CN113004033B - Zirconia ceramic and preparation method and application thereof - Google Patents

Zirconia ceramic and preparation method and application thereof Download PDF

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CN113004033B
CN113004033B CN201911326641.5A CN201911326641A CN113004033B CN 113004033 B CN113004033 B CN 113004033B CN 201911326641 A CN201911326641 A CN 201911326641A CN 113004033 B CN113004033 B CN 113004033B
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zirconia
ceramic
powder
cordierite
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CN113004033A (en
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唐威
林信平
陈戈
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BYD Co Ltd
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Abstract

The invention relates to the field of zirconia ceramics and disclosesA zirconia ceramic and a preparation method and application thereof are provided. The zirconia ceramic comprises, in elemental terms: y, zr, mg, al, si, and Nb, and the phase of the zirconia ceramic comprises: monoclinic phase zirconia, tetragonal phase zirconia, zirconium silicate and cordierite; wherein the zirconia ceramic comprises, in elemental terms: 50.6 to 61.1 weight percent of Zr, 5.1 to 12.6 weight percent of Al + Mg + Si, 3.2 to 3.9 weight percent of Y and 0.3 to 2.7 weight percent of Nb; the phase of the zirconia ceramic comprises: 60-80wt% of monoclinic phase zirconia, 3-30wt% of tetragonal phase zirconia, 8-22wt% of cordierite and 0.5-3wt% of zirconium silicate. The zirconia ceramic can simultaneously have a dielectric constant of less than 30 and a density of less than 5.40g/cm 3 Toughness greater than 6.5MPam 0.5 The mobile phone backboard has the advantages of being low in dielectric constant, low in density and good in toughness.

Description

Zirconia ceramic and preparation method and application thereof
Technical Field
The invention relates to the field of zirconia ceramics, in particular to zirconia ceramics and a preparation method and application thereof.
Background
The zirconia-based ceramic material has excellent toughness, strength, oxidation resistance, corrosion resistance, wear resistance and other properties, and is widely applied as functional ceramics and structural ceramics. However, with the arrival of 5G, the zirconia ceramic mobile phone back plate has the problems of heavy weight, high dielectric constant, high processing difficulty and the like, and the application of the zirconia ceramic in the field of 5G mobile phones is limited.
The prior art has reduced the density and dielectric constant of zirconia-based ceramic materials by the addition of alumina. However, the addition of alumina leads to increased hardness and reduced toughness of the material, increasing processing costs. Therefore, it is very important to develop a zirconia-based ceramic material having a low density, a low dielectric constant, and good toughness.
Disclosure of Invention
The invention aims to solve the problems of improving the dielectric constant and density of zirconia ceramics and having good toughness, and provides the zirconia ceramics and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a zirconia ceramic comprising, in terms of elements: y, zr, mg, al, si, and Nb, and the phase of the zirconia ceramic comprises: monoclinic phase zirconia, tetragonal phase zirconia cordierite and zirconium silicate; wherein the zirconia ceramic comprises, in elemental terms: 50.6 to 61.1 weight percent of Zr, 5.1 to 12.6 weight percent of Al + Mg + Si, 3.2 to 3.9 weight percent of Y and 0.3 to 2.7 weight percent of Nb; the phase of the zirconia ceramic comprises: 60-80wt% of monoclinic phase zirconia, 3-30wt% of tetragonal phase zirconia, 8-22wt% of cordierite and 0.5-3wt% of zirconium silicate.
Preferably, the dielectric constant of the zirconia ceramic is less than 30, and the density of the zirconia ceramic is not more than 5.40g/cm 3 The toughness of the zirconia ceramic is more than 6.5MPam 0.5 。
The second aspect of the present invention provides a method for preparing a zirconia ceramic, comprising:
(1) Carrying out wet grinding on yttria-containing zirconia, niobium pentoxide and cordierite powder, a dispersing agent and water, and then forming slurry with a binder;
(2) Drying the slurry to obtain composite zirconia powder;
(3) Forming the composite zirconia powder, and then sintering in air to obtain ceramic;
wherein the content of cordierite is 10-25wt%, the content of niobium pentoxide is 0.5-4wt%, the content of zirconia containing yttria is 72.5-87.5wt%, and the zirconia contains yttria in an amount of 1.5-4mol% based on the total amount of the powder.
The third aspect of the present invention provides a zirconia ceramic produced by the production method of the present invention.
The fourth aspect of the invention provides the application of the zirconia ceramics in the preparation of the back shell of the mobile phone.
Through the technical scheme, the zirconia ceramic provided by the invention can contain phases of tetragonal zirconia, monoclinic zirconia, cordierite and zirconium silicate, and the content of each phase is in the range defined by the invention, so that the zirconia ceramic has low dielectric constant and density and good toughness. The zirconia ceramic can simultaneously have a dielectric constant of less than 30 and a density of less than 5.40g/cm 3 Toughness greater than 6.5MPam 0.5 Can be provided withThe mobile phone backboard has low dielectric constant, low density and good toughness.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides, in a first aspect, a zirconia ceramic comprising, in terms of elements: y, zr, mg, al, si, and Nb, and the phase of the zirconia ceramic comprises: tetragonal zirconia, monoclinic zirconia, cordierite and zirconium silicate; wherein the zirconia ceramic comprises, in elemental terms: 50.6 to 61.1 weight percent of Zr, 5.1 to 12.6 weight percent of Al + Mg + Si, 3.2 to 3.9 weight percent of Y and 0.3 to 2.7 weight percent of Nb; the phase of the zirconia ceramic comprises: 60-80wt% of monoclinic phase zirconia, 3-30wt% of tetragonal phase zirconia, 8-22wt% of cordierite and 0.5-3wt% of zirconium silicate.
The zirconia ceramic provided by the invention contains a cordierite structure, and can realize low dielectric constant and light weight of the ceramic.
According to embodiments provided herein, the elemental composition may be tested by an energy dispersive X-ray fluorescence spectrometer EDX-7000 for XRF. Wherein, al + Mg + Si represents the sum of the elements of aluminum, magnesium and silicon in the zirconia ceramic, and is carried by cordierite. Preferably, the zirconia ceramic comprises, in elemental terms: 51.3-59.6% of Zr, 6.1-12.1wt% of Al + Mg + Si, 3.3-3.8wt% of Y and 0.7-2.1wt% of Nb. The zirconia ceramic may also contain other elements, such as oxygen; the sum of all elements contained is 100wt%.
According to the invention, particular phases are present in the zirconia ceramic, which can be determined by XRD. Preferably, the phase of the zirconia ceramic comprises: 65-76wt% of monoclinic phase zirconia, 5-25wt% of tetragonal phase zirconia, 9-20wt% of cordierite and 1-2wt% of zirconium silicate. The zirconia ceramic provided by the invention has the phase, and can realize low dielectric constant, light weight and good toughness of the ceramic. The zirconia ceramic may also contain other phases, but does not adversely affect the zirconia ceramic of the present invention. In the present invention, the content of the phase contained in the zirconia ceramic is based on the zirconia ceramic. The zirconia ceramic comprises all phases, the sum of which is 100wt%.
When the element composition and the phase structure of the zirconia ceramic provided by the invention contain the compositions, the dielectric property, the density and the toughness of the zirconia ceramic are improved.
In the present invention, although the effects of each of the oxides added may be considered, for example, yttria and niobia may play a role in stabilizing and toughening zirconia, and cordierite mainly plays a role in reducing the dielectric constant, density and hardness. However, when the zirconia ceramic provided by the invention contains various elements and phase structures with the specific contents, the synergistic effect can be generated, so that the ceramic has low dielectric property and density and good toughness. Outside the above-defined range, the obtained zirconia ceramic cannot simultaneously have a low dielectric constant, a low density and good toughness.
The zirconia ceramic provided by the invention has low dielectric constant, low density, light weight and good toughness. Preferably, the dielectric constant of the zirconia ceramic is less than 30, and the density of the zirconia ceramic is not more than 5.40g/cm 3 (ii) a Preferred toughness greater than 6.5MPam 0.5 More preferably has a toughness of 7 to 8MPa m 0.5 . The zirconia ceramic provided by the invention has low dielectric constant and low density and good toughness.
The second aspect of the present invention provides a method for preparing a zirconia ceramic, comprising: (1) Wet grinding powder of zirconia, niobium pentoxide and cordierite containing yttria, a dispersing agent and water, and then mixing with a binder to form slurry; (2) Drying the slurry to obtain composite zirconia powder; (3) And forming the composite zirconia powder, and sintering in air to obtain the ceramic.
In the present invention, the yttria-containing zirconia, niobium pentoxide, and cordierite powders may be provided in the form of high purity powders, either individually or in combination. For example, yttria and zirconia can be prepared by using a stabilized zirconia powder (particle diameter median of 0.3-0.6 μm, specific surface area of 7-13 m) containing 1.5-4mol% of yttria 2 In terms of/g), wherein the content of yttrium oxide is based on zirconium oxide. Niobium oxide can be niobium pentoxide (with a median particle size of 8-10 μm) powder. The cordierite is powder with particle size less than 0.44 μm.
In the present invention, step (1) is carried out by grinding powders of the above-mentioned oxides as raw materials to reduce the particle diameter and obtain a slurry. The grinding process is wet grinding, and the specific process can comprise the following steps: mixing the above powder of various oxides with water to obtain slurry, ball milling, and grinding to obtain nanometer oxide particles with a median diameter of 250-500 nm. More specifically, the various oxides are added with water in a ball milling tank according to the content of the oxides for ball milling for 8-10h, then a dispersing agent and water are added in a sand mill for sand milling for 8-10h, and finally a binding agent (such as PVA and/or polyethylene glycol 4000, which is beneficial to powder forming) with a proper proportion is added to form slurry for spraying. Ball milling pots and sand mills use zirconia ceramic liners and zirconia milling balls. The selected particle size of the zirconia grinding balls, the proportion of the grinding balls with different particle sizes, the weight ratio of the grinding balls to the powder and the amount of water can be controlled to realize the expected particle size of the oxide.
According to the invention, a method is provided in which the powder is composed of various materials. The material amount of each material can meet the composition requirement of the obtained zirconia ceramics. Preferably, the content of cordierite is 10 to 25wt%, the content of niobium pentoxide is 0.5 to 4wt%, the content of zirconia containing yttria is 72.5 to 87.5wt%, and the zirconia contains yttria in an amount of 1.5 to 4mol% based on the total amount of the powder; preferably, the cordierite content is 12 to 24wt%, the niobium pentoxide content is 1 to 3wt%, the yttria-containing zirconia content is 73.5 to 85.5wt%, and the zirconia contains 2 to 4mol% yttria. The content of yttrium oxide is based on the zirconium oxide. The powder may also contain negligible impurities that do not affect the properties of the zirconia ceramic of the present invention. The sum of the feeding materials of all the materials in the powder is 100 percent by weight. More preferably, the content of cordierite is 12 to 20wt%, the content of niobium pentoxide is 1 to 3wt%, the content of yttria-containing zirconia is 77.5 to 85.5wt%, and the zirconia contains 2 to 4mol% of yttria.
According to the invention, the dispersing agent can promote the components in the powder to be uniformly mixed. Preferably, in the step (1), the dispersant is at least one selected from hypromellose, sodium carboxymethylcellulose and triethanolamine. In the present invention, the dispersant is commercially available.
According to the invention, the dispersant is preferably added in an amount of 0.005-0.5wt%, preferably 0.01-0.1wt%, of the powder.
According to the invention, the binder contributes to the moldability of the powder. Preferably, the binder is selected from polyvinyl alcohol and/or polyethylene glycol. Preferably, the binder is polyvinyl alcohol and polyethylene glycol. More preferably, the molar ratio of the polyvinyl alcohol to the polyethylene glycol is 1:1-2, preferably 1. Wherein the polyvinyl alcohol has an average molecular weight of 60000-200000. The average molecular weight of polyethylene glycol is 2000-6000. Polyethylene glycol 4000 may be selected as the specific polyethylene glycol. In the present invention, the binder is commercially available.
According to the invention, the binder is preferably added in an amount of 0.5 to 8wt%, preferably 3 to 8wt%, of the powder.
According to the invention, the solids content of the slurry is preferably 20 to 60% by weight, preferably 25 to 55% by weight. A better abrasive effect can be achieved.
In the present invention, various drying methods may be adopted in step (2), for example, spray drying may be adopted to form spherical powder having a high fluidity. Preferably, the air inlet temperature of spray drying is 220-280 ℃, the air outlet temperature is 100-120 ℃, and the centrifugal rotating speed is 10-20 r/s.
According to the invention, the step (3) can be used for preparing the composite zirconia powder into ceramic. The composite zirconia powder can be formed and then sintered. The molding can adopt dry pressing, isostatic pressing, injection molding, hot-press molding and other molding modes. Preferably, the molding is performed by dry pressing, and can be performed by using a press with the tonnage of 180-200 tons and the oil pressure of 8MPa, such as the shape of a rear cover of a mobile phone. The sintering may be air sintering. Preferably, in the step (3), the sintering temperature is 1280-1340 ℃, and the sintering time is 1-3h.
In the invention, the ceramic obtained by sintering and re-sintering also comprises the steps of flat grinding and polishing, and cutting into final products by using a laser.
The third aspect of the present invention provides a zirconia ceramic produced by the production method of the present invention. The zirconia ceramic has low dielectric constant, low density, high impact resistance, high toughness and easy processability.
The zirconia ceramic comprises the following components in terms of elements: y, zr, mg, al, si, and Nb, and the phase of the zirconia ceramic comprises: tetragonal zirconia, monoclinic zirconia, cordierite and zirconium silicate; wherein the zirconia ceramic comprises, in elemental terms: 50.6 to 61.1 weight percent of Zr, 5.1 to 12.6 weight percent of Al + Mg + Si, 3.2 to 3.9 weight percent of Y and 0.3 to 2.7 weight percent of Nb; the phase of the zirconia ceramic comprises: 60-80wt% of monoclinic phase zirconia, 3-30wt% of tetragonal phase zirconia, 8-22wt% of cordierite and 0.5-3wt% of zirconium silicate.
In the zirconia ceramic, preferably, the zirconia ceramic comprises: 51.3-59.6% of Zr, 6.1-12.1wt% of Al + Mg + Si, 3.3-3.8wt% of Y and 0.7-2.1wt% of Nb; the phase of the zirconia ceramic comprises: 65-76wt% of monoclinic phase zirconia, 5-25wt% of tetragonal phase zirconia, 9-20wt% of cordierite and 1-2wt% of zirconium silicate.
Preferably, the dielectric constant of the zirconia ceramic is less than 30, and the density of the zirconia ceramic is not more than 5.40g/cm 3 The toughness of the zirconia ceramic is more than 6.5MPam 0.5 。
The fourth aspect of the invention provides the application of the zirconia ceramics in the preparation of the back shell of the mobile phone.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
fracture toughness K ic : indenter indentation (diamond indenter, force 10kg, pressure test time 15 s).
Hardness Hv: a hardness meter and an indentation method (a diamond indenter, a force of 10kg, a pressure test time of 15 s).
Dielectric constant: the dielectric constant of the material at 2GHz was measured using a network analyzer.
XRD test: the phase species and content were tested using an X-ray diffractometer Smartlab (3 kW).
And (4) XRF detection: the element content of the polished sample was measured using an energy dispersive X-ray fluorescence spectrometer EDX-7000.
Example 1
Niobium pentoxide (Nb) 2 O 5 ) 25g of stabilized zirconia powder containing 3.2mol% of yttria, 855g of cordierite, 77.78g of binder (polyvinyl alcohol) and 1g of dispersant (triethanolamine).
Grinding zirconium oxide, cordierite, niobium pentoxide, water and a dispersing agent in a sand mill for 10 hours, and adding a binder to form slurry for spraying, wherein the solid content is 25 wt%;
feeding the slurry into a spray tower for spray drying (the inlet air temperature is 250 ℃, the outlet air temperature is 110 ℃, the centrifugal rotating speed is 15 r/s) to form spherical powder with stronger fluidity for dry pressing, and then forming by dry pressing (a press with 200 tons of tonnage uses the oil pressure of 8 MPa);
and sintering the formed powder in air at 1320 ℃ for 2h.
The sintered product was polished and laser cut to produce a final sample having a cell phone back cover shape and size of 150 x 75 x 0.6mm.
And (3) carrying out high-energy XRF detection on the prepared sample, wherein the prepared sample contains the following components: 59.6wt% of Zr, 3.8wt% of Y, 1.7wt% of Nb and 6.0wt% of Al + Mg + Si.
XRD detected phases included: the contents of monoclinic zirconia, tetragonal zirconia, cordierite and zirconium silicate were 66.2wt%, 23.5wt%, 9.2wt% and 1.1wt%, respectively.
Example 2
Niobium pentoxide (Nb) 2 O 5 ) 25g, 815g of stabilized zirconia powder containing 3.2mol% of yttria, 160g of cordierite, 77.78g of binder (polyvinyl alcohol), and 1g of dispersant (triethanolamine).
Grinding zirconium oxide, cordierite, niobium pentoxide, water and a dispersing agent in a sand mill for 10 hours, and adding a binder to form slurry for spraying, wherein the solid content is 25 wt%;
feeding the slurry into a spray tower for spray drying (the inlet air temperature is 250 ℃, the outlet air temperature is 110 ℃, and the centrifugal rotating speed is 15 revolutions per second) to form spherical powder with stronger fluidity for dry pressing, and then performing dry pressing (a press with 200 tons of tonnage uses the oil pressure of 8 MPa);
and sintering the formed powder in air at 1320 ℃ for 2h.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 × 75 × 0.6mm, and the size of the final sample is the shape and the size of the mobile phone rear cover.
And (3) carrying out high-energy XRF detection on the prepared sample, wherein the prepared sample contains the following components: 56.9wt% of Zr, 3.6wt% of Y, 1.7wt% of Nb and 8.1wt% of Al + Mg + Si.
XRD detected phases included: 70.0wt% for monoclinic zirconia, 16.7wt% for tetragonal zirconia, 12.1wt% for cordierite, and 1.2wt% for zirconium silicate.
Example 3
Niobium pentoxide (Nb) 2 O 5 ) 25g of stabilized zirconia powder containing 3.2mol% of yttria 775g, cordierite 200g, binder (polyvinyl alcohol) 77.78g and dispersant (triethanolamine) 1g.
Grinding zirconium oxide, cordierite, niobium pentoxide, water and a dispersing agent in a sand mill for 10 hours, and adding a binder to form slurry for spraying, wherein the solid content is 25 wt%;
feeding the slurry into a spray tower for spray drying (the inlet air temperature is 250 ℃, the outlet air temperature is 110 ℃, and the centrifugal rotating speed is 15 revolutions per second) to form spherical powder with stronger fluidity for dry pressing, and then performing dry pressing (a press with 200 tons of tonnage uses the oil pressure of 8 MPa);
and sintering the formed powder in air at 1320 ℃ for 2h.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 × 75 × 0.6mm, and the size of the final sample is the shape and the size of the mobile phone rear cover.
And (3) carrying out high-energy XRF detection on the prepared sample, wherein the prepared sample contains the following components: 54.1wt% Zr, 3.4wt% Y, 1.7wt% Nb, 10.1wt% Al + Mg + Si.
XRD detected phases included: 72.9wt% for monoclinic zirconia, 11.0wt% for tetragonal zirconia, 14.8wt% for cordierite and 1.3wt% for zirconium silicate.
Example 4
Niobium pentoxide (Nb) 2 O 5 ) 25g, containing 735g of stabilized zirconia powder containing 3.2mol% yttria, 240g of cordierite, 77.78g of binder (polyvinyl alcohol), and 1g of dispersant (triethanolamine).
Grinding zirconium oxide, cordierite, niobium pentoxide, water and a dispersing agent in a sand mill for 10 hours, and adding a binder to form slurry for spraying, wherein the solid content is 25 wt%;
feeding the slurry into a spray tower for spray drying (the inlet air temperature is 250 ℃, the outlet air temperature is 110 ℃, and the centrifugal rotating speed is 15 revolutions per second) to form spherical powder with stronger fluidity for dry pressing, and then performing dry pressing (a press with 200 tons of tonnage uses the oil pressure of 8 MPa);
and sintering the formed powder in air at 1320 ℃ for 2h.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 × 75 × 0.6mm, and the size of the final sample is the shape and the size of the mobile phone rear cover.
And (3) carrying out high-energy XRF detection on the prepared sample, wherein the prepared sample contains the following components: 51.3wt% Zr, 3.3wt% Y, 1.7wt% Nb, 12.1wt% Al + Mg + Si.
XRD detected phases included: 74.1wt% monoclinic zirconia, 5.0wt% tetragonal zirconia, 19.2wt% cordierite, 1.7wt% zirconium silicate.
Example 5
Niobium pentoxide (Nb) 2 O 5 ) 25g of stabilized zirconia powder containing 3.2mol% yttria 865g and cordierite110g of stone, 77.78g of binder (polyvinyl alcohol) and 1g of dispersant (triethanolamine).
Grinding zirconium oxide, cordierite, niobium pentoxide, water and a dispersing agent in a sand mill for 10 hours, and adding a binder to form slurry for spraying, wherein the solid content is 25 wt%;
feeding the slurry into a spray tower for spray drying (the inlet air temperature is 250 ℃, the outlet air temperature is 110 ℃, the centrifugal rotating speed is 15 r/s) to form spherical powder with stronger fluidity for dry pressing, and then forming by dry pressing (a press with 200 tons of tonnage uses the oil pressure of 8 MPa);
and sintering the formed powder in air at 1320 ℃ for 2h.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 × 75 × 0.6mm, and the size of the final sample is the shape and the size of the mobile phone rear cover.
And (3) carrying out high-energy XRF detection on the prepared sample, wherein the prepared sample contains the following components: 60.4wt% Zr, 3.9wt% Y, 1.7wt% Nb, 5.6wt% Al + Mg + Si.
XRD detected phases included: 65.0wt% monoclinic zirconia, 25.4wt% tetragonal zirconia, 8.6wt% cordierite and 1.0wt% zirconium silicate.
Example 6
Niobium pentoxide (Nb) 2 O 5 ) 25g, 730g of stabilized zirconia powder containing 3.2mol% of yttria, 245g of cordierite, 77.78g of binder (polyvinyl alcohol) and 1g of dispersant (triethanolamine).
Grinding zirconium oxide, cordierite, niobium pentoxide, water and a dispersing agent in a sand mill for 10 hours, and adding a binder to form slurry for spraying, wherein the solid content is 25 wt%;
feeding the slurry into a spray tower for spray drying (the inlet air temperature is 250 ℃, the outlet air temperature is 110 ℃, and the centrifugal rotating speed is 15 revolutions per second) to form spherical powder with stronger fluidity for dry pressing, and then performing dry pressing (a press with 200 tons of tonnage uses the oil pressure of 8 MPa);
and sintering the formed powder in air at 1320 ℃ for 2h.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 × 75 × 0.6mm, and the size of the final sample is the shape and the size of the mobile phone rear cover.
And (3) carrying out high-energy XRF detection on the prepared sample, wherein the prepared sample contains the following components: 50.9wt% Zr, 3.3wt% Y, 1.7wt% Nb, 12.4wt% Al + Mg + Si.
XRD detected phases included: 75.0wt% monoclinic zirconia, 3.8wt% tetragonal zirconia, 19.4wt% cordierite and 1.8wt% zirconium silicate.
Example 7
Niobium pentoxide (Nb) 2 O 5 ) 15g, 865g of stabilized zirconia powder containing 2.5mol% of yttria, 120g of cordierite, 77.78g of binder (polyvinyl alcohol), and 1g of dispersant (triethanolamine).
Grinding zirconium oxide, cordierite, niobium pentoxide, water and a dispersing agent in a sand mill for 10 hours, and adding a binder to form slurry for spraying, wherein the solid content is 25 wt%;
feeding the slurry into a spray tower for spray drying (the inlet air temperature is 250 ℃, the outlet air temperature is 110 ℃, and the centrifugal rotating speed is 15 revolutions per second) to form spherical powder with stronger fluidity for dry pressing, and then performing dry pressing (a press with 200 tons of tonnage uses the oil pressure of 8 MPa);
and sintering the formed powder in air at 1320 ℃ for 2h.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 × 75 × 0.6mm, and the size of the final sample is the shape and the size of the mobile phone rear cover.
And (3) carrying out high-energy XRF detection on the prepared sample, wherein the prepared sample contains the following components: 60.3wt% Zr, 3.9wt% Y, 1.05wt% Nb, 6.1wt% Al + Mg + Si.
XRD detected phases included: 66.0wt% of monoclinic zirconia, 23.4wt% of tetragonal zirconia, 9.5wt% of cordierite and 1.1wt% of zirconium silicate.
Comparative example 1
The powder contains 1000g of zirconia powder stabilized by 3.2mol% of yttrium oxide, 77.78g of binder (polyvinyl alcohol) and 1g of dispersant (triethanolamine).
Sanding zirconia, water and a dispersing agent in a sand mill for 10 hours, and adding a binder to form slurry for spraying, wherein the solid content is 25 percent by weight;
feeding the slurry into a spray tower for spray drying (the inlet air temperature is 250 ℃, the outlet air temperature is 110 ℃, and the centrifugal rotating speed is 15 revolutions per second) to form spherical powder with stronger fluidity for dry pressing, and then performing dry pressing (a press with 200 tons of tonnage uses the oil pressure of 8 MPa);
and sintering the formed powder in air at 1480 ℃ for 2h.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 × 75 × 0.6mm, and the size of the final sample is the shape and the size of the mobile phone rear cover.
And (3) carrying out high-energy XRF detection on the prepared sample, wherein the prepared sample contains the following components: zr content was 69.8wt% and Y content was 4.4wt%.
XRD detected phases included: the tetragonal zirconia was 100wt%.
Comparative example 2
The powder contains 880g of zirconia powder stabilized by 3.2mol% of yttria, 120g of cordierite, 77.78g of a binder (polyvinyl alcohol) and 1g of a dispersant (triethanolamine).
Sanding zirconia, cordierite, water and a dispersing agent in a sand mill for 10 hours, and adding a binder to form slurry for spraying, wherein the solid content is 25 percent by weight;
feeding the slurry into a spray tower for spray drying (the inlet air temperature is 250 ℃, the outlet air temperature is 110 ℃, the centrifugal rotating speed is 15 r/s) to form spherical powder with stronger fluidity for dry pressing, and then forming by dry pressing (a press with 200 tons of tonnage uses the oil pressure of 8 MPa);
and sintering the formed powder in air at 1320 ℃ for 2h.
The sintered product was polished and laser cut to produce a final sample having a cell phone back cover shape and size of 150 x 75 x 0.6mm.
And (3) carrying out high-energy XRF detection on the prepared sample, wherein the prepared sample contains the following components: 61.4wt% Zr, 3.9wt% Y, 6.1wt% Al + Mg + Si.
XRD detected phases included: 65.0wt% of monoclinic zirconia, 23.2wt% of tetragonal zirconia, 10.5wt% of cordierite and 1.3wt% of zirconium silicate.
Comparative example 3
Niobium pentoxide (Nb) 2 O 5 ) 25g, 975g of stabilized zirconia powder containing 3.2mol% of yttria, 77.78g of binder (polyvinyl alcohol), and 1g of dispersant (triethanolamine).
Grinding zirconium oxide, niobium pentoxide, water and a dispersing agent in a sand mill for 10 hours, and adding a binder to form slurry for spraying, wherein the solid content is 25 wt%;
feeding the slurry into a spray tower for spray drying (the inlet air temperature is 250 ℃, the outlet air temperature is 110 ℃, and the centrifugal rotating speed is 15 revolutions per second) to form spherical powder with stronger fluidity for dry pressing, and then performing dry pressing (a press with 200 tons of tonnage uses the oil pressure of 8 MPa);
and sintering the formed powder in air at 1480 ℃ for 2h.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 × 75 × 0.6mm, and the size of the final sample is the shape and the size of the mobile phone rear cover.
And (3) carrying out high-energy XRF detection on the prepared sample, wherein the prepared sample contains the following components: 68.1wt% Zr, 4.4wt% Y and 1.7wt% Nb.
XRD detected phases included: the tetragonal zirconia was 100wt%.
Comparative example 4
Niobium pentoxide (Nb) 2 O 5 ) 25g, 925g of stabilized zirconia powder containing 3.2mol% of yttria, 50g of cordierite, 77.78g of binder (polyvinyl alcohol) and 1g of dispersant (triethanolamine).
Grinding zirconium oxide, cordierite, niobium pentoxide, water and a dispersing agent in a sand mill for 10 hours, and adding a binder to form slurry for spraying, wherein the solid content is 25 wt%;
feeding the slurry into a spray tower for spray drying (the inlet air temperature is 250 ℃, the outlet air temperature is 110 ℃, and the centrifugal rotating speed is 15 revolutions per second) to form spherical powder with stronger fluidity for dry pressing, and then performing dry pressing (a press with 200 tons of tonnage uses the oil pressure of 8 MPa);
and sintering the formed powder in air at 1320 ℃ for 2h.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 × 75 × 0.6mm, and the size of the final sample is the shape and the size of the mobile phone rear cover.
And (3) carrying out high-energy XRF detection on the prepared sample, wherein the prepared sample contains the following components: 64.6wt% Zr, 1.7wt% Y, 2.5wt% Al + Mg + Si.
XRD detected phases included: the contents of monoclinic zirconia, tetragonal zirconia, cordierite and zirconium silicate were 19.7wt% and 75.6wt%, respectively, and 4.2wt% and 0.5wt%, respectively.
Comparative example 5
Niobium pentoxide (Nb) 2 O 5 ) 25g of stabilized zirconia powder containing 3.2mol% of yttria 675g, cordierite 300g, binder (polyvinyl alcohol) 77.78g and dispersant (triethanolamine) 1g.
Grinding zirconium oxide, cordierite, niobium pentoxide, water and a dispersing agent in a sand mill for 10 hours, and adding a binder to form slurry for spraying, wherein the solid content is 25 wt%;
feeding the slurry into a spray tower for spray drying (the inlet air temperature is 250 ℃, the outlet air temperature is 110 ℃, and the centrifugal rotating speed is 15 revolutions per second) to form spherical powder with stronger fluidity for dry pressing, and then performing dry pressing (a press with 200 tons of tonnage uses the oil pressure of 8 MPa);
and sintering the formed powder in air at 1320 ℃ for 2h.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 × 75 × 0.6mm, and the size of the final sample is the shape and the size of the mobile phone rear cover.
And (3) carrying out high-energy XRF detection on the prepared sample, wherein the prepared sample contains the following components: 47.1wt% Zr, 3.0wt% Y, 1.7wt% Nb, 15.2wt% Al + Mg + Si.
XRD detected phases included: the contents of monoclinic zirconia, tetragonal zirconia, cordierite and zirconium silicate were 73.5wt%, 2.3wt%, 22.2wt% and 2.0wt%, respectively.
Test example 1
The samples obtained in examples 1 to 7 and comparative examples 1 to 5 were subjected to hardness, toughness, dielectric constant and density tests, and the results are shown in Table 1.
TABLE 1
Figure BDA0002328556340000151
As can be seen from Table 1, the zirconia ceramics prepared by the method of the present invention have the characteristics of low dielectric constant, low density, good processability and high strength. In particular, it may have both a dielectric constant of less than 30 and a density of less than 5.40g/cm 3 Toughness of more than 6.5MPam 0.5 The characteristics of (1). However, none of the conventional zirconia provided in comparative examples 1 to 5 has the above-mentioned various properties at the same time, and the overall properties are inferior to those of the zirconia ceramics of the present invention.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (13)

1. A zirconia ceramic comprising, on an elemental basis: y, zr, mg, al, si, and Nb, and the phase of the zirconia ceramic comprises: tetragonal zirconia, monoclinic zirconia, cordierite and zirconium silicate; wherein the zirconia ceramic comprises, in elemental terms: 50.6 to 61.1 weight percent of Zr, 5.1 to 12.6 weight percent of Al + Mg + Si, 3.2 to 3.9 weight percent of Y and 0.3 to 2.7 weight percent of Nb; the phase of the zirconia ceramic comprises: 60-80wt% of monoclinic phase zirconia, 3-30wt% of tetragonal phase zirconia, 8-22wt% of cordierite and 0.5-3wt% of zirconium silicate;
the preparation method of the zirconia ceramic comprises the following steps:
(1) Carrying out wet grinding on yttria-containing zirconia, niobium pentoxide and cordierite powder, a dispersing agent and water, and then forming slurry with a binder;
(2) Drying the slurry to obtain composite zirconia powder;
(3) Forming the composite zirconia powder, and then sintering in air to obtain ceramic;
wherein, based on the total amount of the powder, the content of cordierite is 10-25wt%, the content of niobium pentoxide is 0.5-4wt%, the content of zirconia containing yttria is 72.5-87.5wt%, and the zirconia contains yttria in an amount of 1.5-4 mol%;
in the step (3), the sintering temperature is 1280-1340 ℃.
2. The ceramic of claim 1, wherein the zirconia ceramic comprises: 51.3-59.6% of Zr, 6.1-12.1wt% of Al + Mg + Si, 3.3-3.8wt% of Y and 0.7-2.1wt% of Nb.
3. The ceramic of claim 1 or 2, wherein the zirconia ceramic phase comprises: 65-76wt% of monoclinic phase zirconia, 5-25wt% of tetragonal phase zirconia, 9-20wt% of cordierite and 1-2wt% of zirconium silicate.
4. The ceramic of claim 1 or 2, wherein the zirconia ceramic has a dielectric constant of less than 30 and a density of no greater than 5.40g/cm 3 The toughness of the zirconia ceramic is more than 6.5MPam 0.5 。
5. The ceramic of claim 3, wherein the zirconia ceramic has a dielectric constant of less than 30 and a density of no greater than 5.40g/cm 3 The toughness of the zirconia ceramic is more than 6.5MPam 0.5 。
6. A method for preparing zirconia ceramics comprises the following steps:
(1) Wet grinding the powder of zirconia, niobium pentoxide and cordierite containing yttrium oxide, a dispersing agent and water, and then forming slurry with a binder;
(2) Drying the slurry to obtain composite zirconia powder;
(3) Forming the composite zirconia powder, and then sintering in air to obtain ceramic;
wherein, based on the total amount of the powder, the content of cordierite is 10-25wt%, the content of niobium pentoxide is 0.5-4wt%, the content of zirconia containing yttria is 72.5-87.5wt%, and the zirconia contains yttria in an amount of 1.5-4 mol%;
in the step (3), the sintering temperature is 1280-1340 ℃.
7. The production method according to claim 6, wherein the content of cordierite is 12 to 24wt%, the content of niobium pentoxide is 1 to 3wt%, the content of yttria-containing zirconia is 73.5 to 85.5wt%, and the zirconia contains 2 to 4mol% of yttria, based on the total amount of the powder.
8. The preparation method according to claim 6 or 7, wherein in the step (1), the dispersant is selected from at least one of hypromellose, sodium carboxymethylcellulose, and triethanolamine;
and/or the addition amount of the dispersing agent is 0.005-0.5wt% of the powder;
and/or, the binder is selected from polyvinyl alcohol and/or polyethylene glycol;
and/or the addition amount of the binder is 0.5-8wt% of the powder.
9. The preparation method of claim 8, wherein the dispersant is added in an amount of 0.01 to 0.1wt% of the powder;
and/or the addition amount of the binder is 3-8wt% of the powder.
10. The production method according to any one of claims 6 to 7 and 9, wherein the sintering time is 1 to 3 hours.
11. The method of claim 8, wherein the sintering time is 1 to 3 hours.
12. A zirconia ceramic produced by the production method according to any one of claims 6 to 11.
13. Use of the zirconia ceramic of any one of claims 1 to 5 and 12 in the preparation of a back cover for a mobile phone.
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