WO2020010813A1 - 无机非金属与塑料的结合体及其制备方法 - Google Patents

无机非金属与塑料的结合体及其制备方法 Download PDF

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Publication number
WO2020010813A1
WO2020010813A1 PCT/CN2018/124710 CN2018124710W WO2020010813A1 WO 2020010813 A1 WO2020010813 A1 WO 2020010813A1 CN 2018124710 W CN2018124710 W CN 2018124710W WO 2020010813 A1 WO2020010813 A1 WO 2020010813A1
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Prior art keywords
plastic
oxide layer
inorganic non
oxide
treatment
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PCT/CN2018/124710
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English (en)
French (fr)
Inventor
孔德洲
夏庆路
俞胜平
张法亮
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歌尔股份有限公司
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Publication of WO2020010813A1 publication Critical patent/WO2020010813A1/zh

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    • 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
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5035—Silica
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment

Definitions

  • the present invention relates to the technical field of bonded bodies, and more particularly, to a combined body of inorganic nonmetal and plastic and a preparation method thereof.
  • the enclosure should meet the requirements of beautiful appearance and delicate texture while satisfying the non-signal shielding.
  • the outer shell of electronic products mostly uses a combination of non-metallic materials and plastic.
  • non-metallic materials such as ceramics, sapphire, or glass are bonded by means of adhesion or mechanical engagement. But these combined methods have certain defects.
  • Adopting the bonding method on the one hand, during the compounding process of the inorganic non-metallic material and plastic through the adhesive, problems such as glue overflow and poor bonding will affect the stability of the bonded body; on the other hand, the bonding method is affected by The environmental factors are large, and the temperature and the proficiency of the operator are affected to varying degrees.
  • An object of the present invention is to provide a new technical solution of a combination of an inorganic nonmetal and a plastic.
  • a combination of an inorganic nonmetal and a plastic including: an inorganic nonmetal, a plastic, and a multiple oxide layer, the inorganic nonmetal having a first surface, and the multiple oxidation
  • An object layer is formed on the first surface by calcining.
  • the multi-oxide layer is made of silicon oxide and an alkaline oxide.
  • the multi-oxide layer has honeycomb micropores, mesopores, and macropores. One or more of the pore-like structures, the plastic is incorporated in the pore-like structure of the multiple oxide layer.
  • the basic oxide is at least one of sodium oxide or potassium oxide.
  • the regulator is zirconia, titanium oxide or aluminum oxide.
  • the thickness of the multiple oxide layer is 10 nm-100 ⁇ m.
  • the plastic includes a host material and a modified material
  • the main material is at least one of polyethylene terephthalate plastic, polyphenylene sulfide plastic, polybutylene terephthalate plastic, and polyamide plastic;
  • the modified material is any one of glass fiber, carbon fiber, glass flake, calcium carbonate, magnesium carbonate, silica, and talc, and the modified material is added to the host material.
  • the diameter of the pore structure is 1 nm-10 ⁇ m, and the depth is 1-100 ⁇ m.
  • the material of the inorganic non-metal part is olivine, spinel, sapphire, glass or ceramic.
  • a method for preparing a combination of an inorganic nonmetal and a plastic including the following steps:
  • the inorganic non-metal part has a first surface
  • Plastic is injection-molded on the multiple oxide layer to form a combined body.
  • the method further includes: surface pretreatment, the surface pretreatment is used to remove grease on the first surface.
  • the precursor layer is prepared by using any one or more of coating, dipping, and spraying processes.
  • the temperature of the heat treatment is 500-1200 ° C.
  • the surface treatment is an alkali etching treatment
  • the temperature of the alkali etching treatment is 50-100 ° C
  • the treatment time is 10min-2h.
  • a pore-clearing treatment is further included, and the pore-clearing treatment is used to remove powdery particles in the pore-like structure.
  • the temperature of the injection mold is 100-280 ° C.
  • the injection pressure is 30-80 Mpa
  • the injection speed is 10-20 mm / s.
  • the invention provides a technical solution of a combination of an inorganic non-metal and a plastic.
  • the combination is formed by forming a multi-oxide layer on the surface of an inorganic non-metal part, and forming a honeycomb-shaped microporous, intermediary layer on the multi-oxide layer.
  • One or more pore-like structures in holes and macropores, and then the plastic is combined with the multiple oxide layer by injection molding.
  • the porous structure can not only improve the bonding force between the plastic and the inorganic non-metallic part, but also not cause damage to the structure of the inorganic non-metallic part, and will not affect the mechanical properties of the inorganic non-metallic material.
  • the plastic injection-molded in the honeycomb porous structure increases the bonding area between the plastic and the multiple oxide layer. The two are tightly combined by means of mechanical occlusion, which significantly improves the bonding force between the inorganic non-metallic part and the plastic.
  • FIG. 1 is a schematic structural diagram of a combination of an inorganic nonmetal and a plastic according to an embodiment of the present invention
  • FIG. 2 is a schematic scanning electron microscope diagram of a combination of an inorganic non-metal and a plastic according to an embodiment of the present invention
  • FIG. 3 is a flowchart of a method for preparing a combination of an inorganic non-metal and a plastic according to an embodiment of the present invention.
  • any specific value should be construed as exemplary only and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values.
  • FIG. 1 shows a schematic structural diagram of a combination of an inorganic non-metal and plastic
  • FIG. 2 shows a scanning electron microscope schematic of a combination of an inorganic non-metal and plastic
  • FIG. 3 is a flow chart of a method for preparing the combination of an inorganic non-metal and plastic Illustration.
  • the invention provides a combination of an inorganic non-metal and a plastic.
  • the combination includes an inorganic non-metal, a plastic, and a multiple oxide layer.
  • Inorganic non-metallic parts are processed parts made of inorganic non-metallic materials.
  • Inorganic non-metallic materials are widely used in various industries due to their high melting point, high strength, corrosion resistance and good oxidation resistance. In practical applications, it is often necessary to combine inorganic non-metallic parts with plastics.
  • the inorganic non-metallic part 10 has a first surface 31, and the first surface 31 is used for bonding with the plastic 20.
  • a tightly-bonded multi-oxide layer 30 is formed on the first surface 31.
  • the multi-oxide layer 30 is formed on the first surface 31 by calcining.
  • the multi-oxide layer 30 is formed by oxidation.
  • the silicon oxide is mixed with a plurality of types of basic oxides to form a film-forming slurry, which is disposed on the first surface 31 of the inorganic non-metallic part 10 after a certain treatment.
  • the multi-element oxide layer 30 has one or more pore-like structures 32 among honeycomb micropores, mesopores, and macropores.
  • the microstructure of the pore-like structure 32 is nano-sized or micro-sized.
  • the pore-like structure increases the bonding area between plastic and inorganic metal parts.
  • Plastic injection molding in the pore-like structure of the multi-oxide layer can cause the inorganic non-metallic parts and plastic to mechanically engage during the bonding process. , Thereby effectively improving the binding force between inorganic non-metallic parts and plastics.
  • the inorganic non-metallic part and the plastic are tightly bonded, and the combined inorganic non-metallic part can maintain superior mechanical properties.
  • the basic oxide is at least one of sodium oxide or potassium oxide.
  • the alkaline oxide helps prevent cracking of the multiple oxide layer formed on the first surface of the inorganic non-metal part during the post-processing.
  • the multiple oxide layer further includes a regulator, and the regulator is zirconia, titanium oxide, or aluminum oxide. Adding a regulator is beneficial to tightly bond the inorganic non-metallic parts and the multiple oxide layer.
  • This embodiment shows several optional regulators, but the type of the regulator is not limited. Those skilled in the art can select a suitable regulator according to the type of the inorganic non-metal part.
  • the thickness of the multiple oxide layer is 10 nm-100 ⁇ m. It can be understood that a variety of pore-like structures are formed on the multi-oxide layer, and the multi-oxide layers having different thicknesses can be processed to form pore-like structures with different pore diameters and depths.
  • the material of the inorganic non-metal part provided in this embodiment is olivine, spinel, sapphire, glass or ceramic.
  • the above materials are all rigid inorganic non-metallic materials.
  • the combination formed by combining the rigid inorganic non-metallic materials with plastics can give full play to the characteristics of the beautiful appearance of the inorganic non-metallic materials without signal shielding, and at the same time have high hardness. , Applied to the shell or parts of electronic products, not easy to produce scratches.
  • one or more pore-like structures having honeycomb-shaped micropores, mesopores, and macropores are formed on the multi-oxide layer of the inorganic non-metallic part.
  • the diameter is 1 nm-10 ⁇ m, and the depth is 1-100 ⁇ m.
  • the honeycomb-like pore structure may be formed by one or more of micropores, mesopores, and macropores having different diameters and depths through alkali etching treatment or other surface treatment methods, which is not limited in this embodiment.
  • the honeycomb pore structure increases the bonding strength of plastic and inorganic non-metallic parts.
  • an uneven structure is formed on the multiple oxide layer of the inorganic non-metal part, and plastic can be filled in the uneven structure on the multiple oxide layer to achieve bonding.
  • the plastic includes a host material and a modified material, wherein the host material is polyethylene terephthalate plastic, polyphenylene sulfide plastic, polybutylene terephthalate plastic At least one of polyamide plastics.
  • the host material has good electrical insulation, heat resistance and strength, and is easy to process.
  • a modified material is further added to the plastic in this embodiment.
  • the modified material can be used as a filler and filled in the host material to enhance the performance of the host material and expand the application range of the host material.
  • the modified material is any one of glass fibers, carbon fibers, glass flakes, calcium carbonate, magnesium carbonate, silica, and talc.
  • the added modified material can reduce the thermal expansion coefficient between the inorganic non-metallic parts and the plastic, prevent the plastic from shrinking, warping or falling off; meanwhile, it can improve the bending resistance of the plastic and help strengthen the combination of the inorganic non-metallic parts and the plastic .
  • a method for preparing a combined body is also provided, which is applied to the foregoing combined body. Referring to FIG. 3, the method includes the following steps:
  • the inorganic non-metal part has a first surface
  • the material of the inorganic non-metallic part is olivine, spinel, sapphire, glass or ceramic.
  • the method further includes: a surface pretreatment, the surface pretreatment is used to remove grease on the first surface.
  • the first surface of the ceramic substrate can be treated with a degreaser or degreaser for a certain period of time, such as: 300s; finally, it can be washed in deionized water and completely dried.
  • a precursor layer is prepared on the first surface, and the precursor layer is heat-treated to obtain a multiple oxide layer;
  • the precursor layer of the multiple oxide includes zirconia nanospheres, zirconium hydroxide, zirconium n-propoxide, zirconia dichloride, butyl titanate, titanium oxide nanospheres, ammonium aluminum sulfate, silicon oxide nanospheres, and silicon.
  • the prepared film-forming slurry is set on the first surface by one or more methods of coating, dipping, and spraying to form a precursor layer.
  • the temperature at which the precursor layer is heat-treated is 500-1200 ° C.
  • the temperature of performing alkaline etching treatment on the multiple oxide layer is 50-100 ° C, and the treatment time is 10min to 2h.
  • the porous oxide layer is cleaned by ultrasonic cleaning.
  • the surface of the multiple oxide layer will have powder particles falling off, forming honeycomb-shaped micropores, mesopores and macropores.
  • One or more porous structures are provided.
  • Nano injection molding is used to inject plastic onto the multiple oxide layers of inorganic non-metallic materials.
  • the injection temperature is controlled at 100-280 ° C, and the plastic is injected into the porous structure of the multi-oxide layer at an injection pressure of 30-80 Mpa and an injection speed of 10-20 mm / s.
  • plastic is made by adding a modified material to the host material.
  • the main material is at least one of polyethylene terephthalate plastic, polyphenylene sulfide plastic, polybutylene terephthalate plastic, and polyamide plastic.
  • the host material has good electrical insulation, heat resistance and strength, and is easy to process.
  • the modified material is any one of glass fibers, carbon fibers, glass flakes, calcium carbonate, magnesium carbonate, silica, and talc.
  • the modified material is added to the host material as a filler, which can reduce the thermal expansion coefficient between the inorganic non-metal parts and the plastic, prevent the plastic from shrinking, warping, or falling off; at the same time, it can improve the bending resistance of the plastic and help To enhance the combination of inorganic non-metallic parts and plastics.
  • the inorganic non-metal part is a zirconia ceramic sheet.
  • the zirconia ceramic sheet has a first surface, and the first surface is used for bonding with plastic to form a combined body.
  • the first surface is pretreated with a degreasing agent or a degreasing agent to remove oily dirt on the first surface.
  • the first surface of the ceramic substrate can be treated with a degreaser or degreaser for a certain period of time, such as: 300s; finally, it can be washed in deionized water and completely dried.
  • the prepared slurry is placed in a spraying device, and then sprayed on the first surface of the zirconia ceramic sheet to form a film, and the film thickness is controlled to be 5-20 ⁇ m, and then dried at 50 ° C for 2 hours.
  • Multilayer oxide precursor layer is controlled to be 5-20 ⁇ m, and then dried at 50 ° C for 2 hours.
  • the inorganic thin film is subjected to a high-temperature hardening treatment.
  • the high temperature treatment is divided into three steps.
  • heat preservation is required at 280 ° C for 3 hours to discharge low molecular weight organic matter.
  • calcination is performed at 750 ° C for 5 hours to solidify the film.
  • the temperature is raised to 1100 Incubate at °C for 1h to ensure that the film is tightly bonded to the zirconia ceramic sheet.
  • a zirconia ceramic sheet having a porous structure was placed in an injection molding mold, and a polybutylene terephthalate (PBT) resin composition containing 20% glass fiber was contained in an injection-molded plastic raw material.
  • PBT polybutylene terephthalate
  • the zirconia ceramic sheet and Plastic test pieces are fixed on a universal material testing machine for product tensile testing. Six groups of test pieces are tested respectively, and the average bonding strength of the test pieces is about 30 MPa. The test results are shown in Table 1 below.
  • the test piece After the test piece is pulled off, more plastic remains on the multi-oxide layer, indicating that the surface multi-oxide layer has better pore formation effect.
  • the plastic is embedded in the porous structure of the multi-oxide layer, and the anchor is firmly anchored in the multi-oxide. In the inorganic non-metallic part of the material layer.
  • the inorganic non-metal part is a glass sheet, the glass sheet has a first surface, and the first surface is used for bonding with plastic to form a combined body.
  • the first surface is pretreated with a degreasing agent or a degreasing agent to remove oily dirt on the first surface.
  • the first surface of the ceramic substrate can be treated with a degreaser or degreaser for a certain period of time, such as: 300s; finally, it can be washed in deionized water and completely dried.
  • n-butanol In a beaker, add 50 parts of n-butanol, 5 parts of diethanolamine, 50 parts of tetrabutyl titanate, and 200 parts of zirconium n-propoxide, and mix them by stirring; weigh 20 parts of nanometer Silica microspheres, 50 parts of nano-silica microspheres, put into a ball mill tank, then add 50 parts of n-butanol, and add 2 parts of silane coupling agent to n-butanol, and then add 5 parts of Dispersant; Pour the solution in the beaker into a ball mill tank and perform ball milling on a horizontal ball mill for 0.5 h to control the viscosity of the slurry below 500 cps.
  • the glass flakes are immersed in the prepared slurry, and then dried at 50 ° C. for 2 hours to prepare a precursor layer of multiple oxides.
  • the inorganic thin film is subjected to a high-temperature hardening treatment.
  • the high temperature treatment is divided into three steps.
  • the first step requires holding at 280 ° C for 3 hours to discharge low molecular weight organics.
  • the second step is calcination at 750 ° C for 5 hours to solidify the film.
  • the last step is to raise the temperature to 1000 ° C. 1h to ensure that the film is tightly bonded to the glass sheet.
  • the glass sheet with the porous structure formed was placed in an injection molding mold.
  • the plastic raw material for injection molding contained 20% glass fiber of polybutylene terephthalate (PBT) resin composition.
  • PBT polybutylene terephthalate
  • the glass sheet and the test piece of plastic The product was fixed on a universal material testing machine for tensile testing. Six groups of test pieces were tested. The average bonding strength of the test pieces was about 30 MPa. The test results are shown in Table 2 below.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Injection Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种无机非金属与塑料的结合体及其制备方法，该结合体，包括：无机非金属件（10）、塑料（20）以及多元氧化物层（30），所述无机非金属件（10）具有第一表面（31），所述多元氧化物层（30）通过煅烧的方式形成在所述第一表面上（31），所述多元氧化物层（30）由氧化硅以及碱性氧化物制成；所述多元氧化物层（30）具有蜂窝状的微孔、介孔、大孔中的一种或多种孔状结构（32），所述塑料（20）结合在所述多元氧化物层（30）的孔状结构（32）中。提供的结合体，无机非金属与塑料结合形成的结合件，结合强度高。

Description

无机非金属与塑料的结合体及其制备方法 技术领域
本发明涉及结合体技术领域，更具体地，涉及一种无机非金属与塑料的结合体及其制备方法。
背景技术
随着手机、平板电脑等电子产品的快速发展，用户对电子产品的外壳、构件提出了更高的要求。外壳在满足无信号屏蔽的同时，还应具备外表美观、质感细腻等要求。
目前，电子产品的外壳多采用非金属材料和塑料的结合体。例如，将陶瓷、蓝宝石或者玻璃等无机非金属材料通过粘接或者机械卡合等方式结合。但这些结合方式具备一定的缺陷。
采用粘接的方式，一方面，无机非金属材料与塑料通过粘接剂在复合的过程中会出现溢胶、结合不良等问题，影响结合体的稳定性；另一方面，粘接的方式受环境影响因素大，温度以及操作者的熟练程度都有不同程度的影响。
另外还可以通过机械卡合的方式，将无机非金属件与塑料以特定形态卡合在一起。但这种结合的方式，只适用于结构简单的无机非金属件和塑料，二者结合强度低，结合处存在缝隙，影响产品美观。
发明内容
本发明的一个目的是提供一种无机非金属与塑料的结合体的新技术方案。
根据本发明的第一方面，提供了一种无机非金属与塑料的结合体，包括：无机非金属件、塑料以及多元氧化物层，所述无机非金属件具有第一表面，所述多元氧化物层通过煅烧的方式形成在所述第一表面上，所述多 元氧化物层由氧化硅以及碱性氧化物制成；所述多元氧化物层具有蜂窝状的微孔、介孔、大孔中的一种或多种孔状结构，所述塑料结合在所述多元氧化物层的孔状结构中。
可选地，所述碱性氧化物是氧化钠或者氧化钾中的至少一种。
可选地，还包括：调节剂，所述调节剂是氧化锆、氧化钛或者氧化铝。
可选地，所述多元氧化物层的厚度为10nm-100μm。
可选地，所述塑料包括主体材料和改性材料，
其中，所述主体材料是聚对苯二甲酸乙二醇酯塑料、聚亚苯基硫醚塑料、聚对苯二甲酸丁二醇脂塑料、聚酰胺塑料中的至少一种；
所述改性材料是玻璃纤维、碳纤维、玻璃片、碳酸钙、碳酸镁、二氧化硅、滑石中的任意一种，所述改性材料添加在所述主体材料中。
可选地，所述孔状结构的直径是1nm-10μm，深度是1-100μm。
可选地，所述无机非金属件的材质是橄榄石、尖晶石、蓝宝石、玻璃或陶瓷。
根据本发明的第二方面，提供一种无机非金属与塑料的结合体的制备方法，包括以下步骤：
提供一种无机非金属件，所述无机非金属件具有第一表面；
在所述第一表面上制备前驱体层，对所述前驱体层进行热处理，得到多元氧化物层；
对所述多元氧化物层进行表面处理，在所述多元氧化物表面形成蜂窝状的微孔、介孔、大孔中的一种或多种孔状结构；
将塑料注塑在所述多元氧化物层上，形成结合体。
可选地，在对所述无机非金属件的第一表面处理之前，还包括：表面预处理，所述表面预处理用于去除所述第一表面上的油垢。
可选地，所述前驱体层的制备采用涂覆、浸渍、喷涂工艺中的任意一种或多种。
可选地，所述热处理的温度为500-1200℃。
可选地，所述表面处理是碱蚀处理，所述碱蚀处理的温度为50-100℃，处理时间为10min-2h。
可选地，在所述碱蚀处理后，还包括清孔处理，所述清孔处理用于清除所述孔状结构中的粉状颗粒。
可选地，所述注塑件注塑在所述多元氧化物层上的过程中，注塑模具的温度为100-280℃，注射压力为30-80Mpa，注射速度为10-20mm/s。
本发明提供了一种无机非金属与塑料的结合体的技术方案，该结合体是通过在无机非金属件表面形成多元氧化物层，并在多元氧化物层上形成蜂窝状的微孔、介孔、大孔中的一种或多种孔状结构，然后通过注塑成型的方式，将塑料与多元氧化物层结合。该多孔结构不仅能够提高塑料与无机非金属件之间的结合力，而且对无机非金属件的结构不会造成损害，不会对无机非金属材料的力学性能产生影响。蜂窝状多孔结构中注塑的塑料，增加了塑料与多元氧化物层之间的结合面积，二者通过机械咬合的方式紧密结合，显著提高了无机非金属件和塑料之间的结合力。
通过以下参照附图对本发明的示例性实施例的详细描述，本发明的其它特征及其优点将会变得清楚。
附图说明
被结合在说明书中并构成说明书的一部分的附图示出了本发明的实施例，并且连同其说明一起用于解释本发明的原理。
图1是本发明实施例提供的无机非金属与塑料的结合体的结构示意图；
图2是本发明实施例提供的无机非金属与塑料的结合体的扫描电镜示意图；
图3是本发明实施例提供的无机非金属与塑料的结合体的制备方法的流程图。
具体实施方式
现在将参照附图来详细描述本发明的各种示例性实施例。应注意到：除非另外具体说明，否则在这些实施例中阐述的部件和步骤的相对布置、数字表达式和数值不限制本发明的范围。
以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作 为对本发明及其应用或使用的任何限制。
对于相关领域普通技术人员已知的技术、方法和设备可能不作详细讨论，但在适当情况下，所述技术、方法和设备应当被视为说明书的一部分。
在这里示出和讨论的所有例子中，任何具体值应被解释为仅仅是示例性的，而不是作为限制。因此，示例性实施例的其它例子可以具有不同的值。
应注意到：相似的标号和字母在下面的附图中表示类似项，因此，一旦某一项在一个附图中被定义，则在随后的附图中不需要对其进行进一步讨论。
本发明提供一种结合体，可用于电子产品的外壳或零部件。该结合体能够满足无机非金属件与塑料结合的强度要求，同时不会对无机非金属件的表面造成损伤，影响无机非金属件的力学性能。图1示出无机非金属与塑料的结合体的结构示意图，图2示出了无机非金属与塑料的结合体的扫描电镜示意图，图3是无机非金属与塑料的结合体的制备方法的流程图。现以图1至图3为例，对本发明的结合体的结构特征、原理及其制备方法等进行描述。
本发明提供一种无机非金属与塑料的结合体，该结合体包括：无机非金属件、塑料以及多元氧化物层。无机非金属件是由无机非金属材料制成的加工件，无机非金属材料由于具备高熔点、高强度、耐腐蚀性以及良好的抗氧化性广泛的应用于各个行业。在实际应用中，常常需要将无机非金属件与塑料结合。
如图1所示，所述无机非金属件10具有第一表面31，所述第一表面31是用于与塑料20相互结合。在所述第一表面31上形成有结合紧密的多元氧化物层30，所述多元氧化物层30通过煅烧的方式形成在所述第一表面31上，所述多元氧化物层30是由氧化硅以及碱性氧化物制成。通过将氧化硅以及多种碱性氧化物混合，制成成膜浆料，在经过一定的处理，设置在无机非金属件10的第一表面31上。
如图1和图2所示，所述多元氧化物层30具有蜂窝状的微孔、介孔、大孔中的一种或多种孔状结构32，直径不同的孔状结构32分布在多元氧 化物层30上，所述孔状结构32的微观结构是纳米尺寸或微米尺寸。所述孔状结构增加了塑料与无机分金属件之间的结合面积，塑料注塑在所述多元氧化物层的孔状结构中，可以使无机非金属件与塑料在结合的过程中产生机械咬合，从而有效提升无机非金属件与塑料之间的结合力。本发明提供的结合体，无机非金属件与塑料之间结合紧密，结合后的无机非金属件能够保持较优的力学性能。
可选地，所述碱性氧化物是氧化钠或者氧化钾中的至少一种。碱性氧化物有助于在后期处理过程中，防止形成在无机非金属件第一表面上的多元氧化层开裂。
另外，多元氧化物层中还包括：调节剂，调节剂是氧化锆、氧化钛或者氧化铝。添加调节剂有利于使无机非金属件和多元氧化物层结合紧密。本实施例示出了几种可选的调节剂，但对调节剂的种类不做限定，本领域技术人员可根据无机非金属件的种类，选择适宜的调节剂。
具体地，所述多元氧化物层的厚度为10nm-100μm。可以理解的，多种孔状结构是形成在多元氧化物层上，不同厚度的多元氧化物层经过处理，可以对应形成不同孔径和深度的孔状结构。
本实施例提供的无机非金属件的材质是橄榄石、尖晶石、蓝宝石、玻璃或陶瓷。上述材料都属于硬质无机非金属材料，将硬质的无机非金属材料与塑料结合形成的结合体，可充分发挥无机非金属材料外表美观、不产生信号屏蔽的特性，同时具备较高的硬度，应用于电子产品外壳或零部件上，不易产生划痕。
在一种可选的实施方式中，无机非金属件的多元氧化物层上形成具有蜂窝状的微孔、介孔、大孔中的一种或多种孔状结构，所述孔状结构的直径是1nm-10μm，深度是1-100μm。该蜂窝状的孔状结构可通过碱蚀处理或其他表面处理方式，形成直径和深度不同的微孔、介孔、大孔中的一种或者多种，本实施例对此不做限制。蜂窝状的孔状结构，增加了塑料与无机非金属件的结合强度。
在另一种可选的实施方式中，无机非金属件的多元氧化物层上形成有凹凸不平的结构，塑料可填充在多元氧化物层上凹凸不平的结构中，从而 实现结合。
进一步地，所述塑料包括主体材料和改性材料，其中，所述主体材料是聚对苯二甲酸乙二醇酯塑料、聚亚苯基硫醚塑料、聚对苯二甲酸丁二醇酯塑料、聚酰胺塑料中的至少一种。上述主体材料具备较好的电绝缘性、耐热性以及强度，便于加工。
为了进一步提高塑料的力学性能和机械性能，本实施例在塑料中还添加有改性材料。所述改性材料可作为填料，填充在主体材料中，以增强主体材料的性能，扩大主体材料的应用范围。
例如，所述改性材料是玻璃纤维、碳纤维、玻璃片、碳酸钙、碳酸镁、二氧化硅、滑石中的任意一种。添加的改性材料可以降低无机非金属件与塑料之间的热膨胀系数，防止塑料发生收缩、翘曲或者脱落；同时可以提升塑料的抗弯性能，有助于增强无机非金属件与塑料的结合。
本实施例的另一方面，还提供一种结合体的制备方法，应用于上述结合体，参见图3，该方法包括如下步骤：
S1、提供一种无机非金属件，所述无机非金属件具有第一表面；
其中，无机非金属件的材质是橄榄石、尖晶石、蓝宝石、玻璃或陶瓷。在对所述无机非金属件的第一表面处理之前，还包括：表面预处理，所述表面预处理用于去除所述第一表面上的油垢。在表面预处理过程中可以采用除油剂或者脱脂剂对陶瓷基体的第一表面处理一定的时间，如：300s；最后放入去离子水中清洗并完全烘干。
S2、在所述第一表面上制备前驱体层，对所述前驱体层进行热处理，得到多元氧化物层；
所述多元氧化物的前驱体层包含氧化锆纳米球、氢氧化锆、正丙醇锆、二氯氧化锆、钛酸丁酯、氧化钛纳米球、硫酸铝铵、氧化硅纳米球、正硅酸乙酯、正丙醇、油酸、邻苯二甲酸二辛脂、氧化锆、碳酸钙、碳酸钾、碳酸钠、氢氧化钠、氢氧化钾中多种的组合。上述物质混合搅拌后，即可配制好成膜浆料。
将配制好的成膜浆料采用涂覆、浸渍、喷涂中的一种或几种方式设置在所述第一表面上，形成前驱体层。
对所述前驱体层进行热处理的温度为500-1200℃。
S3、对所述多元氧化物层进行表面处理，在所述多元氧化物表面形成蜂窝状的微孔、介孔、大孔中的一种或多种孔状结构；
对该多元氧化物层进行碱蚀处理的温度在50-100℃，处理时间在10min至2h。
在碱蚀处理之后，采用超声波清孔的方式，对多元氧化物层进行清孔处理，多元氧化物层的表面会有粉状颗粒脱落，形成具有蜂窝状的微孔、介孔、大孔中的一种或多种孔状结构。
S4、将塑料注塑在所述多元氧化物层上，形成结合体。
采用纳米注塑的方式，将塑料注塑在无机非金属材料的多元氧化物层上。注塑的温度控制在100-280℃，以30-80Mpa的注射压力、10-20mm/s的注射速度将塑料注塑到多元氧化物层的孔状结构中。
其中，塑料是通过在主体材料中添加了改性材料制成的。主体材料是聚对苯二甲酸乙二醇酯塑料、聚亚苯基硫醚塑料、聚对苯二甲酸丁二醇脂塑料、聚酰胺塑料中的至少一种。主体材料具备较好的电绝缘性、耐热性以及强度，便于加工。所述改性材料是玻璃纤维、碳纤维、玻璃片、碳酸钙、碳酸镁、二氧化硅、滑石中的任意一种。所述改性材料作为填料添加在所述主体材料中，可以降低无机非金属件与塑料之间的热膨胀系数，防止塑料发生收缩、翘曲或者脱落；同时可以提升塑料的抗弯性能，有助于增强无机非金属件与塑料的结合。
实施例1
提供一种无机非金属件，该无机非金属件是氧化锆陶瓷片，所述氧化锆陶瓷片具有第一表面，所述第一表面用于与塑料结合，以形成结合体。
首先，采用除油剂或脱脂剂对所述第一表面进行预处理，去除第一表面上的油垢。
在表面预处理过程中可以采用除油剂或者脱脂剂对陶瓷基体的第一表面处理一定的时间，如：300s；最后放入去离子水中清洗并完全烘干。
其次，配制成膜浆料。
在烧杯中加入50份的正丁醇，5份的二乙醇胺，50份的钛酸四丁酯，200份的正丙醇锆，通过搅拌的方式将其混合均匀；称量20份的纳米二氧化钛微球、50份的纳米二氧化硅微球，放入球磨罐中2份的氢氧化钾、5份的碳酸钙，再加入50份的正丁醇，并在正丁醇中加入2份的硅烷偶联剂，5份的分散剂；最后，将烧杯中的溶液倒入球磨罐中，在卧式球磨机上进行球磨处理0.5h，控制浆料的粘度在500cps以下。
再次，制备无机薄膜。
将制备好的浆料置于喷涂设备中，然后在氧化锆陶瓷片的第一表面上进行喷涂成膜，控制好膜厚在5-20μm，然后在50℃下烘干2h，即可制成多元氧化物的前驱体层。
然后，对无机薄膜进行高温硬化处理。
高温处理分为三步，第一步，需要在280℃下进行保温3h，以排出低分子量的有机物；第二步，在750℃下进行煅烧5h，对薄膜进行固化；最后一步，升温至1100℃保温1h，以保证薄膜与氧化锆陶瓷片结合紧密。
接着，制备纳米多孔结构。
先配制一定量的氢氧化钠、氯化钾等的混合溶液，加热至90℃，然后将氧化锆陶瓷片放置在溶液中浸泡1h，然后将氧化锆陶瓷片置于超声波清洗机中5min，多元氧化物层上会有粉状颗粒脱落，形成有多孔结构，用去离子水对氧化锆陶瓷片进行清洗并烘干。
最后，纳米注塑成型。
将形成有多孔结构的氧化锆陶瓷片置于注塑成型模具内，注塑的塑料原料中含有20％玻璃纤维的聚对苯二甲酸丁二醇酯(PBT)树脂组合物，将氧化锆陶瓷片和塑料的测试片固定于万能材料试验机上进行产品拉伸测试，分别测试6组测试片，测试片平均结合强度约为30MPa，测试结果如下表1所示。
Figure PCTCN2018124710-appb-000001
测试片拉断后，多元氧化物层上残留较多的塑料，说明表面多元氧化物层上成孔效果较好，塑料嵌入到多元氧化物层的多孔结构内，牢牢的锚栓于在多元氧化物层的无机非金属件内。
实施例2
提供一种无机非金属件，该无机非金属件是玻璃片，所述玻璃片具有第一表面，所述第一表面用于与塑料结合，以形成结合体。
首先，采用除油剂或脱脂剂对所述第一表面进行预处理，去除第一表面上的油垢。
在表面预处理过程中可以采用除油剂或者脱脂剂对陶瓷基体的第一表面处理一定的时间，如：300s；最后放入去离子水中清洗并完全烘干。
其次，配制成膜浆料。
在烧杯中加入50份的正丁醇，5份的二乙醇胺，50份的钛酸四丁酯，200份的正丙醇锆，通过搅拌的方式将其混合均匀；称量20份的纳米二氧化硅微球、50份的纳米二氧化硅微球，放入球磨罐中，接着加入50份的正丁醇，并在正丁醇中加入2份的硅烷偶联剂，然后加入5份的分散剂；将烧杯中的溶液倒入球磨罐中，在卧式球磨机上进行球磨处理0.5h，控制浆料的粘度在500cps以下。
再次，制备无机薄膜。
将玻璃片浸渍在制备好的浆料中，然后在50℃下烘干2h，即可制成多元氧化物的前驱体层。
然后，对无机薄膜进行高温硬化处理。
高温处理分为三步，第一步，需要在280℃下进行保温3h，以排出低分子量的有机物，第二步在750℃下进行煅烧5h，对薄膜进行固化，最后一步升温至1000℃保温1h，以保证薄膜与玻璃片结合紧密。
接着，制备纳米多孔结构。
先配制一定量的氢氧化钾、氯化钾的混合溶液，加热至90℃，然后将玻璃片放置在溶液中浸泡1h，然后用去离子水清洗，烘干备用。
最后，纳米注塑成型。
将形成有多孔结构的玻璃片置于注塑成型模具内，注塑的塑料原料中含有20％玻璃纤维的聚对苯二甲酸丁二醇酯(PBT)树脂组合物，将玻璃片和塑料的测试片固定于万能材料试验机上进行产品拉伸测试，分别测试6组测试片，测试片平均结合强度约为30MPa，测试结果如下表2所示。
Figure PCTCN2018124710-appb-000002
测试片拉断后，多元氧化物层上残留较多的塑料，说明该多元表面氧化物层成孔效果较好，塑料嵌入到多元氧化物层的多孔结构内，牢牢的锚栓于在多元氧化物层的基材内。
虽然已经通过例子对本发明的一些特定实施例进行了详细说明，但是本领域的技术人员应该理解，以上例子仅是为了进行说明，而不是为了限制本发明的范围。本领域的技术人员应该理解，可在不脱离本发明的范围和精神的情况下，对以上实施例进行修改。本发明的范围由所附权利要求来限定。

Claims (14)

  1. 一种无机非金属与塑料的结合体，其特征在于，包括：无机非金属件、塑料以及多元氧化物层，
    所述无机非金属件具有第一表面，所述多元氧化物层通过煅烧的方式形成在所述第一表面上，所述多元氧化物层由氧化硅以及碱性氧化物制成；
    所述多元氧化物层具有蜂窝状的微孔、介孔、大孔中的一种或多种孔状结构，所述塑料结合在所述多元氧化物层的孔状结构中。
  2. 根据权利要求1所述的结合体，其特征在于，所述碱性氧化物是氧化钠或者氧化钾中的至少一种。
  3. 根据权利要求1所述的结合体，其特征在于，还包括：调节剂，所述调节剂是氧化锆、氧化钛或者氧化铝。
  4. 根据权利要求1所述的结合体，其特征在于，所述多元氧化物层的厚度为10nm-100μm。
  5. 根据权利要求1所述的结合体，其特征在于，所述塑料包括主体材料和改性材料，
    其中，所述主体材料是聚对苯二甲酸乙二醇酯塑料、聚亚苯基硫醚塑料、聚对苯二甲酸丁二醇脂塑料、聚酰胺塑料中的至少一种；
    所述改性材料是玻璃纤维、碳纤维、玻璃片、碳酸钙、碳酸镁、二氧化硅、滑石中的任意一种，所述改性材料添加在所述主体材料中。
  6. 根据权利要求1所述的结合体，其特征在于，所述孔状结构的直径是1nm-10μm，深度是1-100μm。
  7. 根据权利要求1所述的结合体，其特征在于，所述无机非金属件的材质是橄榄石、尖晶石、蓝宝石、玻璃或陶瓷。
  8. 一种如权利要求1-7任一所述的结合体的制备方法，其特征在于，包括以下步骤：
    提供一种无机非金属件，所述无机非金属件具有第一表面；
    在所述第一表面上制备前驱体层，对所述前驱体层进行热处理，得到多元氧化物层；
    对所述多元氧化物层进行表面处理，在所述多元氧化物表面形成蜂窝状的微孔、介孔、大孔中的一种或多种孔状结构；
    将塑料注塑在所述多元氧化物层上，形成结合体。
  9. 根据权利要求8所述的制备方法，其特征在于，
    在对所述无机非金属件的第一表面处理之前，还包括：表面预处理，所述表面预处理用于去除所述第一表面上的油垢。
  10. 根据权利要求8所述的制备方法，其特征在于，所述前驱体层的制备采用涂覆、浸渍、喷涂工艺中的任意一种或多种。
  11. 根据权利要求8所述的制备方法，其特征在于，所述热处理的温度为500-1200℃。
  12. 根据权利要求8所述的制备方法，其特征在于，所述表面处理是碱蚀处理，所述碱蚀处理的温度为50-100℃，处理时间为10min-2h。
  13. 根据权利要求12所述的制备方法，其特征在于，在所述碱蚀处理后，还包括清孔处理，所述清孔处理用于清除所述孔状结构中的粉状颗粒。
  14. 根据权利要求8所述的制备方法，其特征在于，所述注塑件注塑在所述多元氧化物层上的过程中，注塑模具的温度为100-280℃，注射压力为30-80Mpa，注射速度为10-20mm/s。
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