CN115093217A - Preparation method of gray zirconia ceramic and gray zirconia ceramic - Google Patents
Preparation method of gray zirconia ceramic and gray zirconia ceramic Download PDFInfo
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Abstract
The invention relates to a preparation method of gray zirconia ceramics, which comprises the following steps: s1: adding a ceramic base material and a dispersing agent into pure water to obtain primary slurry, and grinding the primary slurry to obtain primary slurry; s2: stirring the primary slurry, adding a coloring agent, then adding an alkaline solution, and adjusting the pH to 7-10 to obtain a secondary slurry; s3: sequentially adding a plasticizer and a lubricant into the obtained secondary slurry to prepare a tertiary slurry; s4: carrying out spray granulation, press forming, glue discharging treatment and sintering treatment on the obtained three-level slurry in sequence to obtain gray zirconia ceramic; the sintering treatment is performed in a weakly reducing atmosphere. Also relates to a gray zirconia ceramic. The grey zirconia ceramic can be molded within a temperature range suitable for sintering zirconia ceramic, has better physical properties and can present grey tone; and the main raw material components used are yttrium-stabilized zirconia ceramic powder and the raw materials for preparing the colorant are easy to obtain and low in price, so that the production cost is saved.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a preparation method of gray zirconia ceramic and the gray zirconia ceramic.
Background
In recent years, color ceramics have been used in high-grade decoration fields such as ceramic cover plates for press-type fingerprint identification, watch cases, watch chains, mobile phone cases and buttons due to their excellent mechanical properties, unique colors, non-toxicity, innocuousness and other properties. Among them, the gray ceramic material is highly appreciated by consumers as a decorative material which is not raised and has a high-grade feeling. The coloring material used for preparing the prior gray ceramic comprises rutile antimony tin gray material or oxides such as manganese oxide, nickel oxide and the like. Wherein, the rutile antimony tin gray material is mainly synthesized by a high-temperature solid-phase synthesis method, the sintering process of the pigment has strict requirements on the atmosphere, and the stable color development temperature of the pigment is between 1200 and 1350 ℃, so that good color formation effect cannot be shown in a normal temperature environment; the limit service temperature of the grey pigment prepared from oxides such as manganese oxide, nickel oxide and the like is lower than 1300 ℃, the sintering temperature of the zirconia ceramic is generally 1350-1550 ℃, and at the sintering temperature, the grey pigment cannot stably develop color after being co-fired with the ceramic, so that the color formation and the performance of the prepared grey ceramic are influenced.
Disclosure of Invention
An object of the present invention is to solve the above problems and to provide a method for preparing a gray zirconia ceramic capable of exhibiting a stable gray color-forming effect under high-temperature sintering conditions.
The technical scheme adopted by the preparation method of the gray zirconia ceramic is as follows:
a preparation method of gray zirconia ceramics comprises the following steps:
s1: adding a ceramic base material and a dispersing agent into pure water to obtain primary slurry with the solid content of 45-55%, grinding the primary slurry to obtain primary slurry with the granularity of 0.2-0.5 mu m, wherein the particles of the primary slurry are uniformly dispersed in the granularity range, and the raw material components have good dispersibility, so that a foundation is provided for subsequently obtaining uniformly-colored gray zirconia ceramic; the grinding treatment adopts ball milling treatment; the mass ratio of the dispersing agent to the ceramic base material is 0.2-2.0%; in the present invention, the particle size is represented by a median particle diameter D (50);
s2: stirring the obtained primary slurry, adding a coloring agent into the primary slurry, then adding an alkaline solution into the primary slurry added with the coloring agent, and adjusting the pH value to 7-10 to obtain a secondary slurry; the colorant comprises a cobalt metal salt solution with the concentration of 0.02-0.5mol/L, the mass ratio of the colorant to the ceramic base material is 0.1-3%, and the concentration of the alkaline solution is 10-30%;
s3: sequentially adding a plasticizer and a lubricant into the obtained secondary slurry, and uniformly stirring to obtain a tertiary slurry; the mass ratio of the plasticizer to the ceramic base stock is 0.5-8.0%, and the mass ratio of the lubricant to the ceramic base stock is 0.3-2.0%;
s4: carrying out spray granulation, press forming, glue discharging treatment and sintering treatment on the obtained three-level slurry in sequence to obtain gray zirconia ceramic; wherein the sintering treatment temperature is 1380-; the sintering treatment is carried out in a vacuum environment when the sintering temperature is less than 500 ℃, and is carried out in a weak reducing atmosphere when the sintering temperature is greater than or equal to 500 ℃.
Preferably, the weak reducing atmosphere is formed by a mixed gas of nitrogen and hydrogen, the volume ratio of the hydrogen to the nitrogen is 12:88, and the gas flow rate of the mixed gas is 5-20L/min. During the sintering treatment, cobalt ions first decomposed from cobalt ions decomposed by the cobalt metal salt become cobalt oxide, and then the cobalt oxide is reduced to metallic cobalt in a weakly reducing atmosphere, so that the zirconia ceramic appears gray.
The purpose of the glue discharging treatment is to volatilize and remove the organic additives contained in the obtained dry pressing forming blank. The glue discharging treatment is carried out at the glue discharging temperature of 0-450 ℃, the heating rate of 0.4 ℃/min and the heat preservation time of 180 min.
The spray granulation is carried out in a spray granulator, the air inlet temperature of the spray granulator is 210-250 ℃, the air exhaust temperature is 90-120 ℃, and the rotation speed of an atomizer is 18000-22000 r/min. Wherein, the addition of the adhesive increases the binding force between the granulation powder bodies.
Preferably, the cobalt metal salt comprises one or more of cobalt acetate tetrahydrate, cobalt nitrate hexahydrate or cobalt chloride hexahydrate.
The metal cobalt salt is easy to decompose to obtain Co 2+ The reaction mechanism of the cobalt ion in the aqueous ammonia solution and the colorant includes:
Co 2+ +NH 3 ·H 2 O＝Co(OH) + ↓+NH 4 +
Co(OH) + +NH 3 ·H 2 O＝Co(OH) 2 +NH 4 +
Co(OH) 2 +6NH 3 ·H 2 O＝[Co(NH 3 ) 6 ](OH) 2 +6H 2 O
cobalt ions react with excessive ammonia water solution to generate [ Co (NH) with cis-trans isomer structure 3 ) 6 ] 2+ ,[Co(NH 3 ) 6 ] 2+ Uniformly dispersing the particles on the surface of the ceramic powder particles in an ion form to ensure that the surface of the ceramic powder particles is coated with a dispersing agent and [ Co (NH) 3 ) 6 ] 2+ The cis-trans isomer is partially or completely covered, so that the agglomeration of ceramic powder particles is hindered, and the suspension stability of slurry and the color development stability of subsequent ceramic materials are improved; and gray after the sintering process. Compared with the method of mixing materials by adopting a solid colorant, the slurry system prepared by the scheme of the invention has more uniform dispersion, and avoids the occurrence of large product color difference or color spots of the prepared gray zirconia ceramics.
Preferably, the alkaline solution comprises an aqueous ammonia solution.
Preferably, in step S4, the granulated powder obtained after the spray granulation is subjected to a 180-mesh screen treatment and then to a press molding treatment. Preferably, the press forming in the invention adopts dry press forming, wherein the dry press forming pressure is 5MPa, the dwell time is 10s, and the size of the press forming blank is 150X 80X 2mm 3 。
Preferably, the ceramic base material comprises yttrium-stabilized zirconia ceramic powder, and the content of yttrium oxide in the yttrium-stabilized zirconia ceramic powder is 2-6%.
Preferably, the dispersant comprises one or more of polyacrylic acid, ammonium polyacrylate or ammonium polymethacrylate.
Preferably, the plasticizer comprises one or more of polyvinyl alcohol, xanthan gum or gelatin.
Preferably, the lubricant comprises a calcium stearate emulsion or a stearic acid polyethylene glycol ester.
It is another object of the present invention to provide a gray zirconia ceramic obtained by any of the above-mentioned preparation methods.
Preferably, the bending strength of the gray zirconia ceramic is larger than 1015MPa, and the fracture toughness is larger than 8 MPa-m 1/2 Hardness greater than 1050kgf/mm 2 Density greater than 6.05g/cm 3 。
The beneficial effects of the invention at least comprise:
compared with the prior art, when the colorant selected by the scheme is used for preparing the slurry, cobalt in the colorant is dispersed in a slurry system in an ion form, so that the dispersion uniformity of the prepared slurry is improved, and the cobalt ions in the colorant react in situ under the action of an alkaline solution to generate [ Co (NH) with a cis-trans isomeric structure 3 ) 6 ] 2+ The cobalt-ammonia complex enables the color developing components of the colorant to be uniformly dispersed, and avoids the large color difference or the color spots or color spots of the prepared gray zirconia ceramic product.
In the preparation process of the gray zirconia ceramic, the sintering temperature, the sintering time and the reduction sintering atmosphere are cooperatively matched during sintering treatment, so that a stable gray color forming effect can be presented on the premise of meeting the sintering and forming conditions of the gray zirconia ceramic, the uniform distribution of color developing components in a ceramic matrix is ensured, and the prepared gray zirconia ceramic has a better color forming effect.
In the scheme of the invention, the adjustment of the color forming degree of the gray zirconia ceramic can be realized by regulating and controlling the adding amount of the colorant in the adding range of the colorant, and the color tone adjustment process is simple and easy to implement; according to specific embodiments, the gray zirconia ceramic obtained by the preparation method of the gray zirconia ceramic has the characteristics of high strength, high toughness and high hardness; in addition, the main raw material component used in the invention, namely yttrium-stabilized zirconia ceramic powder and the raw material for preparing the colorant, is easy to obtain and low in price, so that the production cost of the gray zirconia ceramic is saved.
Drawings
FIG. 1 is a schematic view of a sintering curve of a sintering process in example 1 of the present invention.
Detailed Description
The following preferred embodiments are provided to facilitate an understanding of the present invention, and are provided so that the present disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
S1 preparation of first-grade slurry: mixing zirconia ceramic powder, yttria ceramic powder, a dispersing agent and pure water, wherein the mass ratio of zirconia to yttria is 94.5: 5.5; the ratio of the addition amount of pure water to the total mass of the ceramic base material was 1:1, the ceramic dispersant used in this example was ammonium polyacrylate, and the mass ratio of the dispersant to the ceramic base material was 0.5%.
And performing ball milling treatment on the primary slurry to obtain primary slurry, wherein the median particle size Dx (50) of the primary slurry is controlled to be 0.18-0.22 mu m.
Preparation of S2 secondary slurry: fully stirring the primary slurry by using a high-speed dispersion machine, adding a coloring agent solution in the stirring process, wherein the coloring agent in the embodiment of the invention is a cobalt nitrate hexahydrate solution with the solution concentration of 0.05mol/L, the mass ratio of the coloring agent to the ceramic base material is 0.4%, the primary slurry is titrated by using an ammonia water solution with the solution concentration of 25%, and the pH value of the slurry is adjusted to 10.5, so that cis-trans isomer formed by an alkaline solution and cobalt ions is obtained to obtain the secondary slurry. The cis-trans isomers are uniformly dispersed on the surfaces of the ceramic powder particles, so that the surfaces of the ceramic powder particles are partially or completely covered by the dispersing agent and the cis-trans isomers, the agglomeration of the ceramic powder particles is hindered, and the suspension property and the stability of the slurry are improved.
S3: sequentially adding a plasticizer and a lubricant into the secondary slurry to prepare a tertiary slurry; the plasticizer is a polyvinyl alcohol solution with the solution concentration of 5%, and the mass ratio of the plasticizer to the ceramic base material is 2%; the lubricant is calcium stearate emulsion, and the mass ratio of the lubricant to the ceramic base material is 0.5%.
S4: carrying out spray granulation on the obtained three-level slurry, wherein the air inlet temperature of granulation equipment is set to 230 ℃, the air outlet temperature is controlled to 95-100 ℃, the rotating speed of an atomizer is controlled to 19500-; and then carrying out compression molding, binder removal treatment and sintering treatment to obtain the gray zirconia ceramics.
Wherein, the press forming is preferably dry press forming, the dry pressure is 5Mpa, the pressure maintaining time is 10S, and the size of the blank after press forming is 150 multiplied by 80 multiplied by 2mm 3 (ii) a In the glue removing treatment, the glue removing temperature is 0-450 ℃, the heating rate is set to be 0.4 ℃/Min, and the heat preservation time is 180 Min; in the sintering treatment, the sintering curve is 0-800 ℃/240min, 800-. The equipment used for sintering treatment is a vacuum atmosphere sintering furnace, nitrogen and hydrogen mixed gas is used as sintering atmosphere, the inflation pressure is 0.1-10KPa, and the gas flow is 5-20L/min.
Example 2
Preparation of S1 first-level slurry: mixing zirconia ceramic powder, yttria ceramic powder, a dispersing agent and pure water, wherein the mass ratio of zirconia to yttria is 98: 2; the ratio of the addition amount of pure water to the total mass of the ceramic base material is 9:11, polyacrylic acid is selected as the ceramic dispersing agent in the embodiment, and the mass ratio of the dispersing agent to the ceramic base material is 2.0%.
And performing ball milling treatment on the primary slurry to obtain primary slurry, wherein the median particle size Dx (50) of the primary slurry is controlled to be 0.35-0.5 mu m.
Preparation of S2 secondary slurry: fully stirring the primary slurry by using a high-speed dispersion machine, and adding a colorant solution in the stirring process, wherein in the embodiment of the invention, the colorant is a cobalt nitrate hexahydrate solution with the solution concentration of 0.2mol/L, the mass ratio of the colorant to the ceramic base material is 0.1%, the primary slurry is titrated by using an ammonia water solution with the solution concentration of 10%, and the pH value of the slurry is adjusted to 7, so that a cis-trans isomer is formed between an alkaline solution and cobalt ions to obtain the secondary slurry. The cis-trans isomers are uniformly dispersed on the surfaces of the ceramic powder particles, so that the surfaces of the ceramic powder particles are partially or completely covered by the dispersing agent and the cis-trans isomers, the agglomeration of the ceramic powder particles is hindered, and the suspension property and the stability of the slurry are improved.
S3: sequentially adding a plasticizer and a lubricant into the secondary slurry to prepare a tertiary slurry; the plasticizer is xanthan gum solution with the concentration of 10%, and the mass ratio of the plasticizer to the ceramic base material is 6%; the lubricant is stearic acid polyethylene glycol ester, and the mass ratio of the lubricant to the ceramic base material is 2%.
In the sintering treatment in step S4, the sintering curve is 0-800 ℃/240min, 800-; the other steps are the same as those described in step S4 described in example 1.
Example 3
Preparation of S1 first-level slurry: mixing zirconia ceramic powder, yttria ceramic powder, a dispersing agent and pure water, wherein the mass ratio of zirconia to yttria is 94: 6; the ratio of the pure water addition to the total mass of the ceramic base material is 11:9, in this example, the ceramic dispersant is ammonium polyacrylate, and the mass ratio of the dispersant to the ceramic base material is 0.2%.
And performing ball milling treatment on the primary slurry to obtain primary slurry, wherein the median particle size Dx (50) of the primary slurry is controlled to be 0.4-0.5 mu m.
Preparation of S2 secondary slurry: fully stirring the primary slurry by using a high-speed dispersion machine, and adding a colorant solution in the stirring process, wherein in the embodiment of the invention, the colorant is a cobalt chloride hexahydrate solution with the solution concentration of 0.5mol/L, the mass ratio of the colorant to the ceramic base material is 2%, the primary slurry is titrated by using an ammonia water solution with the solution concentration of 30%, and the pH value of the slurry is adjusted to 8, so that a cis-trans isomer is formed between an alkaline solution and cobalt ions to obtain a secondary slurry. The cis-trans isomers are uniformly dispersed on the surfaces of the ceramic powder particles, so that the surfaces of the ceramic powder particles are partially or completely covered by the dispersing agent and the cis-trans isomers, the agglomeration of the ceramic powder particles is hindered, and the suspension property and the stability of the slurry are improved.
S3: sequentially adding a plasticizer and a lubricant into the secondary slurry to prepare a tertiary slurry; the plasticizer is a polyvinyl alcohol solution with the solution concentration of 1%, and the mass ratio of the plasticizer to the ceramic base material is 0.5%; the lubricant is calcium stearate emulsion, and the mass ratio of the lubricant to the ceramic base material is 0.3%.
In the sintering treatment in the step S4, the sintering curve is 0-800 ℃/240min, 800-; the other steps are the same as those described in step S4 described in example 1.
Example 4
S1 preparation of first-grade slurry: mixing zirconia ceramic powder, yttria ceramic powder, a dispersing agent and pure water, wherein the mass ratio of zirconia to yttria is 94.5: 5.5; the ratio of the pure water addition to the total mass of the ceramic base material is 1:1, ammonium polymethacrylate is selected as the ceramic dispersant in the embodiment, and the mass ratio of the dispersant to the ceramic base material is 0.5%.
And performing ball milling treatment on the primary slurry to obtain primary slurry, wherein the median particle size Dx (50) of the primary slurry is controlled to be 0.2-0.3 mu m.
Preparation of S2 secondary slurry: fully stirring the primary slurry by using a high-speed dispersion machine, and adding a colorant solution in the stirring process, wherein in the embodiment of the invention, the colorant is a cobalt acetate tetrahydrate solution with the solution concentration of 0.02mol/L, the mass ratio of the colorant to the ceramic base material is 3%, the primary slurry is titrated by using an ammonia water solution with the solution concentration of 25%, and the pH value of the slurry is adjusted to 10, so that a cis-trans isomer is formed between an alkaline solution and cobalt ions to obtain a secondary slurry. The cis-trans isomers are uniformly dispersed on the surfaces of the ceramic powder particles, so that the surfaces of the ceramic powder particles are partially or completely covered by the dispersing agent and the cis-trans isomers, the agglomeration of the ceramic powder particles is hindered, and the suspension property and the stability of the slurry are improved.
S3: sequentially adding a plasticizer and a lubricant into the secondary slurry to prepare a tertiary slurry; the plasticizer is gelatin solution with the concentration of 5%, and the mass ratio of the plasticizer to the ceramic base material is 8%; the lubricant is calcium stearate emulsion, and the mass ratio of the lubricant to the ceramic base material is 0.5%.
In the sintering treatment in the step S4, the sintering curve is 0-800 ℃/240min, 800-; the other steps are the same as those described in step S4 described in example 1.
And (3) performance testing:
the gray zirconia ceramics obtained in examples 1 to 4 were processed into test pieces having dimensions of 52mm × 56mm × 1mm, and then the test pieces were subjected to flexural strength, fracture toughness, vickers hardness, density, and color difference tests using a universal material testing machine, a vickers hardness tester, a solid density meter, and a color difference meter, respectively.
The bending strength test is carried out according to a standard GB/T4741-1999 bending strength test method of the ceramic material, the Vickers hardness test is carried out according to a standard GB/T16534-2009 fine ceramic room temperature hardness test method, the fracture toughness test is carried out according to a standard GB/T14389-1993 engineering ceramic impact toughness test method, the density test is carried out according to a standard GB/T2413-1980 volume density measurement method of the piezoceramic material, and the color difference test is characterized by color parameters L, a and b value of Lab mode. The results of the performance tests are shown in the table below.
Referring to the performance test table, it can be seen from the test results of the bending strength test, the fracture performance test, the hardness test and the density test that the gray zirconia ceramics prepared by the schemes of examples 1 to 4 have the bending strength of more than 1015MPa and the fracture toughness of more than 8MPa · m 1/2 Hardness greater than 1050kgf/mm 2 Density of more than 6g/cm 3 . Therefore, the gray zirconia ceramics prepared by the invention has better strength and hardness, and has good fracture toughness and compactness. The values of L, a and b of the gray zirconia ceramics prepared in example 1 are close to the color with the color number of PANTONE 430CP, the values of L, a and b of the gray zirconia ceramics prepared in example 2 are close to the color with the color number of PANTONE18-4005 TPG, the values of L, a and b of the gray zirconia ceramics prepared in example 3 are close to the color with the color number of PANTONE P176-15U, and the values of L, a and b of the gray zirconia ceramics prepared in example 4 are close to the color with the color number of PANTONE 19-3906 TPX. According to PANTONE color chart, the zirconium oxide ceramic obtained by the technical scheme of the invention can be sintered within a temperature range suitable for sintering the zirconium oxide ceramic, and the obtained gray zirconium oxide ceramic has better physical properties and stable gray color.
Comparative example 1
Comparative example 1 is compared to example 1 with the difference that no weakly reducing atmosphere is used during sintering. So that cobalt reacts with aluminum in the sintering furnace to generate spinel aluminum cobaltate, and the color parameter is L: 8. a: -70, B: 105, the obtained zirconia ceramic is close to the color with the color number of PANTONE P115-8C and is blue.
Comparative example 2
Comparative example 2 is compared with example 1, with the difference that cobalt oxide was directly selected as the colorant, and in the preparation step of the S2 secondary slurry: and fully stirring the primary slurry by using a high-speed dispersion machine, and adding a coloring agent in the stirring process to obtain a secondary slurry.
The zirconia ceramics obtained in comparative example 2 had a non-uniform color development and a bluish color tone.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only express preferred embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of gray zirconia ceramics is characterized by comprising the following steps:
s1: adding a ceramic base material and a dispersing agent into pure water to obtain primary slurry with the solid content of 45-55%, and grinding the primary slurry to obtain primary slurry with the particle size of 0.2-0.5 mu m; the mass ratio of the dispersing agent to the ceramic base material is 0.2-2.0%;
s2: stirring the obtained primary slurry, adding a coloring agent into the primary slurry, then adding an alkaline solution into the primary slurry added with the coloring agent, and adjusting the pH value to 7-10 to obtain a secondary slurry; the colorant comprises a cobalt metal salt solution with the concentration of 0.02-0.5mol/L, and the mass ratio of the colorant to the ceramic base material is 0.1-3%;
s3: sequentially adding a plasticizer and a lubricant into the obtained secondary slurry, and uniformly stirring to obtain a tertiary slurry; the mass ratio of the plasticizer to the ceramic base stock is 0.5-8.0%, and the mass ratio of the lubricant to the ceramic base stock is 0.3-2.0%;
s4: carrying out spray granulation, press forming, glue discharging treatment and sintering treatment on the obtained three-level slurry in sequence to obtain gray zirconia ceramic; wherein the sintering treatment temperature is 1380-1550 ℃, and the sintering treatment time is 2-4 h; the sintering treatment is carried out in a vacuum environment when the sintering temperature is less than 500 ℃, and is carried out in a weak reducing atmosphere when the sintering temperature is greater than or equal to 500 ℃.
2. A method of preparing a grey zirconia ceramic according to claim 1 characterised in that: the cobalt metal salt comprises one or more of cobalt acetate tetrahydrate, cobalt nitrate hexahydrate or cobalt chloride hexahydrate.
3. A method of preparing a grey zirconia ceramic according to claim 1 characterised in that: the alkaline solution includes an aqueous ammonia solution.
4. A method of preparing a grey zirconia ceramic according to claim 1 characterised in that: in step S4, the granulated powder obtained after the spray granulation is processed through a 180-mesh screen and then is subjected to a press molding process.
5. The method for preparing a gray zirconia ceramic according to claim 1, wherein the ceramic base material comprises yttrium-stabilized zirconia ceramic powder, and the content of yttrium oxide in the yttrium-stabilized zirconia ceramic powder is 2-6%.
6. The method for preparing a gray zirconia ceramic according to claim 1 wherein the dispersant comprises one or more of polyacrylic acid, ammonium polyacrylate or ammonium polymethacrylate.
7. The method for preparing a gray zirconia ceramic according to claim 1 wherein the plasticizer comprises one or more of polyvinyl alcohol, xanthan gum or gelatin.
8. The method for preparing a gray zirconia ceramic according to claim 1, wherein the lubricant comprises calcium stearate emulsion or polyethylene glycol stearate.
9. A gray zirconia ceramic characterized by: the gray zirconia ceramic is produced by the method of making the gray zirconia ceramic of any of claims 1-8.
10. A gray zirconia ceramic according to claim 9 wherein: the bending strength of the gray zirconia ceramic is larger than 1015MPa, and the fracture toughness is larger than 8 MPa-m 1/2 Hardness greater than 1050kgf/mm 2 Density greater than 6.05g/cm 3 。
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