CN115745601B - Zirconia sintered body, method for producing the same and use thereof in dental material - Google Patents
Zirconia sintered body, method for producing the same and use thereof in dental material Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000005548 dental material Substances 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000005245 sintering Methods 0.000 claims abstract description 46
- 230000000694 effects Effects 0.000 claims abstract description 31
- 238000002834 transmittance Methods 0.000 claims abstract description 10
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 8
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 7
- 230000007704 transition Effects 0.000 claims description 57
- 239000000843 powder Substances 0.000 claims description 43
- 239000003086 colorant Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 19
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000006467 substitution reaction Methods 0.000 abstract description 5
- 229910052691 Erbium Inorganic materials 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 21
- 238000005520 cutting process Methods 0.000 description 18
- 238000009472 formulation Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000004321 preservation Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004737 colorimetric analysis Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000003247 decreasing effect Effects 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- 241001270131 Agaricus moelleri Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000004053 dental implant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- 210000004195 gingiva Anatomy 0.000 description 1
- 210000004283 incisor Anatomy 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 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 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
- 238000010186 staining Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000001060 yellow colorant Substances 0.000 description 1
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; the first region comprises 4.5-5mol% Yb 2 O 3 Stabilized ZrO 2 The second region comprises 3.5 to 4.5mol% Tm 2 O 3 Stabilized ZrO 2 The third region comprises 2.5-3.5mol% Er 2 O 3 Stabilized ZrO 2 . The invention uses Yb 2 O 3 、Tm 2 O 3 、Er 2 O 3 Layered substitution Y 2 O 3 As the stabilizer, the zirconia is stabilized, so that the transmittance and the color of each layer are gradually changed, the overall fluorescence effect is kept uniform, a better aesthetic effect is achieved, and the effect that the color difference value is not obviously different in the sintering temperature range of 1450-1550 ℃ 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, with 3mol% yttria-stabilized zirconia and 5mol% yttria-stabilized zirconia being widely used in the field of dental restorations. As doctor and patient demand for aesthetics is increasing, layered tiles can mimic natural teeth to provide a gradual change from cut end to neck, with gum portions often achieved by external staining with porcelain powder.
The natural tooth has fluorescent effect and can emit blue-white fluorescence under the irradiation of light with special wavelengthMany repair materials also attempt to simulate such a fluorescence effect, but often the fluorescence effect is layered and the overall fluorescence effect is uneven. Meanwhile, fe element can not be added as a colorant for realizing the fluorescence effect, and for Y 2 O 3 Stabilized ZrO 2 Other yellow colorants can suffer from relatively large color deviations at different sintering temperatures, and limit the application of such materials.
The prior layered zirconia ceramic block realizes the gradient effect of the transmittance through the different content of yttrium oxide of each layer, realizes the gradient effect of the color through the different content of coloring materials of each layer, and realizes the fluorescence effect through introducing fluorescent agent. However, the mode can cause that the fluorescence effect is obvious when the cut end has high transmittance and light color, and the fluorescence effect is poor when the neck has low transmittance and light color, so that the whole fluorescence effect is uneven.
Disclosure of Invention
The invention aims to provide a zirconia sintered body, a preparation method thereof and application thereof in dental materials, and the zirconia sintered body is prepared from Yb 2 O 3 、Tm 2 O 3 Layered substitution Y 2 O 3 As the stabilizer, the zirconia is stabilized, so that the transmittance and the color of each layer are gradually changed, the overall fluorescence effect is kept uniform, a better aesthetic effect is achieved, and the effect that the color difference value is not obviously different in the sintering temperature range of 1450-1550 ℃ can be realized.
In order to achieve the above object, the present invention provides a zirconia sintered body comprising: a first region and a second region, the first region comprising 4.5-5mol% Yb 2 O 3 Stabilized ZrO 2 The second region comprises 3.5 to 4.5mol% Tm 2 O 3 Stabilized ZrO 2 。
Further, the first region and the second region further comprise a colorant CeO 2 Colorant Er 2 O 3 Colorant Nd 2 O 3 And at least comprises the colorant CeO 2 。
Further, the colorant CeO 2 To contain 4 to 6 weight percent CeO 2 ZrO of (2) 2 The method comprises the steps of carrying out a first treatment on the surface of the The colorant Er 2 O 3 To contain 10wt% to 12wt% of Er 2 O 3 ZrO of (2) 2 The method comprises the steps of carrying out a first treatment on the surface of the The colorant Nd 2 O 3 To contain 1wt% to 2wt% Nd 2 O 3 ZrO of (2) 2 。
Further, said 4.5-5mol% Yb in the first region 2 O 3 Stabilized ZrO 2 The content of (2) is 82-95 wt%, preferably 85-90 wt%; said 3.5-4.5mol% Tm in the second region 2 O 3 Stabilized ZrO 2 The content of (C) is 60-85 wt%, preferably 65-82.5 wt%.
Further, the zirconia sintered body further comprises a third region arranged on the outer layer of the second region, wherein the third region contains 2.5-3.5mol% of Er 2 O 3 Stabilized ZrO 2 。
Further, the second area further comprises 1-6 transition areas, the transition areas gradually deepen from one side close to the first area to one side close to the third area, and the color is regulated and controlled by regulating and controlling the content of the coloring agent. The thickness of the transition regions of the layers may be equal or successively increased.
Further, the first, second and third regions have a thickness ratio of 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, comprising the following steps:
s1, weighing and uniformly mixing the powder according to the raw material proportion of each region, sequentially filling the corresponding powder into a mould according to the region stacking sequence, and dry-pressing to form;
s2, sintering the formed ceramic blocks to obtain a zirconia sintered body, wherein the final sintering temperature is 1450-1550 ℃.
Further, step S2 includes: preserving the temperature of the formed porcelain blocks at 1050-1250 ℃ for 30-180min to obtain a sintered blank; then processing the zirconium oxide sintered body into a target shape restoration body, and sintering the zirconium oxide sintered body at 1450-1550 ℃ for 15-120min.
Further, in step S1, after the second area is filled, a semi-circular pit is formed on the surface of the second area, and then powder in the third area is filled; the radius of the semicircular pit is 0.5-2.5mm; the pressure of the dry press molding is not lower than 160MPa. In this way, the wavy effect of natural teeth and gums can be realized at the interface of the gum region (third region) and the transition region by the special filling mode of the powder, and the simulation purpose is achieved.
Further, the bulk density of the powder in the first region reaches 1.28+/-0.05 g/cm 3 The sintering density reaches 6.28+/-0.05 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The bulk density of the powder in the second area reaches 1.28+/-0.05 g/cm 3 The sintering density reaches 6.28+/-0.05 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The bulk density of the powder in the third area reaches 1.28+/-0.05 g/cm 3 The sintering density reaches 6.28+/-0.05 g/cm 3 . In this way, the shrinkage consistency of each layer is better, and the edge adhesion of the final restoration is ensured.
The invention also provides the use of a zirconia sintered body in a dental material, such as a dental prosthesis, a dental correction product or a dental implant product. Wherein the first region corresponds to a incisor region of the artificial tooth, the second region corresponds to a transition region, and the third region corresponds to a gingival region.
The beneficial effects of the invention are as follows:
1. the zirconium oxide sintered body provided by the invention is prepared by Yb 2 O 3 、Tm 2 O 3 Layered substitution Y 2 O 3 As the stabilizer for stabilizing the zirconia, the aim of keeping the fluorescence effect of each layer basically consistent while gradually reducing the transmittance and gradually deepening the color in the thickness can be realized, so that a better aesthetic effect is achieved.
2. The fluorescent layered zirconia 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 adhesion of the final restoration. Ce is adopted as a colorant in the cutting area and the transition area, and the whole toughness can reach 4.5 MPa.m at maximum 1/2 。
3. According to the invention, the wavy effect of natural gingiva can be realized at the interface of the gingival area and the transition area by a special filling mode of powder, the simulation purpose is achieved, and meanwhile, the integrated sintering molding is realized, so that the preparation method is simple, and the practical application is convenient.
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 of another layer structure 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
For the purpose of making 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 apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, the present invention provides a zirconia sintered body comprising: 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 relative to zirconia) stable ZrO 2 The second region 2 comprises 3.5-4.5mol% Tm 2 O 3 Stabilized ZrO 2 . Thus, by Yb 2 O 3 、Tm 2 O 3 Layered substitution Y 2 O 3 When a pigment is properly added to each layer, the zirconia is stabilized as a stabilizer, and the purpose of keeping the fluorescence effect of each layer uniform while gradually decreasing the transmittance and gradually deepening the color from the first region 1 to the second region 2 can be achieved.
In some embodiments, the first region and the second region further comprise a colorant CeO 2 (yellow material) colorant Er 2 O 3 (red color material), coloringNd agent 2 O 3 (grey material) and at least comprises a colorant CeO 2 . Preferably, the colorant CeO 2 To contain 4 to 6 weight percent CeO 2 ZrO of (2) 2 The method comprises the steps of carrying out a first treatment on the surface of the Coloring agent Er 2 O 3 To contain 10wt% to 12wt% of Er 2 O 3 ZrO of (2) 2 The method comprises the steps of carrying out a first treatment on the surface of the Colorant Nd 2 O 3 To contain 1wt% to 2wt% Nd 2 O 3 ZrO of (2) 2 . The color and the transmittance of the first area 1 and the second area 2 are regulated and controlled by regulating and controlling the proportion of each component, and the fluorescence is not influenced. Wherein, the first area 1 and the second area 2 adopt CeO 2 As a colorant, the overall toughness can reach 4.5 MPa.m 1/2 。
Specifically, 4.5 to 5mol% Yb in the first region 1 2 O 3 Stabilized ZrO 2 The content of (2) is 82-95 wt%, preferably 85-90 wt%; 3.5-4.5mol% Tm in second region 2 2 O 3 Stabilized ZrO 2 The content of (C) is 60-85 wt%, preferably 65-82.5 wt%.
The invention can also add a layer of third area 3 on the second area 2, the third area 3 contains 2.5-3.5mol% Er 2 O 3 Stabilized ZrO 2 (red color material). When used in the preparation of dental materials, such as crowns, the third region 3 corresponds to the gingival area of an artificial tooth and the first and second regions 1 and 2 correspond to the cutting and transition regions, respectively, so that an integrated sintering is achieved. Er in third region 3 2 O 3 Meanwhile, the coloring and stabilizing effects are achieved, so that the sintering stability and interface bonding adhesion of the three-layer area are ensured.
In particular, as shown in fig. 2, the second region 2 further comprises 1-10 transition regions, preferably 1-6 transition regions, wherein the transition regions gradually deepen in color from one side close to the first region 1 to one side of the third region 3, and the color of each transition region is regulated by regulating the content of the colorant. For example, FIG. 2 includes a first transition zone 21, a second transition zone 22, and a third transition zone 23, with 3.5-4.5mol% Tm in the three transition zones 2 O 3 Stabilized ZrO 2 The content of (white material) gradually decreases, and the color yellow and redThe contents of the material and gray material are gradually increased so that the color is gradually deepened.
To achieve the fluorescent effect, fe element can not be added as a colorant for Y 2 O 3 The color deviation of the stabilized zirconia other colorants can be relatively large at different sintering temperatures. The experiment of the invention shows that the sintering according to the formula can realize the effect that the color difference values of all layers have no obvious difference in the sintering temperature range of 1450-1550 ℃, so the practicability and the aesthetic property are higher.
In some embodiments, the specific formulation and process of the invention is as follows:
cut end region (first region 1):
white coloring material: 4.5-5mol% Yb-ZrO 2 ；
Yellow pigment: 4-6wt% CeO 2 ；
Red pigment: 10-12wt% Er 2 O 3 ；
Gray color: 1-2wt% Nd 2 O 3 ；
Bulk density 1.28.+ -. 0.05g/cm 3 Sintered density of 6.28+ -0.05 g/cm 3 。
Transition zone (second zone 2):
white coloring material: 3.5-4.5mol% Tm-ZrO 2 ；
Yellow pigment: 4-6wt% CeO 2 ；
Red pigment: 10-12wt% Er 2 O 3 ；
Gray color: 1-2wt% 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. Respectively weighing four color powders of white, yellow, red and gray in a cutting end area according to a preset proportion, uniformly mixing, taking the powder as a cutting end layer, and filling the powder into a die;
b. respectively weighing four color powders of white, yellow, red and gray in a transition area according to a preset proportion, uniformly mixing, sequentially filling the four color powders into a mold as a transition layer, wherein the transition layer is N layers (N is more than or equal to 1); in the step a and the step b, each layer of powder is scraped after being added into a die, and then the next layer of powder is added;
c. making unequal semicircular pits which are closely arranged on the surface of the last layer of the transition layer by using a die; filling powder in the gingival area; the radius of the semicircular pit is 0.5-2.5mm;
d. dry-pressing and molding under a certain pressure; the pressure is not lower than 160MPa, for example, 160-230MPa.
e. Sintering the formed porcelain blocks; sintering temperature is 1050-1250 ℃; the heat preservation time is 30-180min;
f. the sintered blank is processed into a dental crown through CAD/CAM; carving the sintered blank into a repairing body in a four-axis or five-axis processing machine;
g. sintering the crown into a 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 the zirconia sintered body is shown in table 1.
TABLE 1 powder formulation of example 1
The powder materials of all layers are uniformly mixed according to the formula of the table 1, the powder materials are sequentially filled into a die from a cutting end region, the dry pressing pressure is 180MPa, the sintering temperature is 1100 ℃, the heat preservation time is 120min, the sintered ceramic blocks are processed into 3 half-mouth long bridges in a 5-axis processing machine, the sintering temperature is 1450 ℃, 1500 ℃ and 1550 ℃, and the heat preservation time is 2h.
Example 2
The formulation of each layer of powder of the zirconia sintered body is shown in table 2.
TABLE 2 powder formulation of example 2
Powder materials of all layers are uniformly mixed according to the formula of the table 2, the powder materials are sequentially filled into a die from a cutting end region, 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, and the sintering temperatures are 1450, 1500 and 1550 ℃ respectively, and the heat preservation time is 2h.
Example 3
The formulation of each layer of powder of the zirconia sintered body is shown in table 3.
TABLE 3 powder formulation of example 3
Powder materials of all layers are uniformly mixed according to the formula of the table 3, the powder materials are sequentially filled into a die from a cutting end region, the dry pressing pressure is 220MPa, the sintering temperature is 1050 ℃, the heat preservation time is 60min, the sintered ceramic blocks are processed into 3 half-mouth long bridges in a 5-shaft processing machine, and the sintering temperatures are 1450, 1500 and 1550 ℃ respectively, and the heat preservation time 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
According to the formula shown in Table 4, all layers of powder are uniformly mixed, the powder is sequentially filled into a die from a cutting end region, 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-mouth long bridges in a 5-shaft processing machine, the sintering temperatures are 1450, 1500 and 1550, and the heat preservation time 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
The powder materials of all layers are uniformly mixed according to the formula of the table 5, the powder materials are sequentially filled into a die from a cutting end region, 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-mouth long bridges in a 5-shaft processing machine, the sintering temperature is 1450, 1500 and 1550 ℃ respectively, and the heat preservation time is 1h.
The performance test method comprises the following steps:
(1) Fluorescence
Visual inspection was performed under a UV lamp box with a wavelength of 365nm, and the fluorescence effect was classified into 10 gray scales from weak to strong, 1 being the weakest, and 10 being the strongest.
(2) Fracture toughness:
single sided V-groove beam method (SEVNB), reference: GB30367-2013 dental single sided V-groove crossbeam method (SEVNB) of ceramic materials.
Sample size: width w=4.0 mm±0.2mm;
thickness b=3.0 mm±0.2mm;
length: should be at least 2mm longer than the test support point span.
(2) Color difference:
adopting a desk-top spectrophotometer color 7;
sample size: 15 mm. Times.15 mm. Times.1.6 mm.
(4) Surface roughness
The roughness of the sample is measured by a Waveline portable coarser machine, 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
| Cutting end region | Transition zone 1 | Transition zone 2 | Transition zone 3 | 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, the fluorescence intensity data of each layer of the cutting area and the transition area are basically the same when the stabilizing agent is used for stabilizing zirconia in a layering way; whereas in comparative example 1, conventional Y was used 2 O 3 As a stabilizer, the fluorescence intensity data was gradually decreased as compared with example 4, indicating that the fluorescence effect was gradually decreased as the color was increased. Therefore, the fluorescent effect consistency of the invention is better, and the aesthetics is better.
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 be up to 4.5 MPa.m 1/2 。
The temperature sensitivity test results were as follows: based on 1450 ℃, the difference between the samples and the color difference formula:
ΔE＝[(ΔL) 2 +(Δa) 2 +(Δb) 2 ] 1/2 。
each layer of color test results:
table 8 example 1 colorimetry data sintered at 1450 c
| L | a | b | |
| Cutting end region | 79.2 | 0.1 | 9.2 |
| Transition zone 1 | 77.9 | 0.3 | 10.0 |
| Transition zone 2 | 76.5 | 0.4 | 10.8 |
| Transition zone 3 | 75.1 | 0.6 | 11.5 |
TABLE 9 color difference values of sintering at different temperatures example 1
| 1450℃ | 1500℃ | 1550℃ | |
| Cutting end region | —— | ΔE＝0.5 | ΔE＝0.9 |
| Transition zone 1 | —— | ΔE＝0.6 | ΔE＝1.2 |
| Transition zone 2 | —— | ΔE＝0.6 | ΔE＝1.5 |
| Gingival area | —— | ΔE＝0.5 | ΔE＝1.1 |
Table 10 example 2 colorimetry data sintered at 1450 c
| L | a | b | |
| Cutting end region | 77.2 | 0.2 | 10.2 |
| Transition zone 1 | 75.8 | 0.4 | 11.4 |
| Transition zone 2 | 74.3 | 0.6 | 12.9 |
| Transition zone 3 | 73.1 | 0.9 | 14.2 |
TABLE 11 color difference values of sintering at different temperatures example 2
Table 12 example 3 colorimetry data sintered at 1450 c
| L | a | b | |
| Cutting end region | 74.3 | 0.4 | 12.8 |
| Transition zone 1 | 73.1 | 0.6 | 14.3 |
| Transition zone 2 | 71.8 | 1.1 | 15.9 |
TABLE 13 color difference values of sintering at different temperatures example 3
| 1450℃ | 1500℃ | 1550℃ | |
| Cutting end region | —— | ΔE＝0.9 | ΔE＝1.8 |
| Transition zone 1 | —— | ΔE＝0.8 | ΔE＝1.6 |
| Transition zone 2 | —— | ΔE＝0.7 | ΔE＝1.5 |
| Gingival area | —— | ΔE＝0.4 | ΔE＝1.2 |
Table 14 example 4 colorimetry data sintered at 1450 c
| L | a | b | |
| Cutting end region | 78.0 | 0.2 | 9.8 |
| Transition zone 1 | 77.1 | 0.4 | 10.6 |
| Transition zone 2 | 76.2 | 0.5 | 11.8 |
| Transition zone 3 | 74.8 | 0.6 | 12.9 |
| Transition zone 4 | 73.3 | 0.8 | 14.5 |
TABLE 15 color difference values for sintering at different temperatures example 4
Table 16 comparative example 1 color data sintered at 1450℃
| L | a | b | |
| Cutting end region | 80.2 | 0.1 | 9.3 |
| Transition zone 1 | 79.1 | 0.3 | 10.1 |
| Transition zone 2 | 77.8 | 0.4 | 11.4 |
| Transition zone 3 | 75.8 | 0.5 | 12.5 |
| Transition zone 4 | 73.7 | 0.7 | 13.9 |
Table 17 comparative example 1 color difference values sintered at different temperatures
| 1450℃ | 1500℃ | 1550℃ | |
| Cutting end region | —— | ΔE＝1.6 | ΔE＝2.2 |
| Transition zone 1 | —— | ΔE＝1.7 | ΔE＝2.1 |
| Transition zone 2 | —— | 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 described above, at the same sintering temperature, the L value of the tangential end region gradually decreases and a and b gradually increase, indicating that the color gradually deepens. The color difference ΔE was smaller at 1450 ℃ than at 1500 and 1550 ℃ when the sintering temperature was increased, and the layers remained substantially uniform, indicating the ability to accommodate a wider range of sintering temperatures. The comparative example changed with sintering temperature, and the color fluctuation was large.
As described above, the dental fluorescent layered zirconia green body and sintered body of the present invention are divided in thicknessLayers, each layer adopts zirconium oxide stabilized by different kinds of stabilizers, and the tangential end region adopts 4.5-5mol Yb 2 O 3 Stabilized ZrO 2 The transition zone employs a Tm of 3.5-4.5mol 2 O 3 Stabilized ZrO 2 2.5-3mol Er is adopted in gum region 2 O 3 Stabilized ZrO 2 . The method realizes gradual decrease of the transmittance from the cutting area to the transition area, gradually deepens the color, and simultaneously keeps the fluorescence intensity consistent, thereby ensuring the overall fluorescence effect. By means of special filling, the wavy effect of natural teeth and gums can be achieved at the interface of the gum area and the transition area, and the purpose of simulation is achieved. Meanwhile, the combination of the stabilizers minimizes the color fluctuation and the color difference delta E of the material in the sintering range of 1450-1550 DEG C<1.5. Ce is adopted as a colorant in the cutting area and the transition area, and the overall toughness reaches 4.5 MPa.m 1/2 。
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A zirconia sintered body, comprising: a first region and a second region, the first region comprising 4.5-5mol% Yb 2 O 3 Stabilized ZrO 2 The second region comprises 3.5 to 4.5mol% Tm 2 O 3 Stabilized ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Said 4.5-5mol% Yb in the first region 2 O 3 Stabilized ZrO 2 The content of (2) is 85-90 wt%; said 3.5-4.5mol% Tm in the second region 2 O 3 Stabilized ZrO 2 The content of (2) is 65-82.5 wt%;
the first and second regions further comprise a colorant CeO 2 Colorant Er 2 O 3 Colorant Nd 2 O 3 And at least comprises the colorant CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the The colorant CeO 2 To contain 4 to 6 weight percent CeO 2 ZrO of (2) 2 The method comprises the steps of carrying out a first treatment on the surface of the The colorant Er 2 O 3 To contain 10wt% to 12wt% of Er 2 O 3 ZrO of (2) 2 The method comprises the steps of carrying out a first treatment on the surface of the The colorant Nd 2 O 3 To contain 1wt% to 2wt% Nd 2 O 3 ZrO of (2) 2 The method comprises the steps of carrying out a first treatment on the surface of the So that the transmittance of the first region to the second region is gradually reduced, and the fluorescence effect of each layer is kept consistent while the color is gradually deepened.
2. The zirconia sintered body of claim 1, further comprising a third region disposed on an outer layer of said second region, said third region comprising 2.5 to 3.5mol% er 2 O 3 Stabilized ZrO 2 。
3. The zirconia sintered body according to claim 2, wherein said second region further comprises 1 to 6 layers of transition regions, said transition regions gradually deepening in color from a side near said first region to said third region, and the regulation of color is achieved by regulating the content of the colorant;
the first, second and third regions have a thickness ratio of 15-25%, 25-55% and 30-50%, respectively.
4. A method for producing the zirconia sintered body of any one of claims 1 to 3, comprising:
s1, weighing and uniformly mixing the powder according to the raw material proportion of each region, sequentially filling the corresponding powder into a mould according to the region stacking sequence, and dry-pressing to form;
s2, sintering the formed ceramic blocks to obtain a zirconia sintered body, wherein the final sintering temperature is 1450-1550 ℃.
5. The method for producing a zirconia sintered body as claimed in claim 4, wherein step S2 comprises: preserving the temperature of the formed porcelain blocks at 1050-1250 ℃ for 30-180min to obtain a sintered blank; then processing the zirconium oxide sintered body into a target shape restoration body, and sintering the zirconium oxide sintered body at 1450-1550 ℃ for 15-120min.
6. The method according to claim 4 or 5, wherein in step S1, after the second region is filled, semi-circular pits are formed in a closely arranged surface thereof, and then powder of a third region is filled; the radius of the semicircular pit is 0.5-2.5mm; the pressure of the dry press molding is not lower than 160MPa;
the bulk density of the powder in the first area reaches 1.28+/-0.05 g/cm 3 The sintering density reaches 6.28+/-0.05 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The bulk density of the powder in the second area reaches 1.28+/-0.05 g/cm 3 The sintering density reaches 6.28+/-0.05 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The bulk density of the powder in the third area reaches 1.28+/-0.05 g/cm 3 The sintering density reaches 6.28+/-0.05 g/cm 3 。
7. Use of a zirconia sintered body according to any one of claims 1 to 3 or obtained by the production method according to any one of claims 4 to 6 in a dental material.
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