CN115745601A - Zirconia sintered body, method for producing same, and use thereof in dental material - Google Patents
Zirconia sintered body, method for producing same, and use thereof in dental material Download PDFInfo
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- CN115745601A CN115745601A CN202211493340.3A CN202211493340A CN115745601A CN 115745601 A CN115745601 A CN 115745601A CN 202211493340 A CN202211493340 A CN 202211493340A CN 115745601 A CN115745601 A CN 115745601A
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000005548 dental material Substances 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000005245 sintering Methods 0.000 claims abstract description 39
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 4
- 230000007704 transition Effects 0.000 claims description 58
- 239000000843 powder Substances 0.000 claims description 41
- 239000003086 colorant Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 10
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 9
- 229910052691 Erbium Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 32
- 239000003381 stabilizer Substances 0.000 abstract description 8
- 238000002834 transmittance Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000006467 substitution reaction Methods 0.000 abstract description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 14
- 238000005520 cutting process Methods 0.000 description 12
- 238000009472 formulation Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004321 preservation Methods 0.000 description 5
- 239000001054 red pigment Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000001060 yellow colorant Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a zirconia sintered body and a preparation method thereof, comprising the following steps: a first region, a second region, and a third region; said first region comprising 4.5-5mol% Yb 2 O 3 Stabilized ZrO 2 Said second region comprising 3.5-4.5mol% Tm 2 O 3 Stabilized ZrO 2 Said third region comprising 2.5-3.5mol% 2 O 3 Stabilized ZrO 2 . The invention passes Yb 2 O 3 、Tm 2 O 3 、Er 2 O 3 By layered substitution of Y 2 O 3 The zirconium oxide is stabilized by the stabilizing agent, so that the whole fluorescence effect is kept uniform while the transmittance and the color of each layer are gradually changed, a better aesthetic effect is achieved, and the effect that the color difference value is not obviously different in the 1450-1550 ℃ sintering temperature range can be realized.
Description
Technical Field
The invention relates to the technical field of dental materials, in particular to a zirconia sintered body, a preparation method thereof and application thereof in dental materials.
Background
Yttria-stabilized zirconia has excellent mechanical properties and biocompatibility, and 3mol% yttria-stabilized zirconia and 5mol% yttria-stabilized zirconia are widely used in the field of dental restorations. As the aesthetic requirements of doctors and patients become more and more demanding, the layered porcelain piece can provide a gradual cut-to-neck effect in imitation of natural teeth, and the gingival part is often stained with porcelain powder.
Natural teeth have a fluorescence effect and can emit a blue-white fluorescence effect under the irradiation of light with special wavelength, and many repair materials try to simulate the fluorescence effect, but the fluorescence effect is layered and the overall fluorescence effect is not uniform. Meanwhile, fe element cannot be added as a coloring agent for realizing the fluorescent effect, and Y element cannot be added 2 O 3 Stabilized ZrO 2 Other yellow colorants may have relatively large color deviations at different sintering temperatures, which also limits the use of such materials.
The traditional layered zirconia ceramic block realizes the transparency gradual change effect through the difference of the content of each layer of yttria, realizes the color gradual change effect through the difference of the content of each layer of pigment, and realizes the fluorescence effect through introducing fluorescent agent. However, the mode causes that the fluorescence effect is too obvious when the cut end has high transmittance and light color, the neck has low transmittance and deep color and the fluorescence effect is poor, so that the whole fluorescence effect is not uniform.
Disclosure of Invention
The invention aims to provide a zirconia sintered body, a preparation method thereof and application thereof in dental materials, wherein Yb is used for preparing the zirconia sintered body 2 O 3 、Tm 2 O 3 By layered substitution of Y 2 O 3 As a stabilizer to stabilize the zirconia, the transmittance and the color of each layer are gradually changed, and the whole fluorescence effect is ensuredThe color paste is uniform, achieves better aesthetic effect, and can realize the effect that the color difference value is not obviously different in the sintering temperature range of 1450-1550 ℃.
To achieve the above object, the present invention provides a zirconia sintered body comprising: a first region comprising 4.5 to 5mol% Yb and a second region 2 O 3 Stabilized ZrO 2 Said second region comprising 3.5-4.5mol% Tm 2 O 3 Stabilized ZrO 2 。
Further, the first region and the second region further comprise a colorant CeO 2 Er colorant 2 O 3 Nd, colorant 2 O 3 And at least comprises the colorant CeO 2 。
Further, the colorant CeO 2 Comprises 4-6 wt.% of CeO 2 ZrO of 2 (ii) a The colorant Er 2 O 3 To contain 10wt% -12wt% Er 2 O 3 Of (b) ZrO 2 (ii) a The colorant Nd 2 O 3 To contain 1-2wt% of Nd 2 O 3 Of (b) ZrO 2 。
Further, the 4.5-5mol% of Yb in the first region 2 O 3 Stabilized ZrO 2 The content of (A) is 82wt% -95wt%, preferably 85wt% -90wt%; 3.5-4.5mol% Tm in the second region 2 O 3 Stabilized ZrO 2 The content of (A) is 60wt% to 85wt%, preferably 65wt% to 82.5wt%.
Further, the zirconia sintered body further includes a third region provided in the outer layer of the second region, the third region containing 2.5 to 3.5mol% Er 2 O 3 Stabilized ZrO 2 。
Further, the second region further comprises 1-6 transition regions, the color of the transition regions gradually deepens from the side close to the first region to the side close to the third region, and the color is regulated and controlled by regulating and controlling the content of the colorant. The thickness of the transition regions of each layer may be equal or successively greater.
Further, the thickness of the first region, the second region and the third region is 15-25%, 25-55% and 30-50%, respectively. The total thickness may be 5-30mm, for example 10, 15, 18, 20mm.
The invention also provides a preparation method of the zirconia sintered body, which comprises the following steps:
s1, weighing and uniformly mixing powder according to the raw material proportion of each area, sequentially filling the corresponding powder into a mould according to the area stacking sequence, and performing dry pressing forming;
s2, sintering the formed ceramic block to obtain a zirconia sintered body, wherein the final sintering temperature is 1450-1550 ℃.
Further, step S2 includes: preserving the heat of the formed ceramic block at 1050-1250 ℃ for 30-180min to obtain a sintered blank; then processing the zirconium oxide powder into a target shape restoration, and sintering at 1450-1550 ℃ for 15-120min to obtain a zirconium oxide sintered body.
Further, in step S1, after the second area is filled, semicircular pits are formed on the surface of the second area, and then powder in a third area is filled; the radius of the semicircular concave pit is 0.5-2.5mm; the pressure of the dry pressing is not lower than 160MPa. By the operation, the wavy effect of the natural tooth gum can be realized at the interface of the gum area (third area) and the transition area by the special filling mode of the powder, and the simulation purpose is achieved.
Further, the powder bulk density of the first area reaches 1.28 +/-0.05 g/cm 3 The sintered density reaches 6.28 +/-0.05 g/cm 3 (ii) a The loose packed density of the powder in the second area reaches 1.28 +/-0.05 g/cm 3 The sintered density reaches 6.28 +/-0.05 g/cm 3 (ii) a The loose packed density of the powder in the third area reaches 1.28 +/-0.05 g/cm 3 The sintered density reaches 6.28 +/-0.05 g/cm 3 . By the operation, the shrinkage consistency of each layer is better, and the edge sealing property of the final restoration is ensured.
The invention also provides the use of the zirconia sintered body in a dental material, such as a dental prosthesis, a corrective article or a transplant article. The first area corresponds to a cutting end area of the artificial tooth, the second area corresponds to a transition area, and the third area corresponds to a gum area.
The invention has the following beneficial effects:
1. the zirconia sintered body of the present invention is obtained by Yb 2 O 3 、Tm 2 O 3 By layered substitution of Y 2 O 3 As a stabilizer for stabilizing zirconia, the method can achieve the aim that the fluorescence effect of each layer is basically consistent while the transmittance is gradually reduced and the color is gradually deepened in the thickness, thereby achieving better aesthetic effect.
2. The fluorescent layered zirconia provided by the invention solves the problem of large color difference of common fluorescent zirconia in the sintering temperature range of 1450-1550 ℃, can realize the shrinkage consistency of each layer, and ensures the edge sealing property of the final restoration. The cutting end region and the transition region adopt Ce as a coloring agent, and the overall toughness can reach 4.5 MPa.m 1/2 。
3. According to the invention, through a special powder filling mode, the wavy effect of natural gum can be realized at the interface of the gum area and the transition area, so that the simulation purpose is achieved, and meanwhile, the integrated sintering molding is realized, so that the preparation method is simple and is convenient to put into practical application.
Drawings
FIG. 1 is a schematic view of a layer structure of a zirconia sintered body of the present invention;
FIG. 2 is a schematic view showing the structure of another layer of the zirconia sintered body of the present invention.
Reference numerals
1-a first region; 2-a second region; 3-a third region; 21-a first transition zone; 22-a second transition zone; 23-third transition zone.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Referring to fig. 1, the present invention provides a zirconia sintered body, including: a first region 1 and a second region 2, the first region 1 comprising 4.5-5mol% Yb 2 O 3 (i.e. molar ratio compared to zirconia) stabilized ZrO 2 Second region 2 contains 3.5-4.5mol% Tm 2 O 3 Stabilized ZrO 2 . Operated in such a way as to pass Yb 2 O 3 、Tm 2 O 3 By layered substitution of Y 2 O 3 When a pigment is added to each layer as a stabilizer to stabilize zirconia, the transparency gradually decreases from the first region 1 to the second region 2, the color gradually increases, and the fluorescent effect of each layer is uniform.
In some embodiments, the first region and the second region further comprise a colorant CeO 2 (yellow material) and colorant Er 2 O 3 (Red pigment) and colorant Nd 2 O 3 (Gray material) and at least comprises a colorant CeO 2 . Preferably, the colorant CeO 2 Comprises 4-6 wt.% of CeO 2 Of (b) ZrO 2 (ii) a Colorant Er 2 O 3 Contains 10-12wt% Er 2 O 3 Of (b) ZrO 2 (ii) a Colorant Nd 2 O 3 Contains 1-2wt% of Nd 2 O 3 ZrO of 2 . The color and the transmittance of the first region 1 and the second region 2 are regulated and controlled by regulating and controlling the distribution ratio of each component, and the fluorescence of the first region and the second region is not influenced. Wherein CeO is used for the first region 1 and the second region 2 2 As a colorant, the overall toughness can reach 4.5 MPa.m 1/2 。
Specifically, 4.5-5mol% of Yb in the first region 1 2 O 3 Stabilized ZrO 2 The content of (A) is 82wt% -95wt%, preferably 85wt% -90wt%; 3.5-4.5mol% Tm in the second region 2 2 O 3 Stabilized ZrO 2 The content of (B) is 60wt% -85wt%, preferably 65wt% -82.5wt%.
In the present invention, a third region 3 may be further provided in the second region 2, the third region 3 containing Er in an amount of 2.5 to 3.5mol% 2 O 3 Stabilized ZrO 2 (Red pigment). When used for the preparation of dental material, such as a crown, the third region 3 corresponds to the gingival area of the artificial tooth and the first and second regions 1 and 2 correspond to the cut end and transition areas, respectively, so that an integrated sintering is achieved. Er in the third region 3 2 O 3 And meanwhile, the three-layer ceramic material has coloring and stabilizing functions, so that the sintering stability and the interface bonding adhesion of the three-layer area are ensured.
Specifically, as shown in fig. 2, the second region 2 further includes 1-10 transition regions, preferably 1-6 transition regions, the color of the transition regions gradually deepens from the side close to the first region 1 to the side of the third region 3, and the color of each transition region is controlled by controlling the content of the colorant. For example, FIG. 2 contains a first transition zone 21, a second transition zone 22 and a third transition zone 23, 3.5-4.5mol% of the three transition zones 2 O 3 Stabilized ZrO 2 The content of the (white material) is gradually reduced, and the content of the yellow material, the red material and the gray material is gradually increased, so that the color is gradually deepened.
Fe element cannot be added as a colorant for realizing fluorescent effect, and Y element 2 O 3 Other colorants of stabilized zirconia tend to exhibit a relatively large color shift at different sintering temperatures. Experiments show that the sintering is carried out according to the formula, and the effect that the color difference value of each layer has no obvious difference within the sintering temperature range of 1450-1550 ℃ can be realized, so that the practicability and the attractiveness are higher.
In some embodiments, the specific formulations and processes of the present invention are as follows:
cut end region (first region 1):
white pigment: 4.5-5mol% of Yb-ZrO 2 ；
Yellow material: 4-6 wt.% of CeO 2 ；
Red pigment: 10-12wt% Er 2 O 3 ；
A grey pigment: 1-2wt% of Nd 2 O 3 ；
Bulk density 1.28. + -. 0.05g/cm 3 Sintered density of 6.28 +/-0.05 g/cm 3 。
Transition region (second region 2):
white pigment: 3.5-4.5mol% of Tm-ZrO 2 ；
Yellow material: 4-6 wt.% of CeO 2 ；
Red pigment: 10-12wt% Er 2 O 3 ；
A grey material: 1-2wt% of Nd 2 O 3 ；
Bulk density 1.28. + -. 0.05g/cm 3 Sintered density of 6.28 +/-0.05 g/cm 3 。
Gingival area (third area 3):
2.5-3.5mol％Er-ZrO 2 ；
bulk density 1.28. + -. 0.05g/cm 3 Sintered density of 6.28 +/-0.05 g/cm 3 。
a. Weighing white, yellow, red and gray powder materials of a cutting end region according to a preset proportion, uniformly mixing the powder materials to serve as a cutting end layer, and filling the cutting end layer into a mold;
b. weighing white, yellow, red and gray powder materials in a transition region according to a preset proportion, uniformly mixing, and sequentially filling the mixture into a mold as a transition layer, wherein the transition layer is an N layer (N is more than or equal to 1); in the steps a and b, adding each layer of powder into a mould, leveling, and then adding the next layer of powder;
c. making semicircular pits which are not of equal size and are closely arranged on the surface of the last layer of the transition layer by using a mould; filling powder in the gum area; the radius of the semicircular concave pit is 0.5-2.5mm;
d. dry pressing under certain pressure; the pressure is not lower than 160MPa, for example, 160-230MPa.
e. Sintering the formed ceramic block; the sintering temperature is 1050-1250 ℃; the heat preservation time is 30-180min;
f. processing the sintered blank into a dental crown by CAD/CAM; for example, carving the prosthesis on the sintered blank in a four-axis or five-axis processing machine;
g. sintering the crown into the final restoration. The final sintering temperature is 1450-1550 ℃, and the sintering time is 15-120min.
Example 1
The formulation of each layer of powder of a zirconia sintered body is shown in Table 1.
TABLE 1 powder formulation of example 1
Uniformly mixing powder of each layer according to a formula shown in a table 1, sequentially filling the powder into a die from a cutting end region, carrying out dry pressing under the pressure of 180MPa, sintering at the temperature of 1100 ℃, keeping the temperature for 120min, processing the sintered ceramic blocks into 3 half-opening long bridges in a 5-shaft processing machine, wherein the sintering temperature is 1450 ℃, 1500 ℃ and 1550 ℃, and the keeping temperature is 2h.
Example 2
The formulation of each layer of powder of a zirconia sintered body is shown in Table 2.
TABLE 2 powder formulation of example 2
According to the formula shown in the table 2, all layers of powder are uniformly mixed, the mixture is sequentially filled into a die from a cutting end area, the dry pressing pressure is 200MPa, the sintering temperature is 1150 ℃, the heat preservation time is 60min, the sintered ceramic blocks are processed into 3 half-mouth long bridges in a 5-shaft processing machine, the sintering temperatures are 1450, 1500 and 1550 ℃, and the heat preservation time is 2h.
Example 3
The formulation of each layer of powder of a zirconia sintered body is shown in Table 3.
Table 3 powder formulation of example 3
Uniformly mixing powder of each layer according to a formula shown in a table 3, sequentially filling the powder into a die from a cutting end region, carrying out dry pressing under the pressure of 220MPa, carrying out sintering at the temperature of 1050 ℃, keeping the temperature for 60min, processing the sintered ceramic blocks into 3 half-mouth long bridges in a 5-shaft processing machine, wherein the sintering temperatures are 1450, 1500 and 1550 ℃, and the keeping temperature is 1h.
Example 4
The formulation of each layer of powder of the zirconia sintered body is shown in Table 4.
Table 4 powder formulation of example 4
And uniformly mixing powder of each layer according to a formula shown in the table 4, sequentially filling the powder into a die from a cutting end region, carrying out dry pressing under 160MPa, carrying out sintering at 1250 ℃, keeping the temperature for 60min, processing the sintered ceramic blocks into 3 half-opening long bridges in a 5-shaft processing machine, wherein the sintering temperature is 1450, 1500 and 1550 respectively, and the keeping temperature is 1h.
Comparative example 1
The formulation of each layer of powder of the zirconia sintered body is shown in Table 5.
TABLE 5 powder formulation of comparative example 1
According to the formula shown in the table 5, all layers of powder are uniformly mixed, the mixture is sequentially filled into a die from a cutting end area, the dry pressing pressure is 160MPa, the sintering temperature is 1250 ℃, the heat preservation time is 60min, the sintered ceramic blocks are processed into 3 half-opening long bridges in a 5-shaft processing machine, the sintering temperatures are 1450, 1500 and 1550 ℃, and the heat preservation time is 1h.
The performance test method comprises the following steps:
(1) Fluorescence
The fluorescence effect is visually measured under a UV lamp box with the wavelength of 365nm and is divided into 10 gray levels from weak to strong, wherein 1 is the weakest gray level, and 10 is the strongest gray level.
(2) Fracture toughness:
single V-groove beam method (SEVNB), reference: GB30367-2013 ceramic material single-side V-groove beam method (SEVNB).
Sample size: width w =4.0mm ± 0.2mm;
thickness b =3.0mm ± 0.2mm;
length: should be at least 2mm longer than the test support point span.
(2) Color difference:
a desk-top spectrophotometer color i7 is adopted;
sample size: 15 mm. Times.15 mm. Times.1.6 mm.
(4) Surface roughness
And measuring the roughness of the sample by using a wavelet portable roughness meter, wherein the scanning length is 1.5mm, and the scanning speed is 0.15mm/s.
TABLE 6 fluorescence Effect data for examples 1-4 and comparative example 1
| Cut end | Transition zone | 1 | |
|
Transition zone 4 | Gingival area | |
| Example 1 | 7 | 7 | 7 | —— | —— | 2 | |
| Example 2 | 6 | 6 | 6 | 6 | —— | 2 | |
| Example 3 | 5 | 5 | 5 | —— | —— | 2 | |
| Example 4 | 6 | 6 | 6 | 6 | 6 | 2 | |
| Comparative example 1 | 6 | 5.5 | 5 | 4 | 3.5 | 2 |
As can be seen from Table 6, when the stabilizing agent of the present invention is used for stabilizing zirconia by layering, the fluorescence intensity data of each layer of the tangential region and the transition region are basically the same; while comparative example 1 uses conventional Y 2 O 3 As a stabilizer, the fluorescence intensity data was gradually decreased compared with example 4, which shows that the fluorescence effect gradually decreased as the color was increased. Therefore, the fluorescent effect of the invention has better consistency and better aesthetic property.
TABLE 7 fracture toughness test results
| Example 1 | 4.4MPa·m 1/2 |
| Example 2 | 4.5MPa·m 1/2 |
| Example 3 | 3.9MPa·m 1/2 |
| Example 4 | 4.3MPa·m 1/2 |
As can be seen from Table 7, the fracture toughness of the present invention is high and can reach 4.5 MPa.m 1/2 。
The results of the temperature sensitivity test are as follows: differences among various sheets based on 1450 ℃, and a color difference formula:
ΔE＝[(ΔL) 2 +(Δa) 2 +(Δb) 2 ] 1/2 。
results of color test for each layer:
TABLE 8 color data for example 1 sintering at 1450 deg.C
| L | a | b | |
| Cut end region | 79.2 | 0.1 | 9.2 |
| |
77.9 | 0.3 | 10.0 |
| |
76.5 | 0.4 | 10.8 |
| |
75.1 | 0.6 | 11.5 |
TABLE 9 color difference values for example 1 sintered at different temperatures
| 1450℃ | 1500℃ | 1550℃ | |
| Cut end region | —— | ΔE＝0.5 | ΔE＝0.9 |
| |
—— | ΔE＝0.6 | ΔE＝1.2 |
| |
—— | ΔE＝0.6 | ΔE＝1.5 |
| Gingival area | —— | ΔE＝0.5 | ΔE＝1.1 |
TABLE 10 color data for example 2 sintered at 1450 deg.C
| L | a | b | |
| Cut end region | 77.2 | 0.2 | 10.2 |
| |
75.8 | 0.4 | 11.4 |
| |
74.3 | 0.6 | 12.9 |
| |
73.1 | 0.9 | 14.2 |
TABLE 11 color difference values of example 2 sintered at different temperatures
TABLE 12 color data for example 3 sintering at 1450 deg.C
| L | a | b | |
| Cut end region | 74.3 | 0.4 | 12.8 |
| |
73.1 | 0.6 | 14.3 |
| |
71.8 | 1.1 | 15.9 |
TABLE 13 color difference values for example 3 sintered at different temperatures
| 1450℃ | 1500℃ | 1550℃ | |
| Cut end region | —— | ΔE＝0.9 | ΔE＝1.8 |
| |
—— | ΔE＝0.8 | ΔE＝1.6 |
| |
—— | ΔE＝0.7 | ΔE＝1.5 |
| Gingival area | —— | ΔE＝0.4 | ΔE＝1.2 |
TABLE 14 color data for example 4 sintering at 1450 deg.C
| L | a | b | |
| Cut end region | 78.0 | 0.2 | 9.8 |
| |
77.1 | 0.4 | 10.6 |
| |
76.2 | 0.5 | 11.8 |
| |
74.8 | 0.6 | 12.9 |
| Transition zone 4 | 73.3 | 0.8 | 14.5 |
TABLE 15 color difference values for example 4 sintered at different temperatures
TABLE 16 color data for comparative example 1 sintered at 1450 deg.C
| L | a | b | |
| Cut end region | 80.2 | 0.1 | 9.3 |
| |
79.1 | 0.3 | 10.1 |
| |
77.8 | 0.4 | 11.4 |
| |
75.8 | 0.5 | 12.5 |
| Transition zone 4 | 73.7 | 0.7 | 13.9 |
TABLE 17 color difference values of comparative example 1 sintered at different temperatures
| 1450℃ | 1500℃ | 1550℃ | |
| Cut end region | —— | ΔE＝1.6 | ΔE＝2.2 |
| |
—— | ΔE＝1.7 | ΔE＝2.1 |
| |
—— | ΔE＝1.8 | ΔE＝2.2 |
| Gingival area | —— | ΔE＝0.5 | ΔE＝1.2 |
As can be seen from the chromaticity data and the color difference data of examples 1 to 4, the L values of the cut end regions toward the transition region gradually decrease and a and b gradually increase at the same sintering temperature, indicating that the color gradually deepens. When the sintering temperature was raised to 1500 and 1550 ℃, the color difference Δ E was small compared to 1450 ℃ and the layers remained substantially the same, indicating that a wider range of sintering temperatures could be accommodated. The comparative example varied with sintering temperature, and the color fluctuated greatly.
In summary, the dental fluorescent layered zirconia green body and sintered body of the present invention are layered in thickness, each layer is made of zirconia stabilized with different kinds of stabilizers, and the cut end region is made of 4.5 to 5mol Yb 2 O 3 Stabilized ZrO 2 The transition zone adopts 3.5-4.5mol Tm 2 O 3 Stabilized ZrO 2 The gum area adopts 2.5-3mol Er 2 O 3 Stabilized ZrO 2 . The transmittance is gradually reduced from the cutting end area to the transition area, the color is gradually deepened, and meanwhile, the fluorescence intensity is kept consistent, so that the overall fluorescence effect is ensured. Through a special filling mode, the wavy effect of natural tooth gum can be realized at the interface of the gum area and the transition area, and the simulation purpose is achieved. Meanwhile, the combination of the stabilizers ensures that the material has the minimum color fluctuation and the color difference delta E within the sintering range of 1450-1550 DEG C<1.5. The cutting end region and the transition region adopt Ce as a coloring agent, and the overall toughness reaches 4.5 MPa.m 1/2 。
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A zirconia sintered body, comprising: a first region comprising 4.5-5mol% Yb 2 O 3 Stabilized ZrO 2 Said second region comprising 3.5-4.5mol% Tm 2 O 3 Stabilized ZrO 2 。
2. The zirconia sintered body according to claim 1, wherein the first region and the second region further comprise a colorant CeO 2 Colorant Er 2 O 3 Nd, a colorant 2 O 3 And at least comprises the colorant CeO 2 。
3. The zirconia sintered body as claimed in claim 2, wherein the colorant CeO 2 Comprises 4-6 wt.% of CeO 2 ZrO of 2 (ii) a The colorant Er 2 O 3 To contain 10wt% -12wt% Er 2 O 3 ZrO of 2 (ii) a The colorant Nd 2 O 3 To contain 1-2wt% of Nd 2 O 3 ZrO of 2 。
4. The zirconia sintered body as set forth in claim 1, wherein Yb is reduced by 4.5 to 5mol% in the first region 2 O 3 Stabilized ZrO 2 The content of (A) is 82wt% -95wt%, preferably 85wt% -90wt%; tm in the second region from 3.5 to 4.5mol% 2 O 3 Stabilized ZrO 2 The content of (B) is 60wt% -85wt%, preferably 65wt% -82.5wt%.
5. The zirconia sintered body according to any one of claims 1 to 4, further comprising a third region provided as an outer layer of the second region, the third region comprising 2.5 to 3.5mol％Er 2 O 3 Stabilized ZrO 2 。
6. The zirconia sintered body according to claim 5, wherein the second region further comprises 1 to 6 transition regions, the color of the transition regions gradually deepens from the side close to the first region toward the third region, and the color is controlled by controlling the content of the colorant;
the thicknesses of the first region, the second region and the third region account for 15-25%, 25-55% and 30-50%, respectively.
7. A method for producing the zirconia sintered body according to any one of claims 1 to 6, comprising:
s1, weighing powder materials according to the raw material proportion of each region, uniformly mixing, sequentially filling the corresponding powder materials into a mold according to the region stacking sequence, and performing dry pressing molding;
s2, sintering the formed ceramic block to obtain a zirconia sintered body, wherein the final sintering temperature is 1450-1550 ℃.
8. The method of producing a zirconia sintered body according to claim 7, wherein the step S2 comprises: preserving the heat of the formed ceramic block at 1050-1250 ℃ for 30-180min to obtain a sintered blank; then processing the zirconia powder into a target shape restoration, and sintering the restoration for 15-120min at 1450-1550 ℃ to obtain a zirconia sintered body.
9. The method of producing a zirconia sintered body according to claim 7 or 8, wherein in step S1, after the second region is filled, semi-circular depressions are formed in a close arrangement on the surface thereof, and then the powder of the third region is filled; the radius of the semicircular concave pit is 0.5-2.5mm; the pressure of the dry pressing is not lower than 160MPa;
the powder bulk density of the first area reaches 1.28 +/-0.05 g/cm 3 The sintered density reaches 6.28 +/-0.05 g/cm 3 (ii) a The loose density of the powder in the second area reaches 1.28 +/-0.05 g/cm 3 The sintered density reaches 6.28 +/-0.05 g/cm 3 (ii) a The loose density of the powder in the third area reaches 1.28 +/-0.05 g/cm 3 The sintered density reaches 6.28 +/-0.05 g/cm 3 。
10. Use of the zirconia sintered body according to any one of claims 1 to 6 or the zirconia sintered body obtained by the production method according to any one of claims 7 to 9 in a dental material.
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