CN106810245A - Zirconium base composite ceramic material（Pink colour）And preparation method thereof with shell or ornament - Google Patents
Zirconium base composite ceramic material（Pink colour）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 (pink colour) and preparation method thereof and shell or ornament.The zirconium base composite ceramic material contains zirconia base, and is dispersed in the cubic structure Sr in the zirconia base0.82NbO3Stable phase and ErAlO3Phase.This zirconium base composite ceramic material is by the dispersed cubic structure Sr in zirconia base0.82NbO3Stable phase and ErAlO3Phase, 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 ceramic material and preparation method thereof and shell or ornament.
Background technology
With the high development of science and technology, consumer is to the performance of ceramic material and the requirement more and more higher of quality.Zirconia ceramics is due to extensive application the characteristics of it has than other types ceramics good corrosion resistance, hardness high and intensity high.However, when large area appearance member is made, although the toughness of existing zirconia ceramics (reaches 5-6MPam1/2) higher than other kinds of ceramics, but still have the shortcomings that intolerant to falling.And, the color of existing zirconia ceramics is usually white, too single, and simultaneously unsightly.Therefore, if wanting to make appearance member using zirconia ceramics, in addition it is also necessary to which colourity and toughness (drop resistant) to zirconia ceramics are further improved.
At present, the Zirconium powder of yttrium stabilization is more ripe on the market, and the improvement for zirconia ceramics is generally built upon on the basis of the Zirconium powder of yttrium stabilization.In order to improve the toughness of zirconia ceramics, conventional method for toughening includes：Promote zirconia ceramics to undergo phase transition, or the second structure is added in zirconia ceramics with toughness reinforcing etc..Although existing these conventional method for toughening can to a certain extent play toughening effect, but these methods are typically only capable to be directed to whiteware.So far also without the method that can simultaneously reach toughness reinforcing drop resistant and dyeing.
For example, disclosing a kind of Mg stabilizations TZP ceramics in Chinese patent No.02111146.4.This ceramics can play the effect of a part of toughness reinforcing by the Mg that adulterates, but this DeGrain.And the ceramics sample low strength prepared according to this method, only 590MPa or so, such intensity cannot prepare the thin slice (easily broken) of large area.In addition, this method is also only directed to whiteware, its range of application is narrower.
As shown in the above, the drop resistant performance of current zirconia ceramics also needs to further improvement, to propose a kind of ceramics with excellent drop resistant performance；Also need to further improve the colourity of zirconia ceramics simultaneously, to obtain a kind of zirconia ceramics for having excellent drop resistant performance and colourity concurrently, to be adapted to 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 ornament, 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 material, the zirconium base composite ceramic material contains zirconia base, and is dispersed in the cubic structure Sr in the zirconia base0.82NbO3Stable phase and ErAlO3Phase.
According to the second aspect of the invention, there is provided a kind of preparation method of zirconium base composite ceramic material, the preparation method is comprised the following steps：S1, by Zirconium powder, ErAlO3Powder, SrCO3Powder and Nb2O5Powder and binding agent mix, and mixed slurry are formed, 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 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 composite ceramic material is 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 ornament 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 base0.82NbO3Stable phase and ErAlO3Phase, 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.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, is used to explain the present invention together with following specific embodiment, but be not construed as limiting the invention.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 in conjunction with accompanying drawing.It should be appreciated that specific embodiment described herein is merely to illustrate and explain the present invention, it is not intended to limit the invention.
The drop resistant performance of the current zirconia ceramics as pointed by background section also needs to further improvement, therefore, the present inventor is directed to zirconia ceramics has carried out substantial amounts of research, and proposes a kind of zirconium base composite ceramic material.The zirconium base composite ceramic material contains zirconia base, and the cubic structure Sr for being dispersed in (on internal and surface) in the zirconia base0.82NbO3Stable phase and ErAlO3Phase.
The above-mentioned zirconium base composite ceramic material of the present invention is by the dispersed cubic structure Sr (on internal and surface) in zirconia base0.82NbO3Stable phase and ErAlO3Phase, 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.
In the present invention for cubic structure Sr0.82NbO3Stable phase and ErAlO3The content of phase does not have special requirement, if in zirconia base simultaneously containing both structures mutually just can be to a certain extent to zirconium oxide based composite ceramic material toughness play adjustment effect.Those skilled in the art are referred to the consumption of auxiliary material commonly used in the art and reasonably adjust cubic structure Sr in zirconia base0.82NbO3Stable phase and ErAlO3The content of phase.
In the preferred embodiment of the present invention, with the content of zirconium oxide as 100mol% on the basis of, the cubic structure Sr containing 0.2-8mol% in above-mentioned zirconium base composite ceramic material0.82NbO3The ErAlO of stable phase and 0.8-5mol%3Phase.It is further preferred that with the content of zirconium oxide as 100mol% on the basis of, the cubic structure Sr containing 1-6.1mol% in the zirconium base composite ceramic material0.82NbO3The ErAlO of stable phase and 1-4.5mol%3Phase.By by the cubic structure Sr in ceramic material0.82NbO3Stable phase and ErAlO3The content of phase is limited within the above range, is conducive to obtaining toughness and drop resistant performance is relatively more excellent, and the zirconium base composite ceramic material of pink colour is presented.
During above-mentioned zirconium base composite ceramic material of the invention is prepared, the raw material for being used includes Zirconium powder, ErAlO3Powder, SrCO3(strontium carbonate) powder and Nb2O5(niobium pentaoxide) powder.Wherein preferably, the Zirconium powder for being added is the tetragonal phase zirconium oxide powder of 3mo1% yttriums stabilization, and zirconia base is the zirconia base of 3mo1% yttriums stabilization in the zirconium base composite ceramic material for now being formed；The ErAlO for being added3Powder can form ErAlO in zirconia base3Phase, ErAlO3The formation of phase enables to zirconium base composite ceramic material that pink colour, the SrCO for being added is presented3Powder 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, in the present invention cubic structure Sr0.82NbO3The 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, ErAlO for being used in the present invention3Phase, SrCO3Powder and Nb2O5The factors such as the particle diameter of powder do not have particular/special requirement, are referred to the conventional selection for raw material when this area prepares ceramic material.The particle diameter D of the Zirconium powder for for example being added50It can be 0.1-1 μm；Preferably 0.5-0.8 μm；The ErAlO for being added3The particle diameter D of powder50It is 0.1-2 μm, preferably 0.2-0.7 μm.The SrCO for being added3Powder and Nb2O5The particle diameter of powder is 0.2-5 μm.Wherein particle diameter D50It is volume average particle size, it is dispersed in water by by powder to be measured, and 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 ErAlO3Phase, allow for zirconium base composite ceramic material and pink colour is presented to a certain extent, in order to further optimize the colourity of above-mentioned zirconium base composite ceramic material, make its pure shinny, the L values of preferred zirconium base composite ceramic material are 73-80 in the present invention, a values are 8-15, and b values are (- 6)-(- 0.2).Wherein L, a and b value refer 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, ErAlO3Powder and with cubic structure Sr0.82NbO3After the material powder mixing of stable phase, it is obtained through drying, shaping, sintering processes, its preparation method is referred to the common process method of this area, as long as containing ErAlO in the ceramic material for being formed3Phase and cubic structure Sr0.82NbO3Stable phase.
However, due to existing with cubic structure Sr0.82NbO3The price of the material powder of stable phase is relatively expensive, makes it and is unfavorable for the extensive use of above-mentioned zirconium base composite ceramic material.Therefore, the present inventor employs the SrCO of less expensive3Powder and Nb2O5Powder, will both in molar ratio 1.64:1 sinters 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, ErAlO3Powder, SrCO3Powder and Nb2O5Powder and binding agent mix, and mixed slurry are formed, 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 composite ceramic material.
This method provided by the present invention, by adding SrCO3Powder and Nb2O5Powder (both have the effect 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, the dispersed cubic structure Sr (on internal and surface) in the zirconia base of zirconium base composite ceramic material0.82NbO3Stable phase and ErAlO3Phase, 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.
In above-mentioned preparation method of the invention, the ErAlO for being used3Powder can be commercially available prod, it is also possible to be prepared by a conventional method.In a kind of preferred embodiment of the invention, above-mentioned ErAlO3Raw powder's production technology includes：By the compound (oxide, carbonate or nitrate containing Er) containing Er, (in terms of Er, mol ratio of the compound containing Al in terms of Al is about 1 to the compound containing Er to the compound (oxide, carbonate or nitrate containing Al) containing Al in proportion：1) then ground and mixed (preferably ball milling mixing), 1~2h of heat preservation sintering at 1100 DEG C~1300 DEG C grinds (preferably ball milling dispersion) to micron-sized powder, obtains the ErAlO3Powder.
In the S1 of above-mentioned preparation method of the invention, do not have particular/special requirement for the mixed method of various raw materials, with reference to this area routine method for mixing.In the present invention preferably, the step of S1 forms mixed slurry includes：S11, by Zirconium powder, ErAlO3Powder, SrCO3Powder and Nb2O5Powder mixed grinding (preferably ball milling), forms premixed material；S12, by the premixed material and binding agent mixed grinding (preferably ball milling), form the mixed slurry.Batch mixing is carried out by such mode, each stock dispersion is more uniformly distributed in forming spraying slurry, and then be conducive to obtaining drop resistant performance more preferably, and 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, ErAlO3Powder and SrCO3Powder and Nb2O5The usage ratio of powder does not have particular/special requirement, as long as containing cubic structure Sr in prepared zirconium base composite ceramic material0.82NbO3Stable phase and ErAlO3Mutually just can to a certain extent improve the toughness and drop resistant performance of zirconium base composite ceramics.However, toughness and drop resistant performance in order to optimize prepared zirconium base composite ceramic material, and cause that zirconium base composite ceramic material is presented pink colour, in the present invention in the S1 of above-mentioned preparation method, preferably Zirconium powder, ErAlO3Powder 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 powder of 3mo1% yttriums stabilization.
In the S1 of above-mentioned preparation method of the invention, for the no particular/special requirement of the type and consumption of binding agent, it is referred to selected raw material and consumption in the conventional method of this area, the binding agent that can for example select including but not limited to PVA or Macrogol 4000, the consumption of binding agent is the 0.2-2wt% of Zirconium powder gross weight.
In the S2 of above-mentioned preparation method of the invention, do not have particular/special requirement for dry process conditions, with reference to this area common process method.Preferably using spray drying process, and the condition of the spray drying in the present invention includes：EAT is 220-260 DEG C, and leaving air temp is 100-125 DEG C, and 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 be using traditional molding mode such as dry-pressing formed, isostatic pressing, injection moulding, hot die-casting molding.Preferably use dry-pressing formed in the present invention, preferably described dry-pressing formed condition includes：It is the press of 150-200 to use tonnage, and 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, and sintering is sintered using common Muffle furnace air normal pressure.Preferably, the step of sintering includes, by the prefabricated component of obtained by molding at 1350-1500 DEG C, preferably 1390-1480 DEG C, 1-2h is sintered at more preferably 1430-1470 DEG C.
More preferably, sintering step includes in the S3,1.5-2.5h is incubated after the prefabricated component of the obtained by molding is risen into 550-650 DEG C through 350-450min from room temperature, 1.5-2.5h is incubated after rising to 1100-1200 DEG C through 250-350min again, 1.5-2.5h is incubated after rising to 1250-1350 DEG C through 120-180min again, heat preservation sintering 1-2h after rising to 1430-1470 DEG C through 30-60min again, was then down to 900 DEG C by 120-180min minutes, finally naturally cooled to room temperature.
In above-mentioned preparation method of the invention, for not having particular/special requirement in process of lapping in S1, as long as being sufficiently mixed for raw material can be realized, preferably, the mode of the grinding is ball milling, in mechanical milling process, use the ball grinder with zirconia ceramics liner, and zirconium oxide abrasive ball.
In above-mentioned preparation method of the invention, ball milling step is generally needed to add ball milling solution, and the ball milling solution that can be used in the present invention is included but is not limited to water and/or C1-C5Alcohol, it is preferable that the ball milling solution is water and/or C1-C5Monohydric alcohol.C1-C5Monohydric alcohol can be methyl alcohol, ethanol, normal propyl alcohol, 2- propyl alcohol, n-butanol, 2- butanol, 2- methyl isophthalic acids-propyl alcohol, 2- methyl-2-propanols, n-amyl alcohol, 2-methyl-1-butene alcohol, 3- methyl-1-butanols, 2- methyl -2- butanol, 3- methyl -2- butanol and 2,2- dimethyl -1- propyl alcohol in one or more.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 ceramic material is prepared from by the preparation method of above-mentioned zirconium base composite ceramic material.The zirconium base composite ceramic material, containing zirconia base, and is dispersed in the cubic structure Sr in the zirconia base0.82NbO3Stable phase and ErAlO3Phase.
Preferably, with the content of zirconium oxide as 100mol% on the basis of, the cubic structure Sr containing 0.2-8mol% in the zirconium base composite ceramic material0.82NbO3The ErAlO of stable phase and 0.8-5mol%3Phase.Preferably, with the content of zirconium oxide as 100mol% on the basis of, the cubic structure Sr containing 1-6.1mol% in the zirconium base composite ceramic material0.82NbO3The ErAlO of stable phase and 1-4.5mol%3Phase.Preferably, the L values of the zirconium base composite ceramic material are 73-80, and a values are 8-15, and b values are (- 6)-(- 0.2).
In the preparation method of above-mentioned zirconium base composite ceramic material of the invention, SrCO in presumption raw material3(strontium carbonate) powder and Nb2O5(niobium pentaoxide) powder reacts generation cubic structure Sr completely0.82NbO3Stable phase, so, cubic structure Sr in prepared zirconium base composite ceramic material0.82NbO3The content of stable phase is according to SrCO3(strontium carbonate) powder and Nb2O5The rate of charge metering conversion gained of (niobium pentaoxide) powder.
In addition, additionally providing a kind of shell or ornament in the present invention, the shell or ornament are prepared from by above-mentioned zirconium base composite ceramic material of the invention.Above-mentioned shell or ornament are prepared from by using above-mentioned zirconium base composite ceramic material, not only with preferable toughness and drop resistant performance；And, by the structure phase content in rational configuration zirconium base composite ceramic material, can also obtain that color (pink colour) is pure, surface more bright shell or ornament.
Below with reference to specific embodiment and comparative example so that zirconium base composite ceramic material of the present invention and preparation method thereof to be described in further detail, and illustrate the beneficial effect of zirconium base composite ceramic material of the present invention and preparation method thereof.
First, raw material explanation
(1) Zirconium powder：Commercially available from east Gao Ye companies OZ-3Y-7 models (particle diameter D50It 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 is 99%；
(3)Nb2O5Powder：Commercially available from Yangzhou three and company (granularity D50It is 1 μm), purity is 99.5%；
(4)ErAlO3Powder (particle diameter D50It it is 0.5 μm)：By erbium oxide and aluminum oxide according to 1：1 mol ratio ball milling mixing, drying, the heat preservation sintering 1.5h at 1200 DEG C, then ball mill grinding obtains the ErAlO to micron-sized powder3Powder；
(5) binding agent：Commercially available from the Macrogol 4000 of Kuraray company, and commercially available from the PVA217 of Kuraray 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, and Guan Liuwei 20mA, scan pattern is theta/2theta (θ/2 θ)；Scan mode is continue；Sweep limits：10-80 °, step angle is 0.04 °.
Prove example 1
For proving Nb2O5Powder and SrCO3Powder in molar ratio 1:1.64 in atmosphere sintering cannot 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 mixture for 8 hours, stand-by after drying；
S2, the dry mixture is risen to 600 DEG C through 400min from room temperature after be incubated 2h, 2h is incubated after rising to 1150 DEG C through 300min again, 2h is incubated after rising to 1300 DEG C through 150min again, 1.5h is incubated after rising to 1450 DEG C through 50min again, then 900 DEG C were down to by 150min minutes, room temperature is finally naturally cooled to, sinter is formed, P1 is designated as.
X-ray diffraction facies analysis result：The XRD diffracting spectrums of the P1 prepared by example 1 are proved as shown in figure 1, being shown in Fig. 1, and SrNb6O16(00-045-0228) and Sr2Nb2O7The standard card of (01-070-0114).SrNb is mainly contained in sinter P1 as prepared by can be seen that above-mentioned proof example 1 in Fig. 16O16Phase and Sr2Nb2O7Phase, wherein and not containing cubic structure Sr0.82NbO3Stable phase, it can be seen that, by Nb2O5Powder and SrCO3Powder in molar ratio 1:1.64 in atmosphere sintering cannot produce cubic structure Sr0.82NbO3Stable phase.
Prove example 2
For proving Nb2O5Powder and SrCO3Powder in molar ratio 1:1.64 in zirconia base sintering can generate cubic structure Sr0.82NbO3Stable phase.
Raw material：Zirconium oxide, consumption is 200g；Nb2O5Powder, consumption is the 25mol%, SrCO of zirconium oxide integral molar quantity3Powder, itself and Nb2O5The mol ratio of powder is 1.64:1.
Preparation method：
S1, first by Zirconium powder, SrCO3Powder and Nb2O5Powder is in ball grinder plus alcohol ball milling forms mixture for 8 hours, stand-by after drying；
S2, the dry mixture is risen to 600 DEG C through 400min from room temperature after be incubated 2h, 2h is incubated after rising to 1150 DEG C through 300min again, 2h is incubated after rising to 1300 DEG C through 150min again, 1.5h is incubated after rising to 1450 DEG C through 50min again, then 900 DEG C were down to by 150min minutes, room temperature is finally naturally cooled to, sinter is formed, P2 is designated as.
X-ray diffraction facies analysis result：As shown in Fig. 2 figure 2 illustrates the XRD diffracting spectrums for proving the sinter P2 prepared by example 2, and tetragonal phase zirconium oxide (00-017-0923), monocline phase zircite (01-083-0939) and Sr0.82NbO3The standard card of (00-009-0079), tetragonal phase zirconium oxide, monocline phase zircite and cubic structure Sr are contained in the sinter P2 as prepared by contrast in Fig. 2 can be seen that above-mentioned proof example 20.82NbO3Stable phase, it can be seen that, by Nb2O5Powder and 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, be not under any conditions by Nb2O5Powder and SrCO3Powder in molar ratio 1:1.64 mixing can obtain cubic structure Sr0.82NbO3Stable phase.Inventor has found under accidental chance in the present invention, by Nb2O5Powder and SrCO3Powder in molar ratio 1:1.64 are blended in sintering in zirconia base can produce cubic structure Sr0.82NbO3Stable phase, and this discovery is based on, the present inventor provides zirconium base composite ceramic material of the present invention 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；ErAlO3Powder, consumption is the 1.5mol% of zirconium oxide integral molar quantity；SrCO3Powder, consumption is the 1.5mol% of zirconium oxide integral molar quantity；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 the 0.5wt% of zirconium oxide weight.
Preparation method：
S1, first by Zirconium powder, ErAlO3Powder, SrCO3Powder and Nb2O5Powder is in ball grinder plus alcohol ball milling forms premixed material in 8 hours；Binding agent Macrogol 4000 and PVA ball milling half an hour are added in premixed material, spraying slurry is formed；
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；The spherical powder for being used for dry-pressing 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, 2h is incubated after rising to 1150 DEG C through 300min again, 2h is incubated after rising to 1300 DEG C through 150min again, 1.5h is incubated after rising to 1450 DEG C through 50min again, then 900 DEG C were down to by 150min minutes, room temperature is finally 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, the cubic structure Sr containing 1.83mol% in above-mentioned formed zirconium base composite ceramic material0.82NbO3The ErAlO of stable phase and 1.5mol%3Phase.
S3, by the zirconium base composite ceramic material sanding and polishing and be cut by laser be made length it is generous be the model of 135mm × 65mm × 0.7mm, be 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：ErAlO3The consumption of powder is the 4.5mol%, SrCO of zirconium oxide 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, the cubic structure Sr containing 1mol% in the zirconium base composite ceramic material for being formed0.82NbO3The ErAlO of stable phase and 4.5mol%3Phase.
By the zirconium base composite ceramic material sanding and polishing and be cut by laser be made length it is generous be the model of 135mm × 65mm × 0.7mm, be 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：ErAlO3The consumption of powder is the 1mol%, SrCO of zirconium oxide 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, the cubic structure Sr containing 6.1mol% in the zirconium base composite ceramic material for being formed0.82NbO3The ErAlO of stable phase and 1mol%3Phase.
By the zirconium base composite ceramic material sanding and polishing and be cut by laser be made length it is generous be the model of 135mm × 65mm × 0.7mm, be 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；ErAlO3Powder, 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 SrCO3The 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, the cubic structure Sr containing 8mol% in the zirconium base composite ceramic material for being formed0.82NbO3The ErAlO of stable phase and 5mol%3Phase.
By the zirconium base composite ceramic material sanding and polishing and be cut by laser be made length it is generous be the model of 135mm × 65mm × 0.7mm, be 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；ErAlO3Powder consumption is the 0.8mol% of zirconium oxide integral molar quantity；SrCO3Powder, consumption is the 0.2mol% of zirconium oxide integral molar quantity；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 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, the cubic structure Sr containing 0.24mol% in the zirconium base composite ceramic material for being formed0.82NbO3The ErAlO of stable phase and 0.8mol%3Phase.
By the zirconium base composite ceramic material sanding and polishing and be cut by laser be made length it is generous be the model of 135mm × 65mm × 0.7mm, be 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 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；The spherical powder for being used for dry-pressing 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, zirconia-based ceramic material is formed.
S3, by zirconia-based ceramic material sanding and polishing and be cut by laser be made length it is generous be the model of 135mm × 65mm × 0.7mm, be 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；ErAlO3Powder, consumption is the 1.5mol% of zirconium oxide 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 ErAlO3Powder is in ball grinder plus alcohol ball milling forms premixed material in 8 hours；Binding agent Macrogol 4000 and PVA ball milling half an hour are added in premixed material, spraying slurry is formed；
S3, by zirconia-based ceramic material sanding and polishing and be cut by laser be made length it is generous be the model of 135mm × 65mm × 0.7mm, be 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 the 8mol% of zirconium oxide integral molar quantity；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 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, SrCO3Powder and Nb2O5Powder is in ball grinder plus alcohol ball milling forms premixed material in 8 hours；Binding agent Macrogol 4000 and PVA ball milling half an hour are added in premixed material, spraying slurry is formed；
S3, by zirconia-based ceramic material sanding and polishing and be cut by laser be made length it is generous be the model of 135mm × 65mm × 0.7mm, be designated as D3.
Comparative example 4
For comparative illustration zirconium base composite ceramic material of the present invention and preparation method thereof (referring to embodiment 1 in Chinese patent 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, it is dry-pressing formed under 60MPa after binding agent is granulated to add 3% concentration PVA, and isostatic pressed obtains biscuit under 200MPa.Then by biscuit be placed in Si-Mo rod stove with 2 DEG C/min of programming rate be raised to 1400 DEG C be incubated 2 hours, furnace cooling.
S3, by sintered body sanding and polishing and be cut by laser be made length it is generous be the model of 135mm × 65mm × 0.7mm, be 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 the 1.83mol% of zirconium oxide integral molar quantity；Macrogol 4000, consumption is the 0.5wt% of zirconium oxide weight；PVA, consumption is the 0.5wt% of zirconium oxide weight；Wherein, Sr2Nb2O7Powder is by by SrCO3Powder and Nb2O5Powder in molar ratio 2:1 ball milling mixing, drying, the heat preservation sintering 1.5h at 1200 DEG C, then ball mill grinding is 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 forms premixed material in 8 hours；Binding agent Macrogol 4000 and PVA ball milling half an hour are added in premixed material, spraying slurry is formed；
S3, by zirconia-based ceramic material sanding and polishing and be cut by laser be made length it is generous be the model of 135mm × 65mm × 0.7mm, be designated as D5.
4th, test：
The generous model for 135mm × 65mm × 0.7mm of length prepared by embodiment 1 to 5 and comparative example 1 to 5 is carried out into performance test, to illustrate the beneficial effect of zirconium base composite ceramic material of the present invention and preparation method thereof.
(1), test event and method
(1) colourity test：Contrasted using the L of the color difference meter test sample of promise Soviet Union electronics-China-color1101 models, a, b value and with the standard sample of carbon black nigrescence.
(2) toughness test：It is that Single edge notch beam is measured using GB/T23806 high technology ceramics fracture toughness test methods.
(3) drop resistant test：The generous model for 135mm × 65mm × 0.7mm of prepared length carries out big face perpendicular contact in the eminence of 1.3m with the whereabouts mode of freely falling body and ground in Example 1 to 5 and comparative example 1 to 5, and 10, sample is taken per sample product, takes drop resistant number of times average value.
(4) polishing effect：Defect whether there is by the generous specimen surface for 135mm × 65mm × 0.7mm of length prepared in naked-eye observation embodiment 1 to 5 and comparative example 1 to 5.
(2), test result：As shown in table 1.
Table 1
From data in table 1, the toughness of the model S1-S5 prepared by preparation method according to zirconium base composite ceramic material of the present invention be substantially better than comparative example 1 to comparative example 4 prepared by model D1-D4, and specified conditions can be born lower more than 5 times, or even the drop resistant of 12 to 15 times is tested.
And, add Sr with comparative example 52Nb2O7Model D5 prepared by powder (employing optimal raw material dosage) is compared, the toughness and drop resistant performance of the model S4-S5 prepared by embodiment of the present invention 4-5 are close to model D5, and the toughness of model S1-S3 prepared by preferred embodiment 1 to 3 and drop resistant performance are far superior to model D5.
In addition, under specific material rate or structure phase content, the L values of the model S1-S5 prepared by the present invention are in the range of 73-80, a values are in the range of 8-15, b values are in the range of (- 6)-(- 0.2), it can be seen that prepared ceramic material is presented pink colour, 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 limited to the detail in above-mentioned implementation method; in range of the technology design of the invention; various simple variants can be carried out to technical scheme, these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in the case of reconcilable, can be combined by any suitable means.In order to avoid unnecessary 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 it is without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.
Claims (14)
1. a kind of zirconium base composite ceramic material, it is characterised in that the zirconium base composite ceramic material contains
Zirconia base, and it is dispersed in the cubic structure Sr in the zirconia base0.82NbO3Stable phase and
ErAlO3Phase.
2. zirconium base composite ceramic material according to claim 1, wherein, with the content of zirconium oxide
On the basis of for 100mol%, the cubic structure containing 0.2-8mol% in the zirconium base composite ceramic material
Sr0.82NbO3The ErAlO of stable phase and 0.8-5mol%3Phase.
3. zirconium base composite ceramic material according to claim 2, wherein, with the content of zirconium oxide
On the basis of for 100mol%, the cubic structure containing 1-6.1mol% in the zirconium base composite ceramic material
Sr0.82NbO3The ErAlO of stable phase and 1-4.5mol%3Phase.
4. zirconium base composite ceramic material as claimed in any of claims 1 to 3, wherein,
The zirconia base is the zirconia base of 3mo1% yttriums stabilization.
5. zirconium base composite ceramic material as claimed in any of claims 1 to 3, wherein,
During preparing the zirconium base composite ceramic material, SrCO is added3Powder and Nb2O5Powder is sintering
Form cubic structure Sr0.82NbO3Stable phase.
6. ceramic material as claimed in any of claims 1 to 3, wherein, the ceramics
The L values of material are 73-80, and a values are 8-15, and b values are (- 6)-(- 0.2).
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, ErAlO3Powder, SrCO3Powder and Nb2O5Powder and binding agent are mixed
Close, mixed slurry is formed, 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,
ErAlO3Powder 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 1430-1470 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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| CN101857455A (en) * | 2010-06-25 | 2010-10-13 | 中南大学 | High strength and toughness 3Y-TZP composite 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 |
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| 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 |
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| CN104788095A (en) * | 2015-01-29 | 2015-07-22 | 包头市金格瑞新型陶瓷有限责任公司 | Dental use color zirconia powder preparation method |
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