CN112723885A

CN112723885A - Zirconia-based ceramic back plate and preparation method and application thereof

Info

Publication number: CN112723885A
Application number: CN202110107922.2A
Authority: CN
Inventors: 史伟; 卫义成; 欧阳光华; 刘立瑶
Original assignee: Hunan Kosen New Material Co ltd
Current assignee: Hunan Kosen New Material Co ltd
Priority date: 2021-01-27
Filing date: 2021-01-27
Publication date: 2021-04-30
Anticipated expiration: 2041-01-27
Also published as: CN112723885B

Abstract

The invention provides a zirconia-based ceramic back plate and a preparation method and application thereof. The zirconia ceramic back plate obtained after the blank body is sintered has good sintering density, high strength, strong wear resistance, higher toughness, strength, hardness and excellent wear resistance lattice thermal stability.

Description

Zirconia-based ceramic back plate and preparation method and application thereof

Technical Field

The invention relates to a zirconia-based ceramic material, and preparation and application thereof, in particular to a zirconia-based ceramic back plate, and a preparation method and application thereof, and belongs to the technical field of electronic product back plate production.

Background

With the rapid development of communication and digital technologies, electronic products such as mobile phones have been upgraded and updated for several times in a few decades, and become an epoch epitome of technological progress. The mobile phone shell is not only a powerful protective umbrella for the mobile phone, but also ensures the receiving and sending of electromagnetic signals, reduces the damage caused by accidental dropping, prolongs the service life of the mobile phone, and more importantly, can improve the product experience of users. Therefore, the material for manufacturing the mobile phone shell is required to have the characteristics of no electromagnetic shielding, high toughness, various colors, good texture, wear resistance, good heat conductivity, stable size, beautiful appearance and the like, and the material also puts higher requirements on the quality of the mobile phone back plate.

At present, the materials of the mobile phone back plate mainly comprise plastics, metals, glass and ceramics. The metal material can shield signals, and is not suitable for a mobile phone backboard; the plastic material has high dielectric loss, and cannot meet the requirements of consumers on the acceptance and high-end trend of mobile phones; glass is currently most commonly used for the rear cover, but is quite fragile. The rapid development of modern science and technology puts new and higher requirements on the appearance and performance of objects, and the concept of material design is changed from the development of single material performance indexes to the development of a material system with multiple functions and compounding. Zirconia ceramic (Zirconia ceramics) materials are a typical representative of a class of materials in many cases of material design. The zirconia ceramic material is a great class of very important advanced functional materials, and is a mobile phone backboard material which is superior to metal and glass in terms of relatively low raw material cost, no radiation, unique luster, firmness, wear resistance, no signal shielding, good heat dissipation and good biocompatibility. However, the zirconia ceramics have the defects of large brittleness and small fracture toughness, so the zirconia ceramics are easy to crack during machining; and zirconia is based on phase change toughening to ensure high toughness, frequent impact easily causes microcrack expansion, thereby reducing the application reliability, and zirconia has low hardness and is easy to scratch to influence the beauty of the zirconia. Therefore, the application prospect is limited. The toughening and strengthening of zirconia materials has become a new international research field and hot spot.

The current methods for manufacturing zirconia mobile phone back plates mainly include a dry pressing method, a tape casting method, a gel injection molding method and an injection molding method. 1) And (3) dry pressing and forming process: the ceramic granulated powder containing 3-5% of the binder is processed by a die to obtain a dry-pressed biscuit, but the dry-pressed biscuit has low density and density gradient and large deformation during later sintering. Another solution is to isostatically press the green body to increase the green body density and reduce the density gradient. However, in order to ensure that the green bodies do not deform during isostatic pressing, special fixtures are required to hold the green bodies one by one. And then removing the glue, sintering and machining to obtain the mobile phone backboard. The method has the problems of low efficiency and the like.

2) Tape casting process: adding a plasticizer, a binder, a dispersant and the like accounting for 5-10% of the total amount into ceramic powder, mixing the ceramic powder with a solvent, defoaming in vacuum to obtain casting slurry, casting the slurry to obtain casting sheets, laminating the casting sheets, sealing in vacuum, carrying out over-temperature isostatic pressing to obtain casting biscuit, carrying out gel discharge degreasing on the biscuit, sintering to obtain a sintered blank, and finally carrying out machining to obtain the mobile phone backboard. The method has complex working procedures, and because the added organic matters are more, a large number of air holes are generated during volatilization, the sintering compactness is influenced, and the strength is generally low. 3) Injection molding: adding 15-20% of thermoplastic organic binder into the ceramic powder, and carrying out banburying, granulation, injection molding, degreasing, sintering, machining and other processes to obtain the mobile phone backboard. The strength is lower due to the higher organic content added by injection molding. 4) Gel casting: adding 4-10% of organic monomer, cross-linking agent, initiator and initiator into the ceramic powder, adding a certain amount of solvent (water and the like) to obtain slurry, carrying out injection molding on the slurry, demoulding after curing to obtain a blank, carrying out glue discharging, sintering and machining on the blank to obtain the mobile phone backboard. The organic solvent used in the forming process of the method has certain toxicity, the content of organic matters is high, and the strength of the back plate is low. The methods have the defects of high organic matter content (more than 2 percent), high porosity caused by inevitable generation of pores in the volatilization process of the organic matter, low ceramic compactness and low mechanical strength.

Disclosure of Invention

The invention provides a zirconia-based ceramic back plate and a preparation method and application thereof, which aim to overcome the defects of the prior art, wherein zirconia, zirconium oxychloride and lanthanum hexaboride are used as initial raw materials, and then a blank is obtained by uniformly mixing, hydrolyzing and drying in the presence of a binder and adopting ultrahigh pressure cold isostatic pressing pretreatment, and the blank has no organic volatilization, low porosity and no density gradient. The blank is subjected to presintering, slicing and secondary sintering to obtain the ceramic back plate, and the ceramic back plate obtained after sintering the blank has good sintering density, high strength and strong wear resistance.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

according to a first embodiment of the present invention, a zirconia-based ceramic backing plate is provided.

A zirconia-based ceramic back plate is prepared by taking zirconia, zirconium oxychloride and lanthanum hexaboride as initial raw materials, and then uniformly mixing, hydrolyzing, static pressing, pre-sintering, slicing and re-sintering the raw materials in the presence of a binder.

Or the material is prepared by taking zirconium oxide, zirconium oxychloride, lanthanum hexaboride and titanium boride as initial raw materials, and then uniformly mixing, hydrolyzing, statically pressing, presintering, slicing and re-sintering the raw materials in the presence of a binder.

Preferably, the raw materials comprise the following components in percentage by weight:

zirconia is 60 to 75 wt%, preferably 65 to 70 wt%.

From 15 to 30% by weight, preferably from 20 to 25% by weight, of zirconium oxychloride.

Lanthanum hexaboride 2-9 wt%, preferably 3-7 wt%.

0.5 to 1.5 wt%, preferably 0.8 to 1.2 wt% of a binder.

Or, the raw material components also comprise:

1 to 12 wt.%, preferably 3 to 10 wt.% (based on the total mass of the above-mentioned raw materials, i.e. the total mass of zirconia, zirconium oxychloride, lanthanum hexaboride and binder).

Preferably, the zirconia is nano zirconia stabilized with a phase stabilizer. The particle size of the zirconia is 1-100nm, preferably 5-80 nm. (the particle diameter herein means that the primary particle diameter of zirconia is 1 to 100nm, preferably 5 to 80nm, further, the secondary particle diameter of zirconia D50 is 30 to 500nm, preferably D50 is 60 to 300nm)

Preferably, the phase stabilizer is one of magnesium oxide, calcium oxide, yttrium oxide, scandium oxide, cerium oxide and aluminum oxide. The content of the phase stabilizer is 3 to 20 wt%, preferably 5 to 15 wt%. The total content of the phase stabilizer is 3 to 20 wt%, preferably 5 to 15 wt%.

Or the phase stabilizer is one of a magnesium oxide-yttrium oxide composite stabilizer and a calcium oxide-yttrium oxide composite stabilizer. The content of the composite stabilizer is 5-15 wt%, and preferably 8-12 wt%.

Preferably, the zirconium oxychloride is a nanoscale zirconium oxychloride with an average particle size of 1 to 30nm, preferably 5 to 20 nm.

Preferably, the lanthanum hexaboride is micron-sized lanthanum hexaboride, having an average particle size of 1-25 μm, preferably 5-15 μm.

Preferably, the titanium boride is a micron-sized titanium boride having an average particle size of 1 to 25 μm, preferably 5 to 15 μm.

Preferably, the binder is one or more selected from polyvinyl alcohols (e.g., PVA), polyoxyethylene ethers, polyethylene glycols (e.g., PEG), polyoxyethylenes, and carboxymethylcelluloses.

According to a second embodiment of the present invention, there is provided a method of manufacturing a zirconia-based ceramic backing plate or a method of manufacturing the zirconia-based ceramic backing plate of the first embodiment.

A method of making a zirconia ceramic backing plate, the method comprising the steps of:

1) weighing the raw materials in proportion, and stirring and mixing uniformly. Then placing the blank in an isostatic mould sleeve to obtain an isostatic blank.

2) Placing the isostatic pressing blank obtained in the step 1) in a sintering machine for pre-sintering treatment, and cooling to obtain a pre-sintering blank.

3) And 2) slicing the pre-sintered blank obtained in the step 2) to obtain a slice.

4) Sintering the slice obtained in the step 3) again, and finally carrying out surface treatment to obtain the zirconia ceramic backboard.

Preferably, the adding amount of the raw materials of each component is as follows:

zirconia is 60 to 75 wt%, preferably 65 to 70 wt%.

Lanthanum hexaboride 2-9 wt%, preferably 3-7 wt%.

0.5 to 1.5 wt%, preferably 0.8 to 1.2 wt% of a binder.

Or, the raw material components also comprise:

Preferably, the phase stabilizer is one of magnesium oxide, calcium oxide, yttrium oxide, scandium oxide, cerium oxide and aluminum oxide. The phase stabilizer is added in an amount of 3 to 20 wt%, preferably 5 to 15 wt%. The total content of the phase stabilizer is 3 to 20 wt%, preferably 5 to 15 wt%.

Or the phase stabilizer is one of a magnesium oxide-yttrium oxide composite stabilizer and a calcium oxide-yttrium oxide composite stabilizer. The addition amount of the composite stabilizer is 5-15 wt%, and the preferable addition amount is 8-12%.

Preferably, step 1) is specifically: proportionally adding zirconium oxide (stabilized by phase stabilizer), lanthanum hexaboride and binder into a container, optionally adding or not adding titanium boride, and stirring and mixing uniformly. Then adding an aqueous solution of zirconium oxychloride (for example, a saturated aqueous solution of zirconium oxychloride) and a proper amount of hydrogen peroxide (for example, the addition amount of hydrogen peroxide is 0.5-5 times, preferably 1-4 times, the mass of the added zirconium oxychloride), and then continuously stirring and mixing (for example, stirring at room temperature for 1-72 hours, preferably 3-48 hours) to obtain a mixture. Then drying the mixture (for example, drying at 80-120 ℃ for 0.5-5h, preferably drying at 100 ℃ and 100 ℃ for 1-3h), grinding, and then placing in an isostatic mold sleeve for pressing (for example, keeping the pressure at 200-550MPa for 1-30min, preferably keeping the pressure at 240-500MPa for 3-15min) to obtain the isostatic green body.

Preferably, step 2) is specifically: placing the isostatic pressing blank obtained in the step 1) in a sintering machine for pre-sintering treatment (for example, raising the temperature of the isostatic pressing blank in the sintering machine to 800-1100 ℃ at a speed of 5-20 ℃/h, and then preserving the heat for 2-10h, preferably raising the temperature of the isostatic pressing blank in the sintering machine to 850-1000 ℃ at a speed of 10-15 ℃/h, and then preserving the heat for 3-5 h). After cooling (e.g., to room temperature), the pre-fired green body is obtained.

Preferably, step 3) is specifically: slicing the pre-sintered blank obtained in step 2) (for example, slicing after using 1-20 groups of 0.1-0.3mm saw blades to form an array, preferably, using 3-15 groups of 0.1-0.3mm saw blades to form an array) to obtain a thin slice (the thickness of the thin slice is 0.5-1.2mm, preferably, 0.6-1.0 mm).

Preferably, the step 4) is specifically: and (3) sintering the thin slice obtained in the step 3) again (for example, heating the thin slice to 1300-1600 ℃ at the speed of 10-120 ℃/h in a sintering machine, then preserving heat for 1-6h, preferably heating the isostatic pressing blank to 1350-1450 ℃ at the speed of 15-60 ℃/h in the sintering machine, then preserving heat for 2-3h), and after sintering, performing surface treatment (for example, surface grinding, polishing and edge chamfering) on the sintered thin slice to obtain the zirconia ceramic backboard.

According to a third embodiment of the present invention, there is provided a use of the zirconia-based ceramic backing plate according to the first embodiment or the zirconia-based ceramic backing plate prepared by the method according to the second embodiment.

The zirconia ceramic backboard is used as a mobile phone backboard, a computer backboard and a liquid crystal television backboard. The zirconia ceramic backplate is preferably used as a handset backplate.

In the prior art, the zirconia ceramic material is easy to crack during machining due to the defects of large brittleness and small fracture toughness; and zirconia is based on phase change toughening to ensure high toughness, frequent impact easily causes microcrack expansion, thereby reducing the application reliability, and zirconia has low hardness and is easy to scratch to influence the beauty of the zirconia. Therefore, the application prospect is limited. Furthermore, the current methods for manufacturing zirconia mobile phone back plates mainly include a dry pressing method, a tape casting method, a gel injection molding method and an injection molding method. The methods have the defects of high organic matter content (more than 2 percent), high porosity caused by inevitable generation of pores in the volatilization process of the organic matter, low ceramic compactness and low mechanical strength.

In the invention, zirconium oxide, zirconium oxychloride and lanthanum hexaboride are used as initial raw materials, then a very small amount of binder (about 0.5-1.5% of the total mass of the raw materials, even less) is added, and the raw materials are uniformly mixed, hydrolyzed, subjected to static pressure, pre-sintered, sliced and re-sintered to obtain the zirconium boride/lanthanum hexaboride composite material. The porosity is low due to low organic content, and the method has the characteristics of high compactness, high mechanical strength, strong toughness, simple preparation method and the like. Has very wide application prospect.

In the present invention, pure zirconia is a monoclinic phase at room temperature, and changes to a tetragonal phase when the temperature is raised to about 1173 ℃ and to a cubic phase when the temperature is raised to 2370 ℃ and changes to a liquid phase at 2690 ℃. When the material is cooled from high temperature to room temperature, orthorhombic crystals are converted into monoclinic crystals through phase transition temperature, and the sintered finished product contains microcracks due to severe change of the volume of the monoclinic crystals, so that the material is often unusable. Since zirconia does not exist in a cubic phase (fluorite crystal structure) at room temperature, the doped phase stabilizer can greatly increase the temperature range in which zirconia stably exists in a cubic phase. In the invention, the phase stabilizer is one of magnesium oxide, calcium oxide and yttrium oxide. The content of the phase stabilizer is 3 to 20 wt%, preferably 5 to 15 wt% (generally, when magnesium oxide is used as the phase stabilizer, it is added in an amount of 15 to 20 wt%, when calcium oxide is used as the phase stabilizer, it is added in an amount of 3 to 10 wt%, and when yttrium oxide is used as the phase stabilizer, it is added in an amount of 8 to 13 wt%). Or the phase stabilizer is one of a magnesium oxide-yttrium oxide composite stabilizer and a calcium oxide-yttrium oxide composite stabilizer; the content of the composite stabilizer is 5 to 15% by weight, preferably 8 to 12% (generally, when magnesia-yttria is used as the composite stabilizer, the mass ratio of magnesia to yttria is generally 1:0.2 to 1. when calcia-yttria is used as the composite stabilizer, the mass ratio of calcia to yttria is generally 1:0.2 to 0.5).

In the invention, partial zirconium oxychloride (also called zirconium oxychloride) is adopted to replace partial zirconium oxide (which is beneficial to further reducing the dosage of the adhesive) in the initial raw materials, on one hand, as the zirconium oxychloride is easy to dissolve in water, and then the whole initial raw material system is changed into a slurry system after the aqueous solution of the zirconium oxychloride is added, the initial raw materials of all components can be stirred and mixed more uniformly, and the compactness of the blank formed by static pressure in the follow-up process is better. The compactness of the finished backboard obtained by sintering is better. On the other hand, zirconium oxychloride can be hydrolyzed to obtain a zirconium oxide sol, and the sol zirconium oxide and the raw materials of other components are mixed and uniformly mixed, so that the compactness of the blank formed by static pressure is improved. And the sol-like zirconium oxide can make up for the problems of insufficient material adhesion and density in the material static pressing and blank forming stage when only a small amount of binder is added for reducing the content of organic matters. Further, in order to make the hydrolysis of zirconium oxychloride more complete, a proper amount of hydrogen peroxide (generally, the amount of hydrogen peroxide is 0.5-5 times, preferably 1-4 times, the mass of the added zirconium oxychloride) is added while the aqueous solution of zirconium oxychloride is added, and the hydrogen peroxide can consume the byproducts of the hydrolysis of zirconium oxychloride, so that the hydrolysis of zirconium oxychloride is more rapid and complete. The more zirconium oxychloride is hydrolyzed, the faster the polycondensation reaction proceeds, the smaller the size of the sol particles, the more uniform the distribution, the faster the viscosity of the sol increases, and the shorter the sol-gel time.

In the invention, lanthanum hexaboride is also doped in the zirconia ceramic back plate. On the one hand, the doped lanthanum hexaboride with a proper amount can form a stable and uniformly distributed hard skeleton in a zirconia ceramic particle structure, so that the strength and the thermal stability of the zirconia ceramic back plate can be greatly improved, and meanwhile, the radiation resistance of the zirconia ceramic back plate can be further improved.

In the invention, the zirconia ceramic backboard is further doped with titanium boride, and a proper amount of titanium boride is doped, so that the wear resistance and the chemical stability of the zirconia ceramic backboard can be greatly improved, and the titanium boride forms an alternate composite phase in a zirconia particle structure, so that the phase change toughening of the zirconia ceramic is enhanced. Meanwhile, the titanium boride can form a compact oxidation film at high temperature, so that the wear resistance and oxidation resistance of the zirconia ceramic backboard are further improved.

In the invention, the stable zirconium oxide, lanthanum hexaboride, binder and titanium boride are interpenetrated and crosslinked in a sol system formed by hydrolysis of zirconium oxychloride to obtain a mixture which is uniformly distributed, has higher compactness and has no density gradient. And (3) carrying out static pressure on the mixture (after drying, reducing the moisture content and facilitating the static pressure forming) under ultrahigh pressure to form a blank with higher density. Meanwhile, the blank body is subjected to primary sintering (slowly heated and gradually sintered, so that the sintering effect is prevented from being influenced by overlarge temperature difference jump), through the primary sintering, on one hand, the crosslinking degree among the raw materials of all the components is increased, meanwhile, hydrogen peroxide contained in the blank body can be further removed, a zirconium oxychloride and a zirconium oxide sol system obtained by hydrolyzing the zirconium oxychloride are converted into stable zirconium oxide, and a composite system of lanthanum hexaboride and a titanium boride reinforcing phase is doped in zirconium oxide ceramic particles. Further improving the hardness, strength, compactness, wear resistance, bending resistance and the like of the zirconia ceramic back plate to the maximum extent.

Compared with the prior art, the invention has the following beneficial technical effects:

1. the method comprises the steps of taking zirconium oxide, zirconium oxychloride and lanthanum hexaboride as initial raw materials, uniformly mixing, hydrolyzing, drying and adopting ultrahigh pressure cold isostatic pressing for pretreatment in the presence of a binder to obtain a blank, wherein the blank has no organic volatilization, low porosity and no density gradient. The blank is subjected to presintering, slicing and secondary sintering to obtain the ceramic back plate, and the ceramic back plate obtained after sintering the blank has good sintering density, high strength and strong wear resistance.

2. The invention adopts the sol system obtained by hydrolyzing zirconium oxychloride as the mixing system, thereby greatly improving the mixing degree of the raw materials of each component and the compactness of the subsequent ultra-high static pressure blank. Meanwhile, the sol system further provides excellent places for the extension and crosslinking of the reinforcing phases such as lanthanum hexaboride and titanium boride in a zirconia matrix phase, and greatly promotes the reinforcing effect of the magnetic force of the lanthanum hexaboride and the titanium boride on the performances of zirconia ceramics in the aspects of wear resistance, impact resistance, high toughness and the like.

3. The preparation method is simple, the raw materials are easy to obtain, and the embryo body is obtained through ultrahigh static pressure. Meanwhile, pre-sintering and secondary sintering are adopted to respectively carry out heat treatment on the large blank and the slice obtained by slicing, so that the prepared zirconia composite ceramic has low porosity, high sintering compactness and high mechanical strength.

Detailed Description

The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.

zirconia is 60 to 75 wt%, preferably 65 to 70 wt%.

Lanthanum hexaboride 2-9 wt%, preferably 3-7 wt%.

0.5 to 1.5 wt%, preferably 0.8 to 1.2 wt% of a binder.

Or, the raw material components also comprise:

zirconia is 60 to 75 wt%, preferably 65 to 70 wt%.

Lanthanum hexaboride 2-9 wt%, preferably 3-7 wt%.

0.5 to 1.5 wt%, preferably 0.8 to 1.2 wt% of a binder.

Or, the raw material components also comprise:

Preferably, the zirconia is nano zirconia stabilized with a phase stabilizer. The particle size of the zirconia is 1-100nm, preferably 5-80 nm. (the particle diameter herein means that the primary particle diameter of zirconia is 1 to 100nm, preferably 5 to 80 nm; further, the secondary particle diameter of zirconia D50 is 30 to 500nm, preferably D50 is 60 to 300nm)

Preferably, the step 4) is specifically: the thin slice obtained in the step 3) is sintered again (for example, the temperature of the thin slice is raised to 1300-1600 ℃ in a sintering machine at the speed of 10-120 ℃/h, and then the temperature is preserved for 1-6h, preferably the temperature of the isostatic pressing blank is raised to 1350-1450 ℃ in the sintering machine at the speed of 15-60 ℃/h, and then the temperature is preserved for 2-3 h). After sintering, the sintered sheet is subjected to surface treatment (e.g., surface grinding, polishing, edge chamfering) to obtain the zirconia ceramic back plate.

Example 1

7.5kg of zirconia stabilized with a magnesium oxide-yttrium oxide composite stabilizer (8 wt% of magnesium oxide +2 wt% of yttrium oxide + 90% of zirconium oxide, the average particle size of zirconium oxide is 15nm), 0.6kg of lanthanum hexaboride (the average particle size is 15 μm), 0.1kg of a binder and 0.85kg of titanium boride (the average particle size is 10 μm) were put into a vessel, and then a saturated aqueous solution containing 1.8kg of zirconium oxychloride (the average particle size is 15 μm) and 4kg of hydrogen peroxide were added and stirred at room temperature for 24 hours to obtain a mixed material. The mixture was then dried at 110 ℃ for 1.5h and ground to nanoscale. And after drying and grinding, pressing in an isostatic pressing die sleeve under the pressure of 500MPa, and maintaining the pressure for 15min to obtain an isostatic pressing green body. And then the isostatic pressing blank is heated to 1050 ℃ at the speed of 15 ℃/h in a sintering machine for sintering and heat preservation for 3 h. And after sintering, cooling the blank to room temperature to obtain the pre-sintered blank. Then, the pre-fired green body was sliced using an array saw blade group consisting of 10 groups of 0.15mm saw blades to obtain a 0.8mm thin sheet. And finally, heating the sheet to 1400 ℃ at the speed of 15 ℃/h in a sintering machine, sintering and preserving heat for 4h, and after sintering, grinding, polishing and chamfering the edge of the sintered sheet to obtain the zirconia ceramic backboard I.

Example 2

6.5kg of zirconia stabilized with a magnesium oxide-yttrium oxide composite stabilizer (8 wt% of magnesium oxide +2 wt% of yttrium oxide + 90% of zirconium oxide, the average particle size of zirconium oxide is 15nm), 0.8kg of lanthanum hexaboride (the average particle size is 15 μm), 0.08kg of a binder and 0.8kg of titanium boride (the average particle size is 10 μm) were put into a vessel, and then a saturated aqueous solution containing 2.62kg of zirconium oxychloride (the average particle size is 15 μm) and 5kg of hydrogen peroxide were added and stirred at room temperature for 24 hours to obtain a mixed material. The mixture was then dried at 110 ℃ for 1.5h and ground to nanoscale. And after drying and grinding, pressing in an isostatic pressing die sleeve under the pressure of 500MPa, and maintaining the pressure for 15min to obtain an isostatic pressing green body. And then the isostatic pressing blank is heated to 1050 ℃ at the speed of 15 ℃/h in a sintering machine for sintering and heat preservation for 3 h. And after sintering, cooling the blank to room temperature to obtain the pre-sintered blank. Then, the pre-fired green body was sliced using an array saw blade group consisting of 10 groups of 0.15mm saw blades to obtain a 0.8mm thin sheet. And finally, heating the sheet to 1390 ℃ at the speed of 20 ℃/h in a sintering machine, sintering and preserving heat for 3h, and after sintering, grinding, polishing and chamfering the edge of the sintered sheet to obtain the zirconia ceramic backboard II.

Example 3

7.5kg of zirconia stabilized with a magnesia-yttria composite stabilizer (8 wt% of magnesia +2 wt% of yttria + 90% of zirconia having an average particle size of 15nm), 0.6kg of lanthanum hexaboride (having an average particle size of 15 μm), and 0.1kg of a binder were put into a vessel, and then a saturated aqueous solution containing 1.8kg of zirconium oxychloride (having an average particle size of 15 μm) and 4kg of hydrogen peroxide were added thereto and stirred at room temperature for 24 hours to obtain a mixed material. The mixture was then dried at 110 ℃ for 1.5h and ground to nanoscale. And after drying and grinding, pressing in an isostatic pressing die sleeve under the pressure of 500MPa, and maintaining the pressure for 15min to obtain an isostatic pressing green body. And then the isostatic pressing blank is heated to 1050 ℃ at the speed of 15 ℃/h in a sintering machine for sintering and heat preservation for 3 h. And after sintering, cooling the blank to room temperature to obtain the pre-sintered blank. Then, the pre-fired green body was sliced using an array saw blade group consisting of 10 groups of 0.15mm saw blades to obtain a 0.8mm thin sheet. And finally, heating the sheet to 1450 ℃ at the speed of 25 ℃/h in a sintering machine, sintering and preserving heat for 2h, and after sintering, grinding, polishing and chamfering the edge of the sintered sheet surface to obtain the zirconia ceramic backboard III.

Example 4

7.5kg of zirconia stabilized with a magnesium oxide-yttrium oxide composite stabilizer (8 wt% of magnesium oxide +2 wt% of yttrium oxide + 90% of zirconium oxide, the average particle size of zirconium oxide is 15nm), 0.6kg of lanthanum hexaboride (the average particle size is 15 μm), 0.1kg of a binder and 0.85kg of titanium boride (the average particle size is 10 μm) were put into a vessel, and then a saturated aqueous solution containing 0.3kg of zirconium oxychloride (the average particle size is 15 μm) and 1kg of hydrogen peroxide were added and stirred at room temperature for 24 hours to obtain a mixed material. The mixture was then dried at 110 ℃ for 1.5h and ground to nanoscale. And after drying and grinding, pressing in an isostatic pressing die sleeve under the pressure of 500MPa, and maintaining the pressure for 15min to obtain an isostatic pressing green body. And then the isostatic pressing blank is heated to 1050 ℃ at the speed of 15 ℃/h in a sintering machine for sintering and heat preservation for 3 h. And after sintering, cooling the blank to room temperature to obtain the pre-sintered blank. Then, the pre-fired green body was sliced using an array saw blade group consisting of 10 groups of 0.15mm saw blades to obtain a 0.8mm thin sheet. And finally, heating the sheet to 1550 ℃ at the speed of 15 ℃/h in a sintering machine, sintering, keeping the temperature for 1.5h, and after sintering, grinding, polishing and chamfering the edge of the sintered sheet to obtain the zirconia ceramic backboard IV.

Example 5

7.5kg of zirconia stabilized with a magnesium oxide-yttrium oxide composite stabilizer (8 wt% of magnesium oxide +2 wt% of yttrium oxide + 90% of zirconium oxide, the average particle size of zirconium oxide is 15nm), 0.6kg of lanthanum hexaboride (the average particle size is 15 μm), 0.3kg of a binder and 0.85kg of titanium boride (the average particle size is 10 μm) were put into a vessel, and then a saturated aqueous solution containing 1.8kg of zirconium oxychloride (the average particle size is 15 μm) and 4kg of hydrogen peroxide were added and stirred at room temperature for 24 hours to obtain a mixed material. The mixture was then dried at 110 ℃ for 1.5h and ground to nanoscale. And after drying and grinding, pressing in an isostatic pressing die sleeve under the pressure of 500MPa, and maintaining the pressure for 15min to obtain an isostatic pressing green body. And then the isostatic pressing blank is heated to 1050 ℃ at the speed of 15 ℃/h in a sintering machine for sintering and heat preservation for 3 h. And after sintering, cooling the blank to room temperature to obtain the pre-sintered blank. Then, the pre-fired green body was sliced using an array saw blade group consisting of 10 groups of 0.15mm saw blades to obtain a 0.8mm thin sheet. And finally, heating the thin slice to 1400 ℃ at the speed of 15 ℃/h in a sintering machine for sintering and preserving heat for 3h, and after the sintering is finished, grinding, polishing and chamfering the edge of the sintered thin slice to obtain the zirconia ceramic backboard V.

Example 6

7.5kg of zirconia stabilized with a magnesium oxide-yttrium oxide composite stabilizer (8 wt% of magnesium oxide +2 wt% of yttrium oxide + 90% of zirconium oxide, the average particle size of zirconium oxide is 15nm), 0.1kg of a binder and 0.85kg of titanium boride (the average particle size is 10 μm) were put into a vessel, and then a saturated aqueous solution containing 1.8kg of zirconium oxychloride (the average particle size is 15 μm) and 4kg of hydrogen peroxide were added and stirred at room temperature for 24 hours to obtain a mixed material. The mixture was then dried at 110 ℃ for 1.5h and ground to nanoscale. And after drying and grinding, pressing in an isostatic pressing die sleeve under the pressure of 500MPa, and maintaining the pressure for 15min to obtain an isostatic pressing green body. And then the isostatic pressing blank is heated to 1050 ℃ at the speed of 15 ℃/h in a sintering machine for sintering and heat preservation for 3 h. And after sintering, cooling the blank to room temperature to obtain the pre-sintered blank. Then, the pre-fired green body was sliced using an array saw blade group consisting of 10 groups of 0.15mm saw blades to obtain a 0.8mm thin sheet. And finally, heating the thin slice to 1400 ℃ at the speed of 20 ℃/h in a sintering machine for sintering and preserving heat for 3h, and after sintering, grinding, polishing and chamfering the edge of the sintered thin slice to obtain the zirconia ceramic backboard VI.

Effect test comparison table:

Claims

1. a zirconia-based ceramic backing plate, characterized by: the material is prepared by taking zirconium oxide, zirconium oxychloride and lanthanum hexaboride as initial raw materials, and then uniformly mixing, hydrolyzing, statically pressing, presintering, slicing and re-sintering the raw materials in the presence of a binder;

2. The zirconia-based ceramic backing plate of claim 1, wherein: the raw materials comprise the following components in percentage by weight:

zirconia 60-75 wt%, preferably 65-70 wt%;

15-30 wt%, preferably 20-25 wt% of zirconium oxychloride;

2-9 wt% of lanthanum hexaboride, preferably 3-7 wt%;

0.5-1.5 wt% of binder, preferably 0.8-1.2 wt%;

or, the raw material components also comprise:

1 to 12 wt.%, preferably 3 to 10 wt.% (based on the total mass of the above-mentioned raw materials).

3. The zirconia-based ceramic backing plate of claim 1 or 2, wherein: the zirconia is nano zirconia stabilized by a phase stabilizer; the particle size of the zirconia is 1-100nm, preferably 5-80 nm;

preferably, the phase stabilizer is one or more of magnesium oxide, calcium oxide, yttrium oxide, scandium oxide, cerium oxide and aluminum oxide which are compounded together; the total content of the phase stabilizer is 3 to 20 wt%, preferably 5 to 15 wt%;

or the phase stabilizer is one of a magnesium oxide-yttrium oxide composite stabilizer and a calcium oxide-yttrium oxide composite stabilizer; the content of the composite stabilizer is 5-15 wt%, and preferably 8-12 wt%.

4. The zirconia-based ceramic backplate of any one of claims 1-3, wherein: the zirconium oxychloride is nano-grade zirconium oxychloride, and the average particle size of the zirconium oxychloride is 1-30nm, preferably 5-20 nm; and/or

The lanthanum hexaboride is micron lanthanum hexaboride, and the average grain size of the lanthanum hexaboride is 1-25 μm, preferably 5-15 μm; and/or

The titanium boride is micron-sized titanium boride, and the average grain size of the titanium boride is 1-25 mu m, preferably 5-15 mu m; and/or

The binder is one or more of polyvinyl alcohol, polyoxyethylene ether, polyethylene glycol, polyoxyethylene and carboxymethyl cellulose.

5. A method of preparing a zirconia ceramic backing plate or a method of using a zirconia ceramic backing plate according to any one of claims 1 to 4, wherein: the method comprises the following steps:

1) weighing the raw materials in proportion, and uniformly stirring and mixing; then placing the blank in an isostatic pressing die sleeve to obtain an isostatic pressing blank;

2) placing the isostatic pressing blank obtained in the step 1) in a sintering machine for pre-sintering treatment, and cooling to obtain a pre-sintering blank;

3) slicing the pre-sintered blank obtained in the step 2) to obtain a slice;

6. The method of claim 5, wherein: the proportion of the added amount of the raw materials of each component is as follows:

zirconia 60-75 wt%, preferably 65-70 wt%;

15-30 wt%, preferably 20-25 wt% of zirconium oxychloride;

2-9 wt% of lanthanum hexaboride, preferably 3-7 wt%;

0.5-1.5 wt% of binder, preferably 0.8-1.2 wt%;

or, the raw material components also comprise:

7. The method of claim 6, wherein: the zirconia is nano zirconia stabilized by a phase stabilizer; the particle size of the zirconia is 1-100nm, preferably 5-80 nm;

preferably, the phase stabilizer is one of magnesium oxide, calcium oxide, yttrium oxide, scandium oxide, cerium oxide and aluminum oxide; the addition amount of the phase stabilizer is 3-20 wt%, preferably 5-15 wt%; the total content of the phase stabilizer is 3 to 20 wt%, preferably 5 to 15 wt%;

or the phase stabilizer is one of a magnesium oxide-yttrium oxide composite stabilizer and a calcium oxide-yttrium oxide composite stabilizer; the addition amount of the composite stabilizer is 5-15 wt%, and the preferable addition amount is 8-12%.

8. The method according to claim 6 or 7, characterized in that: the zirconium oxychloride is nano-grade zirconium oxychloride, and the average particle size of the zirconium oxychloride is 1-30nm, preferably 5-20 nm; and/or

9. The method according to any one of claims 5-8, wherein: the step 1) is specifically as follows: putting zirconium oxide, lanthanum hexaboride and a binder into a container according to a proportion, then optionally adding or not adding titanium boride, and uniformly stirring and mixing; then adding an aqueous solution of zirconium oxychloride (for example, a saturated aqueous solution of zirconium oxychloride) and a proper amount of hydrogen peroxide (for example, the addition amount of hydrogen peroxide is 0.5-5 times, preferably 1-4 times, the mass of the added zirconium oxychloride), and then continuing stirring and mixing (for example, stirring at room temperature for 1-72 hours, preferably 3-48 hours) to obtain a mixture; then drying the mixture (for example, drying at 80-120 ℃ for 0.5-5h, preferably drying at 100 ℃ and 100 ℃ for 1-3h), grinding, and then placing the mixture in an isostatic pressing die sleeve for pressing (for example, keeping the pressure at 200-550MPa for 1-30min, preferably keeping the pressure at 240-500MPa for 3-15min) to obtain an isostatic pressing blank;

the step 2) is specifically as follows: placing the isostatic pressing blank obtained in the step 1) in a sintering machine for pre-sintering treatment (for example, raising the temperature of the isostatic pressing blank in the sintering machine to 800-1100 ℃ at a speed of 5-20 ℃/h, and then preserving the heat for 2-10h, preferably raising the temperature of the isostatic pressing blank in the sintering machine to 850-1000 ℃ at a speed of 10-15 ℃/h, and then preserving the heat for 3-5 h); cooling (e.g., to room temperature) to obtain a pre-fired green body;

the step 3) is specifically as follows: slicing the pre-sintered blank obtained in the step 2) (for example, slicing after forming an array by using 1-20 groups of 0.1-0.3mm saw blades, preferably, slicing after forming an array by using 3-15 groups of 0.1-0.3mm saw blades) to obtain a slice (the thickness of the slice is 0.5-1.2mm, preferably 0.6-1.0 mm);

the step 4) is specifically as follows: and (3) sintering the thin slice obtained in the step 3) again (for example, heating the thin slice to 1300-1600 ℃ at the speed of 10-120 ℃/h in a sintering machine, then preserving heat for 1-6h, preferably heating the isostatic pressing blank to 1350-1450 ℃ at the speed of 15-60 ℃/h in the sintering machine, then preserving heat for 2-3h), and after sintering, performing surface treatment (for example, surface grinding, polishing and edge chamfering) on the sintered thin slice to obtain the zirconia ceramic backboard.

10. Use of a zirconia ceramic backplate according to any one of claims 1 to 4 or prepared by a method according to any one of claims 5 to 9, wherein: the zirconia ceramic backboard is used as a mobile phone backboard, a computer backboard and a liquid crystal television backboard.