ceramic composite structure with the polymer, banburying and granulating to form injection molding feed.

S203: The injection molding feed is injected to obtain a polymer ceramic sheet, and the polymer ceramic sheet is pressed to obtain a polymer ceramic layer to obtain a casing.

It can be understood that, for detailed descriptions of S202 and S203, refer to descriptions of corresponding parts of S102 and S103 in the foregoing implementation manners, and details are not repeated here.

In S201, the coating layer 112 is formed on the surface of the ceramic particles 111 by at least one of the solid phase coating method and the liquid phase coating method to obtain a ceramic composite structure 11, thereby preparing a ceramic composite with lubricating properties. Structure 11.

In one embodiment of the present application, the ceramic composite structure 11 is prepared by a solid phase coating method. In one embodiment, the ceramic composite structure 11 is obtained by mixing the ceramic particles 111 with the material of the cladding layer 112 and mechanical grinding. In a specific embodiment, graphene oxide is dispersed in water, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide are added to activate Carboxyl group; subsequently adding ceramic particles 111 grafted with amino groups on the surface, after stirring, filtering and drying, a ceramic composite structure 11 is obtained, wherein the ceramic composite structure 11 includes ceramic particles 111 and a graphene oxide layer coated on the surface of the ceramic particles 111 .

In another embodiment of the present application, the ceramic composite structure 11 is prepared by a liquid phase coating method. Specifically, the ceramic composite structure 11 can be prepared, but not limited to, by a hydrothermal method. In one embodiment, the ceramic composite structure 11 can be obtained by dispersing the ceramic particles 111 in the precursor solution, followed by a hydrothermal reaction. It can be understood that in the hydrothermal method, the precursor solution forms the coating layer 112 coated on the surface of the ceramic particles 111 through hydrothermal reaction, and the specific material of the precursor solution can be selected according to the material of the coating layer 112, and no further description is made here. limited. Optionally, the concentration of the precursor solution is 50mg/ml-200mg/ml. Further, the concentration of the precursor solution is 80mg/ml-170mg/ml. Further, the concentration of the precursor solution is 100mg/ml-150mg/ml. Specifically, the concentration of the precursor solution may be, but not limited to, 50 mg/ml, 60 mg/ml, 75 mg/ml, 90 mg/ml, 100 mg/ml, 105 mg/ml, 120 mg/ml, 125 mg/ml or 140 mg/ml, etc. The use of the precursor solution with the above concentration can not only ensure the progress of the hydrothermal reaction, avoid the reaction being too slow, but also avoid the agglomeration caused by the reaction, which is conducive to the formation of a uniform covering layer 112 . In this application, the liquid-phase coating process can be carried out, but not limited to, in a reactor. In a specific embodiment, ceramic particles 111 are dispersed in a graphite precursor solution, heated and annealed to form a ceramic composite structure 11 . Specifically, the solute of the graphite precursor solution includes at least one of glucose, fructose, sucrose, and polyvinylpyrrolidone, an amorphous carbon layer is formed on the surface of the ceramic particles 111 by heating, and then the carbon layer is changed into a graphite layer by annealing. Optionally, the heating temperature is 140°C-200°C, and the heating time is 5h-20h; the annealing temperature is 700°C-1000°C, and the annealing time is 2h-5h. The above-mentioned heating process ensures the progress of the hydrothermal reaction, improves the formation of reaction products, and at the same time avoids the agglomeration of the reaction; the above-mentioned annealing process can transform the amorphous carbon layer into a graphite layer, and at the same time avoids the occurrence of agglomeration. Further, the heating temperature is 150°C-280°C, and the heating time is 8h-15h; the annealing temperature is 800°C-900°C, and the annealing time is 2.5h-4h. In this application, annealing is carried out in an inert atmosphere such as nitrogen, argon, etc., so as to prevent oxidation and burning of the carbon layer. Optionally, drying treatment is also included before the annealing, the drying temperature is 80°C-120°C, and the heating time is 2h-5h.

Please refer to FIG. 9 , which is a flow chart of a method for preparing a housing provided in another embodiment of the present application. The preparation method prepares the housing 100 of any of the above embodiments, including:

S301: forming a coating layer on the surface of the ceramic particles to obtain a ceramic composite structure, and the material of the coating layer includes a layered material.

S302: After the ceramic composite structure is modified, it is blended with the polymer, mixed and granulated to form injection molding feed.

S303: The injection molding feed is injected to obtain a polymer ceramic sheet, and the polymer ceramic sheet is pressed to obtain a polymer ceramic layer to obtain a casing.

It can be understood that, for detailed descriptions of S301 and S303, refer to the descriptions of the corresponding parts of S101 and S103 in the foregoing implementation manners, and details are not repeated here.

In S302, the ceramic composite structure 11 is modified and then blended with the polymer to further improve the compatibility and interfacial adhesion between the ceramic composite structure 11 and the polymer. In the embodiment of the present application, the modification of the ceramic composite structure 11 includes: mixing the ceramic composite structure 11 with a surface modifier and drying. In this application, the surface modifier may include, but is not limited to, at least one of coupling agent, surfactant, silicone, dispersant, etc., and the surface modifier may be selected according to the properties of the polymer. In one embodiment, a coupling agent can be selected for modification. Specifically, the coupling agent may be, but not limited to, a silane coupling agent, a titanate coupling agent, and the like. In another embodiment, the mass of the surface modifier accounts for 0.5%-3% of the mass of the ceramic composite structure 11, so that the surface modification of the ceramic composite structure 11 can be completed without causing a gap between the surface modifiers. A reunion happens. Further, the mass of the surface modifier accounts for 0.8%-2.5% of the mass of the ceramic composite structure 11 . Specifically, the mass of the surface modifier accounts for 0.6%, 1%, 1.5%, 2%, 2.5%, or 3% of the mass of the ceramic composite structure 11 . For example, the mass of the coupling agent accounts for 0.5%-3% of the mass of the ceramic composite structure 11 and so on. In a specific embodiment, the modification is carried out by mixing and grinding the ceramic composite structure 11 , the surface modifier and sanding beads.

In an embodiment of the present application, the manufacturing method of the housing 100 further includes performing computer digital control precision machining (CNC machining) on the housing 100 . The housing 100 with the final required assembly size is obtained through CNC machining. For example, the casing 100 is made flatter by CNC machining. In another embodiment of the present application, the manufacturing method of the housing 100 further includes grinding the housing 100 . By polishing and grinding the surface of the housing 100 , the roughness of the surface of the housing 100 is reduced, and the ceramic texture and hardness of the surface of the housing 100 are improved. In one embodiment, the surface roughness of the casing 100 is less than 0.1 μm. By providing the casing 100 with a small surface roughness, it is beneficial to enhance its surface gloss and ceramic texture, and improve the visual effect. Further, the surface roughness of the casing 100 is 0.02 μm-0.08 μm. In another embodiment, the surface hardness of the casing 100 is greater than or equal to 2H.

In an embodiment of the present application, the manufacturing method of the casing 100 further includes spraying or evaporating a protective material on the surface of the polymer ceramic layer 10 to form the protective layer 20 . In one embodiment, an anti-fingerprint layer is formed by vapor-depositing an anti-fingerprint material on the surface of the polymer ceramic layer 10 to improve the anti-fingerprint effect of the casing 100 .

The present application also provides an electronic device 200, including the casing 100 in any one of the above-mentioned implementation manners. 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. Please refer to FIG. 10 , which is a schematic structural diagram of an electronic device provided in an embodiment of the present application, wherein the electronic device 200 includes a casing 100 . The casing 100 can improve the mechanical properties of the electronic device 200, and the electronic device 200 has a ceramic-like appearance and has excellent product competitiveness. Please refer to FIG. 11 , which 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, 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 to receive and send signals; the memory 220 is used to store data instruction information; the input unit 230 is used to input 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 preparation method of the housing provided by the implementation of the present application and the performance of the prepared housing will be further described through specific examples and comparative examples below; wherein, the alumina raw materials in the housings of the examples and comparative examples of the application are purchased from Shanghai Bai Tugao New Material Technology Co., Ltd., the specification is BAK-1; the raw material of polyphenylene sulfide is purchased from Zhejiang NHU Co., Ltd., and the specification is 3450.

Example 1

A shell comprising a ceramic composite structure and polyphenylene sulfide (PPS), wherein the ceramic composite structure includes Al ₂ O ₃ and a graphite layer coated with Al ₂ O ₃ , the Al ₂ O ₃ and graphite in the ceramic composite structure The mass ratio is 8:2, and the mass proportion of the ceramic composite structure in the casing is 70%.

Example 2

_A casing comprising a ceramic composite structure and PPS, wherein the ceramic composite structure includes _Al2O3 and a graphite layer coated with _Al2O3 , and the mass ratio of _Al2O3 and graphite in the ceramic composite structure is ₈ : ₂ , the mass proportion of the ceramic composite structure in the housing is 80%.

Example 3

_A casing comprising a ceramic composite structure and PPS, wherein the ceramic composite structure includes _Al2O3 and a graphite layer coated with _Al2O3 , and the mass ratio _of _Al2O3 and _graphite in the ceramic composite structure is 9.8:0.2 , the mass proportion of the ceramic composite structure in the housing is 70%.

Example 4

_A shell comprising a ceramic composite structure and PPS, wherein the ceramic composite structure includes _Al2O3 and a molybdenum _disulfide layer covering _Al2O3 , the mass ratio _of _Al2O3 and molybdenum disulfide in the ceramic composite structure The ratio is 8:2, and the mass proportion of the ceramic composite structure in the housing is 70%.

Example 5

_A casing comprising a ceramic composite structure and PPS, wherein the ceramic composite structure _includes _Al2O3 and a black phosphorus layer coated with _Al2O3 , and the mass ratio of _Al2O3 to black phosphorus in the ceramic composite structure is ₈ :2, the mass proportion of the ceramic composite structure in the shell is 70%.

Comparative example 1

A casing comprising Al ₂ O ₃ and PPS, wherein the mass ratio of Al ₂ O ₃ in the casing is 70%.

Comparative example 2

A casing comprising Al ₂ O ₃ and PPS, wherein the mass ratio of Al ₂ O ₃ in the casing is 80%.

performance testing

By adopting the GB/T 3682-2000 standard to detect the melting index of the injection molding feedstock formed by the ceramic composite structure and PPS in the preparation process of the housing provided in the above-mentioned examples, the ceramics in the preparation process of the housing provided in the above comparative example The melt index of the injection molding feed that particle and PPS forms detects; GB/T 6739-1996 standard detects the pencil hardness of the shell surface that above-mentioned embodiment and comparative example provide; Adopt GB/T 8807-1988 to above-mentioned embodiment The glossiness of the shell surface provided by the comparative example is detected, and the angle of the gloss meter is 60°; the shells in the above-mentioned embodiment and the comparative example are provided, and the shell size is 150mm * 73mm * 0.8mm, respectively. The body is supported on the jig (the four sides are supported by 3mm, and the middle is suspended), and a 32g stainless steel ball is used to drop freely from a certain height to the surface to be tested. There are five points in the four corners and the center of the shell, and each point is measured 5 times until Broken, record the height of the falling ball, the results are shown in Table 1.

Table 1 performance test results

Compared with the housing provided in Comparative Example 1, the melt index of the injection molding feedstock in the preparation process of Example 1 and Examples 3-5 of the present application is high and the fluidity is strong, so that the hardness of the prepared housing is good and the gloss is good. The detection value of the accuracy and the falling ball height has been improved to a certain extent, that is, the ceramic texture and toughness of the shell made in the embodiment of the present application have been improved. Compared with Comparative Example 2, Example 2 of the present application has a high melt index and strong fluidity of the injection molding feed during the preparation process, and Comparative Example 2 cannot make a complete shell on the basis of high solid content, while the implementation of the present application In Example 2, a normal and complete shell can be produced, and at the same time, the hardness, gloss and toughness of the shell are excellent. Therefore, compared with the comparative example, the housing provided by the present application has excellent mechanical properties and good ceramic texture, which is beneficial to its application.

The content provided by the embodiment of the application has been introduced in detail above, and the principle and implementation of the application have been elaborated and explained, but the above description is only used to help understand the method of the application and its core idea; at the same time, for this field Those of ordinary skill in the art will have changes in specific implementation methods and application scopes based on the ideas of the present application. To sum up, the contents of this specification should not be understood as limiting the application.

Claims

A housing, characterized in that the housing includes a polymer ceramic layer, the polymer ceramic layer includes a ceramic composite structure and a polymer, and the ceramic composite structure includes ceramic particles and ceramic particles arranged on the surface of the ceramic particles The cladding layer, the material of the cladding layer includes a layered material.
The casing according to claim 1, wherein the mass ratio of the ceramic particles to the cladding layer in the ceramic composite structure is 2.5-20.
The casing according to claim 1, wherein the mass proportion of the ceramic particles in the ceramic composite structure is 70%-95%, and the mass proportion of the coating layer is 5%-30%. .
The casing according to claim 1, wherein the layered material comprises a two-dimensional material, the number of layers of the two-dimensional material is at least two, and the two-dimensional material comprises graphene, graphene oxide, At least one of a transition metal family compound and black phosphorus.
The housing of claim 1 wherein said layered material comprises at least one of graphite and graphite oxide.
The shell according to claim 1, wherein the coating rate of the coating layer on the surface of the ceramic particles is greater than or equal to 70%.
The casing according to claim 1, wherein the particle size of the ceramic particles is 0.5 μm-2 μm, and the thickness of the coating layer is 20 nm-150 nm.
The casing according to claim 1, wherein the mass proportion of the ceramic composite structure in the polymer ceramic layer is 50%-95%, and the mass proportion of the polymer is 5%-50% %.
The housing according to claim 1, wherein the ceramic particles comprise at least one of Al 2 O 3 , ZrO 2 , Si 3 N 4 , SiO 2 , TiO 2 , AlN, SiC and Si, and the The polymer includes at least one of polyphenylene sulfide, polycarbonate, polyamide, polybutylene terephthalate and polymethyl methacrylate.
The housing according to claim 1, wherein the particle size of the ceramic particles is 0.5 μm-2 μm.
The casing according to claim 1, wherein the glossiness of the surface of the polymer ceramic layer is greater than or equal to 120; the pencil hardness of the surface of the polymer ceramic layer is greater than or equal to 2H.
The casing according to claim 1, characterized in that the casing further comprises a protective layer, and the protective layer is disposed on the surface of the polymer ceramic layer.
A method for preparing a shell, characterized in that it comprises:

Forming a coating layer on the surface of the ceramic particles to obtain a ceramic composite structure, the material of the coating layer includes a layered material;

The ceramic composite structure is blended with a polymer, banburyed and granulated to form an injection molding feed;

The injection molding feed is injected to obtain a polymer ceramic sheet, and the polymer ceramic sheet is pressed to obtain a polymer ceramic layer to obtain a casing.
The preparation method according to claim 13, characterized in that, forming a coating on the surface of ceramic particles comprises:

The coating layer is formed on the surface of the ceramic particles by at least one of a solid phase coating method and a liquid phase coating method.
The preparation method according to claim 14, characterized in that the ceramic particles are dispersed in the graphite precursor solution, and the coating layer is formed on the surface of the ceramic particles by heating and annealing to form the ceramic composite structure.
The preparation method according to claim 15, wherein the solute of the graphite precursor solution comprises at least one of glucose, fructose, sucrose, and polyvinylpyrrolidone;

The concentration of the graphite precursor solution is 50mg/ml-200mg/ml;

The temperature of the heating is 140°C-200°C, and the time is 5h-20h;

The annealing temperature is 700°C-1000°C, and the time is 2h-5h.
The preparation method according to claim 13, wherein, before the ceramic composite structure is blended with the polymer, further comprising:

The ceramic composite structure is mixed with a surface modifier and dried, and the mass of the surface modifier accounts for 0.5%-3% of the mass of the ceramic composite structure.
The preparation method according to claim 13, wherein pressing the polymer ceramic sheet comprises: performing warm isostatic pressing on the polymer ceramic sheet, and the temperature of the warm isostatic pressing is 80°C-300°C. °C, and the temperature of the warm isostatic pressing is higher than the glass transition temperature of the polymer, the pressure of the warm isostatic pressing is 50MPa-500MPa, and the time of the warm isostatic pressing is 0.5h-2h.
The preparation method according to claim 13, characterized in that, the melt index of the injection molding feedstock is greater than or equal to 10g/10min.
An electronic device, characterized in that it includes a casing, the casing includes a polymer ceramic layer, the polymer ceramic layer includes a ceramic composite structure and a polymer, the ceramic composite structure includes ceramic particles and is arranged on the A coating layer on the surface of the ceramic particle, the material of the coating layer includes a layered material.