WO2021047574A1 - 氧化锆陶瓷、制备氧化锆陶瓷的方法及其应用和组合物 - Google Patents

氧化锆陶瓷、制备氧化锆陶瓷的方法及其应用和组合物 Download PDF

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WO2021047574A1
WO2021047574A1 PCT/CN2020/114398 CN2020114398W WO2021047574A1 WO 2021047574 A1 WO2021047574 A1 WO 2021047574A1 CN 2020114398 W CN2020114398 W CN 2020114398W WO 2021047574 A1 WO2021047574 A1 WO 2021047574A1
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zirconia
alumina
powder
content
composition
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PCT/CN2020/114398
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French (fr)
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陈戈
林信平
唐威
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比亚迪股份有限公司
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Priority to US17/641,937 priority Critical patent/US20220356121A1/en
Priority to KR1020227011740A priority patent/KR20220062050A/ko
Priority to JP2022515674A priority patent/JP7357149B2/ja
Publication of WO2021047574A1 publication Critical patent/WO2021047574A1/zh

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    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646Optical properties
    • C04B2235/9661Colour

Definitions

  • This application relates to the field of zirconia ceramics, in particular to zirconia ceramics, methods for preparing zirconia ceramics, and applications and compositions thereof.
  • Zirconia ceramics have the characteristics of good corrosion resistance, high hardness, high strength, and high toughness (up to 5-6MPa m 1/2 ), but they still have the disadvantage of weak impact resistance when they are made into large-area appearance parts.
  • high density and dielectric constant
  • the density and dielectric constant can be reduced by adding more alumina, the high hardness and high brittleness of alumina will lead to a significant increase in processing difficulty, resulting in low yield and high cost. Therefore, the development of a ceramic with high impact resistance and toughness is very important for the application of ceramic back covers in the 5G era.
  • the purpose of this application is to overcome the existing problems of zirconia ceramics that cannot have both impact resistance and toughness, and to provide zirconia ceramics, methods for preparing zirconia ceramics, and applications and compositions thereof.
  • the first aspect of the present application provides a zirconia ceramic
  • the zirconia ceramic contains 60.5-70.5wt% of Zr, 2.5-5.45wt% of Y, and 0.05-2.65wt% of Al in terms of elements.
  • the M includes at least one of Nb and Ta; and the phase composition of the zirconia ceramic includes: tetragonal zirconia, alumina and The sum of the content of zirconium silicate, alumina and zirconium silicate is 0.2-12wt%, the content of the tetragonal zirconia is 84-99.3wt%; the tetragonal zirconia includes yttrium oxide, M x O y and A solid solution formed by zirconia; the x satisfies 1 ⁇ x ⁇ 3, and the y satisfies 3 ⁇ y ⁇ 6.
  • the second aspect of the present application provides a zirconia ceramic
  • the phase composition of the zirconia ceramic includes: tetragonal zirconia, alumina and zirconium silicate, the sum of the content of alumina and zirconium silicate is 0.2-12wt%
  • the content of the tetragonal zirconia is 84-99.3wt%
  • the tetragonal zirconia includes a solid solution formed by yttrium oxide, M x O y and zirconia, and the content of Y in the zirconia ceramic is 2.5-5.45wt%, the content of M is 0.34-2.8wt%
  • the M includes at least one of Nb and Ta, and the x satisfies 1 ⁇ x ⁇ 3, and the y satisfies 3 ⁇ y ⁇ 6.
  • the third aspect of the present application provides a composition
  • a composition comprising: a zirconium oxide-containing component, aluminum oxide, zirconium silicate, and M x O y ; wherein the total amount of the zirconium oxide-containing component is used as a reference ,
  • the zirconium oxide-containing component contains zirconium oxide and 2-4 mol% yttrium oxide;
  • the content of the zirconia-containing component is 84-99.3wt%
  • the total content of alumina and zirconium silicate is 0.2-12wt%
  • the content of M x O y is 0.5-4wt %.
  • the fourth aspect of the present application provides a method for preparing zirconia ceramics, including:
  • the fifth aspect of the present application provides an application of the above-mentioned zirconia ceramics in the preparation of electronic product housings or decorations.
  • the present application provides a zirconia ceramic
  • the zirconia ceramic contains in terms of elements: 60.5-70.5wt% Zr, 2.5-5.45wt% Y, 0.05-2.65wt% Al, 0.015-1.07wt% Si , And 0.34-2.8wt% Nb and/or Ta; and the phase composition of the zirconia ceramic includes: 84-99.3wt% tetragonal zirconia, 0.2-12wt% alumina and zirconium silicate;
  • the tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and/or tantalum oxide and zirconium oxide.
  • the mass ratio of the alumina and zirconium silicate is (1:1)-(1:5).
  • the present application provides a composition for preparing the zirconia ceramic of the present application, the composition comprising zirconia powder, alumina powder, zirconium silicate powder, and niobium oxide and/or tantalum oxide powder; wherein The total amount of the zirconia powder is a reference, and the zirconia powder contains 2-4 mol% of yttrium oxide;
  • the content of zirconia powder is 84-99.3wt%
  • the total content of alumina powder and zirconium silicate powder is 0.2-12wt%
  • niobium oxide and/or tantalum oxide The content is 0.5-4wt%.
  • the mass ratio of alumina to zirconium silicate is (1:1)-(1:5).
  • This application provides a method for preparing zirconia ceramics, including:
  • the present application provides zirconia ceramics with excellent impact resistance and high toughness at the same time.
  • Figure 1 is an SEM image of the ceramic prepared in Example 1 of this application.
  • Figure 2 is an SEM image of the ceramic prepared in Comparative Example 2 of the application.
  • the first aspect of the present application provides a zirconia ceramic
  • the zirconia ceramic contains in terms of elements: 60.5-70.5wt% Zr, 2.5-5.45wt% Y, 0.05-2.65wt% Al, 0.015-1.07wt % Si, and 0.34-2.8wt% M
  • the M includes at least one of Nb and Ta
  • the phase composition of the zirconia ceramic includes: tetragonal zirconia, alumina and zirconium silicate, alumina and The sum of the content of zirconium silicate is 0.2-12wt%, and the content of tetragonal zirconia is 84-99.3wt%.
  • the tetragonal zirconia includes a solid solution formed by yttrium oxide, M x O y and zirconia, and x satisfies 1 ⁇ x ⁇ 3, the y satisfies 3 ⁇ y ⁇ 6.
  • the phase composition of zirconia ceramics includes: tetragonal phase zirconia, alumina and zirconium silicate, the sum of the content of alumina and zirconium silicate is 0.2-12wt%, the tetragonal phase zirconia The content is 84-99.3wt%, the tetragonal phase zirconia includes a solid solution formed by yttrium oxide, M x O y and zirconia. The content of Y in the zirconia ceramic is 2.5-5.45wt%, and the content of M is 2.5-5.45wt%. 0.34-2.8wt%, M includes at least one of Nb and Ta, x satisfies 1 ⁇ x ⁇ 3, and y satisfies 3 ⁇ y ⁇ 6.
  • the zirconia ceramic contains 60.5-70.5wt% Zr, 2.5-5.45wt% Y, 0.05-2.65wt% Al, 0.015-1.07wt% Si, and 0.34-2.8wt% M in terms of elements.
  • the zirconia ceramic further includes an appropriate amount of O.
  • O element can be determined according to the content of Zr, Y, Al, Si and M elements to form but not limited to zirconia, oxide Yttrium, zirconium silicate, alumina, M x O y, etc.
  • x and y can determine x and y according to the valence of M required.
  • x may be 2, y may be 5, and M x O y may include at least one of Nb 2 O 5 and Ta 2 O 5.
  • the ceramic has high density, high toughness and high impact resistance, and the color can be white.
  • the zirconia ceramic comprises: 63-68.75wt% Zr, 3.35-4.7wt% Y, 0.53-1.58wt% Al, 0.15-0.92wt% Si, and 0.68-2.1wt% %M. That is, the zirconia ceramic contains 0.68-2.1 wt% of Nb and/or Ta, that is, the zirconia ceramic contains at least one of Nb and Ta, and the content of at least one of Nb and Ta is 0.68-2.1 wt%. According to the embodiment of the present application, the zirconia ceramic further includes an appropriate amount of O.
  • the mass ratio of alumina and zirconium silicate is 1:(1-5), preferably 1:(1-2.25).
  • limiting the content relationship between Al and Si in zirconia ceramics is beneficial to improve the performance of the ceramics, and has both high impact resistance and toughness.
  • the mass ratio of Al:Si is (2:3)-(5:1), more preferably (1.6:1)-(3.5:1).
  • the mass ratio can be selected from (1.6:1), (1.8:1), (2.0:1), (2.2:1), (2.4:1), (2.6:1), (2.8:1), (3.0 : 1), (3.2:1), (3.4:1) and (3.5:1), and the range consisting of any of the above values.
  • the content of the above-mentioned elements can be detected by high-energy XRF.
  • the elemental composition of zirconia ceramics may also contain other elements, such as oxygen.
  • the zirconia ceramics provided in this application can be measured by XRD.
  • the phase composition of the zirconia ceramic includes: tetragonal zirconia, alumina and zirconium silicate, wherein the sum of the content of alumina and zirconium silicate is 2-9wt%, and the content of the tetragonal zirconia is 88- 97wt%.
  • the diffraction peak of the tetragonal phase of zirconia appears, which is due to the addition of yttrium oxide, niobium oxide and/or tantalum oxide in the preparation of zirconia ceramics, which form a solid solution with zirconia.
  • the solid solution may be a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide, a solid solution formed by yttrium oxide, tantalum oxide and zirconium oxide, or a solid solution formed by yttrium oxide, niobium oxide, tantalum oxide and zirconium oxide.
  • the zirconia ceramics may also contain other phases, but they have no negative impact on the zirconia ceramics of the present application. In this application, the above-mentioned content of the phase contained in the zirconia ceramic is based on the zirconia ceramic.
  • the zirconia ceramic of the present application has high impact resistance and toughness.
  • the toughness of zirconia ceramic is 10.0MPa m 1/2 or more, preferably 10.9-13MPa m 1/2.
  • the Vickers hardness of the zirconia ceramics is 1170-180Hv.
  • the average drop weight height is greater than or equal to 27.5 cm, and the average drop weight height is preferably 30.5-37 cm.
  • the deformation ratio of the zirconia ceramic is 0%. That is, the defective rate is low in the tested samples.
  • the zirconia ceramics can also have other improved mechanical properties at the same time.
  • the second aspect of the present application provides a composition comprising: a zirconium oxide-containing component, aluminum oxide, zirconium silicate, and M x O y .
  • the zirconia-containing component contains zirconia and 2-4 mol% of yttrium oxide. Based on the total composition, the content of zirconia-containing components is 84-99.3 wt%, the total content of alumina and zirconium silicate is 0.2-12 wt%, and the content of M x O y is 0.5-4 wt%.
  • each component in the above composition may exist in powder form.
  • the provided composition contains various oxides to obtain zirconia ceramics, and has high toughness and high impact resistance.
  • the color of the zirconia ceramics can be white.
  • the amount of each oxide used further preferably satisfies: based on the total composition, the content of the zirconia-containing component is 88-97wt%, and the total content of alumina and zirconium silicate is 2-9wt% , The content of M x O y is 1-3wt%.
  • the total amount of each oxide in the composition is 100% by weight.
  • zirconia ceramics can bring stabilization and toughening effects
  • alumina has a reinforcing effect
  • zirconium silicate can aggregate with alumina to produce heterogeneous particles (composite of zirconium silicate and alumina). Aggregate state) to increase the toughness and impact resistance of the composition.
  • zirconia ceramics provided by the present application particularly contain various elements and phases in the above-mentioned specific contents, zirconia ceramics with improved toughness and impact resistance can be obtained synergistically.
  • zirconia ceramics meeting the mechanical properties of the application cannot be provided.
  • zirconia ceramics that meet the above requirements can also have a white color.
  • the mass ratio of alumina to zirconium silicate in the composition is 1: (1-5).
  • the zirconium silicate and alumina components are directly added to the composition, and the alumina and zirconium silicate are combined in a specific ratio to interact.
  • the aggregate state formed in the zirconia ceramic can realize the improvement of the impact resistance of the zirconia ceramic, and the ceramic has good deformation resistance and high drop weight performance.
  • the mass ratio of alumina to zirconium silicate is (1:1)-(1:2.25), and the mass ratio can be selected from (1:1.1), (1:1.2), (1:1.3), (1: 1.4), (1:1.5), (1:1.6), (1:1.7), (1:1.8), (1:1.9), (1:2.0), (1:2.1), (1:2.2) And (1:2.25), and a range consisting of the above-mentioned values arbitrarily.
  • the composition is a composition for preparing the above-mentioned zirconia ceramic.
  • the third aspect of the present application provides a method for preparing zirconia ceramics, including:
  • the powder of each component in the composition of the present application is formed into a slurry.
  • step (1) in step (1), forming a slurry includes: mixing the powder, dispersant and binder of each component in the composition to obtain the slurry material.
  • the application does not limit the particle size of the powder of each component in the composition.
  • a powder with a smaller particle size can be used as a raw material, and each powder, a dispersant, and a binder in the composition can be mixed to obtain a slurry. It is also possible to use a powder with a larger particle size as a raw material to wet-grind each powder, dispersant and binder in the composition, and reduce the particle size of the powder through wet grinding to obtain a slurry, which is beneficial Reduce the cost of preparing zirconia ceramics.
  • a powder containing a zirconium oxide component contains yttrium oxide, with a median particle size of 0.3-0.6 ⁇ m and a specific surface area of 7-13 m 2 /g.
  • the median particle size of the M x O y powder is 8-12 ⁇ m.
  • M x O y is niobium oxide
  • the median particle size of the niobium oxide powder is 8-12 ⁇ m.
  • M x O y is tantalum oxide
  • the median particle size of the tantalum oxide powder is 8-12 ⁇ m.
  • the median particle size of zirconium silicate powder is 0.5-1 ⁇ m.
  • the median particle size of the alumina powder is 0.15-0.6 ⁇ m.
  • Step (1) realizes grinding various oxide powders as raw materials to reduce particle size and obtain slurry.
  • the grinding process is wet grinding, and the specific process can include: mixing various oxide powders and water into a slurry, first ball milling and mixing, and then sand milling to make the median size of various oxide powders to nanometer level (Such as 250-500nm). More specifically, the various oxide powders are milled in a ball mill tank with water for 8-10 hours according to the content of the application, and then the dispersant and water are added to the sand mill for 8-10 hours, and finally an appropriate ratio is added The binder (such as PVA and/or polyethylene glycol 4000) is stirred for another 2-4h.
  • the binder such as PVA and/or polyethylene glycol 4000
  • the ball mill tank and sand mill use zirconia ceramic lining and zirconia grinding balls.
  • the selected particle size of the zirconia grinding balls, the ratio of the grinding balls of different particle sizes, the weight ratio of the grinding balls to the powder, and the amount of water can be controlled to achieve the desired particle size of the oxide powder.
  • the dispersant is selected from at least one of hypromellose, sodium carboxymethyl cellulose and triethanolamine.
  • the binder is selected from polyvinyl alcohol and/or polyethylene glycol 4000, that is, the binder contains one or two of polyvinyl alcohol and polyethylene glycol 4000.
  • the dispersant can promote the uniform mixing of the components in the powder.
  • the binder is beneficial to the moldability of the powder.
  • the binder is polyvinyl alcohol (PVA) and polyethylene glycol 4000 (PEG4000), and the molar ratio of polyvinyl alcohol and polyethylene glycol 4000 is 1:(1-2), preferably 1:1.
  • both the dispersant and the binder are commercially available.
  • the added amount of the dispersant is 0.005-0.5wt% of the total powder of each component in the composition, preferably 0.01-0.1wt%.
  • the amount of the binder added is 0.5 to 5% by weight of the total powder of each component in the composition, preferably 2 to 5% by weight.
  • the solid content of the slurry is 20-60 wt%, preferably 25-55 wt%. Can have better abrasive effect.
  • step (2) various drying methods can be used in step (2), for example, spray drying can be used to form a spherical powder with strong fluidity, wherein the spherical powder with strong fluidity refers to: powder
  • the spherical powder with strong fluidity refers to: powder
  • the powder is solid, that is, the powder is dense.
  • the inlet air temperature of spray drying is 220-280°C
  • the outlet air temperature is 100-120°C
  • the centrifugal speed is 10-20 revolutions per second.
  • step (3) can be used to prepare the composite zirconia powder into ceramics.
  • the composite zirconia powder can be formed first and then sintered. Molding can adopt dry pressing molding, isostatic pressing molding, injection molding, hot die casting molding and other molding methods. Dry press molding is preferred. A press with a tonnage of 180-220 tons can be used for molding with a hydraulic pressure of 6-10MPa. By using different molds, the molded ceramics can have different shapes, such as a mobile phone back cover after molding. shape. Sintering can be carried out in air. Alternatively, sintering can be divided into two steps, first sintering in air, and then re-sintering in a reducing atmosphere.
  • the sintering procedure includes: heating from room temperature to 600°C over 400min and holding for 2h, from 600°C over 300min to 1150°C and holding for 2h, from 1150°C over 150min to 1370-1480°C and holding for 1-2h, After 150 minutes, the temperature was lowered to 900°C, and finally cooled to room temperature.
  • the sintering procedure can also include: heating from room temperature to 600°C and holding for 2h in 400min, heating from 600°C to 1150°C and holding for 2h in 300min, heating from 1150°C to 1300°C in 150min and holding holding for 2h, and holding at 1300°C for 50min Warm up to 1380-1480°C and keep for 1-2h, then cool down to 900°C after 150min, and finally cool to room temperature naturally.
  • the ceramic obtained by sintering further includes flat grinding and polishing, and cutting into a final product using a laser.
  • the final product can have a specific shape and a high degree of smoothness after being ground, polished and cut, and can be used as an electronic product shell or decoration.
  • the fourth aspect of the present application provides a ceramic piece, which contains the aforementioned zirconia ceramic.
  • the fifth aspect of the present application provides an application of the zirconia ceramic provided in the present application in the preparation of electronic product housings or decorations.
  • Fracture toughness K ic Hardness tester indentation method (diamond indenter, force 10kg, pressure test time 15s).
  • Hardness Hv Hardness tester and indentation method (diamond indenter, force 10kg, pressure test time 15s).
  • Falling weight impact use a falling weight impact tester (manufacturer CKSI, model E602SS), place the sample on the platform, use a 60g weight drop hammer to reposition the sample, starting from a height of 5cm, if it does not crack, follow the steps of 5cm each time Increase the height until the sample shows visible cracks and stop, and record the height value.
  • Deformation ratio burn out 20 ceramic samples, of which the flatness is greater than 0.4mm as bad.
  • the percentage of the number of defective samples in 20 samples is the deformation ratio. The lower the value, the better the yield rate in the sample.
  • XRD test Use X-ray diffractometer Smartlab (3kW) to test the type and content of phases.
  • XRF detection Use energy dispersive X-ray fluorescence spectrometer EDX-7000 to test the element content of polished samples.
  • composition and dosage of the raw materials and the prepared samples are shown in Table 1.
  • Raw materials 200g composite powder, which contains 2.5wt% niobium pentoxide (Nb 2 O 5 ), 2wt% alumina (Al 2 O 3 ), 3wt% zirconium silicate (ZrSiO 4 ), and the rest contains 3 mol% yttrium oxide Of zirconia powder.
  • the mass ratio of alumina: zirconium silicate is 1:1.5.
  • the raw materials were ball milled with water in a ball mill for 8 hours, and then 0.02wt% sodium carboxymethyl cellulose of the composite powder and water were added to the sand mill for 10 hours, and finally 4wt% of the binder of the composite powder (mole) was added to the sand mill.
  • PEG4000 and PVA with a ratio of 1:1 were stirred for 0.5h to form a spray slurry with a solid content of 25wt%.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the molded powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the prepared sample was observed by SEM.
  • the photo is shown in Figure 1.
  • the circle contains heterogeneous particles, and the heterogeneous particles are aggregates of zirconium silicate and alumina. It can be seen from the figure that after adding alumina and zirconium silicate, the sintered ceramic presents heterogeneous particles shown in the circle, that is, there is an aggregate state of zirconium silicate and alumina in the ceramic.
  • Raw material 200g composite powder, which contains 2.5wt% of niobium pentoxide (Nb 2 O 5 ), 4.5wt% of alumina (Al 2 O 3 ), 4.5wt% of zirconium silicate (ZrSiO 4 ), and the rest contains 2mol% Zirconium oxide powder of yttrium oxide. Among them, the mass ratio of alumina: zirconium silicate is 1:1.
  • the raw materials are ball milled with water in a ball mill for 8 hours, then 0.01wt% of triethanolamine of composite powder and water are added to the sand mill for 10 hours, and finally 5wt% of binder of composite powder is added (the molar ratio is 1: 1 PEG4000 and PVA) were stirred for 0.5h to form a spray slurry with a solid content of 55wt%.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the formed powder is heated from room temperature to 600°C for 400min and kept for 2h, from 600°C to 1150°C for 300min and kept for 2h, from 1150°C to 1370°C for 150min and kept for 2h, and then cooled to 900°C for 150min Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the prepared sample was observed by SEM, and an image similar to Fig. 1 was obtained.
  • Raw material 200g composite powder, which contains 2.5wt% of niobium pentoxide (Nb 2 O 5 ), 1wt% of alumina (Al 2 O 3 ), 1.5wt% of zirconium silicate (ZrSiO 4 ), and the rest contains 4 mol% of oxide Zirconium oxide powder of yttrium.
  • the mass ratio of alumina: zirconium silicate is 1:1.5.
  • the raw materials were ball milled with water in a ball mill for 8 hours, then 0.1wt% of powdered sodium hydroxymethyl cellulose and water were added to the sand mill for 10 hours, and finally 2wt% of powder was added to the binder (mole PEG4000 and PVA with a ratio of 1:1 were stirred for 0.5h to form a spray slurry with a solid content of 40 wt%.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the formed powder is heated from room temperature to 600°C for 400min and kept for 2h, from 600°C to 1150°C for 300min and kept for 2h, from 1150°C to 1370°C for 150min and kept for 2h, and then cooled to 900°C for 150min Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the prepared sample was observed by SEM, and an image similar to that in Fig. 1 was obtained.
  • There are heterogeneous particles in the ceramic that is, there are aggregates of zirconium silicate and alumina in the ceramic.
  • Raw material 200g of composite powder, which contains 2wt% of niobium pentoxide (Nb 2 O 5 ), 2wt% of alumina (Al 2 O 3 ), 3wt% of zirconium silicate (ZrSiO 4 ), and the remainder contains 3 mol% of yttrium oxide Zirconia powder.
  • the mass ratio of alumina: zirconium silicate is 1:1.5.
  • the raw materials are ball milled with water in a ball mill for 8 hours, and then 0.02wt% hypromellose (dispersant) of the powder is added to the sand mill and sand milled with water for 10 hours, and finally 4wt% of the powder is added for bonding (PEG4000 and PVA with a molar ratio of 1:1) were stirred for 0.5h to form a spray slurry with a solid content of 25% by weight.
  • 0.02wt% hypromellose (dispersant) of the powder is added to the sand mill and sand milled with water for 10 hours, and finally 4wt% of the powder is added for bonding (PEG4000 and PVA with a molar ratio of 1:1) were stirred for 0.5h to form a spray slurry with a solid content of 25% by weight.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the molded powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the prepared sample was observed by SEM, and an image similar to Fig. 1 was obtained.
  • Raw material 200g of composite powder, which contains 3wt% of niobium pentoxide (Nb 2 O 5 ), 2wt% of alumina (Al 2 O 3 ), 3wt% of zirconium silicate (ZrSiO 4 ), and the remainder contains 3 mol% of yttrium oxide Zirconia powder.
  • the mass ratio of alumina: zirconium silicate is 1:1.5.
  • the raw materials are ball milled with water in a ball mill for 8 hours, and then 0.02wt% hypromellose (dispersant) of the powder is added to the sand mill and sand milled with water for 10 hours, and finally 4wt% of the powder is added for bonding (PEG4000 and PVA with a molar ratio of 1:1) were stirred for 0.5h to form a spray slurry with a solid content of 25% by weight.
  • 0.02wt% hypromellose (dispersant) of the powder is added to the sand mill and sand milled with water for 10 hours, and finally 4wt% of the powder is added for bonding (PEG4000 and PVA with a molar ratio of 1:1) were stirred for 0.5h to form a spray slurry with a solid content of 25% by weight.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the molded powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the prepared sample was observed by SEM, and an image similar to Fig. 1 was obtained.
  • Raw material 200g of composite powder, which contains 2.5wt% of niobium pentoxide (Nb 2 O 5 ), 3wt% of alumina (Al 2 O 3 ), 3wt% of zirconium silicate (ZrSiO 4 ), and the rest contains 3 mol% of yttrium oxide Of zirconia powder.
  • the mass ratio of alumina: zirconium silicate is 1:1.
  • the raw materials are ball milled with water in a ball mill for 8 hours, and then 0.02wt% hypromellose (dispersant) of the powder is added to the sand mill and sand milled with water for 10 hours, and finally 4wt% of the powder is added for bonding (PEG4000 and PVA with a molar ratio of 1:1) were stirred for 0.5h to form a spray slurry with a solid content of 25% by weight.
  • 0.02wt% hypromellose (dispersant) of the powder is added to the sand mill and sand milled with water for 10 hours, and finally 4wt% of the powder is added for bonding (PEG4000 and PVA with a molar ratio of 1:1) were stirred for 0.5h to form a spray slurry with a solid content of 25% by weight.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the molded powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the prepared sample was observed by SEM, and an image similar to Fig. 1 was obtained.
  • Raw material 200g composite powder, which contains 2.5wt% of niobium pentoxide (Nb 2 O 5 ), 2wt% of alumina (Al 2 O 3 ), 4.5wt% of zirconium silicate (ZrSiO 4 ), and the rest contains 3 mol% of oxide Zirconium oxide powder of yttrium.
  • the mass ratio of alumina: zirconium silicate is 1:2.25.
  • the raw materials are ball milled with water in a ball mill for 8 hours, and then 0.02wt% hypromellose (dispersant) of the powder is added to the sand mill and sand milled with water for 10 hours, and finally 4wt% of the powder is added for bonding (PEG4000 and PVA with a molar ratio of 1:1) were stirred for 0.5h to form a spray slurry with a solid content of 25% by weight.
  • 0.02wt% hypromellose (dispersant) of the powder is added to the sand mill and sand milled with water for 10 hours, and finally 4wt% of the powder is added for bonding (PEG4000 and PVA with a molar ratio of 1:1) were stirred for 0.5h to form a spray slurry with a solid content of 25% by weight.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the molded powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the prepared sample was observed by SEM, and an image similar to Fig. 1 was obtained.
  • Raw material 200g composite powder, which contains 2.5wt% tantalum pentoxide (Ta 2 O 5 ), 2wt% alumina (Al 2 O 3 ), 3wt% zirconium silicate (ZrSiO 4 ), and the rest contains 3 mol% yttrium oxide Of zirconia powder.
  • the mass ratio of alumina: zirconium silicate is 1:1.5.
  • the raw materials were ball milled with water in a ball mill for 8 hours, and then 0.02wt% sodium carboxymethyl cellulose of the composite powder and water were added to the sand mill for 10 hours, and finally 4wt% of the binder of the composite powder (mole) was added to the sand mill.
  • PEG4000 and PVA with a ratio of 1:1 were stirred for 0.5h to form a spray slurry with a solid content of 25wt%.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the molded powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconium oxide is a solid solution formed by yttrium oxide, tantalum oxide and zirconium oxide.
  • the prepared sample was observed by SEM, and an image similar to Fig. 1 was obtained.
  • Raw material 200g composite powder, which contains 2.5wt% niobium pentoxide, 4wt% alumina, 6wt% zirconium silicate, and the rest is zirconia powder containing 3mol% yttrium oxide. Among them, the mass ratio of alumina: zirconium silicate is 1:1.5.
  • the raw materials were ball milled with water in a ball mill for 8 hours, and then 0.02wt% sodium carboxymethyl cellulose of the composite powder and water were added to the sand mill for 10 hours, and finally 4wt% of the binder of the composite powder (mole) was added to the sand mill.
  • PEG4000 and PVA with a ratio of 1:1 were stirred for 0.5h to form a spray slurry with a solid content of 25wt%.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the molded powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the prepared sample was observed by SEM, and an image similar to Fig. 1 was obtained.
  • Raw material 200g composite powder, which contains 2.5wt% niobium pentoxide, 3wt% alumina, 2wt% zirconium silicate, and the rest is zirconia powder containing 3mol% yttrium oxide. Among them, the mass ratio of alumina: zirconium silicate is 1:0.67.
  • the raw materials were ball milled with water in a ball mill for 8 hours, and then 0.02wt% sodium carboxymethyl cellulose of the composite powder and water were added to the sand mill for 10 hours, and finally 4wt% of the binder of the composite powder (mole) was added to the sand mill.
  • PEG4000 and PVA with a ratio of 1:1 were stirred for 0.5h to form a spray slurry with a solid content of 25wt%.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the molded powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the prepared sample was observed by SEM, and an image similar to Fig. 1 was obtained.
  • Raw material 200g composite powder, which contains 2.5wt% niobium pentoxide, 1wt% alumina, 6wt% zirconium silicate, and the rest is zirconia powder containing 3mol% yttrium oxide. Among them, the mass ratio of alumina: zirconium silicate is 1:6.
  • the raw materials were ball milled with water in a ball mill for 8 hours, and then 0.02wt% sodium carboxymethyl cellulose of the composite powder and water were added to the sand mill for 10 hours, and finally 4wt% of the binder of the composite powder (mole) was added to the sand mill.
  • PEG4000 and PVA with a ratio of 1:1 were stirred for 0.5h to form a spray slurry with a solid content of 25wt%.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the formed powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the prepared sample was observed by SEM, and an image similar to Fig. 1 was obtained.
  • Raw material 200g composite powder, which contains 4wt% niobium pentoxide, 2wt% alumina, 3wt% zirconium silicate, and the rest is zirconia powder containing 3mol% yttrium oxide. Among them, the mass ratio of alumina: zirconium silicate is 1:1.5.
  • the raw materials were ball milled with water in a ball mill for 8 hours, and then 0.02wt% sodium carboxymethyl cellulose of the composite powder and water were added to the sand mill for 10 hours, and finally 4wt% of the binder of the composite powder (mole) was added to the sand mill.
  • PEG4000 and PVA with a ratio of 1:1 were stirred for 0.5h to form a spray slurry with a solid content of 25wt%.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the molded powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the prepared sample was observed by SEM, and an image similar to Fig. 1 was obtained.
  • Raw material 200g of composite powder, which contains 2.5wt% of niobium pentoxide, 6wt% of alumina, 6wt% of zirconium silicate, and the rest is zirconia powder containing 3mol% of yttrium oxide. Among them, the mass ratio of alumina: zirconium silicate is 1:1.
  • the raw materials were ball milled with water in a ball mill for 8 hours, and then 0.02wt% sodium carboxymethyl cellulose of the composite powder and water were added to the sand mill for 10 hours, and finally 4wt% of the binder of the composite powder (mole) was added to the sand mill.
  • PEG4000 and PVA with a ratio of 1:1 were stirred for 0.5h to form a spray slurry with a solid content of 25wt%.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the molded powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the prepared sample was observed by SEM, and an image similar to Fig. 1 was obtained.
  • Raw material 200 g of composite powder, of which alumina (Al 2 O 3 ) is 0.25 wt%, and the remainder is zirconia powder containing 3 mol% of yttria.
  • the raw materials are ball milled with water in a ball milling tank for 8 hours, then 0.02wt% hypromellose powder and water are added to the sand mill for 10 hours, and finally 4wt% binder of the powder is added (molar ratio PEG4000 and PVA (1:1) were stirred for 0.5h to form a slurry for spraying.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the molded powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide and zirconia.
  • Raw material 200g composite powder, which contains 2.5wt% of niobium pentoxide, 0.25wt% of aluminum oxide (Al 2 O 3 ), and the rest is zirconia powder containing 3 mol% of yttrium oxide.
  • the raw materials are ball milled with water in a ball milling tank for 8 hours, then 0.02wt% hypromellose powder and water are added to the sand mill for 10 hours, and finally 4wt% binder of the powder is added (molar ratio PEG4000 and PVA (1:1) were stirred for 0.5h to form a slurry for spraying.
  • the slurry is sent to the spray tower for spray drying (the inlet air temperature is 250°C, the outlet air temperature is 110°C, and the centrifugal rotation speed is 15 revolutions per second) to form a spherical powder with strong fluidity for dry pressing, and then dry pressing and forming (The 200-ton press uses 8MPa oil pressure).
  • the molded powder is heated from room temperature to 600°C for 400 minutes and kept for 2 hours, from 600°C to 1150°C for 300 minutes and kept for 2 hours, from 1150°C to 1410°C for 150 minutes and kept for 2 hours, and then cooled to 900°C for 150 minutes Finally, the process of natural cooling to room temperature is sintered in air.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the difference is that there is no zirconium silicate, and the preparation of zirconium oxide ceramics is carried out.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • Example 1 According to the method of Example 1, the difference is that there is no alumina and the preparation of zirconia ceramics is carried out.
  • the size is the shape and size of the back cover of the mobile phone, 150*75*0.6mm.
  • tetragonal zirconia is a solid solution formed by yttrium oxide, niobium oxide and zirconium oxide.
  • the zirconia ceramics provided in the present application can have significantly improved impact resistance while simultaneously having suitable toughness. And can have suitable hardness.
  • Example 10 the mass ratio of alumina to zirconium silicate is not in the range of 1:(1-5), and the impact resistance of ceramics is poor.
  • Examples 1-13 the worst impact resistance is in Example 11.
  • the average drop weight height of the zirconium oxide ceramics in 1 is 27.5 cm, but it is still higher than the average drop weight height in Comparative Examples 1-4, indicating that the impact resistance of the zirconia ceramics of the present application is better than that of the comparative examples.
  • the toughness of the zirconia ceramics of the present application can be as high as 13 MPa m 1/2 .

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Abstract

提出了氧化锆陶瓷、制备氧化锆陶瓷的方法及其应用和组合物。所述氧化锆陶瓷以元素计包含:60.5-70.5wt%的Zr、2.5-5.45wt%的Y、0.05-2.65wt%的Al、0.015-1.07wt%的Si,以及0.34-2.8wt%的M,所述M包括Nb和Ta的至少之一;且所述氧化锆陶瓷的物相组成包含:四方相氧化锆、氧化铝和硅酸锆,氧化铝和硅酸锆的含量之和为0.2-12wt%,所述四方相氧化锆的含量为84-99.3wt%;所述四方相氧化锆包括氧化钇、M xO y与氧化锆形成的固溶体;所述x满足1≤x≤3,所述y满足3≤y≤6。

Description

氧化锆陶瓷、制备氧化锆陶瓷的方法及其应用和组合物 技术领域
本申请涉及氧化锆陶瓷领域,具体涉及氧化锆陶瓷、制备氧化锆陶瓷的方法及其应用和组合物。
背景技术
氧化锆陶瓷由于具有耐腐蚀性好硬度高强度高的特点,其韧性(达到5-6MPa m 1/2)高,但在做成大面积外观件时,仍存在抗冲击性弱的缺点。另外,在制备成手机等电子设备的后盖产品时,存在密度较高带来的重量大的问题,高介电常数带来的信号传输问题。针对这些问题,虽然可以通过多加入氧化铝的方式来降低密度和介电常数,但氧化铝的高硬度高脆性会导致加工难度大幅上升,从而导致良品率低下,成本高。因此,研发出一种兼具高抗冲击性和韧性的陶瓷,对陶瓷后盖在5G时代应用非常重要。
发明内容
本申请的目的是为了克服现有氧化锆陶瓷存在的不能兼具抗冲击性能和韧性的问题,提供了氧化锆陶瓷、制备氧化锆陶瓷的方法及其应用和组合物。
为了实现上述目的,本申请第一方面提供一种氧化锆陶瓷,所述氧化锆陶瓷以元素计包含:60.5-70.5wt%的Zr、2.5-5.45wt%的Y、0.05-2.65wt%的Al、0.015-1.07wt%的Si,以及0.34-2.8wt%的M,所述M包括Nb和Ta的至少之一;且所述氧化锆陶瓷的物相组成包含:四方相氧化锆、氧化铝和硅酸锆,氧化铝和硅酸锆的含量之和为0.2-12wt%,所述四方相氧化锆的含量为 84-99.3wt%;所述四方相氧化锆包括氧化钇、M xO y与氧化锆形成的固溶体;所述x满足1≤x≤3,所述y满足3≤y≤6。
本申请第二方面提供一种氧化锆陶瓷,所述氧化锆陶瓷的物相组成包含:四方相氧化锆、氧化铝和硅酸锆,氧化铝和硅酸锆的含量之和为0.2-12wt%,所述四方相氧化锆的含量为84-99.3wt%;所述四方相氧化锆包括氧化钇、M xO y与氧化锆形成的固溶体,所述氧化锆陶瓷中以元素计Y的含量为2.5-5.45wt%,M的含量为0.34-2.8wt%;所述M包括Nb和Ta的至少之一,且所述x满足1≤x≤3,所述y满足3≤y≤6。
本申请第三方面提供一种组合物,该组合物包含:含氧化锆组分、氧化铝、硅酸锆,以及M xO y;其中,以所述含氧化锆组分的总量为基准,所述含氧化锆组分中含有氧化锆以及2-4mol%的氧化钇;
以所述组合物的总量为基准,含氧化锆组分的含量为84-99.3wt%,氧化铝和硅酸锆的总含量为0.2-12wt%,M xO y的含量为0.5-4wt%。
本申请第四方面提供一种制备氧化锆陶瓷的方法,包括:
(1)将本申请上述组合物中的各组分的粉体形成浆料;
(2)将所述浆料进行干燥,得到复合氧化锆粉体;
(3)将所述复合氧化锆粉体进行成型和烧结,得到氧化锆陶瓷。
本申请第五方面提供一种本申请上述的氧化锆陶瓷在制备电子产品外壳或装饰品中的应用。
本申请提供一种氧化锆陶瓷,所述氧化锆陶瓷以元素计包含:60.5-70.5wt%的Zr、2.5-5.45wt%的Y、0.05-2.65wt%的Al、0.015-1.07wt%的Si,以及0.34-2.8wt%的Nb和/或Ta;且所述氧化锆陶瓷的物相组成包含:84-99.3wt%的四方相氧化 锆、0.2-12wt%的氧化铝和硅酸锆;所述四方相氧化锆为氧化钇、氧化铌和/或氧化钽与氧化锆形成的固溶体。
优选地,所述氧化铝和硅酸锆的质量比为(1:1)-(1:5)。
本申请提供一种制备本申请的氧化锆陶瓷的组合物,该组合物包含氧化锆粉体、氧化铝粉体、硅酸锆粉体,以及氧化铌和/或氧化钽粉体;其中,以所述氧化锆粉体的总量为基准,所述氧化锆粉体中含有2-4mol%的氧化钇;
以所述组合物的总量为基准,氧化锆粉体的含量为84-99.3wt%,氧化铝粉体和硅酸锆粉体的总含量为0.2-12wt%,氧化铌和/或氧化钽的含量为0.5-4wt%。
优选地,所述组合物中,氧化铝与硅酸锆的质量比为(1:1)-(1:5)。
本申请提供一种氧化锆陶瓷的制备方法,包括:
(1)将本申请的组合物中的各粉体加水、分散剂和粘结剂进行湿磨,得到浆料;
(2)将所述浆料进行干燥,得到复合氧化锆粉体;
(3)将所述复合氧化锆粉体进行成型,然后在空气中进行烧结,得到陶瓷。
通过上述技术方案,本申请提供了具有优异的抗冲击性,同时具有高韧性的氧化锆陶瓷。
附图说明
图1为本申请实施例1制得的陶瓷的SEM图像;
图2为本申请对比例2制得的陶瓷的SEM图像。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
本申请第一方面提供一种氧化锆陶瓷,所述氧化锆陶瓷以元素计包含:60.5-70.5wt%的Zr、2.5-5.45wt%的Y、0.05-2.65wt%的Al、0.015-1.07wt%的Si,以及0.34-2.8wt%的M,所述M包括Nb和Ta的至少之一,且氧化锆陶瓷的物相组成包含:四方相氧化锆、氧化铝和硅酸锆,氧化铝和硅酸锆的含量之和为0.2-12wt%,四方相氧化锆的含量为84-99.3wt%,四方相氧化锆包括氧化钇、M xO y与氧化锆形成的固溶体,x满足1≤x≤3,所述y满足3≤y≤6。
根据本申请的示例,氧化锆陶瓷的物相组成包含:四方相氧化锆、氧化铝和硅酸锆,氧化铝和硅酸锆的含量之和为0.2-12wt%,所述四方相氧化锆的含量为84-99.3wt%,所述四方相氧化锆包括氧化钇、M xO y与氧化锆形成的固溶体,氧化锆陶瓷中以元素计Y的含量为2.5-5.45wt%,M的含量为0.34-2.8wt%,M包括Nb和Ta的至少之一,且x满足1≤x≤3,所述y满足3≤y≤6。
氧化锆陶瓷以元素计包含:60.5-70.5wt%的Zr、2.5-5.45wt%的Y、0.05-2.65wt%的Al、0.015-1.07wt%的Si,以及0.34-2.8wt%的M。根据本申请的实施方式,氧化锆陶瓷还包括适量的O。本领域技术人员能够理解的是,氧化锆陶瓷中必然含有O元素,O元素的含量可根据Zr、Y、Al、Si以及M元素的含量确定,以用于形成包括但不限于氧化锆、氧化钇、硅酸锆、氧化铝、M xO y等。
本领域技术人员可根据需要M的化合价来确定x与y。例如,x可以为2,y可以为5,M xO y可以包括Nb 2O 5以及Ta 2O 5的至少之一。该陶瓷具有高致密性、高韧性和高抗冲性,颜色可以为白色。
本申请提供的实施方式中,氧化锆陶瓷包含:63-68.75wt%的Zr、3.35-4.7wt%的Y、0.53-1.58wt%的Al、0.15-0.92wt%的Si,以及0.68-2.1wt%的M。也就是说,氧化锆陶瓷包含0.68-2.1wt%的Nb和/或Ta,即氧化锆陶瓷包含Nb和Ta的至少之一,且Nb和Ta的至少之一的含量为0.68-2.1wt%。根据本申请的实施方式,氧化锆陶瓷还包括适量的O。本申请提供的实施方式中,氧化铝和硅酸锆的质量比为1:(1-5),优选为1:(1-2.25)。进一步地,氧化锆陶瓷中限定Al和Si的含量关系,有利于改善陶瓷的性能,兼具高抗冲性和韧性。优选地,Al:Si的质量比为(2:3)-(5:1),进一步优选为(1.6:1)-(3.5:1)。质量比可以是选自(1.6:1)、(1.8:1)、(2.0:1)、(2.2:1)、(2.4:1)、(2.6:1)、(2.8:1)、(3.0:1)、(3.2:1)、(3.4:1)和(3.5:1),以及由上述数值任意组成的范围。
本申请提供的实施方式中,上述元素的含量可以通过高能XRF检测。氧化锆陶瓷的元素组成还可能含有其他元素,如氧元素。
本申请提供的氧化锆陶瓷,含有的物相能够通过XRD测定。优选地,氧化锆陶瓷的物相组成包含:四方相氧化锆、氧化铝和硅酸锆,其中氧化铝和硅酸锆的含量之和为2-9wt%,四方相氧化锆的含量为88-97wt%。在XRD谱图中,出现氧化锆的四方相的衍射峰,是氧化锆陶瓷制备中加入了氧化钇、氧化铌和/或氧化钽,与氧化锆形成固溶体。其中,固溶体可以是氧化钇、氧化铌与氧化锆形成的固溶体,也可以是氧化钇、氧化钽与氧化锆形成的固溶体,还可以是氧化钇、氧化铌、氧化钽与氧化锆形成的固溶体。氧化锆陶瓷中可能还含 有其他物相,但对本申请的氧化锆陶瓷没有负面影响。本申请中,氧化锆陶瓷包含的物相的上述含量以氧化锆陶瓷为基准。
本申请的氧化锆陶瓷具有高的抗冲击性和韧性。优选地,氧化锆陶瓷的韧性为10.0MPa m 1/2以上,优选为10.9-13MPa m 1/2
本申请提供的实施方式中,氧化锆陶瓷的维式硬度为1170-1280Hv。
本申请提供的实施方式中,氧化锆陶瓷的落锤冲击测试结果中,平均落锤高度大于等于27.5cm,优选平均落锤高度为30.5-37cm。
本申请提供的实施方式中,氧化锆陶瓷的变形比例为0%。即检测样品中,不良率低。
本申请提供的实施方式中,氧化锆陶瓷还可以同时具有其他改进的力学性能。
本申请第二方面提供一种组合物,该组合物包含:含氧化锆组分、氧化铝、硅酸锆、以及M xO y
其中,以含氧化锆组分的总量为基准,含氧化锆组分中含有氧化锆以及2-4mol%的氧化钇。以组合物的总量为基准,含氧化锆组分的含量为84-99.3wt%,氧化铝和硅酸锆的总含量为0.2-12wt%,M xO y的含量为0.5-4wt%。
根据本申请的一些示例,上述组合物中的各组分可以以粉体形式存在。
本申请提供的实施方式中,提供的组合物含有各种氧化物,可以获得氧化锆陶瓷,并且具有高韧性和高抗冲击性能,氧化锆陶瓷的颜色可以为白色。组合物中,各氧化物的使用量进一步优选满足:以组合物的总量为基准,含氧化锆组分的含量为88-97wt%,氧化铝和硅酸锆的总含量为2-9wt%,M xO y的含量为1-3wt%。优选地,组合物中各氧化物的总量为100wt%。
本申请中,氧化钇、氧化铌和/或氧化钽可以带来稳定和增韧作用,氧化铝 具有增强作用,硅酸锆可以与氧化铝聚集而产生异相颗粒(硅酸锆和氧化铝的聚集态),增加组合物的韧性和抗冲击性。而且本申请提供的氧化锆陶瓷特别含有上述特定含量的各种元素和物相时,可以协同获得韧性和抗冲击性改进的氧化锆陶瓷。当各种氧化物含量不在上述限定范围内时,不能提供满足本申请力学性能的氧化锆陶瓷。并且,满足上述要求的氧化锆陶瓷还可具有白色的颜色。
本申请提供的实施方式中,优选地,组合物中,氧化铝与硅酸锆的质量比为1:(1-5)。采取直接在组合物中加入硅酸锆和氧化铝组分,氧化铝与硅酸锆以特定比例组合,相互作用。在氧化锆陶瓷中形成的聚集态可以实现对氧化锆陶瓷的抗冲击性能的提高,陶瓷具有好的抗变形性和高落锤性能。优选氧化铝与硅酸锆的质量比为(1:1)-(1:2.25),质量比可以是选自(1:1.1)、(1:1.2)、(1:1.3)、(1:1.4)、(1:1.5)、(1:1.6)、(1:1.7)、(1:1.8)、(1:1.9)、(1:2.0)、(1:2.1)、(1:2.2)和(1:2.25),以及由上述数值任意组成的范围。
根据本申请的实施方式,组合物为制备上述氧化锆陶瓷的组合物。
本申请第三方面提供一种制备氧化锆陶瓷的方法,包括:
(1)将本申请的组合物中各组分的粉体形成浆料。
(2)将浆料进行干燥,得到复合氧化锆粉体。
(3)将复合氧化锆粉体进行成型和烧结,得到陶瓷。
本申请提供的实施方式中,根据本申请的实施方式,步骤(1)中,形成浆料包括:将组合物中各组分的粉体、分散剂和粘结剂进行混合,得到所述浆料。
本申请对组合物中各组分的粉体的粒径不作限制。可以使用粒径较小的粉 体作为原料,将组合物中的各粉体、分散剂和粘结剂进行混合,即得到浆料。也可以使用粒径较大的粉体作为原料,将组合物中的各粉体、分散剂和粘结剂进行湿磨,通过湿磨降低粉体的粒径,进而得到浆料,从而有利于降低制备氧化锆陶瓷的成本。
以下以使用粒径较大的粉体作为原料进行说明。例如含氧化锆组分的粉体含有氧化钇,粒径中值为0.3-0.6μm,比表面积为7-13m 2/g。M xO y粉体的粒径中值为8-12μm。当M xO y为氧化铌时,氧化铌粉体的粒径中值为8-12μm。当M xO y为氧化钽时,氧化钽粉体的粒径中值为8-12μm。硅酸锆粉体的粒径中值为0.5-1μm。氧化铝粉体的粒径中值为0.15-0.6μm。
步骤(1)实现将作为原料的各种氧化物粉体研磨,降低粒径并得到浆料。研磨过程为湿磨,具体过程可以包括:将各种氧化物粉体和水混合为浆液,先进行球磨混合,然后再砂磨粉碎,使各种氧化物粉体的粒径中值至纳米级(如250-500nm)。更为具体地,将各种氧化物粉体按本申请的含量在球磨罐中加水进行球磨8-10h,然后再在砂磨机中加入分散剂和水砂磨8-10h,最后加入合适比例的粘结剂(如PVA和/或聚乙二醇4000)再搅拌2-4h。球磨罐和砂磨机使用氧化锆陶瓷的内衬以及氧化锆研磨球。氧化锆研磨球的选用粒径、不同粒径研磨球的配比、研磨球与粉体的重量比,以及水的用量可以控制以实现获得所期望获得的氧化物粉体的粒径。
本申请提供的实施方式中,步骤(1)中,分散剂选自羟丙甲纤维素、羧甲基纤维素钠和三乙醇胺中的至少一种。粘结剂选自聚乙烯醇和/或聚乙二醇4000,也即是说粘结剂含有聚乙烯醇和聚乙二醇4000中的一种或两种。分散剂可以促进粉体中各组分混合均匀。粘结剂有利于粉体的成型性。优选地,粘结剂为聚乙烯醇(PVA)和聚乙二醇4000(PEG4000),聚乙烯醇和聚乙二醇 4000的摩尔比为1:(1-2),优选为1:1。本申请中,分散剂和粘结剂均可商购获得。
本申请提供的实施方式中,分散剂的加入量为组合物中各组分的粉体总量的0.005-0.5wt%,优选为0.01-0.1wt%。
本申请提供的实施方式中,粘结剂的加入量为组合物中各组分的粉体总量的0.5-5wt%,优选为2-5wt%。
本申请提供的实施方式中,浆料的固含量为20-60wt%,优选为25-55wt%。可以有更好的磨料效果。
本申请提供的实施方式中,步骤(2)可以采用各种干燥方式,例如可以采用喷雾干燥,形成流动性较强的球形粉体,其中,流动性较强的球形粉体是指:粉体的球形度较好,粉体为实心状态,即粉体密实。优选喷雾干燥的进风温度为220-280℃,出风为100-120℃,离心转速10-20转每秒。
本申请提供的实施方式中,步骤(3)可以用于将复合氧化锆粉体制备为陶瓷。可以先将复合氧化锆粉体成型,然后烧结。成型可以采用干压成型、等静压成型、注射成型、热压铸成型等成型方式。优选为干压成型,可以使用吨位180-220吨的压机使用6-10MPa的油压压强进行成型,通过使用不同的模具可以使成型后的陶瓷具有不同的形状,例如成型后具有手机后盖形状。烧结可以在空气中进行。或者,烧结可以分为两步,先空气中烧结,再在还原气氛中复烧结。优选地,烧结的程序包括:从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1370-1480℃并保温1-2h,然后经过150min降温至900℃,最后自然冷却至室温。烧结的程序还可以包括:从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1300℃并保温 2h,从1300℃经50min升温至1380-1480℃并保温1-2h,然后经过150min降温至900℃,最后自然冷却至室温。
本申请提供的实施方式中,经过烧结得到的陶瓷还包括进行平磨抛光,使用激光器切成最终产品。本领域技术人员能够理解的是,该最终产品经过平磨抛光和切割,可具有特定的形状以及较高的光滑程度,可作为电子产品外壳或装饰品使用。
本申请的第四方面提供一种陶瓷件,所述陶瓷件含有前面所述的氧化锆陶瓷。
本申请第五方面提供一种本申请提供的氧化锆陶瓷在制备电子产品外壳或装饰品中的应用。
以下将通过实施例对本申请进行详细描述。以下实施例和对比例中,
断裂韧性K ic:硬度计压痕法(金刚压头、力10kg、试压时间15s)。
硬度Hv:硬度计及压痕法(金刚压头、力10kg、试压时间15s)。
落锤冲击:使用落锤冲击试验机(制造商CKSI,型号E602SS),将样品放于平台,使用60g重的落锤砸样品重新位置,从5cm高度开始,如果不裂就按照每次5cm的高度增加,直到样品出现肉眼可见裂纹停止,记录高度值。
变形比例:烧出20片陶瓷样品,其中平面度大于0.4mm的为不良。不良样品的数目占20片样品的百分比为变形比例。此数值越低,说明样品中良品率越好。
SEM图像观察:样品抛光后,使用日本电子公司的型号为JSM-7600F的SEM电镜,拍摄放大200倍的图像。
色度(Lab)测试:采用诺苏电子-China-color1101的色差仪测试样品的L、a、b值并与炭黑发黑的标准样进行对比。L在85-95,a值在-0.5到0.5,b值 在-1到1,说明为白色。
XRD测试:使用X射线衍射仪Smartlab(3kW)测试物相种类和含量。
XRF检测:使用能量色散型X射线荧光光谱仪EDX-7000测试抛光样品的元素含量。
以下实施例和对比例中,原料和制得样品的组成用量见表1。
实施例1
原料:复合粉200g,其中包含五氧化二铌(Nb 2O 5)2.5wt%,氧化铝(Al 2O 3)2wt%,硅酸锆(ZrSiO 4)3wt%,余下为含有3mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:1.5。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入复合粉的0.02wt%的羧甲基纤维素钠和水砂磨10h,最后加入复合粉的4wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为25wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1,其中Al:Si的质量比为2.4。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶 体。
制得样品进行SEM观察,照片如图1所示,其中圆圈内含有异相颗粒,异相颗粒为硅酸锆和氧化铝的聚集态。由图可看出,在加入氧化铝和硅酸锆后,烧结出的陶瓷呈现圆圈内显示的异相颗粒,即陶瓷中存在硅酸锆和氧化铝的聚集态。
实施例2
原料:复合粉200g,其中包含五氧化二铌(Nb 2O 5)2.5wt%,氧化铝(Al 2O 3)4.5wt%,硅酸锆(ZrSiO 4)4.5wt%,余下为含有2mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:1。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入复合粉的0.01wt%的三乙醇胺和水砂磨10h,最后加入复合粉的5wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为55wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1370℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1,其中Al:Si的质量比为3.6。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶 体。
制得样品进行SEM观察,得到类似图1的图像,陶瓷中存在异相颗粒,即陶瓷中存在硅酸锆和氧化铝的聚集态。
实施例3
原料:复合粉200g,其中包含五氧化二铌(Nb 2O 5)2.5wt%,氧化铝(Al 2O 3)1wt%,硅酸锆(ZrSiO 4)1.5wt%,余下为含有4mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:1.5。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入粉体的0.1wt%的羟甲基纤维素钠和水砂磨10h,最后加入粉体的2wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为40wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1370℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测,和XRD检测,结果见表1,其中Al:Si的质量比为2.3。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
制得样品进行SEM观察,得到类似图1的图像,陶瓷中存在异相颗粒, 即陶瓷中存在硅酸锆和氧化铝的聚集态。
实施例4
原料:复合粉200g,其中包含五氧化二铌(Nb 2O 5)2wt%,氧化铝(Al 2O 3)2wt%,硅酸锆(ZrSiO 4)3wt%,余下为含有3mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:1.5。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入粉体的0.02wt%的羟丙甲纤维素(分散剂)和水砂磨10h,最后加入粉体的4wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为25wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1,其中Al:Si的质量比为2.4。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
制得样品进行SEM观察,得到类似图1的图像,陶瓷中存在异相颗粒,即陶瓷中存在硅酸锆和氧化铝的聚集态。
实施例5
原料:复合粉200g,其中包含五氧化二铌(Nb 2O 5)3wt%,氧化铝(Al 2O 3)2wt%,硅酸锆(ZrSiO 4)3wt%,余下为含有3mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:1.5。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入粉体的0.02wt%的羟丙甲纤维素(分散剂)和水砂磨10h,最后加入粉体的4wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为25wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1,其中Al:Si的质量比为2.4。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
制得样品进行SEM观察,得到类似图1的图像,陶瓷中存在异相颗粒,即陶瓷中存在硅酸锆和氧化铝的聚集态。
实施例6
原料:复合粉200g,其中包含五氧化二铌(Nb 2O 5)2.5wt%,氧化铝(Al 2O 3) 3wt%,硅酸锆(ZrSiO 4)3wt%,余下为含有3mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:1。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入粉体的0.02wt%的羟丙甲纤维素(分散剂)和水砂磨10h,最后加入粉体的4wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为25wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1,其中Al:Si的质量比为3.5。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
制得样品进行SEM观察,得到类似图1的图像,陶瓷中存在异相颗粒,即陶瓷中存在硅酸锆和氧化铝的聚集态。
实施例7
原料:复合粉200g,其中包含五氧化二铌(Nb 2O 5)2.5wt%,氧化铝(Al 2O 3)2wt%,硅酸锆(ZrSiO 4)4.5wt%,余下为含有3mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:2.25。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入粉体的0.02wt%的羟丙甲纤维素(分散剂)和水砂磨10h,最后加入粉体的4wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为25wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1,其中Al:Si的质量比为1.6。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
制得样品进行SEM观察,得到类似图1的图像,陶瓷中存在异相颗粒,即陶瓷中存在硅酸锆和氧化铝的聚集态。
实施例8
原料:复合粉200g,其中包含五氧化二钽(Ta 2O 5)2.5wt%,氧化铝(Al 2O 3)2wt%,硅酸锆(ZrSiO 4)3wt%,余下为含有3mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:1.5。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入复合粉的0.02wt%的羧甲基纤维素钠和水砂磨10h,最后加入复合粉的4wt%的粘结剂(摩尔比 为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为25wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1,其中Al:Si的质量比为2.5。其中,四方相氧化锆为氧化钇、氧化钽与氧化锆形成的固溶体。
制得样品进行SEM观察,得到类似图1的图像,陶瓷中存在异相颗粒,即陶瓷中存在硅酸锆和氧化铝的聚集态。
实施例9
原料:复合粉200g,其中包含五氧化二铌2.5wt%,氧化铝4wt%,硅酸锆6wt%,余下为含有3mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:1.5。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入复合粉的0.02wt%的羧甲基纤维素钠和水砂磨10h,最后加入复合粉的4wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为25wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离 心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1,其中Al:Si的质量比为2.3。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
制得样品进行SEM观察,得到类似图1的图像,陶瓷中存在异相颗粒,即陶瓷中存在硅酸锆和氧化铝的聚集态。
实施例10
原料:复合粉200g,其中包含五氧化二铌2.5wt%,氧化铝3wt%,硅酸锆2wt%,余下为含有3mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:0.67。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入复合粉的0.02wt%的羧甲基纤维素钠和水砂磨10h,最后加入复合粉的4wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为25wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1,其中Al:Si的质量比为5.4。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
制得样品进行SEM观察,得到类似图1的图像,陶瓷中存在异相颗粒,即陶瓷中存在硅酸锆和氧化铝的聚集态。
实施例11
原料:复合粉200g,其中包含五氧化二铌2.5wt%,氧化铝1wt%,硅酸锆6wt%,余下为含有3mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:6。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入复合粉的0.02wt%的羧甲基纤维素钠和水砂磨10h,最后加入复合粉的4wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为25wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h, 然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1,其中Al:Si的质量比为0.6。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
制得样品进行SEM观察,得到类似图1的图像,陶瓷中存在异相颗粒,即陶瓷中存在硅酸锆和氧化铝的聚集态。
实施例12
原料:复合粉200g,其中包含五氧化二铌4wt%,氧化铝2wt%,硅酸锆3wt%,余下为含有3mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:1.5。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入复合粉的0.02wt%的羧甲基纤维素钠和水砂磨10h,最后加入复合粉的4wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为25wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖 形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1,其中Al:Si的质量比为2.3。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
制得样品进行SEM观察,得到类似图1的图像,陶瓷中存在异相颗粒,即陶瓷中存在硅酸锆和氧化铝的聚集态。
实施例13
原料:复合粉200g,其中包含五氧化二铌2.5wt%,氧化铝6wt%,硅酸锆6wt%,余下为含有3mol%氧化钇的氧化锆粉。其中,氧化铝:硅酸锆的质量比为1:1。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入复合粉的0.02wt%的羧甲基纤维素钠和水砂磨10h,最后加入复合粉的4wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料,固含量为25wt%。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1,其中Al:Si 的质量比为3.5。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
制得样品进行SEM观察,得到类似图1的图像,陶瓷中存在异相颗粒,即陶瓷中存在硅酸锆和氧化铝的聚集态。
对比例1
原料:复合粉200g,其中氧化铝(Al 2O 3)0.25wt%,余下为含有3mol%氧化钇的氧化锆粉。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入粉体的0.02wt%的羟丙甲纤维素和水砂磨10h,最后加入粉体的4wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1。其中,四方相氧化锆为氧化钇与氧化锆形成的固溶体。
对比例2
原料:复合粉200g,其中包含五氧化二铌2.5wt%,氧化铝(Al 2O 3)0.25wt%,余下为含有3mol%氧化钇的氧化锆粉。
将原料在球磨罐中加水球磨8h,然后再在砂磨机中加入粉体的0.02wt%的羟丙甲纤维素和水砂磨10h,最后加入粉体的4wt%的粘结剂(摩尔比为1:1的PEG4000和PVA)搅拌0.5h,形成喷雾用浆料。
将浆料送入喷雾塔进行喷雾干燥(进风温度为250℃,出风为110℃,离心转速15转每秒)形成用来干压的流动性较强的球形粉体,之后干压成型(吨位200吨的压机使用8MPa的油压压强)。
将成型粉体按照从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1410℃并保温2h,然后经过150min降温至900℃,最后自然冷却至室温的过程在空气中进行烧结。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
制得样品进行SEM观察,如图2所示,图中没有出现异相颗粒。
对比例3
按照实施例1的方法,不同的是,没有硅酸锆,进行氧化锆陶瓷制备。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
对比例4
按照实施例1的方法,不同的是,没有氧化铝,进行氧化锆陶瓷制备。
将烧结产物进行打磨抛光并激光切割后即制成最终样品,尺寸为手机后盖形状和大小,150*75*0.6mm。
将制得样品进行高能XRF检测和XRD检测,结果见表1。其中,四方相氧化锆为氧化钇、氧化铌与氧化锆形成的固溶体。
表1
Figure PCTCN2020114398-appb-000001
Figure PCTCN2020114398-appb-000002
Figure PCTCN2020114398-appb-000003
Figure PCTCN2020114398-appb-000004
Figure PCTCN2020114398-appb-000005
Figure PCTCN2020114398-appb-000006
测试例1
将实施例1-13和对比例1-4制得的样品进行硬度、韧性、变形比例和落锤冲击性测试,结果见表2。
表2
Figure PCTCN2020114398-appb-000007
由表2可看出,实验例与对比例比较,本申请提供的氧化锆陶瓷,可以具有显著提高的抗冲击性的同时兼顾具有合适的韧性。并且可以具有合适的硬度。
实施例10、11氧化铝与硅酸锆的质量比不在1:(1-5)的范围内,陶瓷的抗冲击性较差,实施例1-13中抗冲击性最差的为实施例11中的氧化锆陶瓷,其平均落锤高度为27.5cm,但其仍高于对比例1-4中的平均落锤高度,说明本申请氧化锆陶瓷的抗冲击性优于对比例中的陶瓷。此外,本申请氧化锆陶瓷的韧性可以高达13MPa m 1/2
以上详细描述了本申请的优选实施方式,但是,本申请并不限于此。在本申请的技术构思范围内,可以对本申请的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本申请所公开的内容,均属于本申请的保护范围。

Claims (20)

  1. 一种氧化锆陶瓷,所述氧化锆陶瓷以元素计包含:60.5-70.5wt%的Zr、2.5-5.45wt%的Y、0.05-2.65wt%的Al、0.015-1.07wt%的Si,以及0.34-2.8wt%的M,所述M包括Nb和Ta的至少之一;且所述氧化锆陶瓷的物相组成包含:四方相氧化锆、氧化铝和硅酸锆,氧化铝和硅酸锆的含量之和为0.2-12wt%,所述四方相氧化锆的含量为84-99.3wt%;所述四方相氧化锆包括氧化钇、M xO y与氧化锆形成的固溶体;所述x满足1≤x≤3,所述y满足3≤y≤6。
  2. 根据权利要求1所述的氧化锆陶瓷,所述氧化锆陶瓷包含:63-68.75wt%的Zr、3.35-4.7wt%的Y、0.53-1.58wt%的Al、0.15-0.92wt%的Si,以及0.68-2.1wt%的M。
  3. 根据权利要求1或2所述的氧化锆陶瓷,所述氧化锆陶瓷的物相组成包含:四方相氧化锆、氧化铝和硅酸锆,其中所述氧化铝和硅酸锆的含量之和为2-9wt%,所述四方相氧化锆的含量为88-97wt%。
  4. 根据权利要求1-3中任意一项所述的氧化锆陶瓷,所述氧化铝和硅酸锆的质量比为1:(1-5)。
  5. 一种氧化锆陶瓷,所述氧化锆陶瓷的物相组成包含:四方相氧化锆、氧化铝和硅酸锆,氧化铝和硅酸锆的含量之和为0.2-12wt%,所述四方相氧化锆的含量为84-99.3wt%;所述四方相氧化锆包括氧化钇、M xO y与氧化锆形成的固溶体,所述氧化锆陶瓷中以元素计Y的含量为2.5-5.45wt%,M的含量为0.34-2.8wt%;
    所述M包括Nb和Ta的至少之一,且所述x满足1≤x≤3,所述y满足3≤y≤6。
  6. 一种组合物,该组合物包含:含氧化锆组分、氧化铝、硅酸锆,以及M xO y;其中,以所述含氧化锆组分的总量为基准,所述含氧化锆组分中含有氧化锆以及2-4mol%的氧化钇;
    以所述组合物的总量为基准,含氧化锆组分的含量为84-99.3wt%,氧化铝和硅酸锆的总含量为0.2-12wt%,M xO y的含量为0.5-4wt%。
  7. 根据权利要求6所述的组合物,其中,以所述组合物的总量为基准,含氧化锆组分的含量为88-97wt%,氧化铝和硅酸锆的总含量为2-9wt%,M xO y的含量为1-3wt%。
  8. 根据权利要求6或7所述的组合物,所述组合物中,氧化铝与硅酸锆的质量比为(1:1)-(1:5)。
  9. 一种制备氧化锆陶瓷的方法,包括:
    (1)将权利要求6-8中任意一项所述的组合物中各组分的粉体形成浆料;
    (2)将所述浆料进行干燥,得到复合氧化锆粉体;
    (3)将所述复合氧化锆粉体进行成型和烧结,得到氧化锆陶瓷。
  10. 根据权利要求9所述的方法,步骤(1)中,形成浆料包括:将所述组合物中各组分的粉体、分散剂和粘结剂进行混合,得到所述浆料。
  11. 根据权利要求10所述的方法,步骤(1)中,所述分散剂选自羟丙甲纤维素、羧甲基纤维素钠和三乙醇胺中的至少一种;所述粘结剂选自聚乙烯醇和聚乙二醇4000的至少之一。
  12. 根据权利要求11所述的方法,步骤(1)中,所述分散剂的加入量为所述组合物中各组分的粉体总量的0.005-0.5wt%。
  13. 根据权利要求12所述的方法,步骤(1)中,所述分散剂的加入量为所述组合物中各组分的粉体总量的0.01-0.1wt%。
  14. 根据权利要求11所述的方法,步骤(1)中,所述粘结剂的加入量为所述组合物中各组分的粉体总量的0.5-5wt%。
  15. 根据权利要求9所述的方法,步骤(1)中,所述浆料的固含量为20-60wt%。
  16. 根据权利要求9所述的方法,步骤(3)中,所述烧结在空气中进行。
  17. 根据权利要求9所述的方法,步骤(3)中,所述烧结分为两步,先空气中烧结,再在还原气氛中复烧结。
  18. 根据权利要求9-17任一项所述的方法,所述烧结的程序包括:从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1370-1480℃并保温1-2h,然后经过150min降温至900℃,最后自然冷却至室温。
  19. 根据权利要求9-17任一项所述的方法,所述烧结的程序包括:从室温经400min升温至600℃并保温2h,从600℃经300min升温至1150℃并保温2h,从1150℃经150min升温至1300℃并保温2h,从1300℃经50min升温至1380-1480℃并保温1-2h,然后经过150min降温至900℃,最后自然冷却至室温。
  20. 一种权利要求1-5中任意一项所述的氧化锆陶瓷在制备电子产品外壳或装饰品中的应用。
PCT/CN2020/114398 2019-09-10 2020-09-10 氧化锆陶瓷、制备氧化锆陶瓷的方法及其应用和组合物 WO2021047574A1 (zh)

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