WO2021136063A1 - 陶瓷树脂复合壳体及其制备方法和终端 - Google Patents

陶瓷树脂复合壳体及其制备方法和终端 Download PDF

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Publication number
WO2021136063A1
WO2021136063A1 PCT/CN2020/139055 CN2020139055W WO2021136063A1 WO 2021136063 A1 WO2021136063 A1 WO 2021136063A1 CN 2020139055 W CN2020139055 W CN 2020139055W WO 2021136063 A1 WO2021136063 A1 WO 2021136063A1
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WIPO (PCT)
Prior art keywords
ceramic
resin
elongated holes
resin composite
component
Prior art date
Application number
PCT/CN2020/139055
Other languages
English (en)
French (fr)
Inventor
魏亚蒙
刘显亮
丁科
Original Assignee
荣耀终端有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by 荣耀终端有限公司 filed Critical 荣耀终端有限公司
Priority to US17/636,978 priority Critical patent/US20220288824A1/en
Priority to BR112022009403A priority patent/BR112022009403A2/pt
Priority to JP2022517177A priority patent/JP7351586B2/ja
Priority to EP20909276.6A priority patent/EP4008515B1/en
Publication of WO2021136063A1 publication Critical patent/WO2021136063A1/zh

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    • 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
    • H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
    • H04M1/026—Details of the structure or mounting of specific components
    • 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
    • H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
    • H04M1/026—Details of the structure or mounting of specific components
    • H04M1/0266—Details of the structure or mounting of specific components for a display module assembly
    • 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
    • H04M1/18—Telephone sets specially adapted for use in ships, mines, or other places exposed to adverse environment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • B29C2045/14327—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles anchoring by forcing the material to pass through a hole in the article
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C2045/1486—Details, accessories and auxiliary operations
    • B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
    • B29K2101/12—Thermoplastic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2709/00—Use of inorganic materials not provided for in groups B29K2703/00 - B29K2707/00, for preformed parts, e.g. for inserts
    • B29K2709/02—Ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3481—Housings or casings incorporating or embedding electric or electronic elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the embodiment of the present invention relates to the technical field of terminal housings, and particularly relates to a ceramic resin composite housing, a preparation method thereof, and a terminal.
  • Ceramic materials have good mechanical properties and electrical properties, and at the same time have a jade-like texture in appearance. Used in terminal equipment shells can improve product performance and user experience. However, ceramic materials are difficult to process, difficult to form fine structures, low yields, and high costs.
  • the resin has the advantages of good comprehensive mechanical properties and easy molding, convenient for fine structure molding, and high design freedom. In addition, the resin material has a low density and has a good weight reduction effect when used in the molding of the smart terminal housing.
  • the industry uses ceramic materials and resin materials to form a composite body, but the physical and chemical properties of ceramic materials and resin materials are quite different, it is difficult to achieve a close connection at the micro level, and the bonding strength of the interface between the two is not high. .
  • the embodiment of the present invention provides a ceramic resin composite shell, which solves the problem of low bonding strength between the existing ceramic and resin to a certain extent.
  • the first aspect of the embodiments of the present invention provides a ceramic resin composite housing, including a ceramic member and a resin member injection molded on the ceramic member, and a surface where the ceramic member and the resin member are combined has multiple surfaces.
  • the length of the strip-shaped hole is greater than 100 ⁇ m and less than or equal to 1000 ⁇ m, and the elongated hole is filled with the resin material constituting the resin member.
  • the elongated holes are formed by burning organic fibers, and the elongated holes extend from the surface of the ceramic component to the inside of the ceramic component.
  • the apertures at any position of the elongated holes are the same or substantially the same.
  • the diameter of the elongated hole gradually increases.
  • the diameter of the elongated hole gradually decreases.
  • the volume ratio of the plurality of elongated holes in the ceramic component is 1%-35%.
  • the area ratio of the plurality of elongated holes is 1%-60%.
  • the pore diameter of some or all of the elongated holes is 15 ⁇ m-500 ⁇ m.
  • a plurality of the elongated holes are evenly distributed on the surface where the ceramic member and the resin member are combined.
  • the surface where the ceramic member is combined with the resin member is further provided with a plurality of non-long-shaped holes, and the non-long-shaped holes are filled with the resin material constituting the resin member.
  • the material of the ceramic component includes one or more of oxide ceramic material, nitride ceramic material and carbide ceramic material.
  • the material of the resin member is a thermoplastic resin.
  • the resin member further includes a reinforcing component, and the reinforcing component includes one or more of glass fiber, carbon fiber, glass flake, calcium carbonate, magnesium carbonate, silica, and talc.
  • the resin member may be an integral structure, or may include a plurality of separate structures combined on the surface of the ceramic member.
  • the ceramic resin composite shell provided by the first aspect of the embodiment of the present invention includes a ceramic component and a resin component that are composited into an integrated structure, wherein the ceramic component has micron and/or submicron elongated holes deep from the surface to the inside, The resin material partially penetrates into the elongated hole, so that the bonding interface between the ceramic component and the resin component forms a tight micro-level combination, and the bonding strength is high; at the same time, the resin material infiltrated into the ceramic component will also affect the ceramic component. Toughening effect; and the small diameter of the elongated pores does not significantly damage the integrity of the ceramic, and weakens the mechanical properties of the ceramic substrate to a small extent.
  • an embodiment of the present invention also provides a method for preparing a ceramic resin composite shell, including:
  • Organic fibers are used as a pore-forming agent to prepare a ceramic component with a predetermined shape.
  • the surface of the ceramic component that is pre-injected has a plurality of elongated holes extending from the surface to the inside of the ceramic component.
  • the elongated holes are formed by the burning loss of the organic fiber, the elongated holes have an open-pore structure, the pore diameter of the elongated holes is in the range of 700nm-500 ⁇ m, and the length of at least part of the elongated holes is greater than 100 ⁇ m And less than or equal to 1000 ⁇ m;
  • the ceramic member is impregnated with an aqueous solution of a nitrogen-containing compound, so that the aqueous solution of the nitrogen-containing compound enters the elongated hole, and then is dried to make a layer of the inner wall of the elongated hole adhere to the ceramic member.
  • the nitrogen-containing compound
  • the dried ceramic component is subjected to injection molding, and the resin liquid enters the elongated hole to have an exothermic reaction with the nitrogen-containing compound. After the injection is completed, the resin part is subjected to fine structure processing to obtain a ceramic resin composite shell body.
  • the nitrogen-containing compound includes one or more of ammonia, hydrazine compounds and their derivatives, and water-soluble amines.
  • the specific method for preparing a ceramic component with a predetermined shape using organic fibers as a pore former includes injection molding, casting, 3D printing, hot pressing, and viscous sanding. One or more of.
  • the use of organic fibers as a pore-forming agent to prepare a ceramic component with a predetermined shape includes: mixing ceramic powder, organic fibers, and a binder to prepare a ceramic component blank, and then combining the ceramic component The ceramic component is obtained after the green body is sintered.
  • the organic fiber includes at least one of artificial fiber and natural fiber that can be burnt out.
  • the immersion treatment process is performed under vacuum conditions.
  • ultrasonic vibration is performed during the immersion treatment.
  • the drying treatment is air drying or freeze drying, and the temperature of the air drying is 10°C-80°C.
  • the preparation method provided in the second aspect of the embodiment of the present invention realizes the close connection between the ceramic and the resin under the dual effects of physical interlocking and chemical reaction.
  • the elongated holes deep into the ceramic component are obtained by the preparation of loss of organic fibers, and the resin penetrates into the elongated holes to strengthen the combination of resin and ceramic; on the other hand, the elongated holes are made by impregnation.
  • Nitrogen-containing compound is attached to the inner wall. During the injection molding process, the nitrogen-containing compound reacts exothermically with the resin that penetrates into the hole to provide heat to keep the front end of the resin flow in a low-viscosity flow state, so as to smoothly penetrate into the elongated hole.
  • the embodiment of the present invention creates pores by burning off organic fibers, which does not significantly damage the integrity of the ceramic structure, and does not require the use of strong acids and alkalis. Fibre burnout is completed in the ceramic sintering process, which is environmentally friendly and energy-saving.
  • An embodiment of the present invention also provides a terminal, including the ceramic resin composite housing described in the first aspect of the embodiment of the present invention.
  • the ceramic resin composite shell may be a shell structure such as a front cover, a middle frame, and a rear shell serving as a terminal.
  • the shell of the terminal has both a ceramic appearance and an internal fine structure composed of resin, which enhances market competitiveness.
  • the embodiment of the present invention also provides a mobile phone, which includes a display screen, a casing assembled on the outside of the mobile phone, and a main board and a battery located inside the casing.
  • the whole or part of the shell is the ceramic resin composite shell according to any one of the first aspect of the embodiments of the present invention.
  • the outer shell includes a rear shell assembled on the back side of the mobile phone.
  • the housing includes a front cover assembled on the front side of the mobile phone.
  • the housing includes a middle frame assembled in the mobile phone.
  • the housing includes one or more of a rear shell, a front cover, and a middle frame.
  • the middle frame is located between the front cover and the rear case of the mobile phone. Or, the middle frame is located between the display screen of the mobile phone and the back shell.
  • the rear shell and the middle frame are an integral structure or a separate structure.
  • the rear shell is a ceramic resin composite shell, wherein the ceramic components constitute the main appearance of the mobile phone rear shell, presenting the appearance and texture of ceramics, and the resin components constitute the rear shell frame and the functional structure inside the rear shell , So that the rear shell has a ceramic texture appearance and internal fine functional structure at the same time.
  • FIG. 1 is a schematic structural diagram of a mobile phone 100 according to an embodiment of the present invention.
  • FIG. 2 is a schematic structural diagram of a mobile phone housing 11 provided by an embodiment of the present invention.
  • FIG. 3 is a schematic structural diagram of a ceramic resin composite shell provided by an embodiment of the present invention.
  • 4A and 4B are respectively partial structural diagrams of the front and back sides of a mobile phone rear case provided by an embodiment of the present invention.
  • FIG. 5 is a schematic structural diagram of a ceramic component prepared in step S101 of the preparation method of an embodiment of the present invention.
  • FIG. 6 is a schematic diagram of ceramic resin composite in the injection molding process in step S102 of the preparation method of the embodiment of the present invention.
  • the embodiment of the present invention provides a ceramic resin composite shell, which can be applied to a terminal shell, so that the terminal shell has a ceramic appearance texture and an internal fine structure composed of resin at the same time, thereby enhancing the market competitiveness of the terminal product.
  • the terminal can be a mobile phone, or an electronic product such as a tablet computer, a notebook, a portable machine, or a smart wearable product.
  • the terminal housing may be part or all of the ceramic resin composite housing provided by the embodiment of the present invention.
  • the terminal shell is used to protect the internal components of the terminal, and the user can directly see and touch the appearance structure.
  • FIG. 1 is a schematic structural diagram of a mobile phone 100 provided by an embodiment of the present invention.
  • the mobile phone 100 includes a casing 11 assembled on the outside of the mobile phone, and components such as a motherboard and a battery located inside the casing 11.
  • the housing 11 may specifically include a front cover 12 assembled on the front side of the mobile phone (that is, on the side of the display screen), and may also include a rear housing 13 assembled on the rear side.
  • the housing 11 It may also include a middle frame 14 located between the front cover 12 and the rear case 13, and the middle frame 14 is used to carry components such as a motherboard and a battery.
  • the front cover 12, the rear shell 13 and/or the middle frame 14 are integrally the ceramic resin composite shell provided by the embodiment of the present invention, or a part of the front cover 12, the rear shell 13 and/or the middle frame 14 is
  • the ceramic resin composite casing for example, a part of the rear case 13 or a part of the front cover 12 and the middle frame 14 is a ceramic resin composite casing.
  • the rear shell 13 and the middle frame 14 may be an integral structure; in other embodiments of the present invention, the rear shell 13 and the middle frame 14 may also be a separate structure.
  • the mobile phone also includes a display screen. In a full-screen mobile phone, the outer shell generally does not include the front cover, and the middle frame is located between the display and the rear shell. Or, for some full-screen mobile phones, the shell may not include the exposed middle frame.
  • the ceramic resin composite housing 10 includes a ceramic component 101 and a resin component 102 injection molded on the ceramic component 101.
  • the surface where the ceramic member 101 and the resin member 102 are combined has a plurality of elongated holes 103 extending from the surface of the ceramic member 101 to the inside of the ceramic member.
  • the elongated hole 103 is an open hole structure.
  • the pore diameter of the elongated hole 103 is in the range of 700 nm to 500 ⁇ m.
  • the length of at least part of the elongated holes 103 is greater than 100 ⁇ m and less than or equal to 1000 ⁇ m.
  • the elongated hole 103 is filled with the resin material constituting the resin member 102.
  • the ceramic resin composite shell provided by the embodiment of the present invention can use a mature injection molding process to complete the integrated molding of ceramic and resin.
  • the composite shell has the appearance and texture of a ceramic material and also has a fine structure composed of a resin material.
  • the ceramic component has micron and/or sub-micron elongated holes deep from the surface to the inside, and the resin material penetrates into the elongated holes to form a microscopic level at the bonding interface between the ceramic component and the resin component. Tightly combined, high bonding strength.
  • the resin material infiltrated into the ceramic component will also have a fiber-like toughening effect on the ceramic component, which will increase the interface energy required for the cracking of the ceramic component through the pull-out effect.
  • the ceramic resin composite shell of the embodiment of the present invention has better toughness than a simple ceramic matrix, and has a lower probability of damage under impact load such as a drop.
  • the elongated holes in the embodiment of the present invention do not significantly damage the integrity of the ceramics, and weaken the mechanical properties of the ceramic substrate to a small extent.
  • the ceramic resin composite shell of the embodiment of the present invention has a lower density than a pure ceramic matrix, which is beneficial to the weight reduction of the terminal device.
  • the elongated holes 103 are formed by the burning loss of organic fibers, and the elongated fibrous holes deep from the surface of the ceramic to the inside of the ceramic are constructed in the ceramic component by the method of burning loss of the fibers.
  • Shaped pores can form an inverted structure, and its glue pulling effect is better than that of granular pores, so it can improve the bonding strength of ceramic and resin; and microscopically elongated pores can activate the internal closed pores of the ceramic component itself, and the holes after injection molding
  • the inside will be filled with resin material (as shown in Figure 3), and there will be a pull-out effect during the destruction process, thereby further improving the bonding strength.
  • the elongated hole 103 zigzags and extends from the surface of the ceramic component 101 to the inside of the ceramic component 102.
  • the zigzag elongated hole is more conducive to improving the bonding strength of the ceramic and resin interface through the pull-out effect after the resin material is injected.
  • the elongated hole 103 has an open structure, the open end of the elongated hole 103 is located on the surface where the ceramic member 101 and the resin member 102 are combined, and the closed end is located inside the ceramic member 101.
  • the resin material can enter the elongated hole from the open end.
  • the elongated holes are formed by the burning loss of the fiber, so the pore size is determined by the thickness of the fiber, and the pore size is easy to control.
  • the apertures of the plurality of elongated holes 103 may be the same or different.
  • the elongated hole 103 can have the same or substantially the same pore diameter at any position; it can also be from the surface of the ceramic component to the inside of the ceramic component, and the pore diameter of the elongated hole gradually increases; or it can be made of ceramic From the surface of the component to the inside of the ceramic component, the diameter of the elongated hole gradually decreases.
  • the pore size at any position is the same or basically the same for easy preparation; and the pore size gradually increases from the surface to the inside to form a better undercut structure, which is conducive to improving the bonding strength; and the gradual decrease from the surface to the inside facilitates the penetration of resin materials , The resin filling in the hole is smoothly realized.
  • the above-mentioned three types of elongated holes may exist at the same time, or only one or two of them may exist.
  • the diameter of the elongated hole may also be irregularly changed from the surface of the ceramic member to the inside.
  • the pore diameter of some or all of the elongated holes 103 is 15 ⁇ m-500 ⁇ m.
  • the volume ratio of the plurality of elongated holes in the ceramic component is controlled to be 1% to 35%. Further, it can be controlled within 10%-25%.
  • the appropriate volume ratio of the elongated pores can ensure the high bonding strength of the ceramic and the resin, and at the same time make the ceramic component body have high strength.
  • the area of the multiple elongated holes on the combined surface of the ceramic component and the resin component is 1%-60%. Further, the area ratio of the plurality of elongated holes may be 10%-30%. The suitable long strip hole area ratio can ensure the high bonding strength between the ceramic and the resin.
  • a plurality of elongated holes are uniformly distributed on the surface where the ceramic member and the resin member are combined.
  • the elongated pores are formed by the burning loss of fibers, there may be a small number of elongated pores with a closed cell structure inside the ceramic component due to the problem of fiber distribution. That is to say, when some fibers are only distributed inside the ceramic and not extended to the surface of the ceramic, the fibers will form long pores with a closed-cell structure inside the ceramic after the fiber is burned out.
  • closed pores refer to cavities and pores in the porous solid that are not connected to the outside world
  • open pores refer to cavities and pores in the porous solid that are connected to the outside world.
  • the surface and the inside of the ceramic component may also have a plurality of non-long-shaped pores 104.
  • These non-long-shaped pores are not formed by the burning loss of fiber, but the ceramic is inevitable due to raw materials and other reasons during the firing process. produced.
  • the shape of the non-long-shaped hole is not limited, and may be a regular or irregular shape, for example, it may be a spherical or quasi-spherical hole, and the pore diameter is mostly micron or sub-micron.
  • These non-long strip pores 104 are partially distributed on the surface of the ceramic component as an open-cell structure, and partially distributed inside the ceramic as a closed-cell structure. Wherein, as shown in FIG. 3, the elongated holes 103 of the open-cell structure can activate the closed-cell non-striped holes 104 connected to the inner part of the ceramic member, so that it is also filled with resin material after injection, thereby further improving the bonding strength.
  • the total volume of the various holes in the ceramic component is controlled to not exceed 40%. Furthermore, the proportion of the total volume of the various pores inside the ceramic component is controlled to not exceed 30%, and furthermore, it may not exceed 25%.
  • the material of the ceramic component includes one or more of oxide ceramic material, nitride ceramic material and carbide ceramic material.
  • the oxide ceramic material can be, for example, one or more of alumina, zirconia, silicon oxide, and kaolin;
  • the nitride ceramic can be, for example, one or more of silicon nitride and boron nitride;
  • the ceramic material may be silicon carbide, for example.
  • the ceramic member may be a ceramic flat plate with a thickness of 0.25 mm-0.7 mm.
  • the material of the resin member is a thermoplastic resin.
  • the resin material can be bonded to the ceramic component through a mature injection molding process, which facilitates the molding of complex and fine structures, has a greater degree of freedom in structural design, is convenient to process, and has low cost.
  • the thermoplastic resin may be one or more of polyester-based and polyamide-based resins, and specifically, the polyamide-based resin may be an aliphatic polyamide resin or an aromatic polyamide resin or a mixture of the two.
  • the resin member may also include reinforcing components, which may include glass fibers, carbon fibers, glass flakes, calcium carbonate, magnesium carbonate, silica, and talc. One or more.
  • the specific shape and structure of the ceramic component and the resin component are not limited, and they can be molded according to actual product requirements.
  • the resin component may be an integral structure, or it may include a plurality of separate structures bonded to the surface of the ceramic component.
  • FIGS. 4A and 4B are schematic diagrams of the structure of the rear case 15 of the mobile phone provided in a specific embodiment of the present invention.
  • the rear case has both a ceramic member 151 that is as warm as jade and a resin member 152 that has a fine structure.
  • the ceramic member 151 constitutes the main appearance of the rear case of the mobile phone, presenting the appearance and texture of ceramic
  • the resin member 152 constitutes the rear case frame and the functional structure inside the rear case, which is convenient for fine processing.
  • ceramic components are less directly impacted, reducing the probability of damage.
  • the interface between the ceramic member 151 and the resin member 152 realizes a micron and/or sub-micron level of bonding, and the bonding strength is high.
  • the resin that penetrates into the ceramic member 151 can also have the effect of fiber toughening, and further optimize the composite.
  • the ceramic resin composite shell provided by the embodiment of the present invention includes a ceramic component and a resin component that are composited into an integrated structure, wherein the ceramic component has micron and/or sub-micron long strip holes deep from the surface to the inside, and the resin material passes through Part of it penetrates into the elongated hole, so that the bonding interface of the ceramic component and the resin component forms a close combination at the micro level, and the bonding strength is high; at the same time, the resin material infiltrated into the ceramic component will also have a toughening effect on the ceramic component. ; And the small size of the pores does not significantly damage the integrity of the ceramic, and the mechanical properties of the ceramic substrate are less weakened.
  • an embodiment of the present invention also provides a method for preparing a ceramic resin composite shell, including:
  • the surface of the ceramic component that is pre-injected has a plurality of elongated holes extending from the surface of the ceramic component to the inside of the ceramic component.
  • the elongated holes are made of organic Fibres are formed by burning loss.
  • the elongated pores have an open-pore structure.
  • the pore diameter of the elongated pores is in the range of 700nm-500 ⁇ m, and the length of at least part of the elongated pores is greater than 100 ⁇ m and less than or equal to 1000 ⁇ m; as shown in Figure 5, Schematic diagram of the structure of a ceramic component with elongated holes.
  • 103 is an elongated hole with an open structure.
  • FIG. 6 shows a schematic diagram of the combination of ceramic and resin during the injection molding process.
  • 105 is the runner into which the resin liquid flows during the injection molding process.
  • the organic fibers may be rayon and/or natural fibers that can be burnt out. Specifically, for example, they may be, but not limited to, one or more of nylon fibers, explosion-proof fibers, and natural wood chips.
  • the diameter of the organic fiber is in the range of 700 nm to 500 m, and the length of at least part of the organic fiber is greater than 100 m and less than or equal to 1000 m.
  • the diameter and length of the organic fiber directly determine the diameter and length of the elongated hole that is finally formed.
  • the amount of organic fiber added is controlled between 0.1wt% and 5% by weight.
  • the addition of a suitable amount of organic fiber can not only construct a sufficient amount of holes, but also avoid excessive weakening of the ceramic matrix.
  • the ceramic component prepared by using organic fiber as the pore former has easy control of the pore size, does not contain macroscopic pores, but contains a large number of micron and/or submicron long strip pores leading into the ceramic matrix.
  • the specific preparation method of the ceramic component with a predetermined shape is not limited, and it may be one of injection molding, casting, 3D printing, hot pressing and viscous sanding. Prepared by a variety of methods. Among them, the layer-by-layer slurry method can better control the distribution of pores and regulate the distribution gradient of the openings along the thickness direction of the ceramic component. In some embodiments of the present invention, the proportion of pores on the ceramic surface is high, and the proportion of internal pores is low, so that injection molding is easy. In other embodiments of the present invention, the proportion of internal holes is high and the proportion of surface holes is low, so that the undercut structure is stronger. Specifically, it can be adjusted according to the specific requirements of the product.
  • the specific preparation process of a ceramic component having a predetermined shape may be: mixing ceramic powder, organic fibers, and a binder to prepare a ceramic component blank, and then sintering the ceramic component blank to obtain the ceramic component .
  • the particle size of the ceramic powder is between 0.1 ⁇ m and 100 ⁇ m;
  • the type of the ceramic powder can be one or more of oxide ceramic materials, nitride ceramic materials and carbide ceramic materials.
  • the oxide ceramic material can be, for example, one or more of aluminum oxide, zirconia, silicon oxide, and kaolin (essentially aluminum silicon oxide compound);
  • the nitride ceramic material can be, for example, silicon nitride or boron nitride.
  • the carbide ceramic material may be silicon carbide, for example.
  • the binder can be silica sol, zirconium sol, water glass, zirconium diacetate and the like. After the preparation of the green body is completed, it can be fired at 850°C-1550°C for 30min-24h and then cooled in the furnace to complete the preparation of the ceramic component.
  • the firing requirements of different ceramics vary greatly. The above firing conditions are only commonly used firing parameters, and the firing parameters for special ceramics may not be within the above range.
  • the ceramic component may be a ceramic flat plate with a thickness of 0.25 mm-0.7 mm.
  • the ceramic powder is alumina powder with a median particle size of 2 ⁇ m
  • the binder is 30wt% silica sol
  • the organic fiber is selected from nylon with a diameter of 10 ⁇ m, and at least part of the length is greater than 100 ⁇ m and less than or equal to 200 ⁇ m. Fiber, the addition amount is 1.2wt%.
  • the ceramic member is a flat plate with a thickness of 0.7 mm.
  • the obtained pores can penetrate deep into the ceramic, not limited to the surface of the ceramic, and can spread over the entire ceramic matrix if necessary; secondly, the method does not use various types of pores. Acid-base, good environmental protection effect; and the process of fiber burning loss is realized simultaneously in the ceramic baking process, and the energy-saving effect is good.
  • the elongated holes are openings, the pore diameter of the elongated holes is in the range of 700nm-500 ⁇ m, and the length of at least part of the elongated holes is greater than 100 ⁇ m and less than or equal to 1000 ⁇ m. Long strip holes with a certain length can better penetrate into the ceramic interior.
  • the nitrogen-containing compound includes one or more of ammonia, hydrazine compounds and their derivatives, and water-soluble amines.
  • concentration of the nitrogen-containing compound aqueous solution may be 1 wt% to 35 wt%, and specifically may be, for example, 5 wt%, 10 wt%, 20 wt%, 30 wt%, or 35 wt%.
  • the immersion treatment time can be 2-60min. The specific time is determined by the morphology of the pores on the ceramic component. The deeper the pores, the smaller the pore size, the longer the immersion time. For example, the immersion time can be 20min, 30min, 40min, 5min, 60min.
  • vacuum conditions and/or ultrasonic vibration are used during the immersion treatment.
  • ultrasonic treatment can also promote the release of gas in the elongated pores of the open-pore structure, thereby promoting the nitrogen-containing compound aqueous solution to enter the inside of the pores.
  • the method of drying the ceramic component after the immersion treatment can be air drying or freeze drying, wherein the air drying temperature is 10°C-80°C, the wind speed can be 3-8m/s, and the time can be 10-24 hours. Controlling the appropriate temperature can reduce the loss of nitrogen.
  • lateral blowing can be used for drying, with a lateral blowing wind speed of 5m/s and a time of 24h. According to the principle of fluid mechanics, the lateral blowing effect is better when the deep hole is dried. After drying, a layer of nitrogen-containing compound will be attached to the inner wall of the hole, and the nitrogen-containing compound will react with the resin to release heat during the injection molding process to promote the penetration of the resin liquid into the hole.
  • the dried ceramic component is placed in an injection molding mold for injection processing.
  • the injection molding material is a thermoplastic resin.
  • This type of resin can react with the nitrogen-containing compound on the inner wall of the hole to cause an exothermic reaction between grease and amine.
  • the thermoplastic resin may be one or more of polyester-based and polyamide-based resins, and specifically, the polyamide-based resin may be an aliphatic polyamide resin or an aromatic polyamide resin or a mixture of the two.
  • Specific injection parameters can be determined according to the types of resin raw materials. Generally, the injection port temperature is 220°C-400°C, and the mold temperature is 180°C-400°C.
  • the temperature of the injection port is between 295°C and 320°C
  • the temperature of the mold is between 230°C and 260°C.
  • the reinforcing components can include one or more of glass fiber, carbon fiber, glass flakes, calcium carbonate, magnesium carbonate, silica and talc. kind.
  • 66 wt% of polybutylene terephthalate (PBT) and 34 wt% of glass fiber are selected as the resin component material.
  • the injection port temperature is 330°C and the mold temperature is 260°C.
  • machining means such as CNC (Computerised Numerical Control) can be used to process the fine structure of the resin part on the composite shell to obtain the target composite shell.
  • the ceramic resin bonding method of the embodiment of the present invention can also be further used in combination with other existing bonding methods, such as further combining with riveting, macro-size hole drawing and so on.
  • the preparation method provided by the embodiment of the present invention realizes the close connection between ceramic and resin under the dual effects of physical interlocking and chemical reaction.
  • the elongated holes deep into the ceramic component are obtained by the preparation of loss of organic fibers, and the resin penetrates into the elongated holes to enhance the combination of resin and ceramic; on the other hand, the pores are rich in content through impregnation treatment. Nitrogen compound.
  • the nitrogen compound reacts with the resin penetrating into the hole exothermicly to provide heat to keep the front end of the injection resin flow in a low-viscosity flow state, and smoothly penetrate into the elongated hole to solve the resin liquid to a certain extent
  • the lowering of the temperature at the front end of the flow leads to the problem that the increase in viscosity cannot smoothly penetrate into the pores; in addition, the embodiment of the present invention creates pores by burning away organic fibers, which does not significantly damage the integrity of the ceramic structure, and does not require the use of strong acids and alkalis. Completed in the ceramic sintering process, environmental protection and energy saving.

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Abstract

一种陶瓷树脂复合壳体（10），包括陶瓷构件（101）和注塑成型在陶瓷构件（101）上的树脂构件（102），陶瓷构件（101）与树脂构件（102）结合的表面，具有多个由陶瓷表面延伸至陶瓷构件（101）内部的长条形孔洞（103），长条形孔洞（103）为开孔结构，孔径在700nm-500μm的范围内，且至少部分长条形孔洞（103）的长度大于100μm且小于或等于1000μm，长条形孔洞（103）内填充有构成树脂构件（102）的树脂材料。该复合壳体（10）同时具有陶瓷质感外观和由树脂构成的内部精细结构，陶瓷和树脂两者之间紧密结合，结合强度高。还提供了该陶瓷树脂复合壳体（10）的制备方法以及包含该复合壳体（10）的终端。

Description

陶瓷树脂复合壳体及其制备方法和终端
本申请要求于2019年12月30日提交中国专利局、申请号为201911424962.9、申请名称为“陶瓷树脂复合壳体及其制备方法和终端”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明实施例涉及终端壳体技术领域，特别是涉及陶瓷树脂复合壳体及其制备方法和终端。
背景技术
陶瓷材料具有良好的力学性能和电学性能，同时外观上具有温润如玉的质感，用于终端设备壳体可提升产品性能和用户体验。但陶瓷材料加工难度高，精细结构成型困难，良品率低，成本居高不下。而树脂具有良好的综合力学性能和易于成型的优势，便于进行精细结构成型，设计自由度高。此外树脂材料密度小，用于智能终端壳体成型时，具有良好的减重作用。为了综合利用两种材料的优势，业界采用陶瓷材料和树脂材料形成复合体，但是陶瓷材料和树脂材料物理化学性能差异较大，难以实现微观层面上的紧密连接，两者结合界面结合强度不高。
发明内容
鉴于此，本发明实施例提供一种陶瓷树脂复合壳体，在一定程度上解决现有陶瓷和树脂两者之间结合强度不高的问题。
具体地，本发明实施例第一方面提供一种陶瓷树脂复合壳体，包括陶瓷构件和注塑成型在所述陶瓷构件上的树脂构件，所述陶瓷构件与所述树脂构件结合的表面，具有多个由所述表面延伸至所述陶瓷构件内部的长条形孔洞，所述长条形孔洞为开孔结构，所述长条形孔洞的孔径在700nm-500μm的范围内，至少部分所述长条形孔洞的长度大于100μm且小于或等于1000μm，所述长条形孔洞内填充有构成所述树脂构件的树脂材料。
本发明实施方式中，所述长条形孔洞由有机纤维烧失形成，所述长条形孔洞由所述陶瓷构件表面向所述陶瓷构件内部曲折延伸。
本发明实施方式中，所述长条形孔洞任意位置处的孔径相同或基本相同。
本发明实施方式中，由所述陶瓷构件表面至所述陶瓷构件内部，所述长条形孔洞的孔径逐渐增大。
本发明实施方式中，由所述陶瓷构件表面至所述陶瓷构件内部，所述长条形孔洞的孔径逐渐减小。
本发明实施方式中，多个所述长条形孔洞在所述陶瓷构件中的体积占比为1％-35％。
本发明实施方式中，所述陶瓷构件与所述树脂构件结合的表面上，多个所述长条形孔洞的面积占比为1％-60％。
本发明实施方式中，部分或全部所述长条形孔洞的孔径为15μm-500μm。
本发明实施方式中，多个所述长条形孔洞均匀分布在所述陶瓷构件与所述树脂构件结合的表面。
本发明实施方式中，所述陶瓷构件与所述树脂构件结合的表面上，还具有多个非长条形孔洞，所述非长条形孔洞中填充有构成所述树脂构件的树脂材料。
本发明实施方式中，所述陶瓷构件的材质包括氧化物陶瓷材料、氮化物陶瓷材料和碳化物陶瓷材料中的一种或多种。
本发明实施方式中，所述树脂构件的材质为热塑性树脂。
本发明实施方式中，所述树脂构件中还包括增强组分，所述增强组分包括玻璃纤维、碳纤维、玻璃片、碳酸钙、碳酸镁、二氧化硅和滑石中的一种或多种。
本发明实施方式中，所述树脂构件可以是一个整体结构，也可以是包括多个结合在陶瓷构件表面的分体结构。
本发明实施例第一方面提供的陶瓷树脂复合壳体，包括复合为一体结构的陶瓷构件和树脂构件，其中，陶瓷构件具有从表面深入到内部的微米和/或亚微米级长条形孔洞，树脂材料通过部分渗入至长条形孔洞中，使陶瓷构件和树脂构件二者的结合界面处形成微观层面的紧密结合，结合强度高；同时陶瓷构件内部渗入的树脂材料也会对陶瓷构件起到增韧作用；而且长条形孔洞孔径小不明显破坏陶瓷的完整性，对陶瓷基材的力学性能削弱较小。
第二方面，本发明实施例还提供了一种陶瓷树脂复合壳体的制备方法，包括:
采用有机纤维作为造孔剂制备具有预设形状的陶瓷构件，所述陶瓷构件预进行注塑的表面，具有多个由所述表面延伸至所述陶瓷构件内部的长条形孔洞，所述长条形孔洞由所述有机纤维烧失形成，所述长条形孔洞为开孔结构，所述长条形孔洞的孔径在700nm-500μm的范围内，至少部分所述长条形孔洞的长度大于100μm且小于或等于1000μm；
采用含氮化合物的水溶液对所述陶瓷构件进行浸渍处理，使所述含氮化合物的水溶液进入到所述长条形孔洞中，随后干燥处理，使所述长条形孔洞内壁上附着一层所述含氮化合物；
将干燥后的陶瓷构件进行注塑处理，并使树脂液进入所述长条形孔洞中与所述含氮化合物发生放热反应，注塑完成后，对树脂部分进行精细结构加工，得到陶瓷树脂复合壳体。
本发明实施方式中，所述含氮化合物包括氨水、肼类化合物及其衍生物、水溶性胺中的一种或多种。
本发明实施方式中，所述采用有机纤维作为造孔剂制备具有预设形状的陶瓷构件的具体方法包括注射成型法、流延成型法、3D打印法、热压法和粘浆撒砂法中的一种或多种。
本发明实施方式中，所述采用有机纤维作为造孔剂制备具有预设形状的陶瓷构件包括：将陶瓷粉体、有机纤维、粘结剂混合后制备陶瓷构件素坯，再将所述陶瓷构件素坯烧结后得到所述陶瓷构件。
本发明实施方式中，所述有机纤维包括可烧失的人造纤维和天然纤维中的至少一种。
本发明实施方式中，所述浸渍处理过程在真空条件下进行。
本发明实施方式中，所述浸渍处理过程中进行超声振动。
本发明实施方式中，所述干燥处理的方式为吹风干燥或冷冻干燥，所述吹风干燥的温度为10℃-80℃。
本发明实施例第二方面提供的制备方法，在物理嵌合和化学反应的双重作用下，实现了陶瓷与树脂的紧密连接。一方面，通过烧失有机纤维制备获得了深入至陶瓷构件内部的长条形孔洞，树脂渗入长条形孔洞中从而增强了树脂与陶瓷的结合；另一方面，通过浸渍处理使长条形孔洞内壁附着含氮化合物，注塑过程中含氮化合物与渗入孔洞中的树脂发生放热反应，以提供热量使树脂液流前端持续保持低粘度流动状态，从而顺利渗入至长条形孔洞中，避免了树脂液流前端因降温导致粘度升高无法顺利渗入至孔洞中的问题；此外，本发明实施例通过烧失有机纤维造孔，不明显破坏陶瓷结构的完整性，而且不需要使用强酸强碱，纤维烧失在陶瓷烧结过程中完成，环保节能。
本发明实施例还提供一种终端，包括本发明实施例第一方面所述的陶瓷树脂复合壳体。陶瓷树脂复合壳体可以是充当终端的前盖、中框、后壳等壳体结构。本发明实施例提供的终端，其壳体同时具有陶瓷质感外观和由树脂构成的内部精细结构，提升了市场竞争力。
本发明实施例还提供一种手机，包括显示屏、组装在手机外侧的外壳，以及位于所述外壳内部的主板和电池。其中，所述外壳的整体或部分为本发明实施例第一方面任一所述的陶瓷树脂复合壳体。
本发明一实施方式中，所述外壳包括组装在手机后侧的后壳。或者，所述外壳包括组装在手机前侧的前盖。或者，所述外壳包括组装在手机中的中框。或者，所述外壳包括后壳、前盖、中框中的一个或多个。
其中，所述中框位于手机的前盖和后壳之间。或者，所述中框位于手机的显示屏和后壳之间。
本发明一实施方式中，所述后壳与所述中框为一体结构或分体结构。
本发明一实施方式中，所述后壳为陶瓷树脂复合壳体，其中陶瓷构件构成手机后壳的外观主体，呈现陶瓷的外观和质感，树脂构件则构成后壳边框和后壳内侧的功能结构，从而使得后壳同时具有陶瓷质感外观和内部精细功能结构。
附图说明
图1为本发明实施例提供的手机100的结构示意图；
图2为本发明实施例提供的手机外壳11的结构示意图；
图3为本发明实施例提供的陶瓷树脂复合壳体的结构示意图；
图4A和图4B分别为本发明实施例提供的手机后壳的正面和反面的局部结构示意图；
图5为本发明实施例制备方法步骤S101中制备得到的陶瓷构件的结构示意图；
图6为本发明实施例制备方法步骤S102的注塑过程中陶瓷树脂复合的示意图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例进行说明。
本发明实施例提供一种陶瓷树脂复合壳体，其可应用于终端外壳，使终端外壳同时具有陶瓷外观质感和由树脂构成的内部精细结构，从而提升终端产品的市场竞争力。该终端可以是手机，也可以是平板电脑、笔记本、便携机、智能穿戴产品等电子产品。其中，终端外壳可以是部分或全部为本发明实施例提供的陶瓷树脂复合壳体。终端外壳是用于保护 终端内部元件，使用者可直接看到和接触到的外观结构件。
以手机为例，图1为本发明实施例提供的手机100的结构示意图，手机100包括组装在手机外侧的外壳11，以及位于外壳11内部的主板和电池等部件。如图2所示，外壳11具体可以包括组装在手机前侧(即显示屏一侧)的前盖12，也可以包括组装在后侧的后壳13，在本发明一些实施方式中，外壳11还可以是包括位于前盖12和后壳13之间的中框14，中框14用于承载主板、电池等部件。本发明实施方式中，前盖12、后壳13和/或中框14整体为本发明实施例提供的陶瓷树脂复合壳体，或者前盖12、后壳13和/或中框14的一部分为陶瓷树脂复合壳体，例如后壳13的一部分或者前盖12、中框14的一部分为陶瓷树脂复合壳体。本发明一些实施方式中，后壳13与中框14可以是一体结构；本发明另一些实施方式中，后壳13与中框14也可以是分体结构。其中，手机还包括显示屏。在全面屏的手机中，外壳一般不包括前盖，中框位于显示屏和后壳之间。或者，某些全面屏的手机，外壳可能不包括暴露在外部的中框。
如图3所示，本发明实施例提供的陶瓷树脂复合壳体10，包括陶瓷构件101和注塑成型在陶瓷构件101上的树脂构件102。陶瓷构件101与树脂构件102结合的表面，具有多个由陶瓷构件101表面延伸至陶瓷构件内部的长条形孔洞103。长条形孔洞103为开孔结构。长条形孔洞103的孔径在700nm-500μm的范围内。至少部分长条形孔洞103的长度大于100μm且小于或等于1000μm。长条形孔洞103内填充有构成树脂构件102的树脂材料。
本发明实施例提供的陶瓷树脂复合壳体，可利用成熟的注塑成型工艺完成陶瓷和树脂的一体化成型，复合壳体具有陶瓷材料的外观和质感，同时还具有树脂材料所构成的精细结构。其中，陶瓷构件具有从表面深入到内部的微米和/或亚微米级长条形孔洞，树脂材料通过渗入至长条形孔洞中，使陶瓷构件和树脂构件二者的结合界面处形成微观层面的紧密结合，结合强度高。同时陶瓷构件内部渗入的树脂材料也会对陶瓷构件起到类似纤维增韧的效果，将通过拔出效应提高陶瓷构件开裂所需的界面能。因此，本发明实施例陶瓷树脂复合壳体相较于单纯的陶瓷基体而言具有更好的韧性，在跌落等受到冲击载荷的情况下，破坏几率更低。本发明实施例长条状孔洞不明显破坏陶瓷的完整性，对陶瓷基材的力学性能削弱较小。另外，本发明实施例陶瓷树脂复合壳体相比于纯陶瓷基体，具有更低的密度，有利于终端设备的减重。
本发明实施方式中，长条形孔洞103由有机纤维烧失形成，通过采用纤维烧失的方法在陶瓷构件中构造出从陶瓷表面深入至陶瓷内部的长条形纤维状孔洞，宏观上长条形孔洞可形成倒扣结构，其拉胶效果优于颗粒状孔洞，因而可以提高陶瓷与树脂的结合强度；而微观上长条形孔洞可激活连通陶瓷构件自身存在的内部闭孔，注塑后孔洞内将填充树脂材料(如图3所示)，破坏过程中存在拔出效应，从而进一步提高结合强度。
本发明实施方式中，长条形孔洞103由陶瓷构件101表面向陶瓷构件102内部曲折延伸。曲折延伸的长条形孔洞在注入树脂材料后，更有利于通过拔出效应提高陶瓷和树脂的界面结合强度。
本发明实施方式中，长条形孔洞103为开孔结构，长条形孔洞103的开口端位于陶瓷构件101与树脂构件102结合的表面，闭口端位于陶瓷构件101内部。树脂材料可以由开口端进入长条形孔洞中。本发明实施例中，长条形孔洞由纤维烧失形成，因此其孔径尺寸 由纤维的粗细决定，孔径尺寸易于控制。本发明实施方式中，多个长条形孔洞103的孔径可以相同，也可以不同。
本发明实施方式中，长条形孔洞103可以是任意位置处的孔径相同或基本相同；也可以是由陶瓷构件表面至陶瓷构件内部，长条形孔洞的孔径逐渐增大；还可以是由陶瓷构件表面至陶瓷构件内部，长条形孔洞的孔径逐渐减小。其中，任意位置处的孔径相同或基本相同便于制备；而孔径由表面向内部逐渐增大可形成更好的倒扣结构，有利于提升结合强度；而由表面向内部逐渐减小便于树脂材料渗入，顺利实现孔洞内树脂填充。本发明实施例中，上述三种形式的长条形孔洞可以同时存在，也可以仅存在其中的一种或两种。当然，在本发明其他一些实施方式中，还可以是长条形孔洞的孔径由陶瓷构件表面向内部呈无规律的变化。
本发明实施方式中，为了使树脂材料更好地渗入到长条形孔洞中，部分或全部长条形孔洞103的孔径为15μm-500μm。
本发明实施方式中，为保证陶瓷具有较高强度，将多个长条形孔洞在陶瓷构件中的体积占比控制在1％-35％。进一步地，可控制在10％-25％。适合的长条形孔洞体积占比能够保证陶瓷与树脂的高结合强度的同时，使陶瓷构件本体具有高强度。
本发明实施方式中，为保证陶瓷与树脂两者的紧密结合，陶瓷构件与树脂构件结合的表面上，多个长条形孔洞的面积占比为1％-60％。进一步地，多个长条形孔洞的面积占比可为10％-30％。适合的长条形孔洞面积占比能够保证陶瓷与树脂两者间的高结合强度。
本发明实施方式中，为使陶瓷与树脂两者形成更好的结合，多个长条形孔洞均匀分布在陶瓷构件与树脂构件结合的表面。
本发明实施方式中，由于长条形孔洞由纤维烧失形成，因此陶瓷构件内部还可能由于纤维分布问题存在少量具有闭孔结构的长条形孔洞。即当一些纤维只分布在陶瓷内部，未分布延伸至陶瓷表面时，纤维烧失后就会在陶瓷内部形成闭孔结构的长条形孔洞。其中，闭孔是指多孔固体中不与外界连通的空腔和孔道，而开孔是指多孔固体中与外界连通的空腔和孔道。
本发明实施方式中，陶瓷构件表面和内部还可能具有多个非长条形孔洞104，这些非长条形孔洞不是由纤维烧失形成的，而是陶瓷在烧制过程中由于原料等原因必然产生的。非长条形孔洞的形状不限，可以是规则或非规则形状，例如可以是球形或类球形孔洞，其孔径大多为微米级或亚微米级。这些非长条形孔洞104部分分布在陶瓷构件表面为开孔结构，部分分布在陶瓷内部为闭孔结构。其中，如图3所示，开孔结构的长条形孔洞103可激活连通陶瓷构件内部部分的闭孔非长条形孔洞104，使其注塑后也被树脂材料填充，从而进一步提高结合强度。
本发明实施方式中，为了保证陶瓷的强度，陶瓷构件内部各种孔洞的总体积占比控制在不超过40％。进一步地，陶瓷构件内部各种孔洞的总体积占比控制在不超过30％，更进一步地可以是不超过25％。
本发明实施方式中，陶瓷构件的材质包括氧化物陶瓷材料、氮化物陶瓷材料和碳化物陶瓷材料中的一种或多种。具体地，氧化物陶瓷材料例如可以是氧化铝、氧化锆、氧化硅、高岭土中的一种或多种；氮化物陶瓷例如可以是氮化硅、氮化硼中的一种或多种；碳化物 陶瓷材料例如可以是碳化硅。本发明实施方式中，陶瓷构件可以是厚度为0.25mm-0.7mm的陶瓷平板。
本发明实施方式中，树脂构件的材质为热塑性树脂。树脂材料可通过成熟的注塑成型工艺结合到陶瓷构件上，方便成型复杂精细结构，在结构设计上具有较大自由度，加工方便，成本较低。具体地，热塑性树脂可以是聚酯类、聚酰胺类树脂中的一种或多种，具体地聚酰胺类树脂可以是脂肪族聚酰胺树脂或芳香族聚酰胺树脂或二者的混合物。
本发明实施方式中，为了优化树脂构件的力学性能，树脂构件中还可以包括增强组分，增强组分可包括玻璃纤维、碳纤维、玻璃片、碳酸钙、碳酸镁、二氧化硅和滑石中的一种或多种。
本发明实施方式中，陶瓷构件和树脂构件的具体形状结构不限，可以根据实际产品需求成型。树脂构件可以是一个整体结构，也可以是包括多个结合在陶瓷构件表面的分体结构。
如图4A和图4B所示，为本发明一具体实施例中提供的手机后壳15的结构示意图。该后壳同时具有温润如玉的陶瓷构件151和具有精细结构的树脂构件152。本实施例中陶瓷构件151构成手机后壳的外观主体，呈现陶瓷的外观和质感，树脂构件152则构成后壳边框和后壳内侧的功能结构，便于精细加工。在日常使用过程中，陶瓷构件较少受到直接冲击，减少了破坏几率。此外陶瓷构件151和树脂构件152之间的界面实现了微米和/或亚微米量级的结合，结合强度高，此外渗入陶瓷构件151内部的树脂还能起到纤维增韧的效果，进一步优化复合壳体的抗冲击破坏性能。
本发明实施例提供的陶瓷树脂复合壳体，包括复合为一体结构的陶瓷构件和树脂构件，其中，陶瓷构件具有从表面深入到内部的微米和/或亚微米级长条形孔洞，树脂材料通过部分渗入至长条形孔洞中，使陶瓷构件和树脂构件二者的结合界面处形成微观层面的紧密结合，结合强度高；同时陶瓷构件内部渗入的树脂材料也会对陶瓷构件起到增韧作用；而且孔洞尺寸小不明显破坏陶瓷的完整性，对陶瓷基材的力学性能削弱较小。
相应地，本发明实施例还提供了一种陶瓷树脂复合壳体的制备方法，包括:
S101、采用有机纤维作为造孔剂制备具有预设形状的陶瓷构件，陶瓷构件预进行注塑的表面，具有多个由陶瓷构件表面延伸至陶瓷构件内部的长条形孔洞，长条形孔洞由有机纤维烧失形成，长条形孔洞为开孔结构，长条形孔洞的孔径在700nm-500μm的范围内，至少部分长条形孔洞的长度大于100μm且小于或等于1000μm；图5所示，为具有长条形孔洞的陶瓷构件的结构示意图。其中，103为开孔结构的长条形孔洞。
S102、采用含氮化合物的水溶液对陶瓷构件进行浸渍处理，使含氮化合物的水溶液进入到长条形孔洞中，随后干燥处理，使长条形孔洞内壁上附着一层含氮化合物；
S103、将干燥后的陶瓷构件进行注塑处理，并使树脂液进入长条形孔洞中与含氮化合物发生放热反应，注塑完成后，对树脂部分进行精细结构加工，得到陶瓷树脂复合壳体。图6所示，为注塑过程中陶瓷与树脂两者复合的示意图。图中，105为注塑成型过程中树脂液流入的浇道。
本发明实施方式中，步骤S101中，有机纤维可选用可烧失的人造纤维和/或天然纤维，具体地，例如可以是但不限于是尼龙纤维、防爆纤维、天然木屑中的一种或多种。有机纤 维直径在700nm-500μm范围内，且至少部分有机纤维的长度大于100μm且小于或等于1000μm。有机纤维的直径和长度直接决定了最终形成的长条形孔洞的孔径和长度。有机纤维添加量控制在0.1wt％-5wt％之间，适合量有机纤维的添加，既能够构造足量的孔洞，又能避免过度削弱陶瓷基体。采用有机纤维作为造孔剂制备得到的陶瓷构件，其孔洞尺寸易控制，不含有宏观孔洞，而含有大量通向陶瓷基体内部的微米级和/或亚微米级长条形孔洞。
本发明实施方式中，具有预设形状的陶瓷构件的具体制备方法不限，可以是采用注射成型法、流延成型法、3D打印法、热压法和粘浆撒砂法中的一种或多种方法制备得到。其中，采用逐层粘浆法可以更好地控制孔洞的分布，调控开孔沿陶瓷构件厚度方向上的分布梯度。本发明一些实施方式中，可以是陶瓷表面孔洞比例高，内部孔洞比例低，这样容易注塑。本发明另一些实施方式中，也可以是内部孔洞比例高，表面孔洞比例低，这样倒扣结构更强。具体地，可以根据产品的具体要求来进行调控。
本发明实施例中，具有预设形状的陶瓷构件的具体制备过程可以是：将陶瓷粉体、有机纤维、粘结剂混合后制备陶瓷构件素坯，再将陶瓷构件素坯烧结后得到陶瓷构件。其中，陶瓷粉末颗粒粒度在0.1μm-100μm之间；陶瓷粉末的种类可为氧化物陶瓷材料、氮化物陶瓷材料和碳化物陶瓷材料中的一种或多种。具体地，氧化物陶瓷材料例如可以是氧化铝、氧化锆、氧化硅、高岭土(实质为铝硅氧化合物)中的一种或多种；氮化物陶瓷例如可以是氮化硅、氮化硼中的一种或多种；碳化物陶瓷材料例如可以是碳化硅。粘结剂可选硅溶胶、锆溶胶、水玻璃、二醋酸锆等。其中素坯制备完成后可在850℃-1550℃下焙烧30min-24h后随炉冷却，完成陶瓷构件的制备。当然，由于陶瓷种类繁多，不同陶瓷的焙烧要求差异很大，上述的焙烧条件只是常用的焙烧参数，对于特种陶瓷的焙烧参数可以不在上述范围内。
本发明实施例中，陶瓷构件可以是厚度为0.25mm-0.7mm的陶瓷平板。
本发明一具体实施例中，陶瓷粉末选用中值粒径为2μm的氧化铝粉，粘结剂选用30wt％的硅溶胶，有机纤维选取直径10μm，至少部分长度大于100μm且小于或等于200μm的尼龙纤维，添加量为1.2wt％。陶瓷构件为厚度0.7mm的平板。
本发明实施方式中，通过采用纤维烧失的方式在陶瓷内部构造孔洞，所获得的孔洞能够深入陶瓷内部，不局限于陶瓷的表面，必要时可以遍布整个陶瓷基体；其次该方法不使用各类酸碱，环保效果良好；而且纤维烧失的过程在陶瓷焙烧过程中同步实现，节能效果良好。
本发明实施方式中，长条形孔洞为开孔，长条形孔洞的孔径在700nm-500μm的范围内，且至少部分长条形孔洞的长度大于100μm且小于或等于1000μm。具有一定长度的长条形孔洞能够更好地深入至陶瓷内部。
本发明实施方式中，步骤S102中，含氮化合物包括氨水、肼类化合物及其衍生物、水溶性胺中的一种或多种。含氮化合物水溶液的浓度可以是1wt％-35wt％，具体例如可以是5wt％、10wt％、20wt％、30wt％、35wt％。浸渍处理的时间可以是2-60min，具体时间根据陶瓷构件上孔洞的形貌确定，孔洞越深孔径越小则浸渍时间越长，例如浸渍的时间可以是20min、30min、40min、5min、60min。
本发明实施方式中，为了使含氮化合物水溶液更顺利地进入到长条形孔洞的内部，更 充分地与长条形孔洞内壁保持接触，在浸渍处理过程中采用真空条件和/或采用超声振动辅助处理。其中，超声处理还能促进开孔结构的长条形孔洞中气体的释放，从而促使含氮化合物水溶液进入孔洞内部。
本发明实施方式中，将浸渍处理后的陶瓷构件进行干燥处理的方式可以是吹风干燥或冷冻干燥，其中吹风干燥的温度为10℃-80℃，风速可以是3-8m/s，时间可以是10-24小时。控制适当的温度可以减少氮元素的损失。本发明一具体实施方式中可采用侧向吹风干燥，侧向吹风风速5m/s，时间24h。根据流体力学原理，深孔干燥时侧向吹风效果更好。干燥后孔内壁将附着一层含氮化合物，该含氮化合物将在注塑过程中通过与树脂反应放热从而促进树脂液向孔洞内部渗入。
本发明实施方式中，步骤S103中，将干燥后的陶瓷构件置入注塑成型的模具中进行注塑处理。注塑材料为热塑性树脂，此类树脂能与孔洞内壁上的含氮化合物发生脂与胺的放热反应。具体地，热塑性树脂可以是聚酯类、聚酰胺类树脂中的一种或多种，具体地聚酰胺类树脂可以是脂肪族聚酰胺树脂或芳香族聚酰胺树脂或二者的混合物。具体注塑参数可根据树脂原料的种类确定，一般地注射口温度为220℃-400℃，模具温度为180℃-400℃。进一步地，注射口温度为295℃-320℃，模具温度在230℃-260℃。注射过程中，具有良好流动性的高温树脂熔体在高压下进入陶瓷构件的长条形孔洞内部，与孔洞内壁的含氮化合物发生脂与胺的放热反应，因此树脂液流前端温度不会剧烈下降，而可以长时间持续保持粘度较低的状态，从而顺利进入陶瓷表面和内部的微米级及亚微米级别的孔洞中，在界面形成微米以及亚微米级别的嵌合结构。
为优化树脂的力学性能，也可在树脂中添加一定量的增强组分，增强组分可包括玻璃纤维、碳纤维、玻璃片、碳酸钙、碳酸镁、二氧化硅和滑石中的一种或多种。
本发明一具体实施方式中，选用66wt％的聚对苯二甲酸丁二醇酯(PBT)与34wt％的玻璃纤维作为树脂构件材料。注塑过程中，注射口温度为330℃，模具温度为260℃。
本发明实施方式中，注塑过程完成后，可使用CNC(Computerised Numerical Control，计算机数字控制)等机械加工手段对复合壳体上的树脂部分进行精细结构的加工，得到目标复合壳体。
当然，本发明实施例的陶瓷树脂结合方式也可以进一步与现有其他结合方式结合使用，如进一步与铆接、宏观尺寸孔洞拉胶结合等。
本发明实施例提供的制备方法，在物理嵌合和化学反应的双重作用下，实现了陶瓷与树脂的紧密连接。一方面，通过烧失有机纤维制备获得了深入至陶瓷构件内部的长条形孔洞，树脂渗入长条形孔洞中增强了树脂与陶瓷的结合；另一方面，通过浸渍处理使孔洞中富含含氮化合物，注塑过程中含氮化合物与渗入孔洞中的树脂发生放热反应，以提供热量使注塑树脂液流前端持续保持低粘度流动状态，顺利渗入至长条形孔洞中，一定程度解决树脂液流前端降温导致粘度升高无法顺利渗入至孔洞中的问题；此外，本发明实施例通过烧失有机纤维造孔，不明显破坏陶瓷结构的完整性，而且不需要使用强酸强碱，纤维烧失在陶瓷烧结过程中完成，环保节能。

Claims (27)

  1. 一种陶瓷树脂复合壳体，其特征在于，包括陶瓷构件和注塑成型在所述陶瓷构件上的树脂构件；
    所述陶瓷构件与所述树脂构件结合的表面，具有多个由所述表面延伸至所述陶瓷构件内部的长条形孔洞；所述长条形孔洞为开孔结构，所述长条形孔洞的孔径在700nm-500μm的范围内，至少部分所述长条形孔洞的长度大于100μm且小于或等于1000μm，所述长条形孔洞内填充有构成所述树脂构件的树脂材料。
  2. 如权利要求1所述的陶瓷树脂复合壳体，其特征在于，所述长条形孔洞由有机纤维烧失形成，所述长条形孔洞由所述陶瓷构件表面向所述陶瓷构件内部曲折延伸。
  3. 如权利要求1或2所述的陶瓷树脂复合壳体，其特征在于，所述长条形孔洞任意位置处的孔径相同或基本相同。
  4. 如权利要求1或2所述的陶瓷树脂复合壳体，其特征在于，由所述陶瓷构件表面至所述陶瓷构件内部，所述长条形孔洞的孔径逐渐增大。
  5. 如权利要求1或2所述的陶瓷树脂复合壳体，其特征在于，由所述陶瓷构件表面至所述陶瓷构件内部，所述长条形孔洞的孔径逐渐减小。
  6. 如权利要求1-5任一项所述的陶瓷树脂复合壳体，其特征在于，多个所述长条形孔洞在所述陶瓷构件中的体积占比为1％-35％。
  7. 如权利要求1-6任一项所述的陶瓷树脂复合壳体，其特征在于，所述陶瓷构件与所述树脂构件结合的表面上，多个所述长条形孔洞的面积占比为1％-60％。
  8. 如权利要求1-7任一项所述的陶瓷树脂复合壳体，其特征在于，部分或全部所述长条形孔洞的孔径为15μm-500μm。
  9. 如权利要求1-8任一项所述的陶瓷树脂复合壳体，其特征在于，多个所述长条形孔洞均匀分布在所述陶瓷构件与所述树脂构件结合的表面。
  10. 如权利要求1-9任一项所述的陶瓷树脂复合壳体，其特征在于，所述陶瓷构件与所述树脂构件结合的表面上，还具有多个非长条形孔洞，所述非长条形孔洞中填充有构成所述树脂构件的树脂材料。
  11. 如权利要求1-10任一项所述的陶瓷树脂复合壳体，其特征在于，所述陶瓷构件的材质包括氧化物陶瓷材料、氮化物陶瓷材料和碳化物陶瓷材料中的一种或多种。
  12. 如权利要求1-11任一项所述的陶瓷树脂复合壳体，其特征在于，所述树脂构件的材质为热塑性树脂。
  13. 如权利要求1-12任一项所述的陶瓷树脂复合壳体，其特征在于，所述树脂构件中还包括增强组分，所述增强组分包括玻璃纤维、碳纤维、玻璃片、碳酸钙、碳酸镁、二氧化硅和滑石中的一种或多种。
  14. 一种陶瓷树脂复合壳体的制备方法，其特征在于，包括:
    采用有机纤维作为造孔剂制备具有预设形状的陶瓷构件；所述陶瓷构件预进行注塑的表面，具有多个由所述表面延伸至所述陶瓷构件内部的长条形孔洞；所述长条形孔洞由所述有机纤维烧失形成，所述长条形孔洞为开孔结构，所述长条形孔洞的孔径在700nm-500μm 的范围内，至少部分所述长条形孔洞的长度大于100μm且小于或等于1000μm；
    采用含氮化合物的水溶液对所述陶瓷构件进行浸渍处理，使所述含氮化合物的水溶液进入到所述长条形孔洞中，随后干燥处理，使所述长条形孔洞内壁上附着一层所述含氮化合物；
    将干燥后的陶瓷构件进行注塑处理，并使树脂液进入所述长条形孔洞中与所述含氮化合物发生放热反应，注塑完成后，对树脂部分进行精细结构加工，得到陶瓷树脂复合壳体。
  15. 如权利要求14所述的制备方法，其特征在于，所述含氮化合物包括氨水、肼类化合物及其衍生物、水溶性胺中的一种或多种。
  16. 如权利要求14或15所述的制备方法，其特征在于，所述采用有机纤维作为造孔剂制备具有预设形状的陶瓷构件的具体方法包括注射成型法、流延成型法、3D打印法、热压法和粘浆撒砂法中的一种或多种。
  17. 如权利要求14-16任一项所述的制备方法，其特征在于，所述采用有机纤维作为造孔剂制备具有预设形状的陶瓷构件包括：将陶瓷粉体、有机纤维、粘结剂混合后制备陶瓷构件素坯，再将所述陶瓷构件素坯烧结后得到所述陶瓷构件。
  18. 如权利要求14-17任一项所述的制备方法，其特征在于，所述有机纤维包括可烧失的人造纤维和天然纤维中的至少一种。
  19. 如权利要求14-18任一项所述的制备方法，其特征在于，所述浸渍处理过程在真空条件下进行。
  20. 如权利要求14-19任一项所述的制备方法，其特征在于，所述浸渍处理过程中进行超声振动。
  21. 如权利要求14-20任一项所述的制备方法，其特征在于，所述干燥处理的方式为吹风干燥或冷冻干燥，所述吹风干燥的温度为10℃-80℃。
  22. 一种终端，其特征在于，包括如权利要求1-13任一项所述的陶瓷树脂复合壳体。
  23. 一种手机，其特征在于，包括显示屏、组装在手机外侧的外壳，以及位于所述外壳内部的主板和电池，所述外壳的整体或部分为权利要求1-13任一项所述的陶瓷树脂复合壳体。
  24. 如权利要求23所述的手机，其特征在于，所述外壳包括组装在手机前侧的前盖，组装在手机后侧的后壳，以及位于前盖和后壳之间的中框。
  25. 如权利要求23所述的手机，其特征在于，所述外壳包括组装在手机后侧的后壳。
  26. 如权利要求23所述的手机，其特征在于，所述外壳包括：组装在手机后侧的后壳，以及位于所述显示屏和所述后壳之间的中框。
  27. 如权利要求24或26所述的手机，其特征在于，所述后壳与所述中框为一体结构或分体结构。
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