CN113443912B - Zirconia ceramic and preparation method and application thereof - Google Patents

Zirconia ceramic and preparation method and application thereof Download PDF

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CN113443912B
CN113443912B CN202010225827.8A CN202010225827A CN113443912B CN 113443912 B CN113443912 B CN 113443912B CN 202010225827 A CN202010225827 A CN 202010225827A CN 113443912 B CN113443912 B CN 113443912B
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zirconia
titanium nitride
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zirconia ceramic
niobium carbide
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CN113443912A (en
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陈戈
林信平
唐威
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BYD Co Ltd
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    • 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
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Abstract

The present invention relates to a zirconia ceramic comprising, in terms of elements: zr, Ti, Y, Ni and Nb, and the phase of the zirconia ceramic comprises: tetragonal zirconia, titanium nitride, niobium carbide and elemental nickel; the zirconia ceramic comprises, in elemental terms: 38.4-57.2wt% of Zr, 9.9-31.2wt% of Ti, 1.5-4.4wt% of Y, 1.8-15.9wt% of Nb and 1-7wt% of Ni; the phase of the zirconia ceramic comprises: 60-80wt% of tetragonal zirconia, 17-30wt% of titanium nitride, 2-15wt% of niobium carbide and 1-7wt% of simple substance nickel. The zirconia ceramic has good mechanical property, excellent appearance and good conductivity.

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
Under the trend of continuous progress of science and technology, the functional requirements on intelligent wearable products (such as intelligent watches) are higher and higher, and the requirements on heart rate and pulse detection are required. In order to be able to detect the heart rate, it is necessary to partially attach a stainless steel part to the back of the watchcase that is in contact with the skin, but the stainless steel part rusts due to the immersion of sweat. The conductive ceramic material can improve the texture, the use convenience and the corrosion resistance of the product. However, the existing conductive ceramic is difficult to ensure the mechanical property and the appearance of the ceramic while simultaneously considering low resistivity.
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.
A first aspect of the present invention provides a zirconia ceramic comprising, in terms of elements: zr, Ti, Y, Ni and Nb, and the phase of the zirconia ceramic comprises: tetragonal zirconia, titanium nitride, niobium carbide and elemental nickel; the zirconia ceramic comprises, in elemental terms: 38.4-57.2wt% of Zr, 9.9-31.2wt% of Ti, 1.5-4.4wt% of Y, 1.8-15.9wt% of Nb and 1-7wt% of Ni; the phase of the zirconia ceramic comprises: 60-80wt% of tetragonal zirconia, 17-30wt% of titanium nitride, 2-15wt% of niobium carbide and 1-7wt% of simple substance nickel.
Preferably, the zirconia ceramic comprises, in elemental terms: 42.4-52.7wt% of Zr, 15.3-26.3wt% of Ti, 1.6-4wt% of Y, 5.1-13.5wt% of Nb and 2-5wt% of Ni; the phase of the zirconia ceramic comprises: 65-75wt% of tetragonal zirconia, 18-25wt% of titanium nitride, 5-13wt% of niobium carbide and 2-5wt% of elementary nickel.
Preferably, the total content of the niobium carbide and the titanium nitride is 25 to 38wt%, and the mass ratio of the niobium carbide to the titanium nitride is as follows: (1:4) - (2:3).
Preferably, the zirconia ceramic has an L value of 70 to 80, an a value of-1 to 0, and a b value of 1 to 4; the zirconia ceramic has the resistivity less than 100 omega cm, the density more than 99 percent and the toughness more than 6.0MPam 0.5 And the height of the drop hammer is more than or equal to 23 cm.
The second aspect of the present invention provides a method for preparing a zirconia ceramic, comprising the steps of:
s1, mixing the powder of zirconia containing yttrium oxide, titanium nitride, niobium carbide, nickel and niobium pentoxide with a dispersant and a binder to form slurry;
s2, drying and molding the slurry, and then sintering the slurry in vacuum or inert gas to obtain zirconia ceramic;
wherein, based on the total amount of the powder, the content of titanium nitride is 17-30wt%, the content of niobium carbide is 2-15wt%, the content of nickel is 1-7wt%, the content of niobium pentoxide is 0.1-4wt%, the content of zirconia containing yttrium oxide is 56-80wt%, and the zirconia contains 2-4mol% of yttrium oxide.
Preferably, based on the total amount of the powder, the content of titanium nitride is 18-25wt%, the content of niobium carbide is 5-13wt%, the content of nickel is 2-5wt%, the content of niobium pentoxide is 1-3wt%, the content of zirconia containing yttria is 61-75wt%, and the zirconia contains 2-4mol% of yttria.
Preferably, the total content of the niobium carbide and the titanium nitride is 25 to 38wt%, and the mass ratio of the niobium carbide to the titanium nitride is as follows: (1:4) - (2:3).
Preferably, in the step S2, the sintering temperature is 1400-1600 ℃, and the sintering time is 1-3 h.
The third aspect of the present invention is to provide a zirconia ceramic obtained by the foregoing production method.
The fourth aspect of the invention provides an application of the zirconia ceramic provided by the invention in preparing electronic product shells.
The zirconia ceramic provided by the invention contains phases of tetragonal zirconia, titanium nitride, niobium carbide and simple substance nickel, and the content of each phase is within the range defined by the invention, so that the zirconia ceramic has the performance characteristics of low resistivity, low density, good toughness and the like.
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 numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a zirconia ceramic, which comprises the following components in terms of elements: zr, Ti, Y, Ni and Nb, and the phase of the zirconia ceramic comprises: tetragonal zirconia, titanium nitride, niobium carbide and elemental nickel; the zirconia ceramic comprises, in elemental terms: 38.4-57.2wt% Zr, 9.9-31.2wt% Ti, 1.5-4.4wt% Y, 1.8-15.9wt% Nb, 1-7wt% Ni; the phase of the zirconia ceramic comprises: 60-80wt% of tetragonal zirconia, 17-30wt% of titanium nitride, 2-15wt% of niobium carbide and 1-7wt% of simple substance nickel.
The zirconia ceramic provided by the invention contains phases of tetragonal zirconia, titanium nitride, niobium carbide and simple substance nickel, and the content of each phase is in the range limited by the invention, so that the resistivity of the ceramic can be reduced, the good mechanical property of the ceramic can be maintained, and the gray and compact appearance effects can be realized.
According to embodiments provided herein, the elemental composition may be tested by an energy dispersive X-ray fluorescence spectrometer EDX-7000 for XRF. Preferably, the zirconia ceramic comprises, in elemental terms: 42.4-52.7wt% Zr, 15.3-26.3wt% Ti, 1.6-4wt% Y, 5.1-13.5wt% Nb, 2-5wt% Ni; 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: 65-75wt% of tetragonal zirconia, 18-25wt% of titanium nitride, 5-13wt% of niobium carbide and 2-5wt% of simple substance nickel, the resistivity of the ceramic can be further reduced, and simultaneously the good mechanical property of the ceramic is maintained, and the gray and compact appearance effects are realized. 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 100 wt%.
In the present invention, although the effects that may be brought by the addition of various substances can be considered, for example, yttrium oxide and niobium pentoxide can form a substitutional solid solution to stabilize and toughen zirconia, titanium nitride and niobium carbide can mainly play roles in reducing resistivity and coloring, and nickel can play roles in increasing compactness and toning. However, when the zirconia ceramic provided by the invention contains various elements and phase structures with the specific content, a synergistic effect can be generated, so that the ceramic has low resistivity, high compactness, good toughness and gray effect. Outside the above-defined range, the obtained zirconia ceramic cannot simultaneously have low resistivity, high compactability, as well as good toughness and achieve a gray effect.
In the invention, in order to further reduce the resistivity of the ceramic and maintain the good mechanical properties of the ceramic, the gray and dense appearance effects are realized. Preferably, the total content of the niobium carbide and the titanium nitride is 25 to 38wt%, and the mass ratio of the niobium carbide to the titanium nitride is as follows: (1:4) - (2:3). Further preferably, the total content of the niobium carbide and the titanium nitride is 27 to 35wt%, and the mass ratio of the niobium carbide to the titanium nitride is: (1:3) - (3:5).
The zirconia ceramic provided by the invention has low resistivity, high compactness, good toughness and gray effect. Preferably, the zirconia ceramic has an L value of 70 to 80, an a value of-1 to 0, and a b value of 1 to 4; further preferably, the L value is 73 to 78, the a value is-0.6- (-0.1) and the b value is 1.5 to 2.5. Preferably, the first and second electrodes are formed of a metal,the zirconia ceramic has a resistivity of less than 100 Ω cm, and more preferably less than 50 Ω cm. Preferably, the compactness of the zirconia ceramic is more than 99%, and the toughness is more than 6.0MPam 0.5 And the height of the drop hammer is more than or equal to 23 cm.
The invention also provides a preparation method of the zirconia ceramic, which comprises the following steps:
s1, mixing the powder of zirconia containing yttria, titanium nitride, niobium carbide, nickel and niobium pentoxide with a dispersant and a binder to form slurry;
s2, drying and molding the slurry, and then sintering the slurry in vacuum or inert gas to obtain zirconia ceramic;
wherein, based on the total amount of the powder, the content of titanium nitride is 17-30wt%, the content of niobium carbide is 2-15wt%, the content of nickel is 1-7wt%, the content of niobium pentoxide is 0.1-4wt%, the content of zirconia containing yttria is 56-80wt%, and the zirconia contains 2-4mol% of yttria.
In the present invention, the powders of yttria-containing zirconia, niobium pentoxide, titanium nitride, niobium carbide and nickel 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 size median of 0.3-0.6 μm, specific surface area of 7-13 m) containing 2-4mol% of yttria 2 In terms of/g), wherein the content of yttrium oxide is based on zirconium oxide. Niobium pentoxide powder (with a median particle size of 8-10 μm) can be used. The niobium carbide adopts powder with the median diameter of 1-5 mu m; the titanium nitride is powder with a median particle size of 0.5-1 μm; the nickel is powder with a median particle size of 5-15 μm.
In the present invention, step S1 is to grind the powder of each of the above-described raw materials to reduce the particle size and obtain a slurry. The specific process can comprise the following steps: mixing the powder of the above substances with water to obtain slurry, ball-milling, and grinding to obtain nanometer oxide with particle size of 250-500 nm. More specifically, the various substances are added with water in a ball milling tank according to the content of the invention 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 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.
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, based on the total amount of the powder, the content of titanium nitride is 18-25wt%, the content of niobium carbide is 5-13wt%, the content of nickel is 2-5wt%, the content of niobium pentoxide is 1-3wt%, the content of zirconia containing yttria is 61-75wt%, and the zirconia contains 2-4mol% of 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.
In the present invention, grey and dense appearance effects are achieved in order to further reduce the resistivity of the ceramic while maintaining the good mechanical properties of the ceramic. Preferably, the total content of the niobium carbide and the titanium nitride is 25 to 38wt%, and the mass ratio of the niobium carbide to the titanium nitride is as follows: (1:4) - (2:3). Further preferably, the total content of the niobium carbide and the titanium nitride is 27 to 35wt%, and the mass ratio of the niobium carbide to the titanium nitride is: (1:3) - (3:5).
According to the invention, the dispersing agent can promote the uniform mixing of all components in the powder. Preferably, in step S1, 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 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: 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, step S2 is to dry and mold the slurry, and then sinter it in vacuum or inert gas to obtain zirconia ceramics. The drying can be carried out by various drying methods, for example, spray drying can be adopted to form spherical powder with stronger fluidity. 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. 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 tonnage of 180 and 200 tons and using oil pressure of 8MPa, for example, the molding is performed into the shape of a rear cover of a mobile phone. The sintering may be in a vacuum or in an inert gas. Preferably, the sintering temperature is 1300-1450 ℃, and the sintering time is 1-3 h.
In the invention, the zirconia ceramics 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 invention also provides the zirconia ceramic prepared by the preparation method. The zirconia ceramic has low resistivity, high compactness, high impact resistance and high toughness, and can realize a grey effect.
The zirconia ceramic comprises the following components in terms of elements: 38.4-57.2wt% of Zr, 9.9-31.2wt% of Ti, 1.5-4.4wt% of Y, 1.8-15.9wt% of Nb and 1-7wt% of Ni; the phase of the zirconia ceramic comprises: 60-80wt% of tetragonal zirconia, 17-30wt% of titanium nitride, 2-15wt% of niobium carbide and 1-7wt% of simple substance nickel.
In the zirconia ceramic, preferably, the zirconia ceramic contains, in terms of elements: 42.4-52.7wt% Zr, 15.3-26.3wt% Ti, 1.6-4wt% Y, 5.1-13.5wt% Nb, 2-5wt% Ni; the phase of the zirconia ceramic comprises: 65-75wt% of tetragonal zirconia, 18-25wt% of titanium nitride, 5-13wt% of niobium carbide and 2-5wt% of simple substance nickel.
In the zirconia ceramic, preferably, the total content of the niobium carbide and the titanium nitride is 25 to 38wt%, and the mass ratio of the niobium carbide to the titanium nitride is: (1:4) - (2:3). Further preferably, the total content of the niobium carbide and the titanium nitride is 27 to 35wt%, and the mass ratio of the niobium carbide to the titanium nitride is: (1:3) - (3:5), the resistivity of the ceramic can be better reduced, the good mechanical property of the ceramic is kept, and the gray and compact appearance effects are realized.
The zirconia ceramic provided by the invention preferably has an L value of 70-80, an a value of-1-0 and a b value of 1-4; further preferably, the L value is 73-78, the a value is-0.6- (-0.1), and the b value is 1.5-2.5. Preferably, the electrical resistivity of the zirconia ceramic is less than 100 Ω cm, and more preferably less than 50 Ω cm. Preferably, the compactness of the zirconia ceramic is more than 99%, and the toughness is more than 6.0MPam 0.5 And the height of the drop hammer is more than or equal to 23 cm.
The invention also provides application of the zirconia ceramic in a shell of an electronic product.
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).
XRD test: the phase type and content were measured using an X-ray diffractometer Smartlab (3 kW).
XRF detection: the element content of the polished sample was measured using an energy dispersive X-ray fluorescence spectrometer EDX-7000.
Compactness: the average number of pits (greater than 20 um) per 10 x 10mm range on the large face of the polished sample was taken.
Density: ρ = m/(m 1/ρ 1+ m2/ρ 2+ m3/ρ 3 … + mn/ρ n), ρ being the theoretical density of the ceramic sample; m is the total mass of the ceramic sample; m1, m2 and m3 … mn are respectively the mass of each phase contained in the ceramic sample; ρ 1, ρ 2, ρ 3 … ρ n are theoretical densities of phases contained in the ceramic sample, respectively.
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.
Resistivity: the test was performed using a low resistance tester (model TH2512B, from Changzhou, Ltd.).
Colorimetric (Lab) test: the L, a, b values of the samples were measured using a color difference meter from Nosu Electron-China-color 1101 and compared with a standard sample of carbon black which was blackened.
Example 1
Raw materials: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 2.5wt%, niobium carbide (NbC) 10wt%, titanium nitride (TiN) 20wt%, nickel (Ni) 3wt%, 64.5wt% stabilized zirconia powder containing 3mol% yttria.
Adding water into the raw materials in a ball milling tank, ball milling for 8 hours, then adding 0.02wt% of hydroxypropyl methylcellulose and water sand milling for 10 hours in a sand mill, and finally adding 4wt% of binder (PEG 4000 and PVA with the molar ratio of 1: 1) of powder, stirring for 0.5 hour 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 for 2 hours at 1500 ℃ in vacuum to perform pressureless sintering.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 45.1wt% of Zr, 2.7wt% of Y, 10.5wt% of Nb, 15.3wt% of Ti and 2.9wt% of Ni.
XRD detected phases included: 66.7wt% tetragonal zirconia, 19.7wt% TiN, 9.7wt% NbC, and 2.9wt% Ni.
Example 2
Raw materials: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 2.5wt%, niobium carbide (NbC) 12.5wt%, titanium nitride (TiN) 22.5wt%, nickel (Ni) 3wt%, 59.5wt% stabilized zirconia powder containing 3mol% yttria.
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 30 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 for 2 hours at 1500 ℃ in vacuum to perform pressureless sintering.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 41.5wt% Zr, 2.3wt% Y, 12.6wt% Nb, 17.4wt% Ti, and 3wt% Ni.
XRD detected phases included: 61.9wt% for tetragonal zirconia, 22.4wt% for TiN, 12.2wt% for NbC, and 3wt% for Ni.
Example 3
The preparation method is the same as that of the example 1, except that the raw materials are proportioned as follows: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 2.5wt%, niobium carbide (NbC) 7.5wt%% titanium nitride (TiN) 17.5wt%, nickel (Ni) 3wt%, 69.5wt% stabilized zirconia powder containing 3mol% yttria.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 48.6wt% Zr, 2.8wt% Y, 8.3wt% Nb, 13.4wt% Ti, 2.9wt% Ni.
XRD detected phases included: 71.2wt% tetragonal zirconia, 17.3wt% TiN, 7.4wt% NbC, and 2.8wt% Ni.
Example 4
The preparation method is the same as that of the example 1, except that the raw materials are proportioned as follows: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 1wt%, niobium carbide (NbC) 10wt%, titanium nitride (TiN) 20wt%, nickel (Ni) 3wt%, 66wt% of stabilized zirconia powder containing 3mol% of yttrium oxide.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 46.3wt% Zr, 2.7wt% Y, 9.4wt% Nb, 15.2wt% Ti, 2.9wt% Ni.
XRD detected phases included: 69.8wt% for tetragonal zirconia, 19.7wt% for TiN, 9.8wt% for NbC, and 2.8wt% for Ni.
Example 5
The preparation method is the same as that of the embodiment 1, and the difference is that the raw materials are proportioned as follows: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 3wt%, niobium carbide (NbC) 10wt%, titanium nitride (TiN) 20wt%, nickel (Ni) 3wt%, and 64wt% of stabilized zirconia powder containing 3mol% of yttrium oxide.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 44.6wt% Zr, 2.5wt% Y, 10.7wt% Nb, 15.1wt% Ti, and 3wt% Ni.
XRD detected phases included: 66.6wt% tetragonal zirconia, 19.8wt% TiN, 9.9wt% NbC, and 3wt% Ni.
Example 6
The preparation method is the same as that of the example 1, except that the raw materials are proportioned as follows: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 2.5wt%, niobium carbide (NbC) 10wt%, titanium nitride (TiN) 20wt%, nickel (Ni) 5wt%, 62.5wt% stabilized zirconia powder containing 3mol% yttria.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 43.7wt% Zr, 2.4wt% Y, 10.4wt% Nb, 15.4wt% Ti and 4.9wt% Ni.
XRD detected phases included: 64.8wt% for tetragonal zirconia, 19.8wt% for TiN, 9.8wt% for NbC, and 4.8wt% for Ni.
Example 7
The preparation method is the same as that of the example 1, except that the raw materials are proportioned as follows: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 2.5wt%, niobium carbide (NbC) 5wt%, titanium nitride (TiN) 20wt%, nickel (Ni) 3wt%, 69.5wt% stabilized zirconia powder containing 3mol% yttria.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 48.6wt% Zr, 2.7wt% Y, 6.1wt% Nb, 15.3wt% Ti, 2.8wt% Ni.
XRD detected phases included: 71.8wt% tetragonal zirconia, 19.9wt% TiN, 4.8wt% NbC, and 2.9wt% Ni.
Example 8
The preparation method is the same as that of the example 1, except that the raw materials are proportioned as follows: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 2.5wt%, niobium carbide (NbC) 13wt%, titanium nitride (TiN) 20wt%, nickel (Ni) 3wt%, 61.5wt% stabilized zirconia powder containing 3mol% yttria.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 43.1wt% Zr, 2.4wt% Y, 13.1wt% Nb, 15.3wt% Ti, 2.8wt% Ni.
XRD detected phases included: 63.8wt% for tetragonal zirconia, 19.8wt% for TiN, 12.9wt% for NbC, and 2.8wt% for Ni.
Example 9
The preparation method is the same as that of the example 1, except that the raw materials are proportioned as follows: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 2.5wt%, niobium carbide (NbC) 13wt%, titanium nitride (TiN) 17wt%, nickel (Ni) 3wt%, 64.5wt% stabilized zirconia powder containing 3mol% yttria.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 45.1wt% of Zr, 2.5wt% of Y, 13.1wt% of Nb, 13.1wt% of Ti and 2.9wt% of Ni.
XRD detected phases included: 66.9wt% for tetragonal zirconia, 16.9wt% for TiN, 12.9wt% for NbC, and 2.9wt% for Ni.
Example 10
The preparation method is the same as that of the example 1, except that the raw materials are proportioned as follows: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 2.5wt%, niobium carbide (NbC) 4wt%, titanium nitride (TiN) 26wt%, nickel (Ni) 3wt%, 64.5wt% stabilized zirconia powder containing 3mol% yttria.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 45.2wt% Zr, 2.4wt% Y, 6.0wt% Nb, 19.1wt% Ti, 2.8wt% Ni.
XRD detected phases included: 66.8wt% tetragonal zirconia, 25.8wt% TiN, 3.9wt% NbC, and 2.8wt% Ni.
Comparative example 1
Raw materials: 200g of composite powder, which comprises 10wt% of niobium carbide (NbC), 20wt% of titanium nitride (TiN), 3wt% of nickel (Ni), and 67wt% of stabilized zirconia powder containing 3mol% of yttrium oxide.
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 sintering the formed powder for 2 hours at 1500 ℃ in vacuum to perform pressureless sintering.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 46.9wt% Zr, 2.6wt% Y, 8.7wt% Nb, 15.2wt% Ti, and 3wt% Ni.
XRD detected phases included: 66.8wt% tetragonal zirconia, 19.7wt% TiN, 9.7wt% NbC, and 2.9wt% Ni.
Comparative example 2
Raw materials: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 2.5wt%, niobium carbide (NbC) 10wt%, titanium nitride (TiN) 20wt%, 67.5wt% stabilized zirconia powder containing 3mol% yttria.
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 ℃, 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 for 2 hours at 1500 ℃ in vacuum to perform pressureless sintering.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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, 2.6wt% Y, 10.4wt% Nb and 15.3wt% Ti.
XRD detected phases included: 69.6wt% for tetragonal zirconia, 19.7wt% for TiN, and 9.7wt% for NbC.
Comparative example 3
Raw materials: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 2.5wt%, niobium carbide (NbC) 5wt%, titanium nitride (TiN) 10wt%, nickel (Ni) 3wt%, 79.5wt% of stabilized zirconia powder containing 3mol% of yttria.
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 ℃, 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 at 1500 ℃ in vacuum for 2 hours for pressureless sintering.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 55.7wt% Zr, 3.1wt% Y, 6.1wt% Nb, 7.6wt% Ti, and 3wt% Ni.
XRD detected phases included: 81.7wt% tetragonal zirconia, 9.8wt% TiN, 4.9wt% NbC, and 2.9wt% Ni.
Comparative example 4
Raw materials: 200g of composite powder containing niobium pentoxide (Nb) 2 O 5 ) 2.5wt%, niobium carbide (NbC) 10wt%, titanium nitride (TiN) 35wt%, nickel (Ni) 3wt%, 49.5wt% stabilized zirconia powder containing 3mol% yttria.
Adding water into the raw materials in a ball milling tank, ball milling for 8 hours, then adding 0.02wt% of hydroxypropyl methylcellulose and water sand milling for 10 hours in a sand mill, and finally adding 4wt% of binder (PEG 4000 and PVA with the molar ratio of 1: 1) of powder, stirring for 0.5 hour 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 for 2 hours at 1500 ℃ in vacuum to perform pressureless sintering.
And grinding, polishing and laser cutting the sintered product to obtain a final sample, wherein the size of the final sample is 150 x 75 x 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: 34.5wt% Zr, 2.1wt% Y, 10.4wt% Nb, 26.9wt% Ti, 2.8wt% Ni.
XRD detected phases included: 51.8wt% tetragonal zirconia, 34.9wt% TiN, 9.8wt% NbC, and 2.9wt% Ni.
TABLE 1
Figure DEST_PATH_IMAGE001
As can be seen from Table 1, the zirconia ceramics provided by the invention can simultaneously have the characteristics of low resistivity, high compactness, good toughness and high strength. In particular, the material can simultaneously have the resistivity of less than 100 omega cm, the compactness of more than 99 percent and the toughness of more than 6.0MPam 0.5 The drop hammer height is more than or equal to 23cm, and the gray effect can be realized. However, none of the zirconia ceramics provided in comparative examples 1 to 4 has the aforementioned characteristics 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 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 (9)

1. A zirconia ceramic, wherein the zirconia ceramic comprises, in elemental terms: zr, Ti, Y, Ni and Nb, and the phase of the zirconia ceramic comprises: tetragonal zirconia, titanium nitride, niobium carbide and elemental nickel; the zirconia ceramic comprises, in elemental terms: 38.4-57.2wt% of Zr, 9.9-31.2wt% of Ti, 1.5-4.4wt% of Y, 1.8-15.9wt% of Nb and 1-7wt% of Ni; the phase of the zirconia ceramic comprises: 60-80wt% of tetragonal zirconia, 17-30wt% of titanium nitride, 2-15wt% of niobium carbide and 1-7wt% of simple substance nickel;
wherein the zirconia ceramic has an L value of 70-80, an a value of-1-0 and a b value of 1-4; the zirconia ceramic has the resistivity less than 100 omega cm, the compactness more than 99 percent and the toughness more than 6.0MPam 0.5 The height of the drop hammer is more than or equal to 23 cm; wherein the L value, the a value and the b value are based on chroma (Lab).
2. The zirconia ceramic of claim 1, wherein the zirconia ceramic comprises, in elemental terms: 42.4-52.7wt% of Zr, 15.3-26.3wt% of Ti, 1.6-4wt% of Y, 5.1-13.5wt% of Nb and 2-5wt% of Ni; the phase of the zirconia ceramic comprises: 65-75wt% of tetragonal zirconia, 18-25wt% of titanium nitride, 5-13wt% of niobium carbide and 2-5wt% of elementary nickel.
3. The zirconia ceramic of claim 1, wherein the total content of niobium carbide and titanium nitride is 25 to 38wt%, and the mass ratio of niobium carbide to titanium nitride is (1:4) - (2: 3).
4. A preparation method of zirconia ceramics is characterized by comprising the following steps:
s1, mixing the powder of zirconia containing yttria, titanium nitride, niobium carbide, nickel and niobium pentoxide with a dispersant and a binder to form slurry;
s2, drying and molding the slurry, and then sintering the slurry in vacuum or inert gas to obtain zirconia ceramic;
wherein, based on the total amount of the powder, the content of titanium nitride is 17-30wt%, the content of niobium carbide is 2-15wt%, the content of nickel is 1-7wt%, the content of niobium pentoxide is 0.1-4wt%, the content of zirconia containing yttrium oxide is 56-80wt%, and the zirconia contains 2-4mol% of yttrium oxide.
5. The production method according to claim 4, wherein the content of titanium nitride is 18 to 25wt%, the content of niobium carbide is 5 to 13wt%, the content of nickel is 2 to 5wt%, the content of niobium pentoxide is 1 to 3wt%, the content of yttria-containing zirconia is 61 to 75wt%, and the zirconia contains 2 to 4mol% of yttria, based on the total amount of the powder.
6. The production method according to claim 4 or 5, wherein the total content of the niobium carbide and the titanium nitride is 25 to 38wt%, and the mass ratio of the niobium carbide to the titanium nitride is (1:4) to (2: 3).
7. The method as claimed in claim 4, wherein in step S2, the sintering temperature is 1400 ℃ and 1600 ℃ and the sintering time is 1-3 h.
8. A zirconia ceramic produced by the production method according to any one of claims 4 to 7.
9. Use of the zirconia ceramic of any one of claims 1 to 3 and 8 for the manufacture of a housing for an electronic product.
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