CN112552042A - Zirconia ceramic and preparation method and application thereof - Google Patents

Zirconia ceramic and preparation method and application thereof Download PDF

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CN112552042A
CN112552042A CN201910908515.4A CN201910908515A CN112552042A CN 112552042 A CN112552042 A CN 112552042A CN 201910908515 A CN201910908515 A CN 201910908515A CN 112552042 A CN112552042 A CN 112552042A
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oxide
stabilizer
toughening agent
mol
zirconia
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陈戈
林信平
唐威
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BYD Co Ltd
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BYD Co Ltd
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K5/00—Casings, cabinets or drawers for electric apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof

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  • Structural Engineering (AREA)
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  • Compositions Of Oxide Ceramics (AREA)

Abstract

本发明涉及一种氧化锆陶瓷及其制备方法和应用，该氧化锆陶瓷包含氧化锆基体、稳定剂和增韧剂，所述稳定剂为氧化钇、氧化铒、氧化钕和氧化钐中的一种或多种，所述增韧剂为氧化铌和/或氧化钽；以氧化锆陶瓷的总摩尔量为基准，所述稳定剂的含量为2‑4mol%，所述增韧剂的含量为0.45‑1.4mol%，所述稳定剂与所述增韧剂的摩尔百分含量差值为1.5‑2.6mol%。通过控制稳定剂与增韧剂的含量，两者相互配合，使氧化锆陶瓷韧性好、抗冲击性能好，且具有良好的耐热老化性能。The invention relates to a zirconia ceramic, a preparation method and application thereof. The zirconia ceramic comprises a zirconia matrix, a stabilizer and a toughening agent, and the stabilizer is one of yttrium oxide, erbium oxide, neodymium oxide and samarium oxide. One or more, the toughening agent is niobium oxide and/or tantalum oxide; based on the total molar amount of zirconia ceramics, the content of the stabilizer is 2-4 mol%, and the content of the toughening agent is 0.45-1.4 mol%, and the molar percentage difference between the stabilizer and the toughening agent is 1.5-2.6 mol%. By controlling the content of stabilizer and toughening agent, the two cooperate with each other, so that the zirconia ceramic has good toughness, good impact resistance and good heat aging resistance.

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 ceramics have the characteristics of good corrosion resistance, high hardness and high strength of the conventional ceramics, so the zirconia ceramics have wide application. The toughness (reaching 5-6MPa m)1/2) Although higher than the conventional other ceramics, the ceramic has the defect of weak impact resistance when being made into a large-area appearance piece; in addition, in order to ensure flatness, a heat leveling process is performed after processing, which causes a significant decrease in impact resistance of the sample after heat leveling, and thus mass-producibility is not achieved. Therefore, the development of zirconia ceramics with high impact resistance is a very good candidate for making zirconia a 5G era backing plate materialIt is important.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides zirconia ceramic, and a preparation method and application thereof.
The first aspect of the invention provides a zirconia ceramic, which comprises a zirconia matrix, a stabilizing agent and a toughening agent, wherein the stabilizing agent is one or more of yttrium oxide, erbium oxide, neodymium oxide and samarium oxide, and the toughening agent is niobium oxide and/or tantalum oxide; based on the total molar weight of the zirconia ceramics, the content of the stabilizing agent is 2-4mol%, the content of the toughening agent is 0.45-1.4mol%, and the difference between the molar percentages of the stabilizing agent and the toughening agent is 1.5-2.6 mol%.
Preferably, the content of the stabilizer is 2.5-3.5mol%, and the content of the toughening agent is 0.65-1.15 mol%.
Preferably, the difference of the molar percentage of the stabilizer and the toughening agent is 1.9-2.4 mol%.
In a second aspect of the present invention, there is provided a method for preparing a zirconia ceramic, the method comprising:
(1) adding water, a dispersing agent and a binder into composite powder containing zirconium oxide, a stabilizing agent and a toughening agent for wet milling to obtain slurry, wherein the stabilizing agent is one or more of yttrium oxide, erbium oxide, neodymium oxide and samarium oxide, and the toughening agent is niobium oxide and/or tantalum oxide; based on the total molar weight of the composite powder, the content of the stabilizer is 2-4mol%, the content of the toughening agent is 0.45-1.4mol%, and the difference between the molar percentages of the stabilizer and the toughening agent is 1.5-2.6 mol%;
(2) and drying and sintering the slurry to obtain the zirconia ceramic.
The third aspect of the present invention is to provide a zirconia ceramic obtained by the foregoing production method.
The invention provides an application of the zirconia ceramic in preparing electronic product shells or ornaments.
The zirconia ceramic provided by the invention has good toughness, good impact resistance and good thermal aging resistance by controlling the contents of the stabilizer and the toughening agent and matching the stabilizer and the toughening agent.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those 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 invention provides zirconia ceramic, which comprises a zirconia matrix, a stabilizer and a toughening agent, wherein the stabilizer is one or more of yttrium oxide, erbium oxide, neodymium oxide and samarium oxide, and the toughening agent is niobium oxide and/or tantalum oxide; based on the total molar weight of the zirconia ceramics, the content of the stabilizing agent is 2-4mol%, the content of the toughening agent is 0.45-1.4mol%, and the difference between the molar percentages of the stabilizing agent and the toughening agent is 1.5-2.6 mol%. By controlling the contents of the stabilizer and the toughening agent, the zirconium oxide ceramic has good toughness, good impact resistance and good thermal aging resistance.
In the present invention, the composition of the above zirconia ceramic may be a ceramic containing zirconia, yttria and niobia; alternatively, zirconium oxide, yttrium oxide, and tantalum oxide; alternatively, zirconium oxide, erbium oxide, and niobium oxide; alternatively, zirconium oxide, erbium oxide, and tantalum oxide; alternatively, zirconium oxide, neodymium oxide, and niobium oxide; alternatively, zirconium oxide, neodymium oxide, and tantalum oxide; alternatively, zirconium oxide, samarium oxide and niobium oxide; alternatively, zirconium oxide, samarium oxide, and tantalum oxide; or zirconium oxide, and two or more of yttrium oxide, erbium oxide, neodymium oxide and samarium oxide, and niobium oxide and/or tantalum oxide.
In the invention, in order to further improve the toughness, the impact resistance and the thermal aging resistance of the zirconia ceramic, preferably, the content of the stabilizer is 2.5-3.5mol%, and the content of the toughening agent is 0.65-1.15 mol%; further preferably, the difference of the molar percentage of the stabilizer and the toughening agent is 1.9-2.4 mol%.
In the present invention, preferably, the zirconia ceramic has a hardness of 1150Hv, preferably 1170-1260 Hv; the drop hammer height of the zirconia ceramics is more than 26 cm; in the test result of the thermal aging resistance of the zirconia ceramic, after the zirconia ceramic is subjected to heat leveling at 1100-1200 ℃, the zirconia ceramic can still keep the drop height before the heat leveling.
The invention also provides a preparation method of the zirconia ceramic, which comprises the following steps:
(1) adding water, a dispersing agent and a binder into composite powder containing zirconium oxide, a stabilizing agent and a toughening agent for wet milling to obtain slurry, wherein the stabilizing agent is one or more of yttrium oxide, erbium oxide, neodymium oxide and samarium oxide, and the toughening agent is niobium oxide and/or tantalum oxide; based on the total molar weight of the composite powder, the content of the stabilizer is 2-4mol%, the content of the toughening agent is 0.45-1.4mol%, and the difference between the molar percentages of the stabilizer and the toughening agent is 1.5-2.6 mol%;
(2) and drying and sintering the slurry to obtain the zirconia ceramic.
In the present invention, zirconia, yttria, erbium oxide, neodymium oxide and samarium oxide in the stabilizer, and niobium oxide and/or tantalum oxide may each be provided in the form of a high purity oxide powder. For example, yttria and zirconia can be prepared by using a tetragonal zirconia powder (median particle diameter of 0.3-0.6 μm, specific surface area of 7-13 m) stabilized with 2-4mol% yttria2In terms of/g), wherein the content of yttrium oxide is based on zirconium oxide. The erbium oxide can be pure erbium oxide powder (the median diameter is 3-7 μm). The neodymium oxide can adopt pure neodymium oxide powder (the median diameter is 3-7 μm). The samarium oxide can be pure samarium oxide powder (samarium oxide)Median particle size of 3-7 μm). Niobium oxide can be niobium pentoxide (with a median particle size of 8-10 μm) powder. The tantalum oxide can be tantalum pentoxide powder (with a median particle size of 8-10 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 powder of the oxides and water into slurry, ball-milling and mixing, and then grinding and crushing to make the particle size median of the oxides to be nano-scale (such as 250-500 nm). More specifically, the 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, finally a binding agent (such as PVA and/or polyethylene glycol 4000) with a proper proportion is added, and then stirring is carried out for 2-4 h. Ball milling pots and sand mills use an inner liner of zirconia ceramic 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.
In the present invention, various oxide feeds make up the powder. The feeding amount of various oxides finally meets the composition requirements of the obtained zirconia ceramics. Preferably, the content of the stabilizer is 2.5-3.5mol%, and the content of the toughening agent is 0.65-1.15 mol%.
In the invention, in order to further improve the toughness, the impact resistance and the thermal aging resistance of the zirconia ceramic, the difference between the molar percentages of the stabilizer and the toughening agent is preferably 1.9-2.4 mol%.
In the present invention, preferably, in step (1), the dispersant is selected from at least one of hypromellose, sodium carboxymethylcellulose, and triethanolamine; the binder is selected from polyvinyl alcohol and/or polyethylene glycol 4000. The dispersing agent can promote the components in the powder to be uniformly mixed. The binder is beneficial to the formability of the powder. Preferably, the binder is polyvinyl alcohol (PVA) and polyethylene glycol 4000 (PEG 4000), and the molar ratio of polyvinyl alcohol to polyethylene glycol 4000 is 1: 1-2, preferably 1: 1. In the present invention, the dispersant and the binder are commercially available.
In the present invention, the dispersant is preferably added in an amount of 0.005 to 0.5% by weight, preferably 0.01 to 0.1% by weight, based on the powder.
In the present invention, the binder is preferably added in an amount of 0.5 to 5% by weight, preferably 2 to 5% by weight, of the powder.
In the present invention, preferably, the solid content of the slurry is 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, for example, spray drying, may be used in the step (2) to form a spherical powder having high flowability. The air inlet temperature of spray drying is preferably 220-280 ℃, the air outlet temperature is preferably 100-120 ℃, and the centrifugal rotating speed is 10-20 r/s.
In the present invention, after the slurry is dried in the step (2), molding may be performed, followed by sintering. The molding can adopt dry pressing, isostatic pressing, injection molding, hot-press molding and other molding modes. Preferably dry pressing molding, a press with 180 and 220 tons of tonnage can be used for molding by using the oil pressure of 6-10MPa, such as the shape of a rear cover of a mobile phone. The sintering procedure comprises: raising the temperature from room temperature to 600 ℃ for 2h after 400min, raising the temperature from 600 ℃ to 1150 ℃ after 300min and preserving the heat for 2h, raising the temperature from 1150 ℃ to 1300 ℃ for 2h after 150min, raising the temperature from 1300 ℃ to 1450-1600 ℃ after 50min and preserving the heat for 1-2h, then reducing the temperature to 900 ℃ after 150min, and finally naturally cooling to room temperature.
In the invention, the zirconia ceramics obtained after sintering also comprises the steps of flat grinding and polishing, and processing and cutting into final products by using a laser. The zirconia ceramics are large-area thin-sheet ceramics and can deform in processing, so that heat leveling treatment is required under the conditions of 1100-1200 ℃. The prior art zirconia ceramics have poor strength, toughness and impact resistance after heat leveling. The zirconia ceramic has good toughness, good impact resistance and good thermal aging resistance (namely, the performance of the zirconia ceramic is kept unchanged before and after heat leveling treatment) by controlling the contents of the stabilizer and the toughening agent in the zirconia matrix.
The invention provides zirconia ceramics prepared by the preparation method. The zirconia ceramic has good toughness, good impact resistance and good thermal aging resistance.
The invention also provides an application of the zirconia ceramic in preparing electronic product shells or ornaments.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
Fracture toughness Kic: indenter indentation method (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).
Drop hammer impact: the sample was placed on a platform using a drop hammer impact tester (manufacturer CKSI, model E602 SS), the center of the sample was hammered with a drop hammer weighing 60g, starting from a height of 5cm, and increasing in height of 5cm each time if no crack occurred, until the sample was visually observed to crack, and the height value was recorded.
Aging rate: the ratio of the drop weight impact height of the sample after being subjected to 1100 ℃ heat leveling to the drop weight impact height before being subjected to heat leveling.
Compactness: taking the average pit number (more than 20 μm) in the range of 10X 10mm on the large surface of the polished sample
XRF detection: the element content of the polished sample was measured using an energy dispersive X-ray fluorescence spectrometer EDX-7000.
Example 1
Raw materials: 200g of composite powder containing 3mol% of yttria-stabilized zirconia, wherein niobium pentoxide (chemical formula Nb)2O5）1mol%。
Adding water into the raw materials in a ball milling tank, ball milling for 8h, then adding 0.02wt% of hydroxypropyl methylcellulose and water into a sand mill, carrying out sand milling for 10h, and finally adding 4wt% of binder (PEG 4000 and PVA with a molar ratio of 1: 1) of powder, stirring for 0.5h 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 (2) heating the formed powder from room temperature to 600 ℃ for 2h after 400min, heating from 600 ℃ to 1150 ℃ for 300min and keeping the temperature for 2h, heating from 1150 ℃ to 1300 ℃ for 150min and keeping the temperature for 2h, heating from 1300 ℃ to 1450 ℃ and 1600 ℃ after 50min and keeping the temperature for 1-2h, then cooling to 900 ℃ after 150min, and finally sintering in the air in the process of naturally cooling to room temperature.
And (3) carrying out CNC (computer numerical control) machining, then carrying out heat smoothing at 1100 ℃, grinding, polishing and laser cutting to obtain a final sample, wherein the size of the final sample is 150 x 75 x 0.6mm, and the shape and the size of the mobile phone rear cover are obtained.
The prepared sample was subjected to high-energy XRF detection, and the constituent elements contained 68.4wt% of Zr, 4.1wt% of Y, and 1.45wt% of Nb.
Example 2
The preparation method is the same as example 1, except that the raw materials: 200g of composite powder containing 3mol% of yttria-stabilized zirconia, wherein niobium pentoxide (chemical formula Nb)2O5）1.35mol%。
The prepared sample was subjected to high-energy XRF detection, and the constituent elements contained 67.8wt% of Zr, 4wt% of Y and 1.9wt% of Nb.
Example 3
The preparation method is the same as example 1, except that the raw materials: 200g of composite powder containing 3mol% of yttria-stabilized zirconia, wherein niobium pentoxide (chemical formula Nb)2O5）0.5mol%。
The prepared sample was subjected to high-energy XRF detection, and the constituent elements contained 69.2wt% of Zr, 4.1wt% of Y, and 0.7wt% of Nb.
Example 4
The preparation method is the same as example 1, except that the raw materials: 200g of zirconia powder containing 2.5mol% of yttria, wherein niobium pentoxide (chemical formula Nb)2O5）0.5mol%。
The prepared sample was subjected to high-energy XRF detection, and the constituent elements contained 69.5wt% of Zr, 3.5wt% of Y, and 0.7wt% of Nb.
Example 5
The preparation method is the same as example 1, except that the raw materials: 200g of a composite powder containing 2.5mol% of yttria-stabilized zirconia, wherein niobium pentoxide (chemical formula Nb)2O5）1mol%。
The prepared sample was subjected to high-energy XRF detection, and the constituent elements contained 69wt% of Zr, 3.4wt% of Y, and 1.44wt% of Nb.
Example 6
The preparation method is the same as example 1, except that the raw materials: 200g of composite powder containing 3.5mol% yttria-stabilized zirconia, wherein niobium pentoxide (chemical formula Nb)2O5）1mol%。
The prepared sample was subjected to high-energy XRF detection, and the constituent elements contained 67.8wt% of Zr, 4.85wt% of Y, and 1.43wt% of Nb.
Example 7
The preparation method is the same as example 1, except that the raw materials: 200g of composite powder containing 3.5mol% yttria-stabilized zirconia, wherein niobium pentoxide (chemical formula Nb)2O5）1.2mol%。
The prepared sample was subjected to high-energy XRF detection, and the constituent elements contained 67.5wt% of Zr, 4.8wt% of Y, and 1.69wt% of Nb.
Comparative example 1
The preparation method is the same as example 1, except that the raw materials: 200g of composite powder containing 3mol% of yttria-stabilized zirconia.
The prepared sample was subjected to high-energy XRF detection, and the constituent elements contained 69.9wt% of Zr and 4.1wt% of Y.
Comparative example 2
The preparation method is the same as example 1, except that the raw materials: 200g of composite powder containing 3mol% of yttria-stabilized zirconia, wherein niobium pentoxide (chemical formula Nb)2O5）0.3mol%。
The prepared sample was subjected to high-energy XRF detection, and the composition elements contained 69.3wt%, Y4.1 wt%, and Nb 0.43 wt%.
Comparative example 3
The preparation method is the same as example 1, except that the raw materials: 200g of composite powder containing 3mol% of yttria-stabilized zirconia, wherein niobium pentoxide (chemical formula Nb)2O5）1.6mol%。
The prepared sample was subjected to high-energy XRF detection, and the constituent elements contained 67.4wt% of Zr, 4.1wt% of Y, and 2.3wt% of Nb.
Comparative example 4
The preparation method is the same as example 1, except that the raw materials: 200g of a composite powder containing 2.15mol% of yttria-stabilized zirconia, wherein niobium pentoxide (chemical formula Nb)2O5）0.15mol%。
The prepared sample is subjected to high-energy XRF detection, and the composition elements comprise 70.5wt% of Zr, 3wt% of Y and 0.2wt% of Nb.
Comparative example 5
The preparation method is the same as example 1, except that the raw materials: 200g of composite powder containing 4mol% of yttria-stabilized zirconia, wherein niobium pentoxide (chemical formula Nb)2O5）1mol%。
The prepared sample was subjected to high-energy XRF detection, and the constituent elements contained 67.1wt% of Zr, 5.4wt% of Y, and 1.43wt% of Nb.
Comparative example 6
The preparation method is the same as example 1, except that the raw materials: 200g of a composite powder containing 2mol% of yttria-stabilized zirconia, wherein niobium pentoxide (chemical formula Nb)2O5）1mol%。
The prepared sample was subjected to high-energy XRF detection, and the constituent elements contained 69.7wt% of Zr, 2.7wt% of Y, and 1.45wt% of Nb.
TABLE 1
Hardness (Hv) Toughness (Mpam0.5) Number of pits (individual) Drop hammer before heat smoothing (cm) Drop hammer (cm) after heat smoothing Aging Rate (%)
Example 1 1210 12.2 0 30 30 0
Example 2 1170 13.2 0 27 27 0
Example 3 1260 9.5 0 26 26 0
Example 4 1250 10.1 0 29 29 0
Example 5 1205 12.6 0 27 27 0
Example 6 1230 11 0 27 27 0
Example 7 1215 12 0 26 26 0
Comparative example 1 1290 5.5 0 22 22 0
Comparative example 2 1290 8 0 23 23 0
Comparative example 3 1140 14 0.15 24 24 0
Comparative example 4 1270 12 0 30 15 50
Comparative example 5 1250 7.5 0 21 21 0
Comparative example 6 1203 12.5 0 30 20 33
As can be seen from Table 1, the zirconia ceramic provided by the invention has the characteristics of good hardness, low density, good toughness, high strength and thermal aging resistance. The difference between the mol percentage content of the stabilizer and the mol percentage content of the toughening agent is controlled within the range of 1.5-2.6mol%, the thermal aging resistance and the strength of the zirconia ceramic can be further improved, while the content of the toughening agent and the stabilizer of the comparative example is not within the range of the invention, and the comprehensive performance of the obtained zirconia ceramic is inferior to that of the zirconia ceramic of the invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1.一种氧化锆陶瓷，其特征在于，该氧化锆陶瓷包含氧化锆基体、稳定剂和增韧剂，所述稳定剂为氧化钇、氧化铒、氧化钕和氧化钐中的一种或多种，所述增韧剂为氧化铌和/或氧化钽；以氧化锆陶瓷的总摩尔量为基准，所述稳定剂的含量为2-4mol%，所述增韧剂的含量为0.45-1.4mol%，所述稳定剂与所述增韧剂的摩尔百分含量差值为1.5-2.6mol%。1. a zirconia ceramic is characterized in that, this zirconia ceramic comprises zirconia matrix, stabilizer and toughening agent, and described stabilizer is one or more in yttrium oxide, erbium oxide, neodymium oxide and samarium oxide The toughening agent is niobium oxide and/or tantalum oxide; based on the total molar amount of zirconia ceramics, the content of the stabilizer is 2-4 mol%, and the content of the toughening agent is 0.45-1.4 mol% mol%, the difference in molar percentage between the stabilizer and the toughening agent is 1.5-2.6 mol%. 2.根据权利要求1所述的氧化锆陶瓷，其特征在于，所述稳定剂的含量为2.5-3.5mol%，所述增韧剂的含量为0.65-1.15mol%。2 . The zirconia ceramic according to claim 1 , wherein the content of the stabilizer is 2.5-3.5 mol %, and the content of the toughening agent is 0.65-1.15 mol %. 3 . 3.根据权利要求1所述的氧化锆陶瓷，其特征在于，所述稳定剂与所述增韧剂的摩尔百分含量差值为1.9-2.4mol%。3 . The zirconia ceramic according to claim 1 , wherein the molar percentage difference between the stabilizer and the toughening agent is 1.9-2.4 mol %. 4 . 4.一种氧化锆陶瓷的制备方法，其特征在于，该制备方法包括：4. a preparation method of zirconia ceramics, is characterized in that, this preparation method comprises: （1）将含有氧化锆、稳定剂和增韧剂的复合粉体加水、分散剂和粘结剂进行湿磨，得到浆料，其中，所述稳定剂为氧化钇、氧化铒、氧化钕和氧化钐中的一种或多种，所述增韧剂为氧化铌和/或氧化钽；以复合粉体的总摩尔量为基准，所述稳定剂的含量为2-4mol%，所述增韧剂的含量为0.45-1.4mol%，所述稳定剂与所述增韧剂的摩尔百分含量差值为1.5-2.6mol%；(1) The composite powder containing zirconia, stabilizer and toughening agent is wet-milled with water, dispersant and binder to obtain slurry, wherein the stabilizer is yttrium oxide, erbium oxide, neodymium oxide and One or more of samarium oxide, the toughening agent is niobium oxide and/or tantalum oxide; based on the total molar amount of the composite powder, the content of the stabilizer is 2-4 mol%, and the The content of the toughening agent is 0.45-1.4 mol%, and the molar percentage difference between the stabilizer and the toughening agent is 1.5-2.6 mol%; （2）将所述浆料进行干燥、烧结，得到氧化锆陶瓷。(2) drying and sintering the slurry to obtain zirconia ceramics. 5.根据权利要求4所述的制备方法，其特征在于，所述步骤（2）中烧结后还包括在1100-1200℃条件下热抚平处理。5 . The preparation method according to claim 4 , wherein after the sintering in the step (2), heat smoothing treatment at 1100-1200° C. is further included. 6 . 6.根据权利要求4所述的制备方法，其特征在于，所述稳定剂的含量为2.5-3.5mol%，所述增韧剂的含量为0.65-1.15mol%；6. The preparation method according to claim 4, wherein the content of the stabilizer is 2.5-3.5mol%, and the content of the toughening agent is 0.65-1.15mol%; 所述稳定剂与所述增韧剂的摩尔百分含量差值为1.9-2.4mol%。The molar percentage difference between the stabilizer and the toughening agent is 1.9-2.4 mol%. 7.根据权利要求4所述的制备方法，其特征在于，所述步骤（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/或聚乙二醇4000；7 . The preparation method according to claim 4 , wherein in the step (1), the dispersing agent is selected from at least one of hypromellose, sodium carboxymethyl cellulose and triethanolamine. 8 . ; Described binder is selected from polyvinyl alcohol and/or polyethylene glycol 4000; 优选地，所述分散剂的加入量为所述粉体的0.005-0.5重量%，优选为0.01-0.1重量%；Preferably, the added amount of the dispersant is 0.005-0.5% by weight of the powder, preferably 0.01-0.1% by weight; 优选地，所述粘结剂的加入量为所述粉体的0.5-5重量%，优选为2-5重量%；Preferably, the addition amount of the binder is 0.5-5% by weight of the powder, preferably 2-5% by weight; 优选地，所述浆料的固含量为20-60重量%，优选为25-55重量%。Preferably, the solid content of the slurry is 20-60% by weight, preferably 25-55% by weight. 8.根据权利要求4所述的制备方法，其特征在于，所述烧结的程序包括：从室温经400min升至600℃保温2h，从600℃经300min升温至1150℃并保温2h，从1150℃经150min升温至1300℃保温2h，从1300℃经50min升温至1450-1600℃并保温1-2h，然后经过150min降温至900℃，最后自然冷却至室温。8 . The preparation method according to claim 4 , wherein the sintering procedure comprises: raising the temperature from room temperature to 600° C. for 2 hours over 400 minutes, heating up from 600° C. to 1150° C. over 300 minutes, and holding the temperature for 2 hours, from 1150° C. The temperature was raised to 1300°C for 2h over 150min, then heated from 1300°C to 1450-1600°C over 50min and kept for 1-2h, then cooled to 900°C over 150min, and finally cooled to room temperature naturally. 9.一种由权利要求4-8中的任意一项所述的制备方法制得的氧化锆陶瓷。9. A zirconia ceramic prepared by the preparation method of any one of claims 4-8. 10.一种权利要求1-3和9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。10. An application of the zirconia ceramics according to any one of claims 1-3 and 9 in the preparation of electronic product casings or decorations.
CN201910908515.4A 2019-09-25 2019-09-25 Zirconia ceramic and preparation method and application thereof Pending CN112552042A (en)

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