CN107311653A - Zirconium base composite ceramic material and preparation method thereof and shell or ornament - Google Patents
Zirconium base composite ceramic material and preparation method thereof and shell or ornament Download PDFInfo
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- CN107311653A CN107311653A CN201610270352.8A CN201610270352A CN107311653A CN 107311653 A CN107311653 A CN 107311653A CN 201610270352 A CN201610270352 A CN 201610270352A CN 107311653 A CN107311653 A CN 107311653A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
- B28B11/243—Setting, e.g. drying, dehydrating or firing ceramic articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C3/00—Processes, not specifically provided for elsewhere, for producing ornamental structures
- B44C3/04—Modelling plastic materials, e.g. clay
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- 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
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- 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
- C04B2235/3255—Niobates or tantalates, e.g. silver niobate
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Abstract
The invention discloses a kind of zirconium base composite ceramic material and preparation method thereof and shell or ornament.The zirconium base composite ceramic material contains zirconia base, and the cubic structure Sr being dispersed in the zirconia base0.82NbO3Stable phase, CeAlO3Phase and FeAlO3Phase.This zirconium base composite ceramic material passes through the dispersed cubic structure Sr in zirconia base0.82NbO3Stable phase, CeAlO3Phase and FeAlO3Phase, can effectively improve the toughness and drop resistant performance of zirconium base composite ceramic material, the large area appearance member for making it be applied to be produced similar to shell or ornament.
Description
Technical field
The present invention relates to ceramic material and its application field, in particular it relates to a kind of zirconium base composite ceramics
Material；The invention further relates to a kind of preparation method of foregoing zirconium base composite ceramic material；It is of the invention further
Further relate to a kind of shell or ornament prepared by foregoing zirconium base composite ceramic material.
Background technology
With the high development of science and technology, quality requirement more and more higher of the consumer to ceramic material.
Zirconia ceramics has good corrosion resistance more ceramic than other types due to it, hardness is high and intensity is high
The characteristics of have a wide range of applications.However, when making large area appearance member, although existing oxidation
The toughness of zircon ceramic (reaches 5-6MPam1/2) higher than other kinds of ceramics, but still exist
Intolerant to the shortcoming fallen.
At present, the stable Zirconium powder of yttrium is more ripe on the market, for zirconia ceramics
Improvement is generally built upon on the basis of the stable Zirconium powder of yttrium.In order to improve the tough of zirconia ceramics
Property, conventional method for toughening includes：Zirconia ceramics is promoted to undergo phase transition, or in zirconia ceramics
The second structure of middle addition is with toughness reinforcing etc..Although these existing conventional method for toughening can be certain
Toughening effect is played in degree, but these methods are typically only capable to be directed to whiteware.So far do not have also
Having can be while the method for reaching toughness reinforcing drop resistant and dyeing.
For example, disclosing a kind of stable TZP ceramics of Mg in Chinese patent No.02111146.4.This
Kind of ceramics can play the effect of a part of toughness reinforcing by the Mg that adulterates, but this DeGrain.And
And the ceramics sample low strength prepared according to this method, only 590MPa or so is such strong
Degree can not prepare the thin slice (easily broken) of large area.In addition, this method is also only for white pottery
Porcelain, its application is narrower.
As shown in the above, the drop resistant performance of current zirconia ceramics also needs to further improvement, with
Propose a kind of ceramics with excellent drop resistant performance；The colourity progress to zirconia ceramics is also needed to simultaneously
Further improve, to obtain a kind of zirconia ceramics for having excellent drop resistant performance and colourity concurrently, with suitable
Should be in the market demand.
The content of the invention
It is an object of the invention to provide a kind of zirconium base composite ceramic material and preparation method thereof and shell or dress
Ornaments, to provide a kind of drop resistant performance preferable zirconium base composite ceramics.
To achieve these goals, there is provided a kind of zirconium base composite ceramic according to the first aspect of the invention
Ceramic material, the zirconium base composite ceramic material contains zirconia base, and is dispersed in the oxidation zirconium base
Cubic structure Sr in body0.82NbO3Stable phase, CeAlO3Phase and FeAlO3Phase.
There is provided a kind of preparation side of zirconium base composite ceramic material according to the second aspect of the invention
Method, the preparation method comprises the following steps：S1, by Zirconium powder, CeAlO3Powder, FeAlO3
Powder, SrCO3Powder, Nb2O5Powder and binding agent mixing, form mixed slurry, wherein described
SrCO3Powder and Nb2O5The mol ratio of powder is 1.64：1；S2, the mixed slurry entered successively
Row is dried, shaping and sintering form the zirconium base composite ceramic material.
According to the third aspect of the present invention there is provided a kind of zirconium base composite ceramic material, the zirconium base is answered
Ceramic material is closed to be prepared from by the preparation method of above-mentioned zirconium base composite ceramic material of the invention.
According to the fourth aspect of the present invention there is provided a kind of shell or ornament, the shell or decoration
Product are prepared from by above-mentioned zirconium base composite ceramic material.
Zirconium base composite ceramic material of the present invention passes through the dispersed cubic structure Sr in zirconia base0.82NbO3
Stable phase, CeAlO3Phase and FeAlO3Phase, can effectively improve the toughness of zirconium base composite ceramic material
With drop resistant performance, the large area appearance member for making it be applied to be produced similar to shell or ornament.
Other features and advantages of the present invention will give specifically in subsequent embodiment part
It is bright.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification,
It is used to explain the present invention together with following embodiment, but does not constitute the limit to the present invention
System.In the accompanying drawings：
Fig. 1, which is shown, proves the XRD diffracting spectrums of the P1 prepared by example 1, and SrNb6O16
(00-045-0228) and Sr2Nb2O7The standard card of (01-070-0114)；
Fig. 2, which is shown, proves the XRD diffracting spectrums of the P2 prepared by example 2, and tetragonal phase zirconium oxide
(00-017-0923), monocline phase zircite (01-083-0939) and Sr0.82NbO3(00-009-0079)
Standard card.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place
The embodiment of description is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The drop resistant performance of current zirconia ceramics as pointed by background section is also needed to further
Improve, therefore, the present inventor, which is directed to zirconia ceramics, has carried out substantial amounts of research, and carry
A kind of zirconium base composite ceramic material is gone out.The zirconium base composite ceramic material contains zirconia base, Yi Jifen
The cubic structure Sr on (on internal and surface) is dispersed in the zirconia base0.82NbO3Stable phase,
CeAlO3Phase and FeAlO3Phase.
The above-mentioned zirconium base composite ceramic material of the present invention, by zirconia base (on internal and surface)
Dispersed cubic structure Sr0.82NbO3Stable phase, CeAlO3Phase and FeAlO3Phase, can be effectively improved
The toughness and drop resistant performance of zirconium base composite ceramic material, make it be applied to be produced similar to shell or decoration
The large area appearance member of product.
According to the zirconium base composite ceramic material of the present invention, for cubic structure Sr0.82NbO3Stable phase,
CeAlO3Phase and FeAlO3The content of phase does not have special requirement, as long as in zirconia base simultaneously
Mutually just zirconium base composite ceramic material can be combined to oxidation zirconium base to a certain extent containing these three structures
Toughness play adjustment effect.Those skilled in the art are referred to the consumption of auxiliary material commonly used in the art
Reasonably adjust cubic structure Sr in zirconia base0.82NbO3Stable phase, CeAlO3Phase and FeAlO3
The content of phase.
In the preferred embodiment of the present invention, on the basis of the content 100mol% of zirconium oxide,
Cubic structure Sr containing 0.2-8mol% in above-mentioned zirconium base composite ceramic material0.82NbO3Stable phase,
0.5-8mol% CeAlO3The FeAlO of phase and 0.13-2mol%3Phase, by by zirconium base composite ceramic
Cubic structure Sr in ceramic material0.82NbO3Stable phase, CeAlO3Phase and FeAlO3The content of phase is limited
Within the above range, be conducive to obtaining a kind of drop resistant better performances, and be rendered proximate to lemon-yellow zirconium base
Composite ceramic material.In order to further optimize the toughness and colourity of zirconium base composite ceramic material of the present invention, more
It is preferred that on the basis of the content 100mol% of zirconium oxide, containing in the zirconium base composite ceramic material
1-6.1mol% cubic structure Sr0.82NbO3Stable phase, 0.7-5mol% CeAlO3Phase, and
0.18-1.25mol%FeAlO3Phase.
In the preferred embodiment of the present invention, the CeAlO3Mutually with the FeAlO3Phase is rubbed
You are than being (3.8-4.2)：1, more preferably 4：1.By by the CeAlO in zirconium base composite ceramic material3
Phase and FeAlO3The content of phase is limited within the above range, is conducive to obtaining the shinny lemon of pure color
The zirconium base composite ceramic material of color.
During above-mentioned zirconium base composite ceramic material of the invention is prepared, used raw material includes oxygen
Change zirconium powder body, CeAlO3Powder, FeAlO3Powder, SrCO3Powder and Nb2O5Powder.It is wherein preferred
The Zirconium powder added is the stable tetragonal phase zirconium oxide powder of 3mo1% yttriums, is now formed
Zirconia base is the stable zirconia base of 3mo1% yttriums in zirconium base composite ceramic material；Addition
CeAlO3Powder in the zirconium base composite ceramic material to form CeAlO3Phase, adds FeAlO3Powder
Body in the zirconium base composite ceramic material to form FeAlO3Phase；Add SrCO3Powder and Nb2O5
Powder forms cubic structure Sr to be sintered in zirconia base0.82NbO3Stable phase；Wherein CeAlO3
Phase, FeAlO3Phase and Sr0.82NbO3The formation in proportion of stable phase can make zirconium base composite ceramic material
Present lemon yellow.
In above-mentioned zirconium base composite ceramic material of the invention, SrCO in presumption raw material3(strontium carbonate) powder
And Nb2O5(niobium pentaoxide) powder can react generation cubic structure Sr completely0.82NbO3Stable phase,
Cubic structure Sr in the present invention0.82NbO3The content of stable phase is according to SrCO3(strontium carbonate) powder
And Nb2O5The rate of charge metering conversion gained of (niobium pentaoxide) powder.
In the present invention for used Zirconium powder, CeAlO3Powder, FeAlO3Powder,
SrCO3Powder and Nb2O5The particle diameter of powder does not have particular/special requirement, is referred to this area and prepares zirconium base
For the conventional selection of raw material particle size during composite ceramic material.The grain of the Zirconium powder for example added
Footpath D50It can be 0.1-1 μm, preferably 0.5-0.8 μm；The CeAlO added3Powder and FeAlO3
The particle diameter D of powder50For 0.1-2 μm, preferably 0.2-0.7 μm.The SrCO added3Powder and
Nb2O5The particle diameter D of powder50For 0.2-5 μm.Wherein particle diameter D50For volume average particle size, it is to pass through
Powder to be measured is dispersed in water, then ultrasonic vibration 30 minutes, granularity survey is carried out with laser particle analyzer
Examination is obtained.
In above-mentioned zirconium base composite ceramic material of the invention, as long as containing cubic structure Sr simultaneously0.82NbO3
Stable phase, CeAlO3Phase and FeAlO3Phase, it becomes possible to so that the compound zirconium base composite ceramic material of zirconium base is in
Now certain color, in order to further optimize the colourity of above-mentioned zirconium base composite ceramic material, is presented
It is lemon yellow, and luminous shinny zirconium base composite ceramic material, preferred zirconium base composite ceramics material in the present invention
The L values of material are 65-72, and a values are (- 1.3)-(- 0.5), and b values are 19-25.Wherein L, a and b
Value refers to the chromaticity coordinates in CIELab color spaces.
The above-mentioned zirconium base composite ceramic material of the present invention can be by by Zirconium powder, CeAlO3Powder,
FeAlO3Powder and with cubic structure Sr0.82NbO3After the material powder mixing of stable phase, through dry
Dry, shaping, sintering processes are made, and its preparation method is referred to the common process method of this area,
As long as containing CeAlO in the zirconium base composite ceramic material formed3Phase, FeAlO3Phase and cube knot
Structure Sr0.82NbO3Stable phase.
However, there is cubic structure Sr due to existing0.82NbO3The price phase of the material powder of stable phase
To costliness, the extensive use for making it be unfavorable for above-mentioned zirconium base composite ceramic material.Therefore, the present invention
Inventor employs the SrCO of relative low price3Powder and Nb2O5Powder, by both in proportion in oxygen
Change and sinter to form cubic structure Sr in zirconium powder body0.82NbO3Stable phase.
A kind of preparation method of zirconium base composite ceramic material is further provided in the present invention.The preparation
Method comprises the following steps：S1, by Zirconium powder, CeAlO3Powder, FeAlO3Powder, SrCO3
Powder, Nb2O5Powder and binding agent mixing, form mixed slurry, wherein the SrCO3Powder and
Nb2O5The mol ratio of powder is 1.64：1；S2, the mixed slurry is dried successively, is molded,
And sintering forms the zirconium base composite ceramic material.
This method provided by the present invention, by adding SrCO3Powder and Nb2O5(both have powder
Play the role of similar to sintering aid), can relative reduction zirconium base composite ceramic material under the same conditions
Sintering temperature, promote obtained zirconium base composite ceramic material structure more fine and close.Meanwhile, SrCO3
Powder and Nb2O5Powder mixes sintering by a certain percentage in Zirconium powder can form cubic structure
Sr0.82NbO3Stable phase, in the zirconia base of zirconium base composite ceramic material (on internal and surface)
Dispersed cubic structure Sr0.82NbO3Stable phase and CeAlO3And FeAlO3Phase, can effectively improve zirconium
The toughness and drop resistant performance of based composite ceramic material, make it be applied to be produced similar to shell or ornament
Large area appearance member.
According to the above method of the present invention, wherein used CeAlO3Powder can be commercially available prod,
Can be made products.In a preferred embodiment, the CeAlO3Raw powder's production technology includes：
By the compound (such as the oxide containing Ce, carbonate or nitrate) containing Ce, contain Al
Compound (such as oxide containing Al, carbonate or nitrate) (for example contain Ce in proportion
Compound in terms of Ce, the mol ratio in terms of Al of the compound containing Al is about 1：1) ground and mixed is (excellent
Select ball milling mixing), then the heat preservation sintering 1-2h at 1100-1300 DEG C grinds (preferred ball milling
It is scattered) to micron-sized powder, obtain the CeAlO3Powder.
According to the above method of the present invention, wherein used FeAlO3Powder can be commercially available prod,
Can be made products.In a preferred embodiment, the FeAlO3Raw powder's production technology includes：
By the compound (such as the oxide containing Fe, carbonate or nitrate) containing Fe, contain Al
Compound (such as oxide containing Al, carbonate or nitrate) (for example contain Fe in proportion
Compound in terms of Fe, the mol ratio in terms of Al of the compound containing Al is about 1：1) ground and mixed is (excellent
Select ball milling mixing), then the heat preservation sintering 1-2h at 1100-1300 DEG C grinds (preferred ball milling
It is scattered) to micron-sized powder, obtain the FeAlO3Powder.
According to the above method of the present invention, the mixed method for various raw materials in S1 does not have special want
Ask, with reference to the conventional method for mixing in this area.In the present invention preferably, the S1 formation mixing
The step of slurry, includes：S11, by Zirconium powder, CeAlO3Powder, FeAlO3Powder, SrCO3
Powder, Nb2O5Powder mixed grinding (being preferably ball milling), forms premixed material；S12, will be described pre-
Mixed body and binding agent mixed grinding (being preferably ball milling), form the mixed slurry.Pass through such side
Formula carries out batch mixing, forms each stock dispersion in slurry of spraying and is more uniformly distributed, and then is conducive to acquisition
Drop resistant performance is more preferable, and the zirconium base composite ceramic material that color is more uniformly distributed.
In the S1 of above-mentioned preparation method of the invention, for Zirconium powder, CeAlO3Powder,
FeAlO3Powder, SrCO3Powder and Nb2O5The usage ratio of powder does not have particular/special requirement, as long as
Contain cubic structure Sr in prepared zirconium base composite ceramic material simultaneously0.82NbO3Stable phase, CeAlO3
Phase and FeAlO3Phase.However, in order to optimize prepared zirconium base composite ceramic material toughness and
Colourity, in the present invention in the S1 of above-mentioned preparation method, preferably Zirconium powder, CeAlO3Powder,
FeAlO3Powder and SrCO3The mol ratio of powder is 100：(0.5-8)：(0.13-2)：(0.164-6.56),
Preferably 100：(0.7-5)：(0.18-1.25)：(0.8-5).
Preferably, the CeAlO3Powder and FeAlO3The mol ratio of powder is (3.8-4.2)：1, more
Preferably 4：1；It is preferred that the Zirconium powder added is the stable tetragonal phase zirconium oxide powder of 3mo1% yttriums
Body.
In the S1 of above-mentioned preparation method of the invention, the type and consumption for binding agent be not special
It is required that, the conventional method for being referred to this area carries out raw material selection and consumption selection, for example, can select
The binding agent selected includes but is not limited to PVA or Macrogol 4000, and the consumption of binding agent is zirconium oxide
The 0.2-2wt% of powder gross weight.
In the S2 of above-mentioned preparation method of the invention, do not have special want for dry process conditions
Ask, with reference to this area common process method.It is preferred to use spray drying process in the present invention,
And the condition of the spray drying includes：EAT is 220-260 DEG C, and leaving air temp is
100-125 DEG C, centrifugal rotational speed is 10-20rpm.
In the S2 of above-mentioned preparation method of the invention, do not have particular/special requirement for the technique of shaping, can
With using traditional molding mode such as dry-pressing formed, isostatic pressing, injection moulding, hot die-casting molding.
Present invention preferably employs dry-pressing formed, preferably described dry-pressing formed condition includes：Use tonnage for
150-200 press, 20-60s is molded under the conditions of dry-pressing pressure is 6-12MPa.
In the S2 of above-mentioned preparation method of the invention, do not have particular/special requirement for the technique of sintering, burn
Knot is sintered using common Muffle furnace air normal pressure.Preferably, the step of sintering includes：Will
The prefabricated component of obtained by molding is at 1400-1500 DEG C, preferably 1410-1480 DEG C, more preferably 1430-1470 DEG C
Lower sintering 1-2h.
It is highly preferred that sintering step includes in the S3：By the prefabricated component of the obtained by molding from room temperature
1.5-2.5h is incubated after rising to 550-650 DEG C through 350-450min, then is risen to through 250-350min
It is incubated 1.5-2.5h after 1100-1200 DEG C, then be incubated after rising to 1350-1450 DEG C through 120-180min
1.5-2.5h, then heat preservation sintering 1-2h after rising to 1430-1470 DEG C through 30-60min, then pass through
It is down to 900 DEG C or so within 120-180min minutes, finally naturally cools to room temperature.
In above-mentioned preparation method of the invention, for not having particular/special requirement in process of lapping in S1, only
Being sufficiently mixed for raw material can be realized, it is preferable that the mode of the grinding is ball milling, in ball
During mill, the ball grinder with zirconia ceramics liner, and zirconium oxide abrasive ball are used.
In above-mentioned preparation method of the invention, ball milling step usually requires to add ball milling solution, in this hair
The ball milling solution that can be used in bright includes but is not limited to use water and/or C1-C5Alcohol, it is preferable that the ball
It is water and/or C to grind solution1-C5Monohydric alcohol.C1-C5Monohydric alcohol can be methanol, ethanol, positive third
Alcohol, 2- propyl alcohol, n-butanol, 2- butanol, 2- methyl isophthalic acids-propyl alcohol, 2- methyl-2-propanols, n-amyl alcohol, 2-
Methyl-1-butanol, 3- methyl-1-butanols, 2- methyl -2- butanol, 3- methyl -2- butanol and 2,2- dimethyl
One or more in -1- propyl alcohol.It is highly preferred that the ball milling solution is water and/or ethanol.
Meanwhile, a kind of zirconium base composite ceramic material is additionally provided in the present invention, the zirconium base composite ceramics
Material is prepared from by the preparation method of above-mentioned zirconium base composite ceramic material.The zirconium base composite ceramics material
Material contains zirconia base, and the cubic structure Sr being dispersed in the zirconia base0.82NbO3Surely
Determine phase, CeAlO3Phase and FeAlO3Phase.
Preferably, on the basis of the content 100mol% of zirconium oxide, in the zirconium base composite ceramic material
Cubic structure Sr containing 0.2-8mol%0.82NbO3The CeAlO of stable phase, 0.5-8mol%3Phase, with
And 0.13-2mol%FeAlO3Phase.Preferably, it is described on the basis of the content 100mol% of zirconium oxide
Cubic structure Sr containing 1-6.1mol% in zirconium base composite ceramic material0.82NbO3Stable phase,
0.7-5mol% CeAlO3Phase, and 0.18-1.25mol% FeAlO3Phase.It is preferred that the zirconium base is multiple
Close CeAlO in ceramic material3Mutually with the FeAlO3The mol ratio of phase is (3.8-4.2)：1, more preferably
For 4：1.Preferably, the L values of the zirconium base composite ceramic material be 65-72, a values for (- 1.3)-
(- 0.5), b values are 19-25.
In the preparation method of above-mentioned zirconium base composite ceramic material of the invention, SrCO in presumption raw material3(carbon
Sour strontium) powder and Nb2O5(niobium pentaoxide) powder reacts generation cubic structure Sr completely0.82NbO3
Stable phase, so, cubic structure Sr in prepared zirconium base composite ceramic material0.82NbO3Stable phase
Content is according to SrCO3(strontium carbonate) powder and Nb2O5The rate of charge meter of (niobium pentaoxide) powder
Amount conversion gained.
In addition, additionally provide a kind of shell or ornament in the present invention, the shell or ornament by
Above-mentioned zirconium base composite ceramic material is prepared from.Above-mentioned shell or ornament are multiple by using above-mentioned zirconium base
Close ceramic material to be prepared from, not only with preferable toughness and drop resistant performance；Moreover, by reasonable
Configuration zirconium base composite ceramic material in structure phase content, it is pure to obtain color (lemon yellow),
Surface more bright shell or ornament.
Below with reference to specific embodiment and comparative example so that zirconium base composite ceramic of the present invention to be described in further detail
Ceramic material and preparation method thereof, and illustrate having for zirconium base composite ceramic material of the present invention and preparation method thereof
Beneficial effect.
First, raw material explanation
(1) Zirconium powder：Commercially available from product (the granularity D of east Gao Ye companies OZ-3Y-7 models50
For 0.7 μm), it is the stable tetragonal phase zirconium oxide powder of 3mo1% yttriums；
(2)SrCO3Powder：Industry (granularity D is raised commercially available from company's Shanghai allusion quotation50For 1 μm), purity
For 99%；
(3)Nb2O5Powder：Commercially available from Yangzhou three and company (granularity D50For 1 μm), purity is
99.5%；
(4)CeAlO3Powder (granularity D50For 0.5 μm)：By CeCO3And Al2O3According to mole
Than 2：1 ball milling mixing, drying, the heat preservation sintering 1.5h at 1200 DEG C, then ball mill grinding is to micron
Level powder, obtains the CeAlO3Powder；
(5)FeAlO3Powder (granularity D50For 0.5 μm)：By FeCO3And Al2O3According to mole
Than 2：1 ball milling mixing, drying, the heat preservation sintering 1.5h at 1200 DEG C, then ball mill grinding is to micron
Level powder, obtains the FeAlO3Powder；
(6) binding agent：Commercially available from the Macrogol 4000 of Kuraray company, and commercially available from Kuraray
The PVA217 of company.
2nd, example is proved
In the X-ray diffraction facies analysis involved by example 1 and 2 is proved as follows：
Tester：X-ray diffraction facies analysis instrument.
Test condition：Radiated using CuKa, testing tube pressure is 40kV, Guan Liuwei 20mA, scans mould
Formula is theta/2theta (θ/2 θ)；Scan mode is continue；Scanning range：10-80 °, stepping angle
Spend for 0.04 °.
Prove example 1
For proving SrCO3Powder and Nb2O5Powder in molar ratio 1.64：1 in atmosphere sintering can not
Generate cubic structure Sr0.82NbO3Stable phase.
Raw material：SrCO3Powder and Nb2O5Powder, both mol ratios are 1.64：1.
Preparation method：
S1, by SrCO3Powder and Nb2O5Powder is in ball grinder plus alcohol ball milling forms mixing in 8 hours
Thing, it is stand-by after drying；
S2, the dry mixture is risen to 600 DEG C through 400min from room temperature after be incubated 2h, then pass through
300min rises to and 2h is incubated after 1150 DEG C, then is incubated 2h after rising to 1300 DEG C through 150min, then through 50min
Rise to and 1.5h is incubated after 1450 DEG C, then by being down within 150min minutes 900 DEG C, last natural cooling
To room temperature, sinter is formed, P1 is designated as.
X-ray diffraction facies analysis result：As shown in figure 1, being shown in Fig. 1 prepared by proof example 1
P1 XRD diffracting spectrums, and SrNb6O16(00-045-0228) and Sr2Nb2O7(01-070-0114)
Standard card.It is main in sinter P1 it can be seen from Fig. 1 prepared by above-mentioned proof example 1
Contain SrNb6O16Phase and Sr2Nb2O7Phase, wherein and not containing cubic structure Sr0.82NbO3Stable phase,
As can be seen here, by SrCO3Powder and Nb2O5Powder in molar ratio 1.64：1 in atmosphere sintering can not
Produce cubic structure Sr0.82NbO3Stable phase.
Prove example 2
For proving SrCO3Powder and Nb2O5Powder in molar ratio 1.64：1 burns in zirconia base
Knot can generate cubic structure Sr0.82NbO3Stable phase.
Raw material：Zirconium oxide, consumption is 200g；Nb2O5Powder, consumption is zirconium oxide integral molar quantity
25mol%, SrCO3Powder, itself and Nb2O5The mol ratio of powder is 1.64：1.
Preparation method：
S1, first by Zirconium powder, SrCO3Powder and Nb2O5Powder adds alcohol ball milling in ball grinder
Mixture is formed within 8 hours, it is stand-by after drying；
S2, the dry mixture is risen to 600 DEG C through 400min from room temperature after be incubated 2h, then pass through
300min rises to and 2h is incubated after 1150 DEG C, then is incubated 2h after rising to 1300 DEG C through 150min, then through 50min
Rise to and 1.5h is incubated after 1450 DEG C, then by being down within 150min minutes 900 DEG C, last natural cooling
To room temperature, sinter is formed, P2 is designated as.
X-ray diffraction facies analysis result：As shown in Fig. 2 figure 2 illustrates prove prepared by example 2
Sinter P2 XRD diffracting spectrums, and tetragonal phase zirconium oxide (00-017-0923), monocline
Phase zircite (01-083-0939) and Sr0.82NbO3The standard card of (00-009-0079), by Fig. 2
It is middle contrast as can be seen that above-mentioned proof example 2 prepared by sinter P2 in containing tetragonal phase zirconium oxide,
Monocline phase zircite and cubic structure Sr0.82NbO3Stable phase, it can be seen that, by SrCO3Powder with
Nb2O5Powder in molar ratio 1.64：1 in zirconia base sintering can produce cubic structure
Sr0.82NbO3Stable phase.
Summarize：From the X-ray diffraction facies analysis result of above-mentioned proof example 1 and 2, cubic structure
Sr0.82NbO3There is certain objective condition requirement in the preparation of stable phase, under any conditions will be not
SrCO3Powder and Nb2O5Powder in molar ratio 1.64：1 mixing can obtain cubic structure
Sr0.82NbO3Stable phase.Inventor has found under accidental chance in the present invention, by SrCO3Powder
With Nb2O5Powder in molar ratio 1.64：1, which is blended in sintering in zirconia base, can produce cubic structure
Sr0.82NbO3Stable phase, and this discovery is based on, the present inventor provides zirconium of the present invention
Based composite ceramic material and preparation method thereof.
3rd, embodiment 1 to 7 and comparative example 1 to 5
Embodiment 1
For illustrating zirconium base composite ceramic material of the present invention and preparation method thereof
Raw material：Zirconium oxide, consumption is 200g；CeAlO3Powder, consumption is zirconium oxide integral molar quantity
1.04mol%；FeAlO3Powder, its consumption and CeAlO3The molar ratio of powder consumption is 1：4；SrCO3
Powder, consumption is the 1.5mol% of zirconium oxide integral molar quantity；Nb2O5Powder, its consumption and SrCO3Powder
The molar ratio of body consumption is 1：1.64；Macrogol 4000, consumption is the 0.5wt% of zirconium oxide weight；
PVA, consumption is the 0.5wt% of zirconium oxide weight.
Preparation method：
S1, first by Zirconium powder, CeAlO3Powder, FeAlO3Powder, SrCO3Powder and Nb2O5
Powder is in ball grinder plus alcohol ball milling forms premixed material in 8 hours；The poly- second of binding agent is added in premixed material
Glycol 4000 and PVA ball milling half an hour, form spraying slurry；
S2, by spraying slurry send into spray tower EAT be 250 DEG C, leaving air temp be 110 DEG C,
Centrifugal rotational speed forms the spherical powder for being used for dry-pressing to carry out being spray-dried under the conditions of 15rpm；It will be used for doing
The spherical powder of pressure is added in dry press (press that 180 tons of tonnage uses 8MPa oil pressure pressure),
Dry-pressing 30s formation prefabricated components；2h is incubated after the prefabricated component is risen into 600 DEG C through 400min from room temperature,
It is incubated 2h after rising to 1150 DEG C through 300min again, then is incubated 2h after rising to 1400 DEG C through 150min, then
1.5h is incubated after rising to 1450 DEG C through 50min, then by being down to 900 DEG C within 150min minutes, finally
Room temperature is naturally cooled to, zirconium base composite ceramic material is formed；
According to the metering that feeds intake of raw material than presumption, on the basis of the content of zirconium oxide is 100mol%, institute's shape
Into zirconium base composite ceramic material in the cubic structure Sr containing 1.83mol%0.82NbO3Stable phase,
1.04mol% CeAlO3Phase, and 0.26mol% FeAlO3Phase.
S3, the zirconium base composite ceramic material sanding and polishing and being cut by laser is made long generous it is
135mm × 65mm × 0.7mm model, is designated as S1.
Embodiment 2
For illustrating zirconium base composite ceramic material of the present invention and preparation method thereof
Raw material：With reference to raw material in embodiment 1, difference is：CeAlO3Powder, consumption is zirconium oxide
The 2mol% of integral molar quantity；FeAlO3Powder, consumption is the 0.5mol% of zirconium oxide integral molar quantity；
Preparation method：Be the same as Example 1.
According to the metering that feeds intake of raw material than presumption, on the basis of the content of zirconium oxide is 100mol%, institute's shape
Into zirconium base composite ceramic material in the cubic structure Sr containing 1.83mol%0.82NbO3Stable phase,
2mol% CeAlO3Phase, and about 0.5mol% FeAlO3Phase.
The zirconium base composite ceramic material sanding and polishing and being cut by laser is made and long generous is
135mm × 65mm × 0.7mm model, is designated as S2.
Embodiment 3
For illustrating zirconium base composite ceramic material of the present invention and preparation method thereof
Raw material：With reference to raw material in embodiment 1, difference is：CeAlO3Powder, consumption is zirconium oxide
The 1.28mol% of integral molar quantity；FeAlO3Powder, consumption is the 0.32mol% of zirconium oxide integral molar quantity；
SrCO3The consumption of powder is the 2mol% of zirconium oxide integral molar quantity；Nb2O5The mole dosage of powder with
SrCO3The ratio of powder mole dosage is 1：1.64；
Preparation method：Be the same as Example 1.
According to the metering that feeds intake of raw material than presumption, on the basis of the content of zirconium oxide is 100mol%, institute's shape
Into zirconium base composite ceramic material in the cubic structure Sr containing 2.4mol%0.82NbO3Stable phase,
1.28mol% CeAlO3Phase, and about 0.32mol% FeAlO3Phase.
The zirconium base composite ceramic material sanding and polishing and being cut by laser is made and long generous is
135mm × 65mm × 0.7mm model, is designated as S3.
Embodiment 4
For illustrating zirconium base composite ceramic material of the present invention and preparation method thereof
Raw material：With reference to raw material in embodiment 1, difference is：CeAlO3Powder, consumption is zirconium oxide
The 0.7mol% of integral molar quantity；FeAlO3Powder, consumption is the 0.18mol% of zirconium oxide integral molar quantity；
SrCO3The consumption of powder is the 5mol% of zirconium oxide integral molar quantity；Nb2O5The consumption and SrCO of powder3
The molar ratio of powder consumption is 1：1.64；
Preparation method：Be the same as Example 1.
According to the metering that feeds intake of raw material than presumption, on the basis of the content of zirconium oxide is 100mol%, institute's shape
Into zirconium base composite ceramic material in the cubic structure Sr containing 6.1mol%0.82NbO3Stable phase,
0.7mol% CeAlO3Phase, and about 0.18mol% FeAlO3Phase.
The zirconium base composite ceramic material sanding and polishing and being cut by laser is made and long generous is
135mm × 65mm × 0.7mm model, is designated as S4.
Embodiment 5
For illustrating zirconium base composite ceramic material of the present invention and preparation method thereof
Raw material：With reference to raw material in embodiment 1, difference is：CeAlO3Powder, consumption is zirconium oxide
The 5mol% of integral molar quantity；FeAlO3Powder, consumption is the 1.25mol% of zirconium oxide integral molar quantity；SrCO3
Powder, consumption is the 0.82mol% of zirconium oxide integral molar quantity；Nb2O5Powder, its mole dosage and SrCO3
The ratio of powder mole dosage is 1：1.64.
Preparation method：Be the same as Example 1.
According to the metering that feeds intake of raw material than presumption, on the basis of the content of zirconium oxide is 100mol%, institute's shape
Into zirconium base composite ceramic material in the cubic structure Sr containing 1mol%0.82NbO3Stable phase, 5mol%
CeAlO3Phase, and 1.25mol% FeAlO3Phase.
The zirconium base composite ceramic material sanding and polishing and being cut by laser is made and long generous is
135mm × 65mm × 0.7mm model, is designated as S5.
Embodiment 6
For illustrating zirconium base composite ceramic material of the present invention and preparation method thereof
Raw material：With reference to raw material in embodiment 1, difference is：Zirconium oxide, consumption is 200g；CeAlO3
Powder, consumption is the 8mol% of zirconium oxide integral molar quantity；FeAlO3Powder, consumption is that zirconium oxide always rubs
The 2mol% of your amount；SrCO3Powder, consumption is the 6.56mol% of zirconium oxide integral molar quantity；Nb2O5Powder
Body, its mole dosage and SrCO3The ratio of powder mole dosage is 1：1.64.
Preparation method：Be the same as Example 1.
According to the metering that feeds intake of raw material than presumption, on the basis of the content of zirconium oxide is 100mol%, institute's shape
Into zirconium base composite ceramic material in the cubic structure Sr containing 8mol%0.82NbO3Stable phase, 8mol%
CeAlO3Phase, and 2mol% FeAlO3Phase.
The zirconium base composite ceramic material sanding and polishing and being cut by laser is made and long generous is
135mm × 65mm × 0.7mm model, is designated as S6.
Embodiment 7
For illustrating zirconium base composite ceramic material of the present invention and preparation method thereof
Raw material：Zirconium oxide, consumption is 200g；CeAlO3Powder, consumption is zirconium oxide integral molar quantity
0.5mol%；FeAlO3Powder, consumption is the 0.13mol% of zirconium oxide integral molar quantity；SrCO3Powder,
Consumption is the 0.2mol% of zirconium oxide integral molar quantity；Nb2O5Powder, its mole dosage and SrCO3Powder
The ratio of mole dosage is 1：1.64；Macrogol 4000, consumption is the 0.5wt% of zirconium oxide weight；
PVA, consumption is the 0.5wt% of zirconium oxide weight；
Preparation method：Be the same as Example 1.
According to the metering that feeds intake of raw material than presumption, on the basis of the content of zirconium oxide is 100mol%, institute's shape
Into zirconium base composite ceramic material in the cubic structure Sr containing 0.24mol%0.82NbO3Stable phase,
0.5mol% CeAlO3Phase, and 0.13mol% FeAlO3Phase.
The zirconium base composite ceramic material sanding and polishing and being cut by laser is made and long generous is
135mm × 65mm × 0.7mm model, is designated as S7.
Comparative example 1：
For comparative illustration zirconium base composite ceramic material of the present invention and preparation method thereof
(1) raw material：Zirconium oxide 200g, Macrogol 4000, consumption is the 0.5wt% of zirconium oxide weight；
PVA, consumption is the 0.5wt% of zirconium oxide weight；
(2) preparation method of ceramic material comprises the following steps：
S1, by Zirconium powder and binding agent Macrogol 4000 and PVA ball milling half an hour, form spray
Mist slurry；
S2, by spraying slurry send into spray tower EAT be 250 DEG C, leaving air temp be 110 DEG C,
Centrifugal rotational speed forms the spherical powder for being used for dry-pressing to carry out being spray-dried under the conditions of 15rpm；It will be used for doing
The spherical powder of pressure is added in dry press (press that 180 tons of tonnage uses 8MPa oil pressure pressure),
Dry-pressing 30s formation prefabricated components；The prefabricated component is warming up into 1480 DEG C to sinter 2 hours, room temperature is cooled to,
Form ceramic material.
S3, ceramic material sanding and polishing and being cut by laser is made long generous it is
135mm × 65mm × 0.7mm model, is designated as D1.
Comparative example 2：
For comparative illustration zirconium base composite ceramic material of the present invention and preparation method thereof
(1) raw material：Zirconium oxide, consumption is 200g；CeAlO3Powder, consumption is zirconium oxide total moles
The 1.04mol% of amount；FeAlO3Powder, its consumption is the 0.26mol% of zirconium oxide integral molar quantity；Poly- second
Glycol 4000, consumption is the 0.5wt% of zirconium oxide weight；PVA, consumption is the 0.5wt% of zirconium oxide weight；
(2) preparation method of ceramic material：With reference to comparative example 1, difference is：
S1, first by Zirconium powder, CeAlO3Powder and FeAlO3Powder adds alcohol ball in ball grinder
Mill forms premixed material in 8 hours；Binding agent Macrogol 4000 and PVA ball millings half are added in premixed material
Hour, form spraying slurry；
S3, ceramic material sanding and polishing and being cut by laser is made long generous it is
135mm × 65mm × 0.7mm model, is designated as D2.
Comparative example 3
For comparative illustration zirconium base composite ceramic material of the present invention and preparation method thereof
(1) raw material：Zirconium oxide, consumption is 200g；SrCO3Powder, consumption is zirconium oxide total moles
The 8mol% of amount；Nb2O5Powder, its mole dosage and SrCO3The ratio of powder mole dosage is 1：
1.64；Macrogol 4000, consumption is the 0.5wt% of zirconium oxide weight；PVA, consumption is zirconium oxide weight
The 0.5wt% of amount；
(2) preparation method of ceramic material：With reference to comparative example 1, difference is：
S1, first by Zirconium powder, SrCO3Powder and Nb2O5Powder adds alcohol ball milling in ball grinder
Form premixed material within 8 hours；Binding agent Macrogol 4000 is added in premixed material and PVA ball millings half are small
When, form spraying slurry；
S3, ceramic material sanding and polishing and being cut by laser is made long generous it is
135mm × 65mm × 0.7mm model, is designated as D3.
Comparative example 4
For comparative illustration zirconium base composite ceramic material of the present invention and preparation method thereof (with reference to Chinese patent
Embodiment 1 in No.02111146.4)
By 0.5vol% ultra-fine YAS sintering aids and (Mg, Y)-TZP powders ((14mol%)
MgO- (1.5mol%) Y2O3- (surplus) ZrO2) mechanical ball mill drying in 12 hours or so, add
3% concentration PVA is dry-pressing formed under 60MPa after being granulated for binding agent, and the isostatic pressed under 200MPa
Obtain biscuit.Then biscuit is placed in Si-Mo rod stove 1400 DEG C of guarantors are raised to 2 DEG C/min of programming rate
Temperature sintering 2 hours, furnace cooling.
Sintered body sanding and polishing and being cut by laser is made long generous for 135mm × 65mm × 0.7mm's
Model, is designated as D4.
Comparative example 5
For comparative illustration zirconium base composite ceramic material of the present invention and preparation method thereof
(1) raw material：Zirconium oxide, consumption is 200g；Sr2Nb2O7Powder, consumption is that zirconium oxide always rubs
The 1.83mol% of your amount；Macrogol 4000, consumption is the 0.5wt% of zirconium oxide weight；PVA, is used
Measure as the 0.5wt% of zirconium oxide weight；Wherein, Sr2Nb2O7Powder is by by SrCO3Powder and Nb2O5
Powder in molar ratio 2：1 ball milling mixing, is dried, the heat preservation sintering 1.5h at 1200 DEG C, then ball milling
It is crushed to D50Obtained for 0.5 μm of powder；
(2) preparation method of ceramic material：With reference to comparative example 1, difference is：
S1, first by Zirconium powder, Sr2Nb2O7Powder is in ball grinder plus alcohol ball milling is formed for 8 hours
Premixed material；Binding agent Macrogol 4000 and PVA ball milling half an hour are added in premixed material, spray is formed
Mist slurry；
S3, zirconia-based ceramic material sanding and polishing and being cut by laser is made long generous it is
135mm × 65mm × 0.7mm model, is designated as D5.
4th, test：
It is by the length prepared by embodiment 1 to 7 and comparative example 1 to 5 is generous
135mm × 65mm × 0.7mm model carries out performance test, is answered with illustrating that zirconium base of the present invention is combined zirconium base
Close the beneficial effect of ceramic material and preparation method thereof.
(1), test event and method
(1) colourity is tested：The color difference meter test sample for electronics-China-color1101 models of being revived using promise
L, a, b values simultaneously with carbon black black standard sample contrasted.
(2) toughness test：It is (i.e. unilateral using GB/T23806 high technology ceramics fracture toughness test methods
Coped beam method) measure.
(3) drop resistant is tested：Prepared length is generous in Example 1 to 7 and comparative example 1 to 5
For 135mm × 65mm × 0.7mm model 1.3m eminence with the whereabouts mode of freely falling body with ground
Face carries out big face perpendicular contact, takes 10, sample per sample product, takes drop resistant number of times average value.
(4) polishing effect：By made in naked-eye observation embodiment 1 to 7 and comparative example 1 to 5
The generous specimen surface for 135mm × 65mm × 0.7mm of standby length whether there is defect.
(2), test result：As shown in table 1.
Table 1
The data in table 1, according to prepared by the preparation method of zirconium base composite ceramic material of the present invention
Model S1-S7 toughness is substantially better than the model D1-D4 prepared by comparative example 1 to comparative example 4, and energy
Enough bear specified conditions lower more than 5 times, or even the drop resistant of 10 to 16 times is tested.
Moreover, adding Sr with comparative example 52Nb2O7Prepared by powder (employing optimal raw material dosage)
Model D5 is compared, and the toughness and drop resistant performance of the model S6-S7 prepared by 6-7 of the embodiment of the present invention connect
Nearly model D5, and the toughness and drop resistant performance of the model S1-S5 prepared by preferred embodiment 1 to 5
Far superior to model D5.
In addition, under specific material rate or structure phase content, the model S1-S7 prepared by the present invention
L values in 65-72 scopes, a values in the range of (- 1.3)-(- 0.5), b values in the range of 19-25,
It can be seen that prepared ceramic material is presented lemon yellow, and pure color, can be very by adult population
Welcome.
The preferred embodiment of the present invention described in detail above, still, the present invention is not limited to above-mentioned
Detail in embodiment, can be to skill of the invention in the range of the technology design of the present invention
Art scheme carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid not
Necessary repetition, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as
It is without prejudice to the thought of the present invention, and it should equally be considered as content disclosed in this invention.
Claims (13)
1. a kind of zirconium base composite ceramic material, it is characterised in that the zirconium base composite ceramic material contains
Zirconia base, and the cubic structure Sr being dispersed in the zirconia base0.82NbO3Stable phase,
CeAlO3Phase and FeAlO3Phase.
2. zirconium base composite ceramic material according to claim 1, wherein, with the content of zirconium oxide
On the basis of 100mol%, the cubic structure containing 0.2-8mol% in the zirconium base composite ceramic material
Sr0.82NbO3The CeAlO of stable phase, 0.5-8mol%3The FeAlO of phase and 0.13-2mol%3Phase.
3. zirconium base composite ceramic material according to claim 2, wherein, with the content of zirconium oxide
On the basis of 100mol%, the cubic structure containing 1-6.1mol% in the zirconium base composite ceramic material
Sr0.82NbO3Stable phase, 0.7-5mol% CeAlO3Phase, and 0.18-1.25mol% FeAlO3
Phase.
4. zirconium base composite ceramic material according to claim 2, wherein, the zirconium base composite ceramic
CeAlO in ceramic material3Mutually with the FeAlO3The mol ratio of phase is (3.8-4.2)：1, preferably 4：1.
5. zirconium base composite ceramic material as claimed in any of claims 1 to 4, wherein,
During preparing the zirconium base composite ceramic material, SrCO is added3Powder and Nb2O5Powder is with institute
State sintering in zirconium base composite ceramic material and form cubic structure Sr0.82NbO3Stable phase.
6. zirconium base composite ceramic material as claimed in any of claims 1 to 4, wherein,
The L values of the zirconium base composite ceramic material are 65-72, and a values are (- 1.3)-(- 0.5), and b values are 19-25.
7. a kind of preparation method of zirconium base composite ceramic material, it is characterised in that the preparation method bag
Include following steps：
S1, by Zirconium powder, CeAlO3Powder, FeAlO3Powder, SrCO3Powder, Nb2O5
Powder and binding agent mixing, form mixed slurry, wherein the SrCO3Powder and Nb2O5Powder rubs
You are than being 1.64：1；
S2, the mixed slurry is dried, be molded and sintered successively form the zirconium base and answer
Close ceramic material.
8. preparation method according to claim 7, wherein, Zirconium powder in the S1,
CeAlO3Powder, FeAlO3Powder and SrCO3The mol ratio of powder is 100：(0.5-8)：(0.13-2)：
(0.164-6.56)；Preferably 100：(0.7-5)：(0.18-1.25)：(0.8-5)；It is preferred that the CeAlO3
Powder and FeAlO3The mol ratio of powder is (3.8-4.2)：1, more preferably 4：1.
9. preparation method according to claim 7, wherein, drying steps are using spray in the S2
The method that mist is dried, the condition of the spray drying includes：EAT is 220-260 DEG C, goes out wind-warm syndrome
Spend for 100-125 DEG C, centrifugal rotational speed is 10-20rpm.
10. preparation method according to claim 7, wherein, forming step is used in the S2
Dry-pressing formed, the dry-pressing formed condition includes：Tonnage is used for 150-200 press, in dry-pressing
Pressure be 6-12MPa under the conditions of be molded 20-60s.
11. preparation method according to claim 7, wherein, sintering step bag in the S2
Include：The prefabricated component of obtained by molding is sintered into 1-2h at 1430-1470 DEG C.
12. a kind of zirconium base composite ceramic material, it is characterised in that the zirconium base composite ceramic material by
The preparation method of zirconium base composite ceramic material in claim 7 to 11 described in any one prepare and
Into.
13. a kind of shell or ornament, it is characterised in that the shell or ornament are by claim 1
Zirconium base composite ceramic material into 6 and 12 described in any one is prepared from.
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