CN100347130C - Ytterbium oxide and yttrium oxide co-stabilized zirconia ceramic material and its prepn process - Google Patents

Ytterbium oxide and yttrium oxide co-stabilized zirconia ceramic material and its prepn process Download PDF

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CN100347130C
CN100347130C CNB2006100243615A CN200610024361A CN100347130C CN 100347130 C CN100347130 C CN 100347130C CN B2006100243615 A CNB2006100243615 A CN B2006100243615A CN 200610024361 A CN200610024361 A CN 200610024361A CN 100347130 C CN100347130 C CN 100347130C
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oxide
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zirconia
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yttrium oxide
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CN1810717A (en
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阚艳梅
王佩玲
约瑟夫·务伦杰
奥默·范德比斯特
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Shanghai Institute of Ceramics of CAS
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Abstract

The present invention relates to ytterbium oxide and yttrium oxide co-stabilized zirconia ceramics and a preparing method thereof, which is characterized in that ytterbium oxide and yttrium oxide are simultaneously used as stabilizing agents, nanometer zirconium oxide powder which is jointly coated by the two kinds of stabilizing agents is prepared by a coating technology, the obtained powder is sintered in air without pressure, and tetragonal zirconia polycrystal (TZP) and fully stabilized cubic zirconia ceramic (FSZ) are respectively obtained under a condition of low stabilizing agent content. Ytterbium oxide (Yb2O3), yttrium oxide (Y2O3) and monoclinic zirconia powder whose purity (mass percentage) is not less than 99.9% are used as raw materials, wherein the average grain size of the monoclinic zirconia powder is less than 100 nanometers; in the final obtained TZP ceramics, the molar percentage of the ytterbium oxide (Yb2O3) is from 1.0 to 2.0%, and the molar percentage of the yttrium oxide (Y2O3) is from 1.0 to 2.0%; in the FSZ ceramics, the molar percentage of the ytterbium oxide (Yb2O3) is from 3.0 to 4.0%, and the molar percentage of the yttrium oxide (Y2O3) is from 1.0 to 2.0%.

Description

Ytterbium oxide and yttrium oxide co-stabilized zirconia ceramics material and preparation method
Technical field
That the present invention relates to is ytterbium oxide and yttrium oxide co-stabilized tetragonal zirconia polycrystal (TZP) and fully stabilized zirconia pottery (FSZ) and preparation method.More precisely provide a kind of with ytterbium oxide (Yb 2O 3), yittrium oxide (Y 2O 3) and the monoclinic zirconia powder be raw material, adopt technique for packing to prepare powder, under low stabiliser content, reach densified acquisition by pressureless sintering and have the TZP pottery of good mechanical property and have fully stabilized zirconia pottery (FSZ) of electric property and preparation method thereof, belong to zirconia-based ceramics product and preparation method field.
Background technology
Zirconium white is a kind of multiduty stupalith, can be divided into tetragonal zirconia polycrystal pottery (TZP), partial stabilization zirconium oxide ceramic (PSZ) and fully stabilized zirconia pottery (FSZ) according to constitutional features.Wherein tetragonal zirconia polycrystal pottery and partial stabilization zirconium oxide ceramic have excellent mechanical property, have obtained important application in fields such as machinery, biology, medical science; The fully stabilized zirconia pottery has good electric property, exists wide application prospect at energy field.
Studies show that the phase transformation of four directions → monocline can take place in cooling procedure zirconia, this phase transition process is accompanied by the Volume Changes of 3-5%, can cause porcelain body seriously to ftracture, and therefore, the pure zirconia pottery can not be used.In order at room temperature to obtain stable four directions or cubic zirconia, usually adopt the mode of adding some metal oxide to avoid the phase transformation of four directions → monocline.These metal oxides and zirconia generate solid solution, stablize Tetragonal and Emission in Cubic.The most frequently used stabilizing agent is CaO, MgO, CeO 2, Y 2O 3Deng, wherein with Y 2O 3For the research of stabilizing agent the most extensive.The tetragonal zirconia polycrystal of stabilized with yttrium oxide (Y-TZP) pottery particularly adds 3mol%Y 2O 3The 3Y-TZP pottery, have good mechanical property.Yet, when the 3Y-TZP pottery was exposed in humidity or the thermal and hydric environment for a long time, the phase transformation that the monocline phase is arrived in spontaneous four directions mutually can take place, cause material property sharply to descend thus, even catastrophic failure, i.e. low temperature aging phenomenon take place.Research is found, the easiest generation in the 3Y-TZP pottery of low temperature aging phenomenon, Y in material 2O 3Content when increasing or reducing, this aging phenomenon all can be inhibited.But, reduce Y 2O 3Content usually can cause undergoing phase transition in the cooling procedure and can not obtain the TZP pottery; Increase Y 2O 3Content can affect its mechanical property to a certain extent.This shows, only use Y 2O 3As the TZP ceramic material of stabilizing agent, its mechanical performance has certain limitation.By in matrix, introducing the second stabilizing agent, can adjust the performance of Y-TZP pottery, can obtain to compare single Y in some situation 2O 3Stablize and have the more ZrO of superior function 2Material [1, M.M.R.Boutz, A.J.A.Winnubst, B.Van Langerak, et al, J.Mater.Sci.30 (1995) 1854.].
For the fully stabilized zirconia pottery, when adopting single oxide as stabilizing agent, usually need to add a large amount of stabilizing agents, and need higher sintering temperature and long heat treatment time could obtain Emission in Cubic.Even like this, the distribution of stabilizing agent in each crystal grain is still inhomogeneous, is segregated on the crystal boundary in a large number.With Y 2O 3Stable FSZ pottery is example, and the content of stabilizing agent is usually above 8.0mol%.There are some researches show, introduce the second stabilizing agent and can greatly promote its solid solution in zirconia crystal grain, make its distribution in each crystal grain be tending towards even.Therefore, by to the selection of another stabilizing agent and preparation technology's control, not only there is the possibility of optimizing the TZP ceramic material property, and exists the possibility that under low stabiliser content, obtains the fully stabilized zirconia pottery.
In addition because Yb 3+Ionic radius in all rare earth elements near the size of Zr-O octahedral voids, infer that thus Yb is to ZrO 2Has stronger stabilization.By in matrix, introducing Yb 2O 3, utilize the synergy of compound stabilizer, can reduce the consumption of stabilizing agent, under low stabiliser content, obtain tetragonal zirconia polycrystal and fully stabilized zirconia pottery, thereby optimize the performance of material.In addition, except that stabilizer type and components selection, the preparation technology of powder and performance thereof also have great influence to the final performance of sintered ceramic.Therefore, the inventor attempts selecting Yb 2O 3And Y 2O 3In the time of as stabilizing agent, utilize technique for packing to prepare Yb 2O 3And Y 2O 3The ZrO of common parcel 2Nano-powder obtains fine and close ZrO by pressureless sintering 2Ceramic material.
Summary of the invention
The object of the present invention is to provide by Yb 2O 3And Y 2O 3Be total to stable zirconia ceramics, that is comply with as co-stabilizer Yb 2O 3And Y 2O 3Amount and prepare TZP or FSZ zirconia ceramics.Obtain that a kind of stabiliser content is low, the ytterbium oxide of good mechanical properties and yttrium oxide co-stabilized tetragonal zirconia ceramics material (TZP) and fully stabilized zirconia ceramic material (FSZ).
The objective of the invention is to implement by following manner: be not less than 99.9% ytterbium oxide (Yb with purity (mass percent) 2O 3), yittrium oxide (Y 2O 3) and average grain size be initiation material less than the monoclinic zirconia powder of 100 nanometers, adopt the nm-class powder of zirconium oxide of the synthetic ytterbium oxide of technique for packing and the common parcel of yittrium oxide, under low stabiliser content, obtain fine and close ytterbium oxide and yttrium oxide co-stabilized tetragonal zirconia polycrystal (TZP) and fully stabilized zirconia pottery (FSZ) material by pressureless sintering.
Concrete processing step is:
(1) for tetragonal zirconia ceramics material (TEP), as co-stabilizer Yb 2O 3And Y 2O 3Mole percent be divided into 1.0-2.0% and 1.0-2.0%; For fully stabilized zirconia ceramic material (FSZ), be 3.0-4.0% according to the ytterbium oxide molar percentage respectively as ytterbium oxide and the yittrium oxide of stabilizing agent, the yittrium oxide molar percentage is design component in the 1.0-2.0% scope.
(2) raw material: comprise that purity is not less than 99.9% ytterbium oxide (Yb 2O 3), yittrium oxide (Y 2O 3) and average grain size less than the monoclinic zirconia powder of 100 nanometers.Composition proportioning according to above-mentioned (1) is selected an amount of corresponding compounds.
(3) powder is synthetic: ytterbium oxide and yttrium oxide are dissolved in the nitric acid that concentration is 0.5-1.5mol/L, cubic polycrystal zirconia ball with stabilized with yttrium oxide in container is a ball-milling medium, with nm-class powder of zirconium oxide in dehydrated alcohol mixing and ball milling 20-30 hour, use the Rotary Evaporators dry suspension then, obtain the presoma of coated powder, presoma obtains the nm-class powder of zirconium oxide of the common parcel of ytterbium oxide and yttrium oxide in 100-400 ℃ of calcining thermolysis in 0.5-2.0 hour in air.
(4) nm-class powder of zirconium oxide of the common parcel of ytterbium oxide and yttrium oxide is through cold isostatic compaction or dry-pressing formed, forming pressure is 100-300MPa, in air in 1400-1500 ℃ of pressureless sintering, soaking time is controlled in 1-5 hour scope, obtains fine and close ytterbium oxide and yttrium oxide co-stabilized tetragonal zirconia polycrystal (TZP) or fully stabilized zirconia pottery (FSZ).
Advantage of the present invention is:
(1) synthesis technique of powder is simple, and cost is low, does not need complex apparatus, enlarges scale production easily.
(2) replace rare earth nitrades as initiation material take rare earth oxide, reduce consumption, reduced preparation cost.
(3) carry out pyrolysis under lower temperature, avoided powder granule in the calcination process to grow up and the generation of hard aggregation, the powder after the pyrolysis can directly use, and does not need secondary ball milling, has further simplified preparation technology.
(4) can under low stabiliser content, obtain ytterbium oxide and yttrium oxide co-stabilized tetragonal zirconia polycrystal (TZP) and fully stabilized zirconia pottery (FSZ) by regulating component.By optimizing sintering condition, it is best that the mechanical property of tetragonal zirconia polycrystal (TZP) reaches.Particularly, as stabilizing agent Y 2O 3And Yb 2O 3Mole percent be TZP when being respectively 1.0-2.0% and 1.0-2.0%; As stabilizing agent Y 2O 3And Yb 2O 3Molal quantity be FSZ when being respectively 1.0-2.0% and 3.0-4.0%.
Description of drawings
The concrete process flow sheet of Fig. 1
Fig. 2 consists of 1.0mol%Yb 2O 3-1.0mol%Y 2O 3-ZrO 2, the XRD collection of illustrative plates of the TZP pottery that obtains under the different sintering conditions and corresponding 1400 ℃/1h of SEM photo (a), (b) 1450 ℃/1h, (d) 1450 ℃/4h
Fig. 3 consists of x mol%Yb 2O 3-1.0mol%Y 2O 3-ZrO 2(x=1.0,2.0,3.0,4.0) are HV at mechanical property (a) figure of 1450 ℃ of potteries of 1 hour of pressureless sintering in air 10(10 kilograms load under Vickers' hardness), unit is GPa, (b) figure is K IC(fracture toughness property), unit is MPam 1/2
Fig. 4 consists of 4.0mol%Yb 2O 3-1.0mol%Y 2O 3-ZrO 2, at XRD collection of illustrative plates and the SEM photo of 1450 ℃ of FSZ potteries of 2 hours of sintering in air
Fig. 5 consists of 1.0mol%Yb 2O 3-2.0mol%Y 2O 3-ZrO 2XRD collection of illustrative plates and SEM photo at 1450 ℃ of TZP potteries that sintering obtained in 1 hour in air
Embodiment
Embodiment 1 is not less than 99.9% ytterbium oxide (Yb with purity 2O 3), yittrium oxide (Y 2O 3) and monoclinic zirconia powder (average grain size is less than 100 nanometers) be raw material, design is final to obtain ytterbium oxide (Yb in the TZP pottery 2O 3) molar percentage is 1.0%, yittrium oxide (Y 2O 3) molar percentage is 1.0%.Select an amount of corresponding compound according to above-mentioned composition and ratio, with ytterbium oxide (Yb 2O 3) and yittrium oxide (Y 2O 3) be dissolved in an amount of nitric acid and obtain settled solution, take the Y-TZP ball as ball-milling medium, in absolute ethyl alcohol, mix less than the monoclinic zirconia powder of 100 nanometers with average grain size and ball milling 24 hours.Use the rotary evaporator dry suspension behind the ball milling, obtain the presoma of coated powder.Presoma was calcined 1 hour in air in 300 ℃, obtained the nm-class powder of zirconium oxide of the common parcel of ytterbium oxide and yittrium oxide.Coated powder in 1450 ℃ of sintering, obtains that (Yb, Y)-the TZP pottery, its prepared step as shown in Figure 1 in air behind cold isostatic compaction.The XRD collection of illustrative plates of the TZP pottery of preparation, microstructure and mechanical property are respectively as shown in Figures 2 and 3.
The final ZrO that obtains of embodiment 2 designs 2Ytterbium oxide (Yb in the pottery 2O 3) molar percentage is 2.0%, yittrium oxide (Y 2O 3) molar percentage is 1.0%, according to the method synthetic powder of embodiment 1, the preparation pottery, sintering time is 1 hour.
The ZrO of preparation 2The mechanical property of pottery as shown in Figure 3.
The final ZrO that obtains of embodiment 3 designs 2Ytterbium oxide (Yb in the pottery 2O 3) molar percentage is 3.0%, yittrium oxide (Y 2O 3) molar percentage is 1.0%, according to the method synthetic powder of embodiment 1, the preparation pottery, sintering time is 1 hour.
The ZrO of preparation 2The mechanical property of pottery respectively as shown in Figure 3.
Ytterbium oxide (Yb in the final acquisition of the embodiment 4 designs FSZ pottery 2O 3) molar percentage is 4.0%, yittrium oxide (Y 2O 3) molar percentage is 1.0%, according to the method synthetic powder of embodiment 1, the preparation pottery, sintering time is 2 hours.
The XRD collection of illustrative plates of the FSZ pottery of preparation and microstructure are as shown in Figure 4.
Ytterbium oxide (Yb in the final acquisition of the embodiment 5 designs TZP pottery 2O 3) molar percentage is 1.0%, yittrium oxide (Y 2O 3) molar percentage is 2.0%, according to the method synthetic powder of embodiment 1, the preparation pottery.The XRD collection of illustrative plates of the TZP pottery of preparation and microstructure are as shown in Figure 5.

Claims (5)

1. one kind by Yb 2O 3And Y 2O 3Stable zirconia ceramics material is characterized in that for tetragonal zirconia ceramics material, as the Yb of stabilizing agent altogether 2O 3And Y 2O 3Mole percent be respectively 1.0-2.0% and 1.0-2.0%.
2. prepare the described Yb of claim 1 2O 3And Y 2O 3The method of stable zirconia ceramics material is characterized in that Yb altogether 2O 3And Y 2O 3Design for component by mole% 1.0-2.0% and 1.0-2.0% respectively, adopt technique for packing to prepare Yb 2O 3And Y 2O 3The predecessor of the nm-class powder of zirconium oxide of common parcel is prepared into Yb after the thermal decomposition 2O 3And Y 2O 3The nm-class powder of zirconium oxide of common parcel is through pressureless sintering and making in air after the moulding.
3. by the described preparation of claim 2 Yb 2O 3And Y 2O 3Be total to the preparation method of stable zirconia polycrystalline ceramic material, it is characterized in that the concrete technology step is:
(a) press Yb 2O 3Molar percentage in the 1.0-2.0% scope, Y 2O 3Molar percentage is design component in the 1.0-2.0% scope;
(b) with Yb 2O 3And Y 2O 3Be dissolved in the nitric acid that concentration is 0.5-1.5mol/L, in container take the cubic polycrystal zirconia ball of stabilized with yttrium oxide as ball-milling medium, with monoclinic zirconia nano-powder in absolute ethyl alcohol mixing and ball milling 20-30 hour, use then the Rotary Evaporators dry suspension, obtain the presoma of coated powder;
(c) presoma obtains Yb in 100-400 ℃ of calcining thermal decomposition in 0.5-2.0 hour in air 2O 3And Y 2O 3The nm-class powder of zirconium oxide of common parcel;
(d) powder through after the moulding in air in 1400-1500 ℃, be incubated 1-5 hour, pressureless sintering obtains Yb 2O 3And Y 2O 3Be total to stable ceramic material.
4. prepare as claimed in claim 2 or claim 3 Yb 2O 3And Y 2O 3The method of stable zirconia ceramics material is characterized in that described Yb altogether 2O 3And Y 2O 3Purity be not less than 99.9%, the average grain diameter of described monoclinic zirconia powder is less than 100 nanometers.
5. by claim 2 or 3 described Yb 2O 3And Y 2O 3The preparation method of stable zirconia ceramics material is characterized in that the described isostatic cool pressing or dry-pressing formed that is shaped to altogether, and briquetting pressure is 100-300MPa.
CNB2006100243615A 2006-03-03 2006-03-03 Ytterbium oxide and yttrium oxide co-stabilized zirconia ceramic material and its prepn process Expired - Fee Related CN100347130C (en)

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CN102344285B (en) 2011-07-04 2013-04-17 辽宁爱尔创生物材料有限公司 Method for improving transmittance of dental zirconia material
CN112159228B (en) * 2020-09-27 2023-02-14 中国科学院上海光学精密机械研究所 Preparation of Y by filling nano powder 2 O 3 Method for producing-MgO composite powder
CN115124343A (en) * 2022-06-01 2022-09-30 上海大学 Zirconia solid solution yttria ceramic, preparation method and application thereof

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