WO2019237692A1 - 一种多色氧化锆陶瓷片及其制备方法和应用 - Google Patents

一种多色氧化锆陶瓷片及其制备方法和应用 Download PDF

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WO2019237692A1
WO2019237692A1 PCT/CN2018/121026 CN2018121026W WO2019237692A1 WO 2019237692 A1 WO2019237692 A1 WO 2019237692A1 CN 2018121026 W CN2018121026 W CN 2018121026W WO 2019237692 A1 WO2019237692 A1 WO 2019237692A1
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slurry
yttrium
ceramic sheet
praseodymium
zirconia ceramic
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French (fr)
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黄荣厦
刘胜岚
李文杰
叶顺达
林华泰
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Guangdong University of Technology
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Guangdong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • C04B35/488—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/29—Producing shaped prefabricated articles from the material by profiling or strickling the material in open moulds or on moulding surfaces
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • C04B35/488—Composites
    • C04B35/4885—Composites with aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • 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
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
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    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties
    • C04B2235/9661—Colour

Definitions

  • the invention belongs to the technical field of functional ceramics, and more particularly, relates to a multi-colored zirconia ceramic sheet, a preparation method and application thereof.
  • zirconia is considered to be one of the ideal materials for the back cover of mobile phones because of its advantages such as high fracture strength, high fracture toughness, and high hardness. And has been gradually applied to mobile phones or wearable products.
  • the color of the back cover of the current zirconia ceramic mobile phone is basically a single color.
  • patent CN104003714B mentions a method for preparing multi-color mobile phone parts by using zirconia ceramics. This method can prepare multi-color mobile phone parts.
  • the so-called multiple colors in this patent means that multiple colors can be prepared for mobile phone parts, but each mobile phone part has only a single color (such as black, titanium silver, white, pink, etc.). If a single zirconia ceramic mobile phone component can have multiple colors at the same time, it will make the product more selective and meet a wider range of needs.
  • the primary object of the present invention is to provide a multicolor zirconia ceramic sheet.
  • Another object of the present invention is to provide a method for preparing the multi-colored zirconia ceramic sheet.
  • Yet another object of the present invention is to provide an application of the above-mentioned multi-colored zirconia ceramic sheet.
  • a multi-colored zirconia ceramic sheet is made of yttrium-stabilized zirconia powder as a main raw material, and by adding a reinforcing agent, a toner, a pH adjuster, an adhesive, a plasticizer, and a dispersant And anhydrous ethanol-butanone azeotrope to obtain a single-color cast slurry by ball milling; a multi-channel cast method was used to prepare a multi-color zirconia ceramic green tape and cut it into The plain green sheet is shaped by warm isostatic pressing to obtain a three-dimensional multi-pigment green body, which is then prepared after debinding and sintering.
  • the particle diameter of the yttrium-stabilized zirconia powder is 30 to 300 nm, and its purity is 99% to 100%;
  • the pH adjusting agent is zirconyl oxychloride;
  • the reinforcing agent is anhydrous aluminum chloride, six More than one type of aluminum chloride hydrochloride or yttrium nitrate hexahydrate;
  • the adhesive is polyvinyl butyral;
  • the plasticizer is triethylene glycol diisocaprylate or dipropylene glycol dibenzoate Acid ester;
  • the dispersant is one or any combination of polyethylene glycol, dodecyldimethylammonium bromide or cetyltrimethylammonium bromide.
  • the toner is a rare earth metal salt or a transition metal salt
  • the rare earth metal salt or a transition metal salt is soluble in ethanol or methyl ethyl ketone.
  • the rare earth metal salt is one or more of a rare earth metal nitrate, a rare earth metal sulfate, a rare earth metal chloride, a rare earth metal oxyfluoride, a rare earth metal citrate or a rare earth metal acetate.
  • the transition metal salt is one or more of a transition metal nitrate, a transition metal sulfate, a transition metal chloride, a transition metal oxyfluoride, a transition metal citrate, or a transition metal acetate.
  • the rare earth metal is cerium, praseodymium, neodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, lanthanum, praseodymium, or praseodymium
  • the transition metal is vanadium, chromium, manganese, iron, cobalt. , Nickel or copper.
  • the mass ratio of the yttrium stabilized zirconia powder and the reinforcing agent is (8 to 100): 1; the mass ratio of the yttrium stabilized zirconia powder and the dispersant is (40 to 60): 1; the yttrium
  • the mass ratio of the stabilized zirconia powder and the binder is (7-20): 1; the mass ratio of the yttrium-stabilized zirconia powder and the plasticizer is (7-20): 1; the toner and yttrium
  • the mass ratio of the stabilized zirconia powder is 1: (5 to 50).
  • the temperature of the isostatic pressing is 75 to 90 ° C, and the pressure is 100 to 150 MPa; the maximum temperature of the debinding is 600 to 1000 ° C, and the temperature increasing rate of the debinding is 0.3 to 3 ° C / min.
  • the maximum temperature for debinding is maintained for 0.5 to 1 hour; the sintering temperature is 1300 to 1500 ° C, the heating rate of sintering is 5 to 15 ° C / min, and the heat preservation time during sintering is 2 to 4h.
  • the preparation method of the multi-colored zirconia ceramic sheet includes the following specific steps:
  • the multi-channel casting method is used to form the single-color slurry C of different colors into a green body.
  • the specific method is as follows: the single-color slurry C of different colors is passed through the casting slurry.
  • the material injection pipe is injected into the separated casting slurry hopper, and the programmable servo motor is controlled by the programmable servo motor unit controller to push the movable hopper partition to move left and right, and adjust the speed of the roll film motor
  • the polyester film is moved by the roll connected to the film rolling motor.
  • two different monochrome pastes adjacent to any movable trough separator will be cast in the caster trough and the casting blade.
  • the spaces between 1 are in contact with each other, and then flow through the casting blade 1 and the casting blade 2, and then dried to obtain a plain strip;
  • step S3 Cut and punch the plain green tape obtained in step S2 to obtain a plain green sheet;
  • the plain green sheet is placed in a mold and formed by warm isostatic pressing to obtain a three-dimensional multi-pigment green body;
  • the multi-pigment green body is embedded in a degreasing furnace to perform powder embedding and debinding, and then sintered to obtain a multi-colored zirconia ceramic sheet.
  • the mass ratio of the total mass of the reinforcing agent and the yttrium-stabilized zirconia powder to the absolute ethanol-butanone azeotrope in step S1 is 1: (1.2 to 1.5), and the first ball milling time is 15-20 hours, the total time of the second ball milling is 15-24 hours; the thickness of the plain green belt in step S2 is 0.6-1.5 mm.
  • nano-yttrium-stabilized zirconia powder is used as a main raw material.
  • a reinforcing agent and a toner required according to color
  • an improved casting machine chute and a multi-color slurry casting are easily used.
  • a formula invented by cracks at the slurry interface a multi-colored zirconia ceramic mobile phone back cover green was prepared by the casting method, and directly cut into a green sheet of a desired shape or after cutting the green sheet through warm isostatic pressing
  • Multi-dimensional zirconia ceramic parts were prepared by three-dimensional modeling, debinding and sintering, and finally processed, rough ground and polished to obtain multi-color zirconia ceramic mobile phone back shells.
  • the present invention has the following beneficial effects:
  • the present invention prepares the same color multi-colored zirconia ceramic sheet by using a multi-channel casting method with slurry of different colors, after molding, degreasing and sintering.
  • This multi-colored zirconia ceramic sheet can be applied to mobile phones Preparation of the back shell.
  • low-cost large-scale production can be achieved, and on the other hand, a single zirconia mobile phone back shell has multiple colors at the same time, which meets the needs of personalization and artistic effects.
  • the method of the present invention makes the multi-colored slurry casting difficult to produce cracks at the slurry interface, so that the prepared green belt has no pores and no cracks.
  • FIG. 1 is a schematic diagram of a multi-channel casting device.
  • Figure 2 is a schematic diagram of a dual-channel hopper.
  • FIG. 3 is a photo of an off-white double-pigment blank prepared by using dual-channel casting in Example 1.
  • the content of the present invention is further described below with reference to specific embodiments, but it should not be construed as limiting the present invention.
  • the technical means used in the embodiments are conventional means well known to those skilled in the art.
  • the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the technical field.
  • FIG. 1 is a schematic diagram of a multi-channel casting device.
  • S1 is the casting slurry injection pipe
  • S2 is the movable trough partition
  • S3 is the movable trough partition connecting rod
  • S4 is the programmable servo motor unit
  • S5 is the programmable servo motor controller
  • S6 Is the casting frame
  • S7 is the casting blade 1
  • S8 is the casting blade 2
  • S9 is the casting slurry tank
  • S10 is the gap between the casting slurry tank S9 and the casting blade 1
  • S11 is a film rolling motor
  • S12 is a roll
  • S13 is a polyester film.
  • the multi-channel casting method is used to use the above-mentioned device to form the blanks of different colors, and the specific method is as follows: the monochrome pastes of different colors are injected into the separated streams through the casting slurry injection pipe S1.
  • the programmable servo motor group S4 is controlled by the programmable servo motor controller S5, and the movable tank partition connecting rod S3 is pushed to move the movable tank partition S2 to the left and right, and adjusted.
  • the speed of the film winding motor S11 causes the roll S12 connected to the film winding motor phase S11 to drive the polyester film S13 to move.
  • slurry A1 Adhesive polyvinyl butyral and plasticizer dipropylene glycol dibenzoate; the mass ratio of plasticizer to yttrium-stabilized zirconia powder is 1:12; the mass of adhesive and yttrium-stabilized zirconia powder is 1:12; mix ball milling again for 24h to prepare slurry B1; 3 degas the slurry B1 under the condition of vacuum 0.1 Pa to obtain a gray cast slurry C1 with a viscosity of about 10000 mPa ⁇ s;
  • Zirconium oxide ball was used as a ball milling medium, and mixed ball milling was performed for 20 hours to obtain slurry A2; 2 added the adhesive polyvinyl butyral and plasticizer dipropylene glycol dibenzoate to slurry A2; the plasticizer and The mass ratio of yttrium-stabilized zirconia powder is 1: 8; the mass ratio of the binder and yttrium-stabilized zirconia powder is 1: 8, and the ball mill is mixed again for 16 hours to obtain slurry B2.
  • slurry D1 is defoamed under the condition of a vacuum of 0.1 Pa to obtain a white cast slurry C2 having a viscosity of about 10,000 mPa ⁇ s;
  • the adjacent gray slurry C1 and white slurry C2 of the movable trough partition S2 will contact each other at the gap between the casting slurry trough S9 and the casting blades 1-S7, and then flow through the casting blade 1 -S7 and casting blade 2-S8, the slurry flows through 25 °C -35 °C -45 °C -55 °C -65 °C after drying in sections, and after drying, an off-white double-pigment green belt is obtained. There are no pores and cracks, and the color and morphology of the gray-white double pigment green belt are shown in Figure 3.
  • slurry A3 Using zirconia ball as a ball milling medium, mixing ball milling for 20 hours to prepare slurry A3; 2 Add adhesive polyvinyl butyral and composite plasticizer (dipropylene glycol dibenzoate: three to slurry A3) The mass ratio of glycol diisocaprylate is 1: 1); the mass ratio of composite plasticizer and yttrium stabilized zirconia powder is 1: 8; the mass ratio of adhesive and yttrium stabilized zirconia powder is 1: 8 , And then mixed with ball milling for 24 hours to prepare slurry B3; 3 defoaming slurry B3 under the condition of a vacuum of 0.1 Pa to obtain a gray slurry C3 having a viscosity of about 10000 mPa ⁇ s;
  • zirconia ball as a ball milling medium, mix ball milling for 20 to obtain slurry A5; 2 Add adhesive polyvinyl butyral and composite plasticizer (dipropylene glycol dibenzoate) to slurry A5:
  • the mass ratio of triethylene glycol diisocaprylate is 1: 1), the mass of plasticizer and yttrium-stabilized zirconia powder is 1: 8; the mass ratio of adhesive and yttrium-stabilized zirconia powder is 1: 8,
  • slurry A6 Material, using zirconia balls as a ball milling medium, and mixing ball milling for 20 hours to prepare slurry A6; 2 adding the adhesive polyvinyl butyral and a composite plasticizer (dipropylene glycol dibenzoate: The mass ratio of triethylene glycol diisocaprylate is 1: 1), the mass of plasticizer and yttrium stabilized zirconia powder is 1: 8; the mass ratio of adhesive and yttrium stabilized zirconia powder is 1: 8, Mix ball milling for 16h again to prepare slurry B6; according to the pH value of yellow slurry C5, add zirconium oxychloride to adjust the pH value of pink slurry C6 to the pH value of yellow slurry C6 , And then continue milling 8h, to prepare a slurry D3.
  • the slurry D3 is defoamed under the condition of a vacuum of 0.1 Pa to obtain a pink slurry C6 with a viscosity of
  • the adjacent yellow slurry C5 and pink slurry C6 of the movable trough partition S2 will contact each other at the gap between the casting slurry trough S9 and the casting blades 1-S7, and then flow through the casting blade 1 -S7 and casting blade 2-S8, the yellow paste C5 and pink paste C6 flow through 25 °C -35 °C -45 °C -55 °C -65 °C and then dried in sections to obtain a yellow powder double pigment green belt.
  • the blank has no pores and cracks.
  • Preparation of yellow powder double-colored zirconia ceramic sheet Place the yellow powder double-colored green body in a crucible, and bury the zirconia powder. After slightly compacting, perform debinding and degreasing in a degreasing furnace.
  • the degreasing temperature rise curve is: 20 °C, heat up to 200 °C at 2 °C / min, then 500 °C at 0.3 °C / min, then 650 °C at 1 °C / min, then 1000 °C at 3 °C / min, and keep it at 1000 °C for 1 h. Then, the temperature of the furnace was reduced to obtain a yellow powder bicolor zirconia green body.
  • the green body was put into a corundum crucible, and the zirconia powder was embedded in a sintering furnace. The temperature was raised to 1400 ° C at 10 ° C / min, and the temperature was maintained for 2 hours. Thereafter, conventional cooling was performed to obtain a three-dimensional yellow powder bicolor zirconia ceramic sheet. After the ceramic sheet is processed by shape, 3D rough grinding, and 3D polishing, a 3D zirconia ceramic mobile phone back cover is obtained. The back cover had a fracture toughness of 8.5 MPa ⁇ m 1/2 and a flexural strength of 1070 MPa.

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Abstract

一种多色氧化锆陶瓷片及其制备方法和应用，所述氧化锆陶瓷片是以钇稳定氧化锆粉体为主要原料，通过添加增强剂、调色剂、pH调整剂、粘接剂、增塑剂、分散剂和无水乙醇-丁酮共沸物，通过球磨获得单色流延浆料；采用多通道流延法将单色流延浆料制备得到多色氧化锆陶瓷素坯带，将其裁切成素坯片后经过温等静压进行成型，得到三维的多色素坯体，再经排胶、烧结后制得。将该氧化锆陶瓷片经过外形加工、粗磨和抛光，可应用在手机背壳制备领域中。

Description

一种多色氧化锆陶瓷片及其制备方法和应用 技术领域
本发明属于功能陶瓷技术领域，更具体地，涉及一种多色氧化锆陶瓷片及其制备方法和应用。
背景技术
近年来，由于氧化锆具有断裂强度高，断裂韧性高，硬度高等优点，被认为是手机后盖的理想材料之一。并且已经逐步应用在手机或者可穿戴产品上。然而，目前的氧化锆陶瓷手机后盖的颜色基本均为单一的颜色，例如专利CN104003714B中提到一种氧化锆陶瓷制备多种颜色手机零件的方法，该方法可以制备出多种颜色的手机零件，此专利所谓的多种颜色，指的是可以制备多种颜色是手机零件，但是每一个手机零件只有单一的颜色(如黑色，钛银色，白色，粉色等)。如果可以使单个氧化锆陶瓷手机零部件上同时具有多种颜色，将会使得产品具有更多的选择性，满足更广泛的需求。
发明内容
为了解决上述现有技术存在的不足和缺点，本发明首要目的在于提供一种多色氧化锆陶瓷片。
本发明的另一目的在于提供上述多色氧化锆陶瓷片的制备方法。
本发明的再一目的在于提供上述多色氧化锆陶瓷片的应用。
本发明的目的通过下述技术方案来实现：
一种多色氧化锆陶瓷片，所述氧化锆陶瓷片是以钇稳定氧化锆粉体为主要原料，通过添加增强剂、调色剂、pH调整剂、粘接剂、增塑剂、分散剂和无水乙醇-丁酮共沸物，通过球磨获得单色流延浆料；采用多通道流延法将单色流延浆料制备得到多色氧化锆陶瓷素坯带，将其裁切成素坯片后经过温等静压进行成型，得到三维的多色素坯体，再经排胶、烧结后制得。
优选地，所述钇稳定氧化锆粉的粒径为30～300nm，其纯度为99％～100％；所述pH调整剂为氧氯化锆；所述增强剂为无水氯化铝、六水氯化铝或六水硝酸钇的一种以上；所述的粘接剂为聚乙烯醇缩丁醛；所述增塑剂为三甘醇二异辛酸酯或/和二丙二醇二苯甲酸酯；所述分散剂为聚乙二醇、双十二烷基二甲基溴化铵或十六烷基三甲基溴化铵的一种或任意两种混合。
优选地，所述调色剂为稀土金属盐或过渡金属盐，所述稀土金属盐或过渡金属盐可溶于乙醇或丁酮。
更为优选地，所述稀土金属盐为稀土金属硝酸盐，稀土金属硫酸盐，稀土金属氯化盐，稀土金属氧氟化盐，稀土金属柠檬酸盐或稀土金属乙酸盐中的一种以上；所述过渡金属盐为过渡金属硝酸盐，过渡金属硫酸盐，过渡金属氯化盐，过渡金属氧氟化盐，过渡金属柠檬酸盐或过渡金属乙酸盐中的一种以上。
进一步地，所述稀土金属为铈、镨、钕、钐、铕、铽、钬、铒、铥、镥、镝、镧、镱或钆，所述过渡金属为钒、铬、锰、铁、钴、镍或铜。
优选地，所述钇稳定氧化锆粉和增强剂的质量比为(8～100)：1；所述钇稳定氧化锆粉和分散剂的质量比为(40～60)：1；所述钇稳定氧化锆粉和粘接剂的质量比为(7～20)：1；所述钇稳定氧化锆粉和增塑剂的质量比为(7～20)：1；所述调色剂和钇稳定氧化锆粉的质量比为1：(5～50)。
优选地，所述温等静压的温度为75～90℃，压力为100～150MPa；所述排胶的最高温度为600～1000℃，排胶的升温速率为0.3～3℃/min，在排胶的最高温度保温0.5～1h；所述烧结的温度为1300～1500℃，烧结的升温速率为5～15℃/min，在烧结的保温时间为2～4h。
所述的多色氧化锆陶瓷片的制备方法，包括如下具体步骤：
S1.多色流延浆料的制备：①称取钇稳定氧化锆粉、增强剂、调色剂、浆料pH调整剂和分散剂，添加无水乙醇-丁酮共沸物，进行第一次球磨，制得浆料A；②将粘接剂和增塑剂加入浆料A中，进行第二次球磨，制得浆料B；③将浆料B在真空度为0.1Pa的条件下脱泡，得到单色浆料C；
S2.多色氧化锆陶瓷素坯带的制备：采用多通道流延法将不同颜色的单色浆料C进行素坯成型，具体方式如下：将不同颜色的单色浆料C通过流延浆料注入管注入到被分隔开的流延浆料料槽内，同时通过可编程伺服电机组控制器控制可编程伺服电机推动可移动料槽隔板进行左右移动，并调节卷膜电机的速率，使与卷膜电机相连接的卷筒带动聚酯膜移动，此时，任一可移动料槽隔板相邻的两种不同单色浆料将在流延浆料料槽和流延刮刀1之间的空隙处相互接触，再流经流延刮刀1和流延刮刀2后，经干燥后，获得素坯带；
S3.将步骤S2所得素坯带裁切和打孔，获得素坯片；
S4.将素坯片放置在模具中，用温等静压成型，得到具有三维的多色素坯体；
S5.将多色素坯体在脱脂炉中进行埋粉排胶，再经过烧结后，获得多色氧化 锆陶瓷片。
优选地，步骤S1中所述增强剂和钇稳定氧化锆粉的总质量与无水乙醇-丁酮共沸物的质量比为1：(1.2～1.5)，所述第一次球磨的时间为15～20h，所述第二次球磨的总时间为15～24h；步骤S2中所述素坯带的厚度为0.6～1.5mm。
所述的多色氧化锆陶瓷片在制备手机背壳领域中的应用。
本发明以纳米钇稳定氧化锆粉体为主要原料，通过添加一定量的增强剂及依据颜色所需的调色剂，采用经过改进的流延机料槽和针对多色浆料流延易于在浆料界面处产生裂纹而发明的配方，使用流延法制备出多色氧化锆陶瓷手机后盖生坯，直接裁切成所需形状的坯片或者裁切坯片后经过温等静压进行三维造型，再经过排胶、烧结制备出多色氧化锆陶瓷件，最后经过外形加工、粗磨和抛光，获得多色氧化锆陶瓷手机背壳。
与现有技术相比，本发明具有以下有益效果：
1.本发明通过配备不同颜色的浆料，采用多通道流延的方式，经造型、脱脂和烧结后，制备出同板多色氧化锆陶瓷片，此多色氧化锆陶瓷片可应用在手机背壳的制备。一方面是可实现低成本大规模生产，另一方面使得单一氧化锆手机背壳同时具有多种颜色，满足个性化和艺术效果的需求。
2.本发明的方法使多色浆料流延在浆料界面处不易于产生裂纹，使所制得的素坯带无气孔、无裂纹。
附图说明
图1是多通道流延装置示意图。
图2是双通道料槽示意图。
图3是实施例1中采用双通道流延制备的灰白双色素坯的照片。
具体实施方式
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
图1是多通道流延装置的示意图。其中，S1为流延浆料注入管；S2为可移动料槽隔板；S3为可移动料槽隔板连接杆；S4为可编程伺服电机组；S5为可编 程伺服电机组控制器；S6为流延机头外框；S7为流延刮刀1；S8为流延刮刀2；S9为流延浆料料槽；S10为流延浆料料槽S9与流延刮刀1之间的间隙；S11为卷膜电机；S12为卷筒；S13为聚酯膜。
利用多通道流延法采用上述装置将不同颜色的单色浆料进行素坯成型，具体方式如下：将不同颜色的单色浆料通过流延浆料注入管S1注入到被分隔开的流延浆料料槽S9内，同时通过可编程伺服电机组控制器S5控制可编程伺服电机组S4，控制可移动料槽隔板连接杆S3推动可移动料槽隔板S2进行左右移动，并调节卷膜电机S11的速率，使与卷膜电机相S11连接的卷筒S12带动聚酯膜S13移动，此时，任一可移动料槽隔板相邻的两种不同单色的浆料将在流延浆料料槽S9和流延刮刀1-S7之间的空隙S10处相互接触，再流经流延刮刀1-S7和流延刮刀2-S8后，经干燥后，获得素坯带。
实施例1
1.灰色流延浆料的制备：①称量钇稳定氧化锆粉(d 50＝300nm)、增强剂六水氯化铝、调色剂六水硝酸钕和分散剂聚乙二醇；其中，增强剂：钇稳定氧化锆粉的重量比为1：10.6；调色剂与钇稳定氧化粉的重量比为1：7，分散剂与钇稳定氧化锆粉的重量比为1：50；添加重量为增强剂与钇稳定氧化锆粉总重量的1.2倍的无水乙醇-丁酮共沸物，以氧化锆球为球磨介质，混合球磨20h，制得浆料A1；②往浆料A1中加入粘接剂聚乙烯醇缩丁醛和增塑剂二丙二醇二苯甲酸酯；增塑剂与钇稳定氧化锆粉的质量比为1：12；粘接剂与钇稳定氧化锆粉的质量为1：12；再次混合球磨24h，制得浆料B1；③将浆料B1在真空度为0.1Pa的条件下脱泡，得到灰色流延浆料C1，其粘度大约为10000mPa·s；
2.白色流延浆料的制备：①称量钇稳定氧化锆粉(d 50＝300nm)、增强剂六水氯化铝和分散剂聚乙二醇；其中，增强剂和钇稳定氧化锆粉的重量比为1：10.6；分散剂与钇稳定氧化锆粉的质量比为1：50；添加重量为增强剂与钇稳定氧化锆粉总重量1.2倍的无水乙醇-丁酮共沸物，以氧化锆球为球磨介质，混合球磨20h，制得浆料A2；②往浆料A2中加入粘接剂聚乙烯醇缩丁醛和增塑剂二丙二醇二苯甲酸酯；增塑剂与钇稳定氧化锆粉的质量比为1：8；粘接剂与钇稳定氧化锆粉的质量比为1：8，再次混合球磨16h，制得浆料B2；依据灰色浆料C2的pH值，添加氧氯化锆，将白色浆料的pH值调整到与灰色浆料pH值相近，再继续球磨8h，制得浆料D1。③将浆料D1在真空度为0.1Pa的条件下脱泡，得到白色流延浆料C2， 其粘度大约为10000mPa·s；
3.灰白双色素坯带的制备：将灰色浆料C1和白色浆料C2采用双通道流延法进行素坯成型，双通道料槽如图2所示。在流延浆料料槽S9中间有一个可移动料槽隔板S2，流延刮刀1-S7刀口距离聚脂膜S13的高度为2mm，流延刮刀2-S8刀口距离聚酯膜S13的高度为1.9mm，将灰色浆料C1倒入可移动料槽隔板S2的一侧，将白色浆料C2倒入料槽隔板S2的另一侧。可移动料槽隔板S2相邻的灰色浆料C1和白色浆料C2将在流延浆料料槽S9和流延刮刀1-S7之间的空隙处相互接触，再流经流延刮刀1-S7和流延刮刀2-S8后，浆料流经25℃-35℃-45℃-55℃-65℃分区段干燥后经干燥后，获得灰白双色素坯带，该灰白双色素坯带无气孔和无裂纹，其灰白双色素坯带的颜色和形貌如图3所示。
实施例2
1.灰色流延浆料的制备：①称量钇稳定氧化锆粉(d 50小于50nm)、增强剂六水氯化铝、调色剂六水硝酸钕和复合分散剂(十六烷基三甲基溴化铵：双十二烷基二甲基溴化铵的质量比为1：1)；增强剂和钇稳定氧化锆粉的重量比为1：10.6；调色剂与钇稳定氧化粉的质量比为1：7；复合分散剂与钇稳定氧化锆粉的质量比为1：40；添加重量为增强剂与钇稳定氧化锆粉总重量1.2倍的无水乙醇-丁酮共沸物，以氧化锆球为球磨介质，混合球磨20h，制得浆料A3；②往浆料A3中加入粘接剂聚乙烯醇缩丁醛和复合增塑剂(二丙二醇二苯甲酸酯：三甘醇二异辛酸酯的质量比为1：1)；复合增塑剂与钇稳定氧化锆粉的质量比为1：8；粘接剂与钇稳定氧化锆粉的质量比为1：8，再次混合球磨24h，制得浆料B3；③将浆料B3在真空度为0.1Pa的条件下脱泡，得到灰色浆料C3，其粘度大约为10000mPa·s；
2.白色流延浆料的制备：①称量钇稳定氧化锆粉(d 50小于50nm)、增强剂六水氯化铝和复合分散剂(十六烷基三甲基溴化铵：双十二烷基二甲基溴化铵的质量比为1：1)；增强剂和钇稳定氧化锆粉的重量比为1：10.6；复合分散剂与钇稳定氧化锆粉的质量比为1：40；添加重量为增强剂与钇稳定氧化锆粉总重量1.2倍的无水乙醇-丁酮共沸物，以氧化锆球为球磨介质，混合球磨20h，制得浆料A4；②往浆料A4中加入粘接剂聚乙烯醇缩丁醛和复合增塑剂(二丙二醇二苯甲酸酯:三甘醇二异辛酸酯的质量比为1：1)，增塑剂与钇稳定氧化锆粉的质量比为1：8；粘接剂与钇稳定氧化锆粉的质量比为1：8，再次混合球磨16h，制得浆料B4；依据灰色流延浆料C3的pH值，添加氧氯化锆，将白色浆料的pH值调整到 与灰色流延浆料C3的pH值相近，再继续球磨8h，制得浆料D2。③将浆料D2在真空度为0.1Pa的条件下脱泡，得到白色浆料C4，其粘度大约为10000mPa·s；
3.灰白双色素坯带的制备：采用双通道流延法将灰色浆料C3和白色C4进行素坯成型，双通道料槽如图2所示。在流延机的料槽S9中间有一个可移动料槽隔板S2，流延刮刀1-S7刀口距离聚酯膜S13的高度为2mm，流延刮刀2-S8刀口距离聚酯膜S13的高度为1.9mm，将灰色浆料C3倒入料槽隔板S2的一侧，将白色浆料C4倒入料槽隔板S2的另一侧，可移动料槽隔板S2相邻的灰色浆料C3和白色浆料C4将在流延浆料料槽S9和流延刮刀1-S7之间的空隙处相互接触，再流经流延刮刀1-S7和流延刮刀2-S8后，浆料流经25℃-35℃-45℃-55℃-65℃分区段干燥后经干燥后，获得灰白双色素坯带，该灰白双色素坯带无气孔也无裂纹。
4.多色氧化锆陶瓷片的制备：将灰白双色素坯带按照所需的要求进行裁切成素坯片，在脱脂炉中进行排胶脱脂，脱脂升温曲线为在20℃，以2℃/min升温到200℃，再以0.3℃/min升温到500℃，再以1℃/min升温到650℃，在650℃保温1h，然后随炉降温，获得生坯；将生坯放入刚玉坩埚中，置入烧结炉中，以10℃/min的速率升温至1450℃，保温2h，之后进行自然冷却，制得灰白双色氧化锆陶瓷片，将该双色陶瓷激光开孔、粗磨和抛光后，获得平板式氧化锆陶瓷后盖，经测试该氧化锆陶瓷的断裂韧性为9.1MPa·m 1/2，抗弯强度为1028MPa。
实施例3
1.黄色流延浆料的制备：①按配比称量钇稳定氧化锆粉(d 50小于50nm)、增强剂六水氯化铝、调色剂六水氯化钐和复合分散剂(十六烷基三甲基溴化铵:双十二烷基二甲基溴化铵＝1:1)；增强剂和钇稳定氧化锆粉的重量比为1：10.6；调色剂与钇稳定氧化粉的重量比为1：7；复合分散剂与钇稳定氧化锆粉的质量比为1：40；添加重量为增强剂与钇稳定氧化锆粉总重量1.2倍的无水乙醇-丁酮共沸物，以氧化锆球为球磨介质，混合球磨20好，制得浆料A5；②往浆料A5中加入粘接剂聚乙烯醇缩丁醛和复合增塑剂(二丙二醇二苯甲酸酯:三甘醇二异辛酸酯的质量比为1：1)，增塑剂与钇稳定氧化锆粉的质量为1：8；粘接剂与钇稳定氧化锆粉的质量比为1:8，再次混合球磨24h，制得浆料B5；③将浆料B5在真空度为0.1Pa的条件下脱泡，得到黄色浆料C5，其粘度约为10000mPa·s；
2.粉色流延浆料的制备：①按配比称量钇稳定氧化锆粉(d 50小于50nm)、调色剂四水醋酸铒、增强剂六水氯化铝和复合分散剂(十六烷基三甲基溴化铵：双 十二烷基二甲基溴化铵的质量比为1：1)；增强剂和钇稳定氧化锆粉的重量比为1：10.6；调色剂与钇稳定氧化粉的重量比为1：6；复合分散剂与钇稳定氧化锆粉的质量为1：40；添加重量为增强剂与钇稳定氧化锆粉总重量1.2倍的无水乙醇-丁酮共沸物，以氧化锆球为球磨介质，混合球磨20h，制得浆料A6；②往浆料A6中加入粘接剂聚乙烯醇缩丁醛和复合增塑剂(二丙二醇二苯甲酸酯:三甘醇二异辛酸酯的质量比为1：1)，增塑剂与钇稳定氧化锆粉的质量为1：8；粘接剂与钇稳定氧化锆粉的质量比为1：8，再次混合球磨16h，制得浆料B6；依据黄色浆料C5的pH值，添加氧氯化锆，将粉色浆料C6的pH值调整到与黄色浆料C6的pH值相近，再继续球磨8h，制得浆料D3。③将浆料D3在真空度为0.1Pa的条件下脱泡，得到粉色浆料C6，其粘度约为10000mPa·s；
3.黄粉双色素坯带的制备：采用双通道流延法将黄色浆料C5和粉色浆料C6进行素坯成型，双通道料槽如图2所示。在流延机的料槽S9中间有一个可移动料槽隔板S2，流延刮刀1-S7刀口距离聚酯膜S13的高度为2mm，流延刮刀2-S8刀口距离聚酯膜S13的高度为1.9mm，将黄色浆料C5倒入料槽隔板S2的一侧，将粉色浆料C6倒入料槽隔板的另一侧。可移动料槽隔板S2相邻的黄色浆料C5和粉色浆料C6将在流延浆料料槽S9和流延刮刀1-S7之间的空隙处相互接触，再流经流延刮刀1-S7和流延刮刀2-S8后，黄色浆料C5和粉色浆料C6流经25℃-35℃-45℃-55℃-65℃分区段干燥后，获得黄粉双色素坯带，该素坯带无气孔、无裂纹。
4.黄粉双色氧化锆素坯体的制备：将黄粉双色素坯带按照所需的要求进行裁切成素坯片后，放入烘箱110℃保温3h去除残余水和有机溶剂，再将素坯片放置在凹型模具中，将素坯片和模具一体放入真空袋中，抽真空，然后放入温等静压机进行立体造型，等静压水温为80℃，压力为100MPa，保压时间为15min，温等静压机泄压后，得到三维的黄粉双色素坯体。
5.黄粉双色氧化锆陶瓷片的制备：将黄粉双色素坯体放置在坩埚中，并埋上氧化锆粉，轻微压实后，在脱脂炉中进行排胶脱脂，脱脂升温曲线为：在20℃，以2℃/min升温至200℃，再以0.3℃/min升温到500℃，再以1℃/min升温到650℃，再以3℃/min升温到1000℃，在1000℃保温1h，然后随炉降温，获得黄粉双色氧化锆生坯；将该生坯体放入刚玉坩埚中，埋上氧化锆粉，置入烧结炉中，以10℃/min升温至1400℃，保温2h，之后进行常规冷却，获得三维的黄粉双色氧化锆陶瓷片。将该陶瓷片经外形加工、3D粗磨、3D抛光后，得到3D氧化锆陶瓷手 机后盖。该后盖断裂韧性为8.5MPa·m 1/2，抗弯强度为1070MPa。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种多色氧化锆陶瓷片，其特征在于，所述氧化锆陶瓷片是以钇稳定氧化锆粉体为主要原料，通过添加增强剂、调色剂、pH调整剂、粘接剂、增塑剂、分散剂和无水乙醇-丁酮共沸物，通过球磨获得单色流延浆料；采用多通道流延法将单色流延浆料制备得到多色氧化锆陶瓷素坯带，将其裁切成素坯片后经过温等静压进行成型，得到三维的多色素坯体，再经排胶、烧结后制得。
  2. 根据权利要求1所述的多色氧化锆陶瓷片，其特征在于，所述钇稳定氧化锆粉的粒径为30～300nm，其纯度为99～100％；所述pH调整剂为氧氯化锆；所述增强剂为无水氯化铝、六水氯化铝或六水硝酸钇中的一种以上；所述粘接剂为聚乙烯醇缩丁醛；所述增塑剂为三甘醇二异辛酸酯或/和二丙二醇二苯甲酸酯；所述分散剂为聚乙二醇、双十二烷基二甲基溴化铵或十六烷基三甲基溴化铵中的一种或任意两种混合。
  3. 根据权利要求1所述的多色氧化锆陶瓷片，其特征在于，所述调色剂为稀土金属盐或过渡金属盐，所述稀土金属盐或过渡金属盐可溶于乙醇或丁酮。
  4. 根据权利要求3所述的多色氧化锆陶瓷片，其特征在于，所述稀土金属盐为稀土金属硝酸盐，稀土金属硫酸盐，稀土金属氯化盐，稀土金属氧氟化盐，稀土金属柠檬酸盐或稀土金属乙酸盐中的一种以上；所述过渡金属盐为过渡金属硝酸盐，过渡金属硫酸盐，过渡金属氯化盐，过渡金属氧氟化盐，过渡金属柠檬酸盐或过渡金属乙酸盐中的一种以上。
  5. 根据权利要求4所述的多色氧化锆陶瓷片，其特征在于，所述稀土金属为铈、镨、钕、钐、铕、铽、钬、铒、铥、镥、镝、镧、镱或钆，所述过渡金属为钒、铬、锰、铁、钴、镍或铜。
  6. 根据权利要求1所述的多色氧化锆陶瓷片，其特征在于，所述钇稳定氧化锆粉和增强剂的质量比为(8～100)：1；所述钇稳定氧化锆粉和分散剂的质量比为(40～60)：1；所述钇稳定氧化锆粉和粘接剂的质量比为(7～20)：1；所述钇稳定氧化锆粉和增塑剂的质量比为(7～20)：1；所述调色剂和钇稳定氧化锆粉的质量比为1：(5～50)。
  7. 根据权利要求1所述的多色氧化锆陶瓷片，其特征在于，所述温等静压的温度为75～90℃，压力为100～150MPa；所述排胶的最高温度为600～1000℃，排胶的升温速率为0.3～3℃/min，在排胶的最高温度保温0.5～1h；所述烧结的温度为1300～1500℃，烧结的升温速率为5～15℃/min，在烧结的保温时间为2～4h。
  8. 根据权利要求1-7任一项所述的多色氧化锆陶瓷片的制备方法，其特征在 于，包括如下具体步骤：
    S1.多色流延浆料的制备：①称取钇稳定氧化锆粉、增强剂、调色剂、浆料pH调整剂和分散剂，添加无水乙醇-丁酮共沸物，进行第一次球磨，制得浆料A；②将粘接剂和增塑剂加入浆料A中，进行第二次球磨，制得浆料B；③将浆料B在真空度为0.1Pa的条件下脱泡，得到单色浆料C；
    S2.多色氧化锆陶瓷素坯带的制备：采用多通道流延法将不同颜色的单色浆料C进行素坯成型，具体方式如下：将不同颜色的单色浆料C通过流延浆料注入管注入到被分隔开的流延浆料料槽内，同时通过可编程伺服电机组控制器控制可编程伺服电机推动可移动料槽隔板进行左右移动，并调节卷膜电机的速率，使与卷膜电机相连接的卷筒带动聚酯膜移动，此时，任一可移动料槽隔板相邻的两种不同单色浆料将在流延浆料料槽和流延刮刀1之间的空隙处相互接触，再流经流延刮刀1和流延刮刀2后，经干燥后，获得素坯带；
    S3.将步骤S2所得素坯带裁切和打孔，获得素坯片；
    S4.将素坯片放置在模具中，用温等静压成型，得到具有三维的多色素坯体；
    S5.将多色素坯体在脱脂炉中进行埋粉排胶，再经过烧结后，获得多色氧化锆陶瓷片。
  9. 根据权利要求8所述的多色氧化锆陶瓷片的制备方法，其特征在于，步骤S1中所述增强剂和钇稳定氧化锆粉的总质量与无水乙醇-丁酮共沸物的质量比为1：(1.2～1.5)，所述第一次球磨的时间为15～20h，所述第二次球磨的总时间为15～24h；步骤S2中所述素坯带的厚度为0.6～1.5mm。
  10. 根据权利要求1-7任一项所述的多色氧化锆陶瓷片在制备手机背壳领域中的应用。
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