TWI806191B - Ceramic material and denture - Google Patents

Abstract

Ceramic material includes 100 parts by weight of yttria-stabilized zirconia (YSZ) doped with 0.1 to 0.6 parts by weight of boron and 0.1 to 3.5 parts by weight of lanthanum, silver, magnesium, or europium. The ceramic material has a transmittance of about 40% to about 45% and a bending stiffness of 600 MPa to 1000 MPa. The ceramic material can be used as denture material.

Description

Ceramic materials and dentures

The disclosure relates to the composition and application of a yttrium stabilized zirconia translucent ceramic material.

The global denture market is expected to reach 18.8 billion US dollars in 2020, while the Chinese denture market will reach more than 2 billion yuan. Zirconia has very good bending strength, so it is very suitable as a ceramic material for making dentures. However, the disadvantage of zirconia is that its transparency is quite low, so it is only suitable for areas that do not require high aesthetics in the mouth, such as the posterior teeth. Therefore, the pre-sintered zirconia-based crown is white, and its milky white with low light transmittance is significantly different from the natural tooth color, which limits its application in anterior tooth restoration. Therefore, it is necessary to modify zirconia to make the finished product as close as possible to the natural tooth color. In addition, modified zirconia must have appropriate strength and toughness in addition to high transparency.

The ceramic material provided in this disclosure includes: 100 parts by weight of yttrium stabilized zirconia, doped with 0.1 to 0.6 parts by weight of boron and 0.1 to 3.5 parts by weight of lanthanum, silver, magnesium, or europium.

In some embodiments, 100 parts by weight of yttrium stabilized zirconia is doped with 0.2 to 0.5 parts by weight of boron and 0.45 to 3.0 parts by weight of lanthanum.

In some embodiments, 100 parts by weight of yttrium stabilized zirconia is doped with 0.2 to 0.5 parts by weight of boron and 0.1 to 0.2 parts by weight of silver.

In some embodiments, 100 parts by weight of yttrium stabilized zirconia is doped with 0.2 to 0.5 parts by weight of boron and 0.75 to 0.85 parts by weight of magnesium.

In some embodiments, 100 parts by weight of yttrium stabilized zirconia is doped with 0.2 to 0.5 parts by weight of boron and 0.5 to 0.6 parts by weight of europium.

In some embodiments, the yttrium stabilized zirconia is tetragonal zirconia doped with yttria, and the weight ratio of yttria to zirconia is 1:99 to 6:94.

In some embodiments, the ceramic material has a grain size of 200 nm to 1000 nm.

In some embodiments, the penetration of the ceramic material is from about 40% to about 45%.

In some embodiments, the ceramic material has a flexural strength of 600 MPa to 1000 MPa.

In some embodiments, the crystalline structure of the ceramic material is cubic.

The denture provided by an embodiment of the present invention comprises 100 parts by weight of yttrium stabilized zirconia; doped with 0.1 to 0.6 parts by weight of boron; and doped with 0.1 to 3.5 parts by weight of lanthanum, silver, magnesium, or europium.

The ceramic material provided in this disclosure includes: 100 parts by weight of yttrium stabilized zirconia, doped with 0.1 to 0.6 parts by weight of boron and 0.1 to 3.5 parts by weight of lanthanum, silver, magnesium, or europium.

For example, 100 parts by weight of yttrium stabilized zirconia is doped with 0.2 to 0.5 parts by weight of boron and 0.45 to 3.0 parts by weight of lanthanum. If the proportion of boron is too low or too high, the ceramic material will have insufficient penetration or insufficient bending strength. If the proportion of lanthanum is too low or too high, the ceramic material will have insufficient penetration or insufficient bending strength.

For example, 100 parts by weight of yttrium stabilized zirconia is doped with 0.2 to 0.5 parts by weight of boron and 0.1 to 0.2 parts by weight of silver. If the proportion of boron is too low or too high, the ceramic material will have insufficient penetration or insufficient bending strength. If the proportion of silver is too low or too high, the ceramic material will have insufficient penetration or insufficient bending strength.

For example, 100 parts by weight of yttrium stabilized zirconia is doped with 0.2 to 0.5 parts by weight of boron and 0.75 to 0.85 parts by weight of magnesium. If the proportion of boron is too low or too high, the ceramic material will have insufficient penetration or insufficient bending strength. If the proportion of magnesium is too low or too high, the ceramic material will have insufficient penetration or insufficient bending strength.

For example, 100 parts by weight of yttrium stabilized zirconia is doped with 0.2 to 0.5 parts by weight of boron and 0.5 to 0.6 parts by weight of europium. If the proportion of boron is too low or too high, the ceramic material will have insufficient penetration or insufficient bending strength. If the proportion of europium is too low or too high, the ceramic material will have insufficient transmittance or insufficient bending strength.

In some embodiments, the yttrium stabilized zirconia is tetragonal zirconia doped with yttria, and the weight ratio of yttria to zirconia is 1:99 to 6:94. If the proportion of yttrium oxide is too low, the penetration will decrease. If the proportion of yttrium oxide is too high, the strength will decrease.

In some embodiments, the ceramic material has a grain size of 200 nm to 1000 nm. The grain size of the original yttrium stabilized zirconia is 200 nm to 600 nm, and there are a lot of holes between the grains. Part (about 5% to 10%) of the ceramic material can be increased in grain size to greater than 600 nm with smaller and fewer voids between the grains (densification) compared to native yttrium stabilized zirconia.

In some embodiments, the penetration of the ceramic material is from about 40% to about 45%. If the penetration of the ceramic material is insufficient or too high, it is not suitable for dentures due to poor visual effect.

In some embodiments, the ceramic material has a flexural strength of 600 MPa to 1000 MPa. If the bending strength of the ceramic material is insufficient, it is easy to break and is not suitable for dentures.

In some embodiments, the crystalline structure of the ceramic material is cubic, distinct from that of native yttrium stabilized zirconia (tetragonal phase).

In some embodiments, the ceramic material is formed as follows. Yttrium stabilized zirconia (YSZ), boron source (such as boron oxide), and lanthanum source (such as lanthanum oxide, lanthanum nitrate, lanthanum chloride, or other suitable lanthanum source), silver source (such as silver oxide, silver nitrate, chloride Silver, or other suitable silver sources), magnesium sources (such as magnesium oxide, magnesium nitrate, magnesium chloride, or other suitable magnesium sources), or europium sources (such as europium oxide, europium nitrate, europium chloride, or other suitable europium sources) are added After a suitable solvent (such as pure water), a dispersant is added for wet ball milling to obtain a slurry. The slurry is dried to form a powder, and the powder is calcined at 650°C to 900°C. After the powder is calcined, a dispersant and a binder are added for mixing and spray drying, and the powder is made into a granulated powder. The granulated powder is dry-pressed, and the dry-pressed ceramic green body is pre-sintered to remove at least part of the binder to obtain a pre-sintered ceramic material. For example, the pre-sintering temperature may be 900° C. to 1050° C., and the sintering time may be about 24 hours to 36 hours.

Then process the pre-fired ceramic material to obtain a product whose size is enlarged in proportion to the predetermined denture size, and perform high-temperature sintering to obtain sintered ceramics with shrinkage in size (slightly larger than the predetermined denture size). In one embodiment, the high-temperature sintering temperature is higher than the pre-sintering temperature, and the pre-fired ceramic material is subjected to high-temperature sintering, heated to 1450° C. to 1550° C. in the atmosphere and sintered for 2 to 6 hours to obtain sintered ceramics. The sintered ceramics are then Polished to obtain dentures.

In some embodiments, the sintered ceramics described above can be used as dentures. Since dentures have a complex three-dimensional structure, dispersants and adhesives can be used to make the composition of ceramic materials in dentures uniform. In some embodiments, the weight ratio of ceramic raw material (such as yttrium stabilized zirconia, boron source, and lanthanum source, silver source, magnesium source, or europium source) to dispersant is 99.3:0.7 to 80:20. In some embodiments, the weight ratio of ceramic raw material (eg, yttrium stabilized zirconia, boron source, and lanthanum source, silver source, magnesium source, or europium source) to binder is 94:6 to 85:15. If the ratio of the dispersing agent to the bonding agent is too low, the ceramic material cannot be uniformly dispersed, resulting in uneven composition of the denture. If the ratio of the dispersing agent to the bonding agent is too high, it may remain in the final denture and deteriorate the properties of the denture.

It can be understood that the above-mentioned ceramic materials are not limited to be used in dentures, but can also be used in other aspects such as: mobile phone back cover shells or artistic ceramic materials. On the other hand, the method of forming ceramic materials and dentures is not limited to the above steps, and other steps and process parameters can be used.

In order to make the above content and other purposes, features, and advantages of this disclosure more comprehensible, the preferred embodiments are listed below and described in detail as follows: [Example]

In the following examples, yttrium stabilized zirconia (YSZ) is 97% zirconia purchased from TOSOH, and the weight ratio of yttrium oxide to zirconia is 3:97. The transmittance of the sample was measured by a UV/Visible Spectrometer (Jasco UV‐670, UV‐VIS SPECTROPHOTOMETER), and the transmittance of a ceramic material sample with a thickness of 1 mm was measured in the range of light wavelength 400-800nm. The measurement method of the flexural strength of ceramic materials is CNS 12701 precision ceramic flexural strength (destruction modulus) test method.

Example 1 YSZ, boron oxide, and lanthanum oxide were taken according to the equivalent ratio, added to pure water, and fine ceramic dispersant D305 (purchased from Zhongjing Oil) was added for wet ball milling to obtain a slurry. After the slurry is dried to form a powder, the powder is calcined at 650°C to 900°C. After calcining, D305 is added and mixed with polyvinyl alcohol to perform spray drying and other processes to make the powder into a granulated powder . Then dry-press the granulated powder, and sinter the dry-pressed ceramic green body at 900°C to 1050°C for 24 hours to 36 hours to remove at least part of the dispersant and binder to obtain pre-fired ceramics Material. Then, the pre-fired ceramic material is sintered at 1450° C. to 1550° C. for 2 to 6 hours in an atmospheric environment to obtain a sintered ceramic material (denture). The characteristics of the sintered ceramic materials such as penetration rate and bending strength were measured. The original YSZ has a penetration rate of 27.92%. The transmittance of YSZ doped with 0.35 parts by weight of boron (YSZ is 100 parts by weight) is 37.89%. The transmittance of YSZ doped with 0.35 parts by weight of boron and 0.45 parts by weight of lanthanum (YSZ is 100 parts by weight) is 41.07%. The transmittance of YSZ doped with 0.35 parts by weight of boron and 1.02 parts by weight of lanthanum (100 parts by weight of YSZ) is 40.29%. The transmittance of YSZ doped with 0.35 parts by weight of boron and 2.07 parts by weight of lanthanum (YSZ is 100 parts by weight) is 37.92%. The transmittance of YSZ doped with 0.72 parts by weight of boron and 0.45 parts by weight of lanthanum (100 parts by weight of YSZ) is 35.71%. The transmittance of YSZ doped with 1.04 parts by weight of boron and 0.45 parts by weight of lanthanum (100 parts by weight of YSZ) is 35.31%. In addition, YSZ doped with 0.35 parts by weight of boron and 0.45 parts by weight of lanthanum (100 parts by weight of YSZ) has a bending strength of 680.09 MPa.

Table 1 Composition of Example 1 Penetration rate (%) Bending strength (MPa) YSZ=100 27.92 996.36 YSZ: B=100: 0.35 37.89 717.94 YSZ: B: La=100: 0.35: 0.45 41.07 680.09 YSZ: B: La=100: 0.35: 1.02 40.29 Not measured YSZ: B: La=100: 0.35: 2.07 37.91 Not measured YSZ: B: La=100: 0.72: 0.45 35.71 Not measured YSZ: B: La=100: 1.04: 0.45 35.31 Not measured

The undoped YSZ was observed by SEM, the grain size was 200 nm to 600 nm, and there were a lot of holes between the grains. Observation by SEM of YSZ doped with 0.35 parts by weight of boron (YSZ is 100 parts by weight), the grain size is about 200 nm to 600 nm, and the holes between the grains become less and smaller (compared with the original YSZ dense). With the YSZ (YSZ is 100 weight parts) of the boron of doping 0.35 weight part and the lanthanum of 0.45 weight part, its grain becomes bigger, and grain size is about 200 nm to 1000 nm (there are 5% to 10% grain greater than 600 nm), and the pores between the grains become less and smaller (compared with the original YSZ, denser).

Example 2 YSZ, boron oxide, and silver oxide are taken according to the equivalent ratio, and the sintered ceramic material is prepared as in the first step of the embodiment, and the properties such as penetration rate and bending strength are measured. The original YSZ has a penetration rate of 27.92%. The transmittance of YSZ doped with 0.35 parts by weight of boron (YSZ is 100 parts by weight) is 37.89%. The transmittance of YSZ doped with 0.35 parts by weight of boron and 0.17 parts by weight of silver (YSZ is 100 parts by weight) is 40.16%. In addition, YSZ doped with 0.35 parts by weight of boron and 0.17 parts by weight of silver (100 parts by weight of YSZ) has a bending strength of 853.28 MPa.

Table 2 Composition of Example 2 Penetration rate (%) Bending strength (MPa) YSZ=100 27.92 996.36 YSZ:B:=100:0.35 37.89 717.94 YSZ: B: Ag=100: 0.35: 0.17 40.16 853.28

Example 3 YSZ, boron oxide, and magnesium oxide were selected according to the equivalent ratio, and the sintered ceramic material was obtained as in the first step of the embodiment, and the penetration rate and bending strength of the original YSZ were measured. The penetration rate of the original YSZ was 27.92%. The transmittance of YSZ doped with 0.35 parts by weight of boron (YSZ is 100 parts by weight) is 37.89%. The transmittance of YSZ doped with 0.35 parts by weight of boron and 0.80 parts by weight of magnesium (100 parts by weight of YSZ) is 38.47%. In addition, YSZ doped with 0.35 parts by weight of boron and 0.80 parts by weight of magnesium (100 parts by weight of YSZ) has a bending strength of 627.20 MPa.

table 3 Composition of Example 3 Penetration rate (%) Bending strength (MPa) YSZ=100 27.92 996.36 YSZ:B:=100:0.35 37.89 717.94 YSZ: B: Mg=100:0.35:0.80 38.47 627.20

Example 4 YSZ, boron oxide, and europium oxide were taken according to the equivalent ratio, and the sintered ceramic material was prepared as in the steps of Example 1, and the properties such as transmittance and bending strength were measured. The original YSZ has a penetration rate of 27.92%. The transmittance of YSZ doped with 0.35 parts by weight of boron (YSZ is 100 parts by weight) is 37.89%. The transmittance of YSZ doped with 0.35 parts by weight of boron and 0.55 parts by weight of europium (YSZ is 100 parts by weight) is 39.77%. In addition, YSZ doped with 0.35 parts by weight of boron and 0.55 parts by weight of europium (100 parts by weight of YSZ) has a bending strength of 615.56 MPa.

Table 4 Composition of Example 4 Penetration rate (%) Bending strength (MPa) YSZ=100 27.92 996.36 YSZ:B:=100:0.35 37.89 717.94 YSZ: B: Eu=100: 0.35: 0.55 39.77 615.56

Comparative example 1 YSZ, boron oxide, and zinc oxide were selected according to the equivalent ratio, and the sintered ceramic material was prepared as in the first step of the embodiment, and the properties such as penetration rate and bending strength were measured. The original YSZ has a penetration rate of 27.92%. The transmittance of YSZ doped with 0.35 parts by weight of boron (YSZ is 100 parts by weight) is 37.89%. The YSZ (YSZ is 100 weight parts) of the zinc doping 0.35 weight parts boron and 1.07 weight parts its transmittance is 35.56%, is lower than the YSZ (YSZ is 100 weight parts) of the boron doping only 0.35 weight parts Penetration rate (27.92%).

table 5 Comparative Example 1 Composition Penetration rate (%) Bending strength (MPa) YSZ=100 27.92 996.36 YSZ:B:=100:0.35 37.89 717.94 YSZ: B: Zn=100: 0.35: 1.07 35.56 888

Comparative example 2 YSZ and lanthanum oxide were selected according to the equivalent ratio, and the sintered ceramic material was obtained as in the first step of the embodiment, and the properties such as the penetration rate and the bending strength were measured. The transmittance of YSZ (YSZ is 100 parts by weight) doped with 0.45 parts by weight of lanthanum is 38.00%, which is lower than that of YSZ (YSZ is 100 parts by weight) doped with 0.35 parts by weight of boron and 0.45 parts by weight of lanthanum. Transmittance (41.07%).

Table 6 Comparative Example 2 Composition Penetration rate (%) Bending strength (MPa) YSZ:La:=100:0.45 38.00 254.18 Example 1 Composition Penetration rate (%) Bending strength (MPa) YSZ: B: La=100: 0.35: 0.45 41.07 680.09

Comparative example 3 YSZ and silver oxide are taken according to the equivalent ratio, and the sintered ceramic material is obtained as in the first step of the embodiment, and the properties such as the penetration rate and the bending strength are measured. The transmittance of YSZ (YSZ is 100 parts by weight) doped with 0.17 parts by weight of silver is 38.39%, which is lower than that of YSZ (YSZ is 100 parts by weight) of silver doped with 0.35 parts by weight of boron and 0.17 parts by weight. Transmittance (40.16%).

Table 7 Comparative Example 3 Composition Penetration rate (%) Bending strength (MPa) YSZ=100 27.92 996.36 YSZ: Ag=100: 0.17 38.39 988.61 Example 2 Composition Penetration rate (%) Bending strength (MPa) YSZ: B: Ag=100: 0.35: 0.17 40.16 853.28

Comparative example 4 YSZ and magnesium oxide are taken according to the equivalent ratio, and the first step of the embodiment is used to obtain a sintered ceramic material for measurement of characteristics such as penetration rate and bending strength. The transmittance of YSZ (YSZ is 100 parts by weight) doped with 0.80 parts by weight of magnesium is 36.68%, which is lower than that of YSZ (YSZ is 100 parts by weight) doped with 0.35 parts by weight of boron and magnesium. Transmittance (38.47%).

Table 8 Comparative Example 4 Composition Penetration rate (%) Bending strength (MPa) YSZ:Mg=100:0.8 36.68 671.42 Example 3 Composition Penetration rate (%) Bending strength (MPa) YSZ: B: Mg=100: 0.35: 0.80 38.47 627.20

Comparative Example 5 YSZ and europium oxide were taken according to the equivalent ratio, and the sintered ceramic material was prepared as in the first step of the embodiment, and the properties such as transmittance and bending strength were measured. The transmittance of YSZ (YSZ is 100 parts by weight) doped with 0.55 parts by weight of europium is 38.17%, which is lower than that of YSZ (YSZ is 100 parts by weight) doped with 0.35 parts by weight of boron and 0.55 parts by weight of europium. Transmittance (39.77%).

Table 9 Comparative Example 5 Composition Penetration rate (%) Bending strength (MPa) YSZ: Eu=100: 0.55 38.17 513.17 Example 4 Composition Penetration rate (%) Bending strength (MPa) YSZ: B: Eu=100: 0.35: 0.55 39.77 615.56

Comparative example 6 The YSZ and tellurium oxide are taken according to the equivalent ratio, and the sintered ceramic material is prepared as in the first step of the embodiment, and the properties such as the transmittance and the bending strength are measured. The transmittance of YSZ doped with 0.21 parts by weight of tellurium (YSZ is 100 parts by weight) is 26.28%, which is lower than that of the original YSZ (27.92%).

Table 10 Comparative Example 6 Composition Penetration rate (%) Bending strength (MPa) YSZ:Te=100:0.21 26.28 756.89 Example 1 Composition Penetration rate (%) Bending strength (MPa) YSZ=100 27.92 996.36

Comparative Example 7 YSZ and calcium oxide were taken according to the equivalent ratio, and the sintered ceramic material was prepared as in the steps of Example 1, and the properties such as penetration rate and bending strength were measured. . The transmittance of YSZ (YSZ is 100 wt%) doped with 1.32 parts by weight of calcium is 28.73%, which is lower than the transmittance of yttrium stabilized zirconia doped with boron and lanthanum, silver, magnesium, or europium in the examples .

Table 11 Comparative Example 7 Composition Penetration rate (%) Bending strength (MPa) YSZ:Ca=100:1.32 28.73 469.80 YSZ:B:La=100:1.04:0.45 35.31 Not measured YSZ:B:Ag=100:0.35:0.17 40.16 Not measured YSZ:B:Mg=100:0.35:0.80 38.47 627.20 YSZ:B:Eu=100:0.35:0.55 39.77 615.56

Although the disclosure has been disclosed above with several preferred embodiments, it is not intended to limit the disclosure. Anyone with ordinary knowledge in the technical field can make any changes without departing from the spirit and scope of the disclosure. and retouching, so the scope of protection of this disclosure should be defined by the scope of the appended patent application.

none.

Claims (11)

A ceramic material comprising: 100 parts by weight of yttrium stabilized zirconia; doped with 0.1 to 0.6 parts by weight of boron; and Doped with 0.1 to 3.5 parts by weight of lanthanum, silver, magnesium, or europium. The ceramic material according to claim 1, wherein 100 parts by weight of yttrium stabilized zirconia is doped with 0.2 to 0.5 parts by weight of boron and 0.45 to 3.0 parts by weight of lanthanum. The ceramic material according to claim 1, wherein 100 parts by weight of yttrium stabilized zirconia is doped with 0.2 to 0.5 parts by weight of boron and 0.1 to 0.2 parts by weight of silver. The ceramic material according to claim 1, wherein 100 parts by weight of yttrium stabilized zirconia is doped with 0.2 to 0.5 parts by weight of boron and 0.75 to 0.85 parts by weight of magnesium. The ceramic material according to claim 1, wherein 100 parts by weight of yttrium stabilized zirconia is doped with 0.5 to 0.5 parts by weight of boron and 0.5 to 0.6 parts by weight of europium. The ceramic material according to claim 1, wherein the yttrium stabilized zirconia includes tetragonal zirconia doped with yttria, and the weight ratio of yttrium oxide to zirconia is 1:99 to 6:94. As the ceramic material of claim 1, the grain size is from 200 nm to 1000 nm. As the ceramic material of claim 1, its penetration is about 40% to about 45%. As the ceramic material of claim 1, its bending strength is 600 MPa to 1000 MPa. As the ceramic material of claim 1, its crystal structure is cubic crystal. A denture consisting of: 100 parts by weight of yttrium stabilized zirconia; doped with 0.1 to 0.6 parts by weight of boron; and Doped with 0.1 to 3.5 parts by weight of lanthanum, silver, magnesium, or europium.