CN115894017A - Zirconia composition, zirconia sintered body and preparation method - Google Patents
Zirconia composition, zirconia sintered body and preparation method Download PDFInfo
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Abstract
The invention provides a zirconia composition, a zirconia sintered body and a preparation method, wherein the zirconia composition comprises zirconia, a stabilizer and a fluorescent agent; the phosphor includes thulium oxide and erbium oxide; wherein, the content of thulium oxide is 6-20wt% based on the mass of the zirconia composition; tm: er = (8-20): 1; the zirconia sintered body is prepared by sequentially performing dry pressing, isostatic pressing and sintering on the zirconia composition; the zirconium oxide composition selects the specific fluorescent agent component and controls the content and the proportion thereof, on one hand, the problem that the prosthesis is greatly different from natural teeth and cannot be coordinated with adjacent teeth under the exposure of ultraviolet light is solved from the bionic aesthetic effect; on the other hand, the problems that a plurality of kinds of powder need to be prepared respectively when the fluorescent zirconia restoration is prepared at present, the operation steps are complicated and the cost is high are solved.
Description
Technical Field
The invention belongs to the technical field of dental restoration, and particularly relates to a zirconia composition, a zirconia sintered body and a preparation method of the zirconia sintered body.
Background
In prosthodontics, the prosthesis has optical properties close to those of natural teeth, in addition to morphology, size, position, etc. The optical property generally considered for current zirconia restorations is color, whereas the fluorescence of simulated natural teeth is often neglected. Under the irradiation of ultraviolet light, natural teeth can emit blue-white fluorescence with the peak value of about 440 nm. The ultraviolet light which is inevitably contacted in daily life, such as fluorescent lamps and some artificial light sources, has an ultraviolet component, if the prosthesis has no fluorescent effect, the difference of the prosthesis exposed to the ultraviolet light and natural teeth is large, and the prosthesis cannot be coordinated with adjacent teeth. Therefore, the realization of the fluorescent effect of the prosthesis is the essential optical performance requirement for simulating natural teeth.
Fluorescent glaze is a common choice for providing fluorescence to a full-profile zirconia restoration. However, the fluorescent glaze has disadvantages in that the generated fluorescence is mottled and non-uniform, and the glaze layer is easily removed and worn in clinical use. In order to obtain a permanent and uniform fluorescent appearance, it is desirable that the full-profile zirconia restoration itself have fluorescence properties that are close to or consistent with those of natural teeth.
Currently, there have been some studies on fluorescent zirconia ceramics:
both CN113105232A and CN113101230A provide a fluorescent zirconia with intrinsic fluorescence, and color and fluorescence close to those of natural teeth. However, the common technical defect of the two is that the related preparation process has very complicated operation steps, different powders containing different fluorescent agents, coloring agents or stabilizing agents are required to be prepared, then a plurality of different powders are uniformly mixed according to the ceramic restoration prepared according to the requirement, and then the ceramic restoration is subjected to dry pressing and forming and optional isostatic pressing to form a blank body, and finally the blank body is sintered. For a processing plant of mass production, the cost is high and the efficiency is low.
CN113105754A discloses a zirconia dental product staining solution, a preparation method of a zirconia dental product and a zirconia dental product. However, the method generates fluorescence on the dental product by soaking, brushing, spraying and other modes of the staining solution, the fluorescent agent in the staining solution cannot completely act on the zirconia dental product, most of the fluorescent agent generates ineffective action and is wasted, and the cost is high.
CN105007883A discloses a coloring solution for giving fluorescence to dental ceramics, and the process means for generating fluorescence related to the method can not determine the content of the fluorescent agent for generating effective action, so that the cost is higher. In addition, the used light-emitting agent is a fluorescent agent containing Bi ions, and the Bi ions have weak radioactivity and may cause certain harm to human bodies.
In summary, most of the prior art is a fluorescent zirconia preparation process containing a colorant or coloring ions, and the existence of the colorant or the coloring ions can cover the finally formed fluorescence intensity to a great extent, thereby affecting the bionic effect of the prosthesis.
Therefore, it is an urgent technical problem to provide a fluorescent zirconia composition, which has the advantages of low cost and simple preparation process, and the fluorescence color and fluorescence intensity of the fluorescent zirconia composition are approximately consistent with those of natural teeth.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a zirconium oxide composition, a zirconium oxide sintered body and a preparation method thereof, wherein the zirconium oxide composition is prepared by matching specific fluorescent components, so that on one hand, the problem that a prosthesis exposed to ultraviolet light is greatly different from natural teeth and cannot be coordinated with adjacent teeth is solved in the bionic aesthetic effect; on the other hand, the problems that various powders need to be prepared respectively when the fluorescence zirconia restoration is prepared at present, the operation steps are complicated and the cost is high are solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a zirconia composition comprising zirconia, a stabilizer, and a fluorescer;
the phosphor includes thulium oxide and erbium oxide;
wherein the thulium oxide is present in an amount of 6 to 20wt%, such as 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, or 20wt%, based on the mass of the zirconia composition, but is not limited to the recited values, and other unrecited values within this range of values are equally applicable.
Tm: er = (8-20): 1, 9, for example, 8.
The zirconia composition avoids the addition of a coloring agent by selecting the specific fluorescent agent component, namely the obtained zirconia sintered body has a fluorescence effect under the irradiation of ultraviolet rays and is white under a D65 natural light source, thereby avoiding the adverse effect on the fluorescence color and the fluorescence intensity of the zirconia sintered body due to the addition of the coloring agent. In the invention, the adding proportion of thulium element and erbium element is crucial to the final fluorescent effect, and compared with erbium element, the fluorescent color can be shifted due to too much or too little adding amount of thulium element, and specifically, the sintered body is blue green due to too little adding amount of thulium element; when the thulium element is added in an excessive amount, the sintered body is bluish purple, and the two effects are greatly different from those of natural teeth, which affects the appearance.
In addition, in order to ensure the final fluorescence effect of the sintered body (prosthesis), the proportion between Tm and Er needs to be controlled, and the addition amount of a fluorescent agent needs to be controlled. If the addition amount of the fluorescent agent is too low, the fluorescence color and the fluorescence intensity of the zirconia sintered body prepared by the zirconia composition are low and cannot be consistent with the fluorescence effect of natural teeth; too high a content of the fluorescent agent affects not only the fluorescent color effect but also the mechanical properties of the sintered body.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferred embodiment of the present invention, the phosphor further comprises any one or a combination of at least two of dysprosium oxide, gadolinium oxide, ytterbium oxide, europium oxide, cerium oxide, or scandium oxide, preferably dysprosium oxide and/or europium oxide.
In the invention, besides thulium oxide and erbium oxide, other rare earth element oxides can be added to enhance the adjustment of the fluorescence effect of the sintered body and improve the surface brightness of the sintered body, and particularly at least one of dysprosium oxide, europium oxide or scandium oxide is added, so that the white fluorescence effect is enhanced, and the fluorescence effect of the finally obtained prosthesis and natural teeth tends to be consistent.
In a preferred embodiment of the present invention, the stabilizer is contained in an amount of 3 to 5mol%, for example, 3mol%, 3.5mol%, 4mol%, 4.5mol%, or 5mol%, based on the total molar amount of the zirconia and the stabilizer, but the stabilizer is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the stabilizer comprises yttria.
As a preferred embodiment of the present invention, the zirconia composition comprises, based on the mass of the zirconia composition, thulium oxide 6-20wt%, such as 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, or 20wt%, etc.; scandia < 1wt%, e.g., 0.1wt%, 0.3wt%, 0.5wt%, 0.7wt%, or 1wt%, etc.; dysprosium oxide is less than or equal to 1wt%, e.g., 0.1wt%, 0.3wt%, 0.5wt%, 0.7wt%, or 1wt%, etc.; gadolinium oxide ≦ 20wt%, such as 0.1wt%, 1wt%, 3wt%, 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, or 20wt%, etc.; ytterbium oxide ≦ 20wt%, such as 0.1wt%, 1wt%, 3wt%, 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, or 20wt%, etc.; europium oxide < 1wt%, such as 0.1wt%, 0.3wt%, 0.5wt%, 0.7wt%, or 1wt%, etc.; cerium oxide ≦ 0.5wt%, for example 0.1wt%, 0.3wt% or 0.5wt%, the above-mentioned numerical ranges are not limited to the recited values, other values not recited in the numerical ranges are equally applicable, and the remainder is erbium oxide, zirconium oxide and yttrium oxide.
In the present invention, the zirconia composition may further include trace elements such as Fe, cr, cu, V, mo, co, etc., but the presence of these trace elements affects the fluorescence color or fluorescence intensity of the zirconia sintered body, for example, fe element blocks the fluorescence effect and absorbs fluorescence; cr element causes discoloration, which is detrimental to the fluorescent effect of the dental zirconia product. Therefore, it is desirable to avoid the presence of such impurities in the zirconia composition, and if not avoided, the amount of each trace element should be controlled to less than 0.01wt%, preferably 0.005wt% or less.
According to the invention, the synthesis method of the zirconia composition comprises but is not limited to a sol-gel method, a post-treatment synthesis method or a hydrothermal method, the zirconia composition synthesized by one step by using the method can be directly prepared into a sintered body, a better fluorescence effect is generated, and the zirconia compositions with different contents do not need to be prepared and then mixed, so that the steps are simplified.
In a second aspect, the present invention provides a zirconia sintered body prepared using the zirconia composition of the first aspect.
In a preferred embodiment of the present invention, the zirconia sintered body exhibits blue-white fluorescence under a light source having a wavelength of 400 to 500 nm.
The zirconia sintered body prepared by the zirconia composition can effectively apply all the added fluorescent agents to generate better fluorescence effect, and compared with the existing fluorescence effect generated by a soaking solution process, the cost can be effectively reduced, and the waste of rare earth elements is avoided.
In a third aspect, the present invention provides a method for producing the zirconia sintered body according to the second aspect, the method comprising the steps of:
the zirconia composition is subjected to dry pressing, isostatic pressing and sintering in sequence to obtain a zirconia sintered body.
By adopting the preparation method, the relative density of the obtained zirconia sintered body can reach more than 99.8 percent, and the total transmittance measured by the specification of less than 1mm is 38 to 55 percent.
"relative density" means the measured density (. Rho.g/cm) 3 ) Relative to theoretical density (p) 0 ：g/cm 3 ) Ratio (%) of (c).
In a preferred embodiment of the present invention, the zirconia composition is in the form of a powder having a particle size of 48 to 150. Mu.m, for example, 48 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm or 150 μm, but is not limited to the values listed, and other values not listed within this range are also applicable.
In a preferred embodiment of the present invention, the pressure for dry pressing is 2 to 20MPa, for example, 2MPa, 4MPa, 6MPa, 8MPa, 10MPa, 12MPa, 14MPa, 16MPa, 18MPa or 20MPa, but the pressure is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the dry-pressing time is 5 to 60 seconds, for example, 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, or 60s, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the pressure of the isostatic pressing is 160-280MPa, such as 160MPa, 180MPa, 200MPa, 220MPa, 240MPa, 260MPa or 280MPa, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the isostatic pressing treatment is carried out for a time of 1-10min, such as 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
In a preferred embodiment of the present invention, the sintering temperature is 1450 to 1600 ℃, for example 1450 ℃, 1500 ℃, 1550 ℃ or 1600 ℃, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the sintering time is 2-10h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the atmosphere of the sintering is an air atmosphere or a protective atmosphere.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the fluorescence color and fluorescence intensity of the zirconia sintered body are regulated and controlled by adjusting the content and proportion of the rare earth element in the zirconia composition, so that the fluorescence color and fluorescence intensity of the zirconia sintered body are consistent with those of natural teeth, and the aesthetics and bionic effect of the restoration body are further enhanced; in addition, the zirconia sintered body is obtained by directly carrying out dry pressing, isostatic pressing and sintering on the zirconia composition containing the rare earth element synthesized in one step, so that the complex steps of preparing various powders and then weighing and mixing various powders in the prior art are omitted, and the method is more beneficial for a processing plant to obtain mass production;
(2) The zirconia sintered body prepared by the zirconia composition can effectively apply all the added fluorescent agents to generate better fluorescence effect, and compared with the existing fluorescence effect generated by a soaking solution process, the cost can be effectively reduced, and the waste of rare earth elements is avoided.
Drawings
FIG. 1 is a graph showing a comparison of the results of blue light diffraction peaks between 400 and 500nm of the zirconia sintered bodies obtained in comparative preparation example 1 and preparation example 1 of the present invention.
FIG. 2 is a graph showing a comparison of the results of blue light diffraction peaks between 400 and 500nm of the zirconia sintered bodies obtained in comparative preparation example 2 and preparation example 1 of the present invention.
FIG. 3 is a graph showing a comparison of the results of blue light diffraction peaks between 400 and 500nm of the zirconia sintered bodies obtained in comparative preparation example 3 and preparation example 2 of the present invention.
FIG. 4 is a graph comparing the results of green diffraction peaks between 500 and 600nm of the zirconia sintered bodies obtained in comparative preparation example 3 and preparation example 2 of the present invention.
FIG. 5 is a graph showing a comparison of the results of green diffraction peaks between 500 and 600nm of the zirconia sintered bodies obtained in comparative preparation example 4 and preparation example 2 of the present invention.
Detailed Description
In order to better explain the present invention and to facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The following are typical, but non-limiting, examples of the present invention:
example 1:
this example provides a zirconia composition comprising 12 wt.% thulium oxide, 1 wt.% erbium oxide, 0.5 wt.% dysprosium oxide, 3 wt.% yttrium oxide, and 83.5 wt.% zirconia, wherein, in terms of single atomic mass, tm: er = 12.
Preparation example 1:
the present production example provides a production method of a zirconia sintered body produced using the zirconia composition as in example 1, the production method including:
performing ball milling on the zirconium oxide composition, and sieving the zirconium oxide composition through a 200-mesh sieve to obtain zirconium oxide composition powder; performing dry pressing molding on the zirconia composition powder, and controlling the pressure to be 4MPa and the time to be 10s; then carrying out isostatic pressing, controlling the pressure to be 180MPa and the time to be 1min, and obtaining a zirconia biscuit; and sintering the zirconia biscuit for 2h at 1530 ℃ in the early stage to obtain a zirconia sintered body.
Example 2:
this example provides a zirconia composition that is comparable to the zirconia composition of example 1, except that: dysprosium oxide is not contained, and the adding mass of other components is not changed (the mass percentage of each component is recalculated on the basis of the total mass of the zirconia composition).
Preparation example 2:
the present production example provides a production method of a zirconia sintered body produced using the zirconia composition as in example 2, the production method including:
performing ball milling on the zirconium oxide composition, and sieving the zirconium oxide composition through a 300-mesh sieve to obtain zirconium oxide composition powder; performing dry pressing molding on the zirconia composition powder, and controlling the pressure to be 4MPa and the time to be 10s; then carrying out isostatic pressing, controlling the pressure to be 180MPa and the time to be 1min, and obtaining a zirconia biscuit; and sintering the zirconia biscuit for 2h at 1530 ℃ in the early stage to obtain a zirconia sintered body.
Example 3:
this example provides a zirconia composition comprising 6wt% thulium oxide, 0.6wt% erbium oxide, 0.3wt% dysprosium oxide, 3wt% ytterbium oxide, 0.1wt% cerium oxide, 0.06wt% scandium oxide, 5.35wt% yttrium oxide, and 84.59wt% zirconia, wherein, in single atomic mass, tm: er = 10.
Preparation example 3:
the present production example provides a production method of a zirconia sintered body produced using the zirconia composition as in example 3, the production method including:
ball-milling the zirconia composition, and sieving the zirconia composition with a 200-mesh sieve to obtain zirconia composition powder; performing dry pressing molding on the zirconia composition powder, and controlling the pressure to be 6MPa and the time to be 5s; then carrying out isostatic pressing, controlling the pressure to be 220MPa and the time to be 3min, and obtaining a zirconia biscuit; and sintering the zirconia biscuit at 1500 ℃ for 2h to obtain a zirconia sintered body.
Example 4:
this example provides a zirconia composition comprising 20 wt.% thulium oxide, 1 wt.% erbium oxide, 0.8 wt.% dysprosium oxide, 8 wt.% ytterbium oxide, 0.2 wt.% cerium oxide, 5.35 wt.% yttrium oxide, and 64.65 wt.% zirconia, wherein Tm: er =20.
The present production example provides a production method of a zirconia sintered body produced using the zirconia composition as in example 4, the production method including:
ball-milling the zirconia composition, and sieving the zirconia composition with a 200-mesh sieve to obtain zirconia composition powder; performing dry pressing molding on the zirconia composition powder, and controlling the pressure to be 6MPa and the time to be 1s; then carrying out isostatic pressing, controlling the pressure to be 260MPa and the time to be 5min, and obtaining a zirconium oxide biscuit; and sintering the zirconia biscuit for 2h at 1530 ℃ in the early stage to obtain a zirconia sintered body.
Comparative example 1:
the present comparative example provides a zirconia composition comprising 5.5wt% thulium oxide, 1wt% erbium oxide, 3wt% yttrium oxide, and 90.5wt% zirconia, wherein Tm: er = 5.5.
Comparative preparation example 1:
this comparative preparation example provides a method for producing a zirconia sintered body, which was produced using the zirconia composition as in comparative example 1, and which was the same as in preparation example 1 except for the raw materials.
Comparative example 2:
the present comparative example provides a zirconia composition comprising 20.5wt% thulium oxide, 1wt% erbium oxide, 3wt% yttrium oxide, and 75.5wt% zirconia, wherein Tm: er = 20.5.
Comparative preparation example 2:
this comparative preparation example provides a method for producing a zirconia sintered body, which was produced using the zirconia composition as in comparative example 2, and which was the same as in preparation example 1 except for the raw materials.
Comparative example 3:
this comparative example provides a zirconia composition that is comparable to the zirconia composition of example 2, except that: ytterbium oxide is used to replace thulium oxide and gadolinium oxide is used to replace erbium oxide.
Comparative preparation example 3:
this comparative preparation example provides a method for producing a zirconia sintered body, which was produced using the zirconia composition as in comparative example 3, and which was the same as in preparation example 2 except for the raw materials.
Comparative example 4:
this comparative example provides a zirconia composition that is comparable to the zirconia composition of example 2, except that: the zirconia powder does not contain erbium oxide, and the adding mass of other components is not changed (the mass percentage of each component is recalculated on the basis of the total mass of the zirconia composition).
Comparative preparation example 4:
this comparative preparation example provides a method for producing a zirconia sintered body, which was produced using the zirconia composition as in comparative example 4, and which was the same as in preparation example 2 except for the raw materials.
Fluorescence emission spectroscopy was performed using Edinburgh FLS1000, with the following fluorescence emission spectroscopy under 377nm laser excitation.
FIG. 1 shows the results of blue light diffraction peaks between 400 and 500nm of the zirconia sintered bodies obtained in comparative preparation example 1 and preparation example 1. As can be seen from fig. 1, the ratio of thulium oxide in comparative preparation example 1 is low, which results in a decrease in the intensity of the blue diffraction peak.
FIG. 2 shows the results of blue light diffraction peaks between 400 and 500nm of the zirconia sintered bodies obtained in comparative preparation example 2 and preparation example 1. As can be seen from fig. 2, the ratio of thulium oxide in comparative preparation example 2 is high, which results in high intensity of the blue diffraction peak.
FIG. 3 shows the results of blue light diffraction peaks between 400 and 500nm of the zirconia sintered bodies obtained in comparative preparation example 3 and preparation example 2. As can be seen from fig. 3, since thulium oxide and erbium oxide are replaced in comparative preparation example 3, the intensity of the blue diffraction peak is lower than that of preparation example 2.
FIG. 4 shows the results of green diffraction peaks between 500 and 600nm of the zirconia sintered bodies obtained in comparative preparation example 3 and preparation example 2. As can be seen from fig. 4, since thulium oxide and erbium oxide were replaced in comparative preparation example 3, no diffraction peak of green light occurred.
FIG. 5 shows the results of green diffraction peaks between 500 and 600nm of the zirconia sintered bodies obtained in comparative preparation example 4 and preparation example 2. As can be seen from fig. 5, since comparative preparation example 4 does not contain erbium oxide, it does not have a diffraction peak of green light.
The zirconia sintered bodies obtained in preparation examples 1 to 4 and comparative preparation examples 1 to 4 were observed for fluorescence color and fluorescence intensity, and if the fluorescence color was observed by naked eyes to be consistent with that of natural teeth, the fluorescence color was judged to be acceptable; the fluorescence intensity is classified into class I and class II from weak to strong, and if the fluorescence intensity is class II, the fluorescence intensity is judged to be qualified. Both of them were qualified, and the results were qualified, as shown in Table 1.
TABLE 1
| Colour of fluorescence | Intensity of fluorescence | Whether it is qualified or not | |
| Preparation example 1 | Blue and white | Class II | Is that |
| Preparation example 2 | Bluish white | Class II | Is that |
| Preparation example 3 | Blue and white | Class II | Is that |
| Preparation example 4 | Blue and white | Class II | Is that |
| Comparative preparation example 1 | Cyan color | Class I | Whether or not |
| Comparative preparation example 2 | Bluish purple | Class II | Whether or not |
| Comparative preparation example 3 | Blue color | Class I | Whether or not |
| Comparative preparation example 4 | Blue color | Class I | Whether or not |
The applicant states that the present invention is illustrated by the above examples to show the products and detailed methods of the present invention, but the present invention is not limited to the above products and detailed methods, i.e. it is not meant that the present invention must rely on the above products and detailed methods to be carried out. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents thereof, additions of additional operations, selection of specific ways, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A zirconia composition, wherein the zirconia composition comprises zirconia, a stabilizer, and a fluorescer;
the phosphor includes thulium oxide and erbium oxide;
wherein, the content of thulium oxide is 6-20wt% based on the mass of the zirconia composition;
tm: er = (8-20): 1 in terms of single atomic mass.
2. The zirconia composition of claim 1 wherein the phosphor further comprises any one or a combination of at least two of dysprosia, gadolinia, ytterbia, europium oxide, cerium oxide or scandium oxide, preferably dysprosia and/or europium oxide.
3. The zirconia composition of claim 1 or 2, wherein the stabilizer is present in an amount of 3 to 5 mole percent, based on the total molar amount of zirconia and stabilizer;
preferably, the stabilizer comprises yttria.
4. The zirconia composition of any of claims 1 to 3, wherein the zirconia composition comprises, based on the mass of the zirconia composition, thulium oxide 6 to 20wt%, scandium oxide < 1wt%, dysprosium oxide < 1wt%, gadolinium oxide < 20wt%, ytterbium oxide < 20wt%, europium oxide < 1wt%, cerium oxide < 0.5wt%, and the balance erbium oxide, zirconium oxide, and yttrium oxide.
5. A zirconia sintered body characterized by comprising a zirconia composition according to any one of claims 1 to 4.
6. The zirconia sintered body according to claim 5, wherein the zirconia sintered body exhibits blue-white fluorescence under a light source having a wavelength of 400 to 500 nm.
7. A method for producing the zirconia sintered body according to claim 5 or 6, comprising the steps of:
the zirconia composition is subjected to dry pressing, isostatic pressing and sintering in sequence to obtain a zirconia sintered body.
8. The method according to claim 7, wherein the zirconia composition is in a powder form and has a particle size of 48 to 150 μm.
9. The production method according to claim 7 or 8, wherein the pressure of the dry-pressing molding is 2 to 20MPa;
preferably, the dry pressing time is 5-60s;
preferably, the pressure of the isostatic pressing treatment is 160-280MPa;
preferably, the time of the isostatic pressing treatment is 1-10min.
10. The method of any one of claims 7 to 9, wherein the sintering temperature is 1450 to 1600 ℃;
preferably, the sintering time is 2-10h;
preferably, the atmosphere of the sintering is an air atmosphere or a protective atmosphere.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009035623A (en) * | 2007-08-01 | 2009-02-19 | Kyushu Institute Of Technology | Inorganic oxide phosphor and light source using the same |
| EP2191809A1 (en) * | 2008-11-27 | 2010-06-02 | 3M Innovative Properties Company | Dental ceramic article, process for production and use thereof |
| CN102438964A (en) * | 2009-03-23 | 2012-05-02 | 株式会社则武 | Fluorescent zirconia material |
| US20150140274A1 (en) * | 2012-05-11 | 2015-05-21 | Ivoclar Vivadent Ag | Pre-sintered blank for dental purposes |
| JP2016088793A (en) * | 2014-10-31 | 2016-05-23 | クラレノリタケデンタル株式会社 | Zirconia sintered body and dental product |
| JP2017197642A (en) * | 2016-04-27 | 2017-11-02 | 京セラ株式会社 | Fluorescent zirconia material and device for detecting beam |
| WO2019068807A1 (en) * | 2017-10-04 | 2019-04-11 | Ceramtec Gmbh | Partially stabilised zirconium oxide material with high sintering activity |
| US20200113661A1 (en) * | 2018-10-10 | 2020-04-16 | Ivoclar Vivadent Ag | Method For Producing A Dental Prosthesis Part |
| CN113105232A (en) * | 2020-10-10 | 2021-07-13 | 深圳爱尔创口腔技术有限公司 | Zirconia composition, zirconia calcined body and method for producing same, zirconia sintered body and method for producing same, and zirconia dental product |
| CN113101230A (en) * | 2021-03-03 | 2021-07-13 | 深圳爱尔创口腔技术有限公司 | Zirconia composition, fluorescent zirconia, preparation method of fluorescent zirconia and zirconia dental product |
| JP2021175698A (en) * | 2020-05-01 | 2021-11-04 | クラレノリタケデンタル株式会社 | Zirconia-calcinated body capable of producing fluorescent zirconia-sintered body |
| CN113710627A (en) * | 2019-04-25 | 2021-11-26 | 可乐丽则武齿科株式会社 | Zirconia calcined body suitable for dental use and method for producing same |
| CN114671684A (en) * | 2022-03-23 | 2022-06-28 | 爱迪特（秦皇岛）科技股份有限公司 | Dental zirconia repair material and preparation method and application thereof |
-
2022
- 2022-12-23 CN CN202211664345.8A patent/CN115894017A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009035623A (en) * | 2007-08-01 | 2009-02-19 | Kyushu Institute Of Technology | Inorganic oxide phosphor and light source using the same |
| EP2191809A1 (en) * | 2008-11-27 | 2010-06-02 | 3M Innovative Properties Company | Dental ceramic article, process for production and use thereof |
| CN102438964A (en) * | 2009-03-23 | 2012-05-02 | 株式会社则武 | Fluorescent zirconia material |
| US20150140274A1 (en) * | 2012-05-11 | 2015-05-21 | Ivoclar Vivadent Ag | Pre-sintered blank for dental purposes |
| JP2016088793A (en) * | 2014-10-31 | 2016-05-23 | クラレノリタケデンタル株式会社 | Zirconia sintered body and dental product |
| JP2017197642A (en) * | 2016-04-27 | 2017-11-02 | 京セラ株式会社 | Fluorescent zirconia material and device for detecting beam |
| WO2019068807A1 (en) * | 2017-10-04 | 2019-04-11 | Ceramtec Gmbh | Partially stabilised zirconium oxide material with high sintering activity |
| US20200113661A1 (en) * | 2018-10-10 | 2020-04-16 | Ivoclar Vivadent Ag | Method For Producing A Dental Prosthesis Part |
| CN113710627A (en) * | 2019-04-25 | 2021-11-26 | 可乐丽则武齿科株式会社 | Zirconia calcined body suitable for dental use and method for producing same |
| JP2021175698A (en) * | 2020-05-01 | 2021-11-04 | クラレノリタケデンタル株式会社 | Zirconia-calcinated body capable of producing fluorescent zirconia-sintered body |
| CN113105232A (en) * | 2020-10-10 | 2021-07-13 | 深圳爱尔创口腔技术有限公司 | Zirconia composition, zirconia calcined body and method for producing same, zirconia sintered body and method for producing same, and zirconia dental product |
| CN113101230A (en) * | 2021-03-03 | 2021-07-13 | 深圳爱尔创口腔技术有限公司 | Zirconia composition, fluorescent zirconia, preparation method of fluorescent zirconia and zirconia dental product |
| CN114671684A (en) * | 2022-03-23 | 2022-06-28 | 爱迪特（秦皇岛）科技股份有限公司 | Dental zirconia repair material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| TAKASHI NAKAMURA 等: "Fluorescence and physical properties of thulium and erbium co-doped dental zirconia", DENTAL MATERIALS JOURNAL, vol. 40, no. 5, pages 1080 - 1085 * |
| 吴南;石连水;王臻石;: "稀土元素在牙科全瓷材料着色中的应用与研究现状", 陶瓷学报, no. 01, pages 1 - 5 * |
| 黄金良 等: "稀土元素应用于牙齿组织修复的研究进展", 稀土, vol. 44, no. 1, pages 112 - 127 * |
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