CN106810241A - Zirconium base composite ceramic material（Black gray expandable）And preparation method thereof with shell or ornament - Google Patents
Zirconium base composite ceramic material（Black gray expandable）And preparation method thereof with shell or ornament Download PDFInfo
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Abstract
The invention discloses a kind of zirconium base composite ceramic material (black gray expandable) and preparation method thereof and shell or ornament.The ceramic material contains zirconia base, and is dispersed in the cubic structure Sr in the zirconia base0.82NbO3Stable phase and La0.8Sr0.2MnO3Phase.This zirconium base composite ceramic material is by the dispersed cubic structure Sr in zirconia base0.82NbO3Stable phase and La0.8Sr0.2MnO3Phase, can effectively improve the toughness and drop resistant performance of zirconium base composite ceramic material, it is applied to the large area appearance member for being 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 and preparation method thereof and shell or ornament.
Background technology
With the high development of science and technology, requirement of the consumer to the performance and quality of ceramic material is got over
Come higher.Zirconia ceramics due to its have it is higher than other types ceramics good corrosion resistance, hardness, with
And intensity it is high the characteristics of extensive application.However, when large area appearance member is made, although existing
The toughness of zirconia ceramics (reach 5-6MPam1/2) higher than other kinds of ceramics, but
It is still present intolerant to the shortcoming fallen.And, the color of existing zirconia ceramics is usually white, too
Cross single, and simultaneously unsightly.Therefore, if wanting to make appearance member using zirconia ceramics, in addition it is also necessary to right
The colourity and toughness (drop resistant) of zirconia ceramics are further improved.
At present, the Zirconium powder of yttrium stabilization is more ripe on the market, for zirconia ceramics
Improvement is generally built upon on the basis of the Zirconium powder of yttrium stabilization.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 existing these 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 Mg stabilizations TZP ceramics in Chinese patent No.02111146.4.This
The ceramic effect that a part of toughness reinforcing can be played by the Mg that adulterates of kind, but this DeGrain.And
And the ceramics sample low strength prepared according to this method, only 590MPa or so is such strong
Degree cannot prepare the thin slice (easily broken) of large area.In addition, this method is also only directed to white pottery
Porcelain, its range of 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；Also need to carry out the colourity of zirconia ceramics 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, according to the first aspect of the invention, there is provided a kind of zirconium base composite ceramic
Ceramic material, the ceramic material contains zirconia base, and is dispersed in vertical in the zirconia base
Square structure Sr0.82NbO3Stable phase and La0.8Sr0.2MnO3Phase.
According to the second aspect of the invention, there is provided a kind of preparation side of zirconium base composite ceramic material
Method, the preparation method is comprised the following steps：S1, by Zirconium powder, La0.8Sr0.2MnO3Powder,
SrCO3Powder and Nb2O5Powder and binding agent mix, and mixed slurry are formed, wherein the SrCO3Powder
Body and Nb2O5The mol ratio of powder is 1.64:1；S2, the mixed slurry is dried successively, into
Type 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 zirconium base composite ceramic material of the present 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 of the invention.
Zirconium base composite ceramic material of the present invention is by the dispersed cubic structure Sr in zirconia base0.82NbO3
Stable phase and La0.8Sr0.2MnO3Phase, can effectively improve the toughness of zirconium base composite ceramic material and resist
Performance is fallen, it is applied to the large area appearance member for being produced similar to shell or ornament.
Other features and advantages of the present invention will give specifically in subsequent specific 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 the part of specification,
It is used to explain the present invention together with following specific embodiment, but does not constitute to limit of the invention
System.In the accompanying drawings：
Fig. 1 shows the XRD diffracting spectrums for proving the P1 prepared by example 1, and SrNb6O16
(00-045-0228) and Sr2Nb2O7The standard card of (01-070-0114)；
Fig. 2 shows the XRD diffracting spectrums for proving 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.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place
The specific 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 the current zirconia ceramics as pointed by background section is also needed to further
Improve, therefore, the present inventor 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 ceramic material contains zirconia base, and is dispersed in institute
State the cubic structure Sr on (on internal and surface) in zirconia base0.82NbO3Stable phase and
La0.8Sr0.2MnO3Phase.
The above-mentioned zirconium base composite ceramic material of the present invention divides by zirconia base (on internal and surface)
Dissipate cubic structure Sr0.82NbO3Stable phase and La0.8Sr0.2MnO3Phase, can effectively improve zirconium base and be combined
The toughness and drop resistant performance of ceramic material, make it be applied to the big face for being produced similar to shell or ornament
Product appearance member.
In the present invention for cubic structure Sr0.82NbO3Stable phase and La0.8Sr0.2MnO3The content of phase is simultaneously
There is no special requirement, as long as mutually just can be in certain journey containing both structures in zirconia base
Toughness on degree to zirconium base composite ceramic material plays adjustment effect.Those skilled in the art are referred to
The consumption of auxiliary material commonly used in the art reasonably adjusts cubic structure Sr in zirconia base0.82NbO3Stabilization
Phase and La0.8Sr0.2MnO3The content of phase.
In the preferred embodiment of the present invention, it is 100mol% as base with the content of zirconium oxide
Standard, the cubic structure Sr containing 0.2-8mol% in above-mentioned zirconium base composite ceramic material0.82NbO3Stabilization
The La of phase and 0.8-5mol%0.8Sr0.2MnO3Phase.Content more preferably with zirconium oxide is as 100mol
On the basis of, the cubic structure Sr containing 1-6.1mol% in the zirconium base composite ceramic material0.82NbO3Surely
Determine the La of phase and 1-4.5mol%0.8Sr0.2MnO3Phase.By by the cubic structure in ceramic material
Sr0.82NbO3Stable phase and La0.8Sr0.2MnO3The content of phase is limited within the above range, is conducive to obtaining
Toughness and drop resistant performance are relatively more excellent, and the zirconium base composite ceramics material of black (preferably black gray expandable) is presented
Material.
During above-mentioned zirconium base composite ceramic material of the invention is prepared, the raw material for being used includes oxygen
Change zirconium powder body, La0.8Sr0.2MnO3Powder, SrCO3Powder and Nb2O5Powder.Wherein preferably, institute
The Zirconium powder of addition is the tetragonal phase zirconium oxide powder of 3mo1% yttriums stabilization, the zirconium for now being formed
Zirconia base is the zirconia base of 3mo1% yttriums stabilization in based composite ceramic material.Addition
La0.8Sr0.2MnO3Powder can form La in zirconia base0.8Sr0.2MnO3Phase,
La0.8Sr0.2MnO3The formation of phase enables to zirconium base composite ceramic material that black, particularly grey black is presented
Color；SrCO3Powder and Nb2O5Powder can be sintered in zirconia base and form cubic structure
Sr0.82NbO3Stable phase.
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 completely react generation cubic structure Sr0.82NbO3Stable phase,
So, 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.
Zirconium powder, La for being used in the present invention0.8Sr0.2MnO3Powder, SrCO3Powder
And Nb2O5The particle diameter of powder does not have particular/special requirement, and it is right when this area prepares ceramic material to be referred to
In the conventional selection of raw material particle size.The particle diameter D of the Zirconium powder for for example being added50Can be
0.1-1μm；Preferably 0.5-0.8 μm；The La for being added0.8Sr0.2MnO3The particle diameter D of powder50For
0.1-2 μm, preferably 0.2-0.7 μm.The SrCO for being added3Powder and Nb2O5The particle diameter of powder is
0.2-5μm.Wherein particle diameter D50It is volume average particle size, it is dispersed in water by by powder to be measured,
Then ultrasonic vibration 30 minutes, testing graininess acquisition is carried out with laser particle analyzer.
In above-mentioned zirconium base composite ceramic material of the invention, by containing La0.8Sr0.2MnO3Phase, with regard to energy
It is above-mentioned in order to further optimize enough so that zirconium base composite ceramic material is presented black to a certain extent
The colourity of zirconium base zirconium base composite ceramic material, makes its pure shinny, in the present invention preferred zirconium base zirconium base
The L values of composite ceramic material are 18.5-20, and a values are 1.5-3, and b values are 1-2.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, La0.8Sr0.2MnO3
Powder and with cubic structure Sr0.82NbO3Stable phase material powder mixing after, through drying, into
Type, sintering processes are obtained, and its preparation method is referred to the common process method of this area, as long as institute
Contain La in the ceramic material of formation0.8Sr0.2MnO3Phase and cubic structure Sr0.82NbO3Stable phase is
Can.
However, due to existing with cubic structure Sr0.82NbO3The price phase of the material powder of stable phase
To costliness, make it and be unfavorable for the extensive use of above-mentioned zirconium base composite ceramic material.Therefore, of the invention
Inventor employ the SrCO of less expensive3Powder and Nb2O5Powder, both are existed in proportion
Sinter to form cubic structure Sr in Zirconium powder0.82NbO3Stable phase.
A kind of preparation method of zirconium base composite ceramic material is further provided in the present invention.The preparation
Method is comprised the following steps：S1, by Zirconium powder, La0.8Sr0.2MnO3Powder, SrCO3Powder
And Nb2O5Powder and binding agent mix, and mixed slurry are formed, wherein the SrCO3Powder and Nb2O5
The mol ratio of powder is 1.64:1；S2, the mixed slurry is dried, be molded and burnt successively
Knot 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 ceramic material structure more fine and close.Meanwhile, SrCO3Powder and
Nb2O5Powder can form cubic structure Sr by mixing sintering0.82NbO3Stable phase, it is compound in zirconium base
Dispersed cubic structure Sr (on internal and surface) in the zirconia base of ceramic material0.82NbO3Stable phase
And La0.8Sr0.2MnO3Phase, can effectively improve the toughness and crash resistance of zirconium base composite ceramic material
Can, it is applied to the large area appearance member for being produced similar to shell or ornament.
In above-mentioned preparation method of the invention, the La for being used0.8Sr0.2MnO3Powder can be commercially available product
Product, it is also possible to be prepared by a conventional method.In the present invention preferably, above-mentioned La0.8Sr0.2MnO3Powder
The preparation method of body includes：By the compound (such as oxide or carbonate containing La) containing La,
Compound (such as oxide or carbonate containing Sr) containing Sr and the compound containing Mn
(such as oxide or carbonate containing Mn) in proportion (for example the compound containing La in terms of La,
Compound containing Sr is counted with Sr, the compound containing Mn counts mol ratio as (0.78-0.82 with Mn：
0.19-0.21：1) ground and mixed (preferably ball milling mixing), the heat preservation sintering at 1100 DEG C~1300 DEG C
1~2h, then grinds (preferably ball milling dispersion) to micron-sized powder, obtains described
La0.8Sr0.2MnO3Powder.
In the S1 of above-mentioned preparation method of the invention, the mixed method for various raw materials is not special
It is required that, with reference to this area routine method for mixing.In the present invention preferably, the S1 forms mixed
The step of closing slurry includes：S11, by Zirconium powder, La0.8Sr0.2MnO3Powder, SrCO3Powder
And Nb2O5Powder mixed grinding (preferably ball milling), forms premixed material；S12, by the premixed material
With binding agent mixed grinding (preferably ball milling), the mixed slurry is formed.Entered by such mode
Row batch mixing, each stock dispersion is more uniformly distributed in forming spraying slurry, and then is conducive to obtaining 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, La0.8Sr0.2MnO3Powder
And SrCO3Powder and Nb2O5The usage ratio of powder does not have particular/special requirement, as long as in prepared zirconium
Contain cubic structure Sr in based composite ceramic material simultaneously0.82NbO3Stable phase and La0.8Sr0.2MnO3It is mutually
The purpose of the present invention can to a certain extent be realized.However, in order to optimize prepared zirconium base composite ceramic
The toughness and drop resistant performance of ceramic material, and cause that zirconium base composite ceramic material is presented black, it is particularly black
Grey, in the present invention in the S1 of above-mentioned preparation method, preferably Zirconium powder, La0.8Sr0.2MnO3
Powder and SrCO3The mol ratio of powder is 100:(0.8-5):(0.164-6.56), preferably 100:(1-4.5):
(0.8-5).Preferably, the Zirconium powder for being added is the tetragonal phase zirconium oxide of 3mo1% yttriums stabilization
Powder.
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, it is referred to conventional method the selection raw material and consumption of this area, the bonding that can for example select
Agent includes but is not limited to PVA or Macrogol 4000, and the consumption of binding agent is Zirconium powder gross weight
The 0.2-2wt% of amount.
In the S2 of above-mentioned preparation method of the invention, do not have special wanting for dry process conditions
Ask, with reference to this area common process method.Spray drying process is preferably used 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, the technique for being molded does not have particular/special requirement, 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
The press of 150-200,20-60s is molded under the conditions of dry-pressing pressure is 6-12MPa.
In the S2 of above-mentioned preparation method of the invention, the technique for sintering does not have particular/special requirement, burns
Knot is sintered using common Muffle furnace air normal pressure.Preferably, the step of sintering includes,
By the prefabricated component of obtained by molding at 1330-1430 DEG C, preferably 1330-1400 DEG C, more preferably
1-2h is sintered at 1350-1390 DEG C.
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 is incubated after rising to 1250-1350 DEG C through 120-180min
1.5-2.5h, then 1-2h is incubated after rising to 1350-1390 DEG C through 30-60min, then pass through
It is down to 900 DEG C 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 generally needs to add ball milling solution, in this hair
The ball milling solution that can be used in bright is included but is not limited to water and/or C1-C5Alcohol, it is preferable that the ball
Mill solution is water and/or C1-C5Monohydric alcohol.C1-C5Monohydric alcohol can be methyl alcohol, 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 ceramic material is containing aerobic
Change zirconium base body, and be dispersed in the cubic structure Sr in the zirconia base0.82NbO3Stable phase and
La0.8Sr0.2MnO3Phase.
Preferably, with the content of zirconium oxide as 100mol% on the basis of, the zirconium base composite ceramic material
In the cubic structure Sr containing 0.2-8mol%0.82NbO3Stable phase and 0.8-5mol%'s
La0.8Sr0.2MnO3Phase.Preferably, with the content of zirconium oxide as 100mol% on the basis of, the zirconium base
Cubic structure Sr containing 1-6.1mol% in composite ceramic material0.82NbO3Stable phase and
The La of 1-4.5mol%0.8Sr0.2MnO3Phase.Preferably, the L values of the ceramic material are 18.5-20, a
It is 1.5-3 to be worth, and b values are 1-2.
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
The above-mentioned zirconium base composite ceramic material of the present invention is prepared from.Above-mentioned shell or ornament are by using above-mentioned
Zirconium base composite ceramic material is prepared from, not only with preferable toughness and drop resistant performance；And, lead to
The structure phase content crossed in rational configuration zirconium base composite ceramic material, can also obtain color (black,
Particularly black gray expandable) pure, 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
It is 0.7 μm), it is the tetragonal phase zirconium oxide powder of 3mo1% yttriums stabilization；
(2)SrCO3Powder：Industry (granularity D is raised commercially available from company's Shanghai allusion quotation50It is 1 μm), purity
It is 99%；
(3)Nb2O5Powder：Commercially available from Yangzhou three and company (granularity D50It is 1 μm), purity is
99.5%；
(4)La0.8Sr0.2MnO3Powder (granularity D50It it is 0.5 μm)：By La2(CO3)3、SrCO3
And MnCO3According to 0.8：0.2：1 mol ratio ball milling mixing, drying, the heat preservation sintering at 1200 DEG C
1.5h, then ball mill grinding obtains the La to micron-sized powder0.8Sr0.2MnO3Powder；
(5) 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 following X-ray diffraction facies analysis proved involved by example 1 and 2：
Tester：X-ray diffraction facies analysis instrument.
Test condition：Radiated using CuKa, testing tube pressure is 40KV, Guan Liuwei 20mA, scanning
Pattern is theta/2theta (θ/2 θ)；Scan mode is continue；Sweep limits：10-80 °, stepping
Angle is 0.04 °.
Prove example 1
For proving Nb2O5Powder and SrCO3Powder in molar ratio 1:1.64 sinter cannot give birth in atmosphere
Into 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 is incubated 2h after rising to 1150 DEG C, then is incubated 2h after rising to 1300 DEG C through 150min, then through 50min
1.5h is incubated after rising to 1450 DEG C, then 900 DEG C, last natural cooling was down to by 150min minutes
To room temperature, sinter is formed, be designated as P1.
X-ray diffraction facies analysis result：As shown in figure 1, being shown prepared by proof example 1 in Fig. 1
The XRD diffracting spectrums of P1, and SrNb6O16(00-045-0228) and Sr2Nb2O7(01-070-0114)
Standard card.It is main in sinter P1 as prepared by can be seen that above-mentioned proof example 1 in Fig. 1
Contain SrNb6O16Phase and Sr2Nb2O7Phase, wherein and not containing cubic structure Sr0.82NbO3Stable phase,
As can be seen here, by Nb2O5Powder and SrCO3Powder in molar ratio 1:1.64 sinter cannot give birth in atmosphere
Produce cubic structure Sr0.82NbO3Stable phase.
Prove example 2
For proving Nb2O5Powder and SrCO3Powder in molar ratio 1:1.64 sinter in zirconia base
Cubic structure Sr can be generated0.82NbO3Stable 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 is incubated 2h after rising to 1150 DEG C, then is incubated 2h after rising to 1300 DEG C through 150min, then through 50min
1.5h is incubated after rising to 1450 DEG C, then 900 DEG C, last natural cooling was down to by 150min minutes
To room temperature, sinter is formed, be designated as P2.
X-ray diffraction facies analysis result：As shown in Fig. 2 figure 2 illustrates prepared by proof 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 Nb2O5Powder with
SrCO3Powder in molar ratio 1:1.64 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
Nb2O5Powder and SrCO3Powder in molar ratio 1:1.64 mixing can obtain cubic structure Sr0.82NbO3
Stable phase.Inventor has found under accidental chance in the present invention, by Nb2O5Powder and SrCO3Powder
Body in molar ratio 1:1.64 are blended in sintering in zirconia base can produce cubic structure Sr0.82NbO3Surely
Determine phase, and be based on this discovery, the present inventor provides zirconium base composite ceramics of the present invention
Material and preparation method thereof.
3rd, embodiment 1 to 5 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；La0.8Sr0.2MnO3Powder, consumption always rubs for zirconium oxide
The 1.5mol% of your amount；SrCO3Powder, consumption is the 1.5mol% of zirconium oxide integral molar quantity；Nb2O5
Powder, 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 the 0.5wt% of zirconium oxide weight.
Preparation method：
S1, first by Zirconium powder, La0.8Sr0.2MnO3Powder, SrCO3Powder and Nb2O5Powder exists
Alcohol ball milling is added to form premixed material in 8 hours in ball grinder；Binding agent polyethylene glycol is added in premixed material
4000 and PVA ball milling half an hour, form spraying slurry；
S2, by spraying slurry feeding spray tower EAT be 250 DEG C, leaving air temp be 110 DEG C,
Centrifugal rotational speed be 15rpm under the conditions of carry out spray drying formed for dry-pressing spherical powder；Will be for doing
The spherical powder of pressure is added in dry press (press that 180 tons of tonnage uses the oil pressure pressure of 8MPa),
Dry-pressing 30s forms prefabricated component；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 1300 DEG C through 150min, then
1.5h is incubated after rising to 1370 DEG C through 50min, then 900 DEG C was down to by 150min minutes, finally
Room temperature is naturally cooled to, zirconium base composite ceramic material is formed；
According to raw material feed intake metering than presumption, with the content of zirconium oxide as 100mol% on the basis of, institute's shape
Into zirconium base composite ceramic material contain the cubic structure Sr of about 1.83mol%0.82NbO3Stable phase and about
The La of 1.5mol%0.8Sr0.2MnO3Phase.
S3, by the zirconium base composite ceramic material sanding and polishing and it is cut by laser and is made length and generous is
The model of 135mm × 65mm × 0.7mm, 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：La0.8Sr0.2MnO3The consumption of powder is oxygen
Change the 4.5mol%, SrCO of zirconium integral molar quantity3Powder consumption is the 0.82mol% of zirconium oxide integral molar quantity；
Nb2O5The mole dosage and SrCO of powder3The ratio of powder mole dosage is 1:1.64；
Preparation method：With embodiment 1.
According to raw material feed intake metering than presumption, with the content of zirconium oxide as 100mol% on the basis of, institute's shape
Into zirconium base composite ceramic material in the cubic structure Sr containing 1mol%0.82NbO3Stable phase and
The La of 4.5mol%0.8Sr0.2MnO3Phase.
By the zirconium base composite ceramic material sanding and polishing and be cut by laser be made length it is generous for 135mm ×
The model of 65mm × 0.7mm, 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：La0.8Sr0.2MnO3The consumption of powder is oxygen
Change the 1mol%, SrCO of zirconium integral molar quantity3The consumption of powder is the 5mol% of zirconium oxide integral molar quantity；
Nb2O5The mole dosage and SrCO of powder3The ratio of powder mole dosage is 1:1.64；
Preparation method：With embodiment 1.
According to raw material feed intake metering than presumption, with the content of zirconium oxide as 100mol% on the basis of, institute's shape
Into zirconium base composite ceramic material in the cubic structure Sr containing 6.1mol%0.82NbO3Stable phase and
The La of 1mol%0.8Sr0.2MnO3Phase.
By the zirconium base composite ceramic material sanding and polishing and be cut by laser be made length it is generous for 135mm ×
The model of 65mm × 0.7mm, 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：Zirconium oxide, consumption is 200g；
La0.8Sr0.2MnO3Powder, consumption is the 5mol% of zirconium oxide integral molar quantity；SrCO3Powder, consumption is
The 6.56mol% of zirconium oxide integral molar quantity；Nb2O5Powder, its mole dosage and SrCO3Powder mole with
The ratio of amount is 1:1.64.
Preparation method：With embodiment 1.
According to raw material feed intake metering than presumption, with the content of zirconium oxide as 100mol% on the basis of, institute's shape
Into zirconium base composite ceramic material in the cubic structure Sr containing 8mol%0.82NbO3Stable phase and
The La of 5mol%0.8Sr0.2MnO3Phase.
By the zirconium base composite ceramic material sanding and polishing and be cut by laser be made length it is generous for 135mm ×
The model of 65mm × 0.7mm, is designated as S4.
Embodiment 5
For illustrating zirconium base composite ceramic material of the present invention and preparation method thereof
Raw material：Zirconium oxide, consumption is 200g；La0.8Sr0.2MnO3Powder, consumption always rubs for zirconium oxide
The 0.8mol% of your amount；SrCO3Powder, consumption is the 0.2mol% of zirconium oxide integral molar quantity；Nb2O5
Powder, 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 the 0.5wt% of zirconium oxide weight；
Preparation method：With embodiment 1.
According to raw material feed intake metering than presumption, with the content of zirconium oxide as 100mol% on the basis of, institute's shape
Into zirconium base composite ceramic material in the cubic structure Sr containing 0.24mol%0.82NbO3Stable phase and
The La of 0.8mol%0.8Sr0.2MnO3Phase.
By the zirconium base composite ceramic material sanding and polishing and be cut by laser be made length it is generous for 135mm ×
The model of 65mm × 0.7mm, is designated as S5.
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 is comprised 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 feeding spray tower EAT be 250 DEG C, leaving air temp be 110 DEG C,
Centrifugal rotational speed be 15rpm under the conditions of carry out spray drying formed for dry-pressing spherical powder；Will be for doing
The spherical powder of pressure is added in dry press (press that 180 tons of tonnage uses the oil pressure pressure of 8MPa),
Dry-pressing 30s forms prefabricated component；The prefabricated component is warming up into 1480 DEG C to sinter 2 hours, room temperature is cooled to,
Form zirconia-based ceramic material.
S3, by zirconia-based ceramic material sanding and polishing and be cut by laser be made length it is generous be 135mm × 65mm
The model of × 0.7mm, 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；La0.8Sr0.2MnO3Powder, consumption is zirconium oxide
The 1.5mol% of integral molar quantity；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：With reference to comparative example 1, difference is：
S1, first by Zirconium powder and La0.8Sr0.2MnO3Powder is in ball grinder plus alcohol ball milling 8 is small
When form premixed material；Binding agent Macrogol 4000 and PVA ball milling half an hour are added in premixed material,
Form spraying slurry；
S3, by zirconia-based ceramic material sanding and polishing and be cut by laser be made length it is generous be 135mm × 65mm
The model of × 0.7mm, 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
0.5wt%；
(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；Add binding agent Macrogol 4000 and PVA ball millings half small in premixed material
When, form spraying slurry；
S3, by zirconia-based ceramic material sanding and polishing and be cut by laser be made length it is generous be 135mm × 65mm
The model of × 0.7mm, 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 the ultra-fine YAS sintering aids of 0.5vol% 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 2 hours, furnace cooling.
S3, by sintered body sanding and polishing and be cut by laser be made length it is generous for 135mm × 65mm ×
The model of 0.7mm, 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 always rubs for zirconium oxide
The 1.83mol% of your amount；Macrogol 4000, consumption is the 0.5wt% of zirconium oxide weight；PVA, uses
It is the 0.5wt% of zirconium oxide weight to measure；Wherein, Sr2Nb2O7Powder is by by SrCO3Powder and Nb2O5
Powder in molar ratio 2:1 ball milling mixing, dries, the heat preservation sintering 1.5h at 1200 DEG C, then ball milling powder
It is broken to D50For 0.5 μm of powder is obtained；
(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, by zirconia-based ceramic material sanding and polishing and be cut by laser be made length it is generous be 135mm × 65mm
The model of × 0.7mm, is designated as D5.
4th, test：
By the length prepared by embodiment 1 to 5 and comparative example 1 to 5 it is generous for 135mm × 65mm ×
The model of 0.7mm carries out performance test, to illustrate zirconium base composite ceramic material of the present invention and preparation method thereof
Beneficial effect.
(1), test event and method
(1) colourity test：The color difference meter test sample of electronics-China-color1101 models of being revived using promise
L, a, b value simultaneously with carbon black black standard sample contrasted.
(2) toughness test：It is unilateral cutting using GB/T23806 high technology ceramics fracture toughness test methods
Mouth beam method is measured.
(3) drop resistant test：Prepared length is generous in Example 1 to 5 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 carries out big face perpendicular contact, and 10, sample is taken per sample product, takes drop resistant number of times average value.
(4) polishing effect：By made in naked-eye observation embodiment 1 to 5 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
From data in table 1, prepared by the preparation method according to zirconium base composite ceramic material of the present invention
The toughness of model S1-S5 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 12 to 15 times is tested.
And, add 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 S4-S5 prepared by embodiment of the present invention 4-5 connect
Nearly model D5, and the toughness and drop resistant performance of the model S1-S3 prepared by preferred embodiment 1 to 3
Far superior to model D5.
Additionally, under specific material rate or structure phase content, the model S1-S5 prepared by the present invention
L values in 18.5-20 scopes, a values are in the range of 1.5-3, and b values are in the range of 1-2, it is seen that made
Standby ceramic material is presented black gray expandable, and pure color, can be welcome by adult population very much.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, but, the present invention is not
It is limited to the detail in above-mentioned implementation method, in range of the technology design of the invention, can be to this
The technical scheme of invention carries out various simple variants, and these simple variants belong to protection model of the invention
Enclose.
It is further to note that each particular technique described in above-mentioned specific 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 is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as
, without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention for it.
Claims (14)
1. a kind of zirconium base composite ceramic material, it is characterised in that the ceramic material contains oxidation zirconium base
Body, and it is dispersed in the cubic structure Sr in the zirconia base0.82NbO3Stable phase and
La0.8Sr0.2MnO3Phase.
2. ceramic material according to claim 1, wherein, the content with zirconium oxide is
On the basis of 100mol%, the cubic structure containing 0.2-8mol% in the zirconium base composite ceramic material
Sr0.82NbO3The La of stable phase and 0.8-5mol%0.8Sr0.2MnO3Phase.
3. ceramic material according to claim 2, wherein, the content with zirconium oxide is
On the basis of 100mol%, the cubic structure containing 1-6.1mol% in the zirconium base composite ceramic material
Sr0.82NbO3The La of stable phase and 1-4.5mol%0.8Sr0.2MnO3Phase.
4. ceramic material as claimed in any of claims 1 to 3, wherein, the oxidation
Zirconium base body is the zirconia base of 3mo1% yttriums stabilization.
5. ceramic material as claimed in any of claims 1 to 3, wherein, prepare described
During ceramic material, SrCO is added3Powder and Nb2O5Powder is with by being sintered in the ceramic material
Cubic structure Sr is formed in material0.82NbO3Stable phase.
6. ceramic material as claimed in any of claims 1 to 3, wherein, the ceramics
The L values of material are 18.5-20, and a values are 1.5-3, and b values are 1-2.
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, La0.8Sr0.2MnO3Powder, SrCO3Powder and Nb2O5Powder and viscous
Knot agent mixing, forms mixed slurry, wherein the SrCO3Powder and Nb2O5The mol ratio of powder is
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,
La0.8Sr0.2MnO3Powder and SrCO3The mol ratio of powder is 100:(0.8-5):(0.164-6.56),
Preferably 100:(1-4.5):(0.8-5).
9. preparation method according to claim 7, wherein, the zirconia powder added in the S1
Body is the tetragonal phase zirconium oxide powder of 3mo1% yttriums stabilization.
10. preparation method according to claim 7, wherein, drying steps are used in the S2
The method of spray drying, the condition of the spray drying includes：EAT is 220-260 DEG C, air-out
Temperature is 100-125 DEG C, and centrifugal rotational speed is 10-20rpm.
11. preparation methods according to claim 7, wherein, forming step is used in the S2
Dry-pressing formed, the dry-pressing formed condition includes：It is the press of 150-200 to use tonnage, in dry-pressing
Pressure be 6-12MPa under the conditions of be molded 20-60s.
12. preparation methods 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 1350-1390 DEG C.
A kind of 13. zirconium base composite ceramic materials, it is characterised in that the zirconium base composite ceramic material by
The preparation method of the zirconium base composite ceramic material in claim 7 to 12 described in any one prepare and
Into.
A kind of 14. shells or ornament, it is characterised in that the shell or ornament are by claim 1
Zirconium base composite ceramic material into 6 and 13 described in any one is prepared from.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59105055A (en) * | 1982-12-07 | 1984-06-18 | Kyocera Corp | Zirconia coloring material |
| CN101439969A (en) * | 2008-12-22 | 2009-05-27 | 西北有色金属研究院 | Rare-earth oxide and manganese oxide co-stable zirconia ceramics and preparation thereof |
| CN101624285A (en) * | 2008-07-08 | 2010-01-13 | 比亚迪股份有限公司 | Composition for preparing zirconia ceramics and ceramics |
| CN102260078A (en) * | 2010-05-31 | 2011-11-30 | 比亚迪股份有限公司 | Zirconia ceramic and preparation method thereof |
| CN102482163A (en) * | 2009-06-30 | 2012-05-30 | 法商圣高拜欧洲实验及研究中心 | Colored sintered zirconia |
| CN103693956A (en) * | 2013-12-17 | 2014-04-02 | 北矿新材科技有限公司 | Preparation method of YSZ-LSM composite thermal barrier coating material |
-
2015
- 2015-11-30 CN CN201510860338.9A patent/CN106810241A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59105055A (en) * | 1982-12-07 | 1984-06-18 | Kyocera Corp | Zirconia coloring material |
| CN101624285A (en) * | 2008-07-08 | 2010-01-13 | 比亚迪股份有限公司 | Composition for preparing zirconia ceramics and ceramics |
| CN101439969A (en) * | 2008-12-22 | 2009-05-27 | 西北有色金属研究院 | Rare-earth oxide and manganese oxide co-stable zirconia ceramics and preparation thereof |
| CN102482163A (en) * | 2009-06-30 | 2012-05-30 | 法商圣高拜欧洲实验及研究中心 | Colored sintered zirconia |
| CN102260078A (en) * | 2010-05-31 | 2011-11-30 | 比亚迪股份有限公司 | Zirconia ceramic and preparation method thereof |
| CN103693956A (en) * | 2013-12-17 | 2014-04-02 | 北矿新材科技有限公司 | Preparation method of YSZ-LSM composite thermal barrier coating material |
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