WO2013003990A1 - 改变牙科氧化锆材料透光性的方法 - Google Patents

改变牙科氧化锆材料透光性的方法 Download PDF

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WO2013003990A1
WO2013003990A1 PCT/CN2011/001934 CN2011001934W WO2013003990A1 WO 2013003990 A1 WO2013003990 A1 WO 2013003990A1 CN 2011001934 W CN2011001934 W CN 2011001934W WO 2013003990 A1 WO2013003990 A1 WO 2013003990A1
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Prior art keywords
soaking
light transmittance
zirconia
sintered
solution
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PCT/CN2011/001934
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English (en)
French (fr)
Inventor
王鸿娟
严庆云
何玲玲
郑艳春
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辽宁爱尔创生物材料有限公司
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Priority to US13/703,610 priority Critical patent/US8697176B2/en
Priority to EP11866437.4A priority patent/EP2573060B1/en
Priority to ES11866437T priority patent/ES2719818T3/es
Priority to KR1020137030585A priority patent/KR101562610B1/ko
Publication of WO2013003990A1 publication Critical patent/WO2013003990A1/zh

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Definitions

  • the present invention relates to a method of modifying the properties of a zirconia material, and more particularly to a method of modifying the light transmission of a dental zirconia material.
  • zirconia ceramics have been used in the bottom of dental fixed prostheses since the 1990s. Crown material.
  • the aesthetic restoration of the anterior teeth used in young patients generally requires porcelain on the inner crown after processing to simulate natural teeth, resulting in an increase in the abutment space, and due to zirconia and There is a difference in the coefficient of thermal expansion of porcelain, and there is a lack of chemical bonding. The bonding strength between porcelain and zirconia is low, which tends to cause the porcelain to peel off, that is, collapse.
  • the present invention is directed to the above problems in the prior art, and provides a method for changing the light transmittance of a dental zirconia material, which solves the problem that the light transmittance of the zirconia material in the prior art cannot meet the translucency of the anterior teeth of a young patient.
  • the problem of the requirements, and the invention is low in cost and stable in quality.
  • the technical solution of the present invention includes the following steps:
  • Preparation preparing water and alcohol-water solution with a concentration of soluble barium salt of 10 to 73 wt%;
  • Soaking I soaking the pre-sintered zirconia in the above solution for 0.5 to 30 minutes; Drying: drying the pre-sintered zirconia after soaking;
  • the above-mentioned dried zirconia sintered body is placed in a box type high-temperature resistance furnace and sintered at 1400 to 1600 ° C for 2 hours to obtain a zirconia material having a high light transmittance or a high overall light transmittance.
  • the drying step and the sintering step further include soaking ⁇ : soaking the soluble strontium salt solution 2 to 10 times.
  • the soaking I and soaking II steps are replaced by a method of applying a soluble barium salt solution, or by soaking in combination with a coating of a soluble barium salt solution.
  • strontium salt solution is replaced with a strontium salt solution.
  • 3Y-TZP is a tetragonal phase, there is phase transformation toughening, the strength is above 100 MPa, but the light transmittance is low, which can not meet the needs of anterior aesthetics; 8Y-FSZ is cubic phase, isotropic, can be translucent or fully transparent
  • the material can meet the requirements of light transmissibility of the anterior cutting end of young patients, but the strength is only about 200 MPa due to the absence of phase transformation and toughening.
  • the strontium or barium salt solution By soaking or brushing the strontium or barium salt solution, the Y content is increased to obtain a material with a high strength and high light transmittance, which is a mixture of tetragonal phase and cubic phase, which satisfies the rupture of the anterior teeth of young patients.
  • Light requirements Moreover, since the light transmittance has met the aesthetic requirements, it is not necessary to polish the porcelain, thereby avoiding the phenomenon of collapse of the porcelain caused by the difference in expansion coefficient between the zirconia and the decorative porcelain.
  • the zirconia material By soaking or brushing the strontium or barium salt solution, the zirconia material can meet the requirements of the light transmissibility of the anterior cut end of the young patient, and the light transmittance of the crown to the cut end is more natural, close to the natural tooth;
  • the crown prepared by adding the colorant itself or dyeing by soaking the dyeing solution has no gradual effect.
  • the color of the crown shows a gradual effect.
  • the operation method of the invention is simple, low in cost and stable in quality. detailed description
  • cerium nitrate polyethylene glycol-water solution a concentration of 10% by weight of cerium nitrate polyethylene glycol-water solution was prepared, and the pre-sintered zirconia was partially immersed in a cerium nitrate solution for 15 minutes, taken out, naturally dried, and finally placed in a box type high temperature resistance furnace at 1400. Sintering at ⁇ 1600 °C, holding for 2 hours, the light-transmissive graded finished product.
  • Specimen size length greater than 20mm, width 4.0mm, thickness 1.2mm span 16mm, loading speed 0.5mm/min o
  • Test results Three-point bending strength 1076MPa.
  • a 30% by weight aqueous solution of cerium nitrate was placed, and the pre-sintered zirconia was partially immersed in a cerium nitrate solution for 30 minutes, taken out, naturally dried, and finally placed in a box type high temperature resistance furnace at 1400 ⁇ 1600.
  • Example 3 The test method was the same as in Example 1. The test results were: three-point bending strength 953 MPa, and reflectance contrast ratio 0.70. Example 3
  • a concentration of 45 wt% of cerium nitrate polyglycol-water solution is set, and the pre-sintered zirconia is partially immersed in a cerium nitrate solution for 5 minutes, taken out, naturally dried, and then the above-mentioned cerium nitrate polyethylene glycol-water The solution is applied to the dried zirconia sintered body, dried naturally, and finally placed in a box type high-temperature resistance furnace at 1400 ⁇ 1600 ⁇ for 2 hours to obtain a light-transmissive graded product.
  • test method was the same as that in the example 1.
  • the test result three-point bending strength 904 MPa, reflectance contrast 0.69.
  • cerium nitrate polyethylene glycol-water solution a concentration of 73% by weight of cerium nitrate polyethylene glycol-water solution was prepared, and the pre-sintered zirconia was partially immersed in a cerium nitrate solution for 0.5 minutes, taken out, naturally dried, and finally placed in a box type high temperature resistance furnace. Sintering at 1400 ⁇ 1600°C, holding for 2h, the light-transmissive graded finished product.
  • Example 5 First, a cerium glycerol nitrate-water solution having a concentration of 60% was placed, and the above-mentioned cerium nitrate-aqueous solution was applied to the pre-sintered zirconia sintered body, dried naturally, and finally placed in a box. The high-temperature resistance furnace is sintered at 1400 ⁇ 1600°C, and the temperature is kept for 2h.
  • Example 6 First, a 50% by weight cerium nitrate tetrahydrofurfuryl alcohol-water solution was placed, and the pre-sintered zirconia was partially immersed in the above-mentioned cerium nitrate tetrahydrofurfuryl alcohol-water solution for 3 minutes, taken out, naturally dried, and then The cerium nitrate tetrahydrofurfuryl alcohol-water solution is applied to the dried zirconia sintered body, dried naturally, and finally sintered in a box type high temperature resistance furnace at 1400 to 1600 ° C for 2 hours to obtain a light transmittance gradient. Finished product.
  • the test method was the same as that in the example 1.
  • the test result three-point bending strength 920 MPa reflectance contrast 0.68.
  • a cerium nitrate polyglycol-water solution having a concentration of 10% by weight was prepared, and the pre-sintered zirconia was partially immersed in a cerium nitrate solution for 10 minutes, taken out, and naturally dried. Repeat soaking 3 times. Finally, it is placed in a box type high temperature resistance furnace and sintered at 1400 ⁇ 1600 °C for 2 hours to obtain a light-transmissive graded finished product.
  • the test method was the same as in Example 1. The test results were: three-point bending strength of 1042 MPa and reflectance contrast of 0.69.
  • a 70 wt% aqueous solution of lanthanum nitrate and a 50% by weight aqueous solution of lanthanum nitrate were placed.
  • the pre-sintered zirconia was partially immersed in a 70 wt% lanthanum nitrate solution for 5 minutes, taken out, naturally dried, and then partially immersed in 50 wt of zirconia. Remove from % aqueous solution of lanthanum nitrate for 5 minutes, and dry naturally. Finally, it is placed in a box type high-temperature resistance furnace and sintered at 1400 ⁇ 1600 °C for 2 hours to obtain a light-transmissive graded finished product.
  • the test method is the same as that in the embodiment 1.
  • the test result is: three-point bending strength 862 MPa, and reflectance contrast 0.67.
  • cerium nitrate polyethylene glycol-water solution a concentration of 73% by weight of cerium nitrate polyethylene glycol-water solution was applied, and the above-mentioned cerium nitrate polyethylene glycol-aqueous solution was applied to the pre-sintered zirconia, taken out, naturally dried, and the coating concentration was 73 wt. % of cerium nitrate polyethylene glycol-water solution was applied twice, and finally placed in a box-type high-temperature resistance furnace at 1400 ⁇ 1600 °C for sintering for 2 hours to obtain a light-transmissive graded finished product.
  • Example 10 The test method was the same as in Example 1. The test results were: three-point bending strength 843 MPa, and reflectance contrast 0.67. Example 10
  • a cerium nitrate polyethylene glycol 600-water solution having a concentration of 10% by weight was prepared, and the pre-sintered zirconia was partially immersed in a cerium nitrate polyethylene glycol 600-water solution for 10 minutes, taken out, and naturally dried. The infusion was repeated 10 times. Finally, it is placed in a box type high temperature resistance furnace and sintered at 1400 ⁇ 1600 °C for 2 hours to obtain a light-transmissive graded finished product.
  • test method is the same as the example 1, the test result: three-point bending strength 905MPa, reflectance contrast

Abstract

一种改变牙科氧化锆材料透光性的方法，包括将经过预烧结的氧化锆通过浸泡或涂刷钇或镱盐溶液，然后干燥并烧结，可得到透光性渐变或整体透光性都很高的氧化锆材料。所述方法简单，成本低，质量稳定。

Description

改变牙科氧化锆材料透光性的方法
技术领域
本发明涉及一种改变氧化锆材料性能的方法， 尤其是改变牙科氧化锆材料 透光性的方法。 背景技术
由于钇稳定四方相氧化锆陶瓷具有良好的生物相容性、 优良的力学性能， 尤其是断裂韧性远高于氧化铝陶瓷， 从上世纪 90年代起氧化锆陶瓷开始用于牙 科固定修复体的底冠材料。 但由于其透光性较差， 用于年轻患者的前牙的美学 修复时一般需要在加工后的内冠上上瓷， 以模拟自然牙， 导致基牙预备空间增 大， 而且由于氧化锆与饰瓷热膨胀系数存在差别， 而且缺少化学结合， 饰瓷与 氧化锆的结合强度低， 易导致饰瓷剥落， 即崩瓷。 氧化锆全瓷牙的临床结果表 明， 氧化锆全瓷牙 5年以后的崩瓷率达到 10%以上。 为了解决崩瓷以及备牙量 大的问题， 不用饰瓷的全解剖形态的透明度较高全氧化锆修复体得到了应用。 但这种修复体的透光性单一， 无法模拟天然牙齿切端较透明的情况， 美学性能 较差。 发明内容
本发明针对上述现有技术中存在的问题， 提供一种改变牙科氧化锆材料透 光性的方法， 解决了现有技术中氧化锆材料透光性不能满足年轻患者前牙切端 对材料透光性的要求的问题， 而且本发明成本低、 质量稳定。 本发明的技术方案包括如下步骤：
配制： 配制可溶性钇盐浓度为 10~73wt%的水、 醇-水溶液；
浸泡 I： 将经过预烧结的氧化锆浸泡在上述溶液中 0.5~30分钟； 干燥： 将上述浸泡后的预烧结氧化锆进行干燥；
烧结： 将上述己干燥的氧化锆烧结体放入箱式高温电阻炉内于 1400~1600 °C烧结， 保温 2h， 得到透光性渐变或整体透光性均很高的氧化锆材料。 所述的干燥步骤与烧结步骤之间还包括浸泡 Π: 浸泡可溶性钇盐溶液 2~10 次。
所述的浸泡 I和浸泡 II步骤替换为涂刷可溶性钇盐溶液的方式， 或者浸泡 与涂刷可溶性钇盐溶液相结合的方式。
所述的钇盐溶液替换为镱盐溶液。
本发明的原理如下：
3Y-TZP为四方相， 存在相变增韧， 强度 lOOOMPa以上， 但是透光率较低， 不能满足前牙美学的需要； 8Y-FSZ为立方相，各向同性， 可获得半透明或全透 明的材料， 可满足年轻患者的前牙切端对材料透光性的要求， 但由于不存在相 变增韧， 强度只有 200MPa左右。 通过浸泡或涂刷钇或镱盐溶液的方式， 增加 Y 含量， 获得相组成为四方相和立方相混合的兼具高强度、 高透光性的材料， 满 足年轻患者的前牙切端对材料透光性的要求。而且由于透光性已满足美学要求， 不需要再上瓷， 从而避免了氧化锆与饰瓷之间膨胀系数差异而导致出现的崩瓷 现象。
本发明的优点效果如下：
通过浸泡或涂刷钇或镱盐溶液， 可使氧化锆材料满足年轻患者的前牙切端 对材料透光性的要求， 牙冠颈部到切端透光性渐变更自然， 与天然牙接近； 并 且通过粉料本身添加着色剂或通过浸泡染色液染色的方式制备的牙冠， 颜色没 有渐变效果， 通过浸泡或涂刷钇或镱盐溶液， 牙冠的颜色呈现渐变的效果。 同 时， 本发明操作方法简明， 成本低， 质量稳定。 具体实施方式
本发明结合具体实施例， 进行详细描述如下。
实施例 1
首先配置浓度为 10wt%的硝酸钇聚乙二醇-水溶液， 将预烧结后的氧化锆部 分浸泡于硝酸钇溶液 15分钟中， 取出， 自然晾干， 最后放入箱式高温电阻炉内 于 1400〜1600°C烧结， 保温 2h， 得透光性渐变成品。
对上述成品的技术指标进行测试如下：
(1)三点弯曲强度 （取样参照氧化锆与饰瓷结合强度测试）
设备： TH8201-S伺服式桌上型万能材料试验机测试。
试样尺寸： 长度大于 20mm， 宽度 4.0mm， 厚度 1.2mm跨距 16mm， 加载 速度 0.5mm/mino
测试结果： 三点弯曲强度 1076MPa。
(2)反射率对比度
试样厚度： 1.0mm。
测试结果： 0.71。 实施例 2
首先配置浓度为 30wt%的硝酸钇水溶液， 将预烧结后的氧化锆部分浸泡于 硝酸钇溶液 30分钟中，取出，自然晾干，最后放入箱式高温电阻炉内于 1400~1600
°C烧结， 保温 2h， 得透光性渐变成品。
测试方法同实施例 1，测试结果:三点弯曲强度 953MPa，反射率对比度 0.70。 实施例 3
首先配置浓度为 45wt%的硝酸镱聚乙二醇-水溶液， 将预烧结后的氧化锆部 分浸泡于硝酸镱溶液 5分钟中， 取出， 自然晾干， 再将上述硝酸镱聚乙二醇-水 溶液涂刷在上述晾干后的氧化锆烧结体上， 自然晾干， 最后放入箱式高温电阻 炉内于 1400~1600Ό烧结， 保温 2h， 得透光性渐变成品。
测试方法同实施例 1，测试结果:三点弯曲强度 904MPa，反射率对比度 0.69。 实施例 4
首先配置浓度为 73^%的硝酸钇聚乙二醇-水溶液， 将预烧结后的氧化锆部 分浸泡于硝酸钇溶液 0.5分钟中， 取出， 自然晾干， 最后放入箱式高温电阻炉内 于 1400~1600°C烧结， 保温 2h， 得透光性渐变成品。
测试方法同实施例 1，测试结果:三点弯曲强度 873MPa，反射率对比度 0.71。 实施例 5 首先配置浓度为 60^%的硝酸钇丙三醇 -水溶液，将上述硝酸钇丙三醇 -水溶 液涂刷在预烧结后的氧化锆烧结体上， 自然晾干， 最后放入箱式高温电阻炉内 于 1400~1600°C烧结， 保温 2h， 得透光性渐变成品。
测试方法同实施例 1，测试结果:三点弯曲强度 898MPa，反射率对比度 0.70。 实施例 6 首先配置浓度为 50^%的硝酸钇四氢糠醇-水溶液， 将预烧结后的氧化锆部 分浸泡于上述硝酸钇四氢糠醇-水溶液中 3分钟， 取出， 自然晾干， 再将上述硝 酸钇四氢糠醇 -水溶液涂刷在上述晾干后的氧化锆烧结体上， 自然晾干， 最后放 入箱式高温电阻炉内于 1400~1600°C烧结， 保温 2h， 得透光性渐变成品。
测试方法同实施例 1，测试结果：三点弯曲强度 920MPa反射率对比度 0.68。 实施例 7
首先配制浓度为 10^%的硝酸钇聚乙二醇-水溶液， 将预烧结后的氧化锆局 部浸泡于硝酸钇溶液 10分钟中， 取出， 自然晾干。 重复浸泡 3次。 最后放入箱 式高温电阻炉内于 1400~1600°C烧结， 保温 2h， 得透光性渐变成品。 测试方法同实施例 1 , 测试结果： 三点弯曲强度 1042MPa， 反射率对比度 0.69。
实施例 8
首先配置浓度为 70wt%硝酸钇水溶液、 50wt%的硝酸镱水溶液， 将预烧结后的 氧化锆局部浸泡于 70wt%硝酸钇溶液中 5分钟， 取出， 自然晾干， 再将氧化锆 局部浸泡于 50wt%的硝酸镱水溶液中 5分钟， 取出， 自然晾干。 最后放入箱式 高温电阻炉内于 1400〜1600°C烧结， 保温 2h, 得透光性渐变成品。
测试方法同实施例 1 ,测试结果:三点弯曲强度 862MPa，反射率对比度 0.67。 实施例 9
首先配置浓度为 73^%的硝酸镱聚乙二醇-水溶液，将上述硝酸镱聚乙二醇- 水溶液涂刷在预烧结后的氧化锆上， 取出， 自然晾干， 再次涂刷浓度为 73wt% 的硝酸镱聚乙二醇-水溶液 2次， 最后放入箱式高温电阻炉内于 1400〜1600°C烧 结， 保温 2h， 得透光性渐变成品。
测试方法同实施例 1，测试结果:三点弯曲强度 843MPa，反射率对比度 0.67。 实施例 10
首先配制浓度为 10wt%的硝酸镱聚乙二醇 600-水溶液， 将预烧结后的氧化 锆局部浸泡于硝酸镱聚乙二醇 600-水溶液 10分钟中， 取出， 自然晾干。 重复浸 泡 10次。 最后放入箱式高温电阻炉内于 1400~1600°C烧结， 保温 2h， 得透光性 渐变成品。
测试方法同实施例 1， 测试结果： 三点弯曲强度 905MPa， 反射率对比度
0.68。
本发明的保护范围以权利要求书为准， 不受具体实施例的限制。

Claims

权 利 要 求
1、 改变牙科氧化锆材料透光性的方法， 其特征在于包括下述步骤： 配制： 配制可溶性钇盐浓度为 10~73wt%的水、 醇-水溶液；
浸泡 I： 将经过预烧结的氧化锆浸泡在上述溶液中 0.5~30分钟；
干燥： 将上述浸泡后的预烧结氧化锆进行干燥；
烧结： 将上述已干燥的氧化锆烧结体放入箱式高温电阻炉内于 1400~1600 °C烧结、 保温 2h， 得到透光性渐变或整体透光性均很高的氧化锆材料。
2、 根据权利要求 1所述的改变牙科氧化锆材料透光性的方法， 其特征在于 可溶性钇盐浓度为 70wt%。
3、 根据权利要求 1所述的改变牙科氧化锆材料透光性的方法， 其特征在于 所述的水、 醇-水溶液中的醇为易溶于水的醇类， 如丙三醇、 乙二醇、 聚乙二醇 600、 四氢糠醇中的任一种。
4、 根据权利要求 1所述的改变牙科氧化锆材料透光性的方法， 其特征在于 所述的干燥步骤与烧结步骤之间还包括浸泡 Π : 浸泡可溶性钇盐溶液 2~10次。
5、 根据权利要求 1或 4所述的改变牙科氧化锆材料透光性的方法， 其特征 在于所述的浸泡 I和浸泡 Π步骤替换为涂刷可溶性钇盐溶液的方式， 或者浸泡 与涂刷可溶性钇盐溶液相结合的方式。
6、 根据权利要求 1、 2、 3或 4所述的改变牙科氧化锆材料透光性的方法， 其特征在于所述的钇盐溶液替换为镱盐溶液。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130224454A1 (en) * 2012-02-23 2013-08-29 Yunoh Jung Non-Pre-Colored Multi-Layer Zirconia Dental Blank that has a Gradual Change in Chroma through a Thickness After Sintering
WO2014021940A1 (en) 2012-08-03 2014-02-06 3M Innovative Properties Company Translucency enhancing solution for zirconia ceramics
US8936848B2 (en) 2012-02-23 2015-01-20 B&D Dental Corp Non-pre-colored multi-layer zirconia dental blank that has a gradual change in translucency through a thickness after sintering
US9668837B2 (en) 2012-02-23 2017-06-06 B & D Dental Corporation Creating a translucent effect within one half of a green body zirconia blank

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102579148A (zh) * 2012-03-05 2012-07-18 深圳市爱尔创科技有限公司 美学全氧化锆修复体的制备方法
US10292795B2 (en) 2012-09-20 2019-05-21 3M Innovation Properties Company Coloring solution for zirconia ceramics
DE102015216056A1 (de) * 2015-08-21 2017-02-23 Dental Direkt GmbH Entfärbeliquid
CN107510514A (zh) * 2016-06-17 2017-12-26 深圳爱尔创口腔技术有限公司 一种牙科氧化锆比色牙片的制备方法及其制备的比色牙片
DE102016009730A1 (de) * 2016-07-28 2018-02-01 Forschungszentrum Jülich GmbH Verfahren zur Verstärkung von transparenten Keramiken sowie Keramik
JP7217699B2 (ja) * 2017-02-21 2023-02-03 株式会社松風 歯科切削加工用ジルコニア被切削体及びその製造方法並びに歯科切削加工用ジルコニア被切削体用透明性向上液及びその使用方法
US11504304B2 (en) * 2017-03-16 2022-11-22 James R. Glidewell Dental Ceramics, Inc. Method for enhancing optical properties in ceramics having applications in dental restorations
EP3601199B1 (de) * 2017-03-23 2024-05-08 Ivoclar Vivadent AG Verfahren zur herstellung eines glasierten keramischen körpers
CN109589270B (zh) * 2017-09-30 2020-10-20 辽宁爱尔创生物材料有限公司 透光率和颜色渐变的牙科材料的制备方法及其制备的产品
KR101925131B1 (ko) 2018-01-11 2019-02-27 이보현 지르코니아 블록의 컬러링 방법
KR20190114849A (ko) * 2018-03-30 2019-10-10 소후 인코포레이티드 지르코니아용 오페이크성 부여액
JP7309395B2 (ja) 2018-03-30 2023-07-18 株式会社松風 ジルコニア用オペーク性付与液
KR102231349B1 (ko) 2019-06-10 2021-03-23 송두빈 6 이상의 반투명도를 갖는 지르코니아 코어-세라믹 치과용 보철물 및 그 제조방법
US20210236389A1 (en) * 2020-02-03 2021-08-05 James R. Glidewell Dental Ceramics, Inc. Method of Masking a Dental Support Structure of a Dental Prosthesis Made of Highly Translucent Ceramic Material
US11672632B2 (en) 2020-10-05 2023-06-13 Pritidenta Gmbh Multi-layered zirconia dental blank with reverse layers, process for its preparation and uses thereof
CN116023135A (zh) * 2022-12-28 2023-04-28 爱迪特（秦皇岛）科技股份有限公司 一种3d打印高透光度陶瓷牙及其制备方法
CN116986921A (zh) * 2023-09-26 2023-11-03 山东新华医疗器械股份有限公司 一种全瓷义齿用彩色氧化锆瓷块的透明处理液及其处理方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001181031A (ja) * 1999-12-20 2001-07-03 Kyocera Corp 光コネクタ用ジルコニア焼結体およびその製造方法
CN1810717A (zh) * 2006-03-03 2006-08-02 中国科学院上海硅酸盐研究所 氧化镱和氧化钇共稳定的氧化锆陶瓷材料及制备方法
CN101265088A (zh) * 2008-04-21 2008-09-17 天津大学 低温烧结氧化锆透明陶瓷材料及其制备方法
WO2010107678A1 (en) * 2009-03-20 2010-09-23 3M Innovative Properties Company Sintering support and methods
CN102028624A (zh) * 2010-12-24 2011-04-27 辽宁爱尔创生物材料有限公司 牙科用高透氧化锆材料及制备工艺

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4421671A (en) * 1982-06-18 1983-12-20 General Electric Company Rare-earth-doped yttria-gadolinia ceramic scintillators
DE19904522C5 (de) * 1999-02-04 2013-11-14 3M Deutschland Gmbh Einfärbung von keramischem Zahnersatz mittels ionischer oder komplexhaltiger Lösungen
FR2822458A1 (fr) * 2001-03-21 2002-09-27 Saint Gobain Ct Recherches Corps en ceramique dense, notamment pour applications dentaires
SE0200007D0 (sv) * 2002-01-03 2002-01-03 Sandvik Ab Method for making ceramic artificial dental bridges
CN1267080C (zh) * 2004-06-04 2006-08-02 李石保 牙体和人体硬组织缺失修复复合材料及其制备方法
KR100910261B1 (ko) * 2005-10-31 2009-07-31 코바렌트 마테리얼 가부시키가이샤 투광성 희토류 산화 소결체 및 그 제조 방법
EP1859757B1 (de) * 2006-05-23 2013-10-09 Ivoclar Vivadent AG Zusammensetzung und Verfahren zur Herstellung von gefärbten Rohlingen und dentalen Formteilen
JP2010509336A (ja) * 2006-11-09 2010-03-25 ニューヨーク ユニバーシティ サンドイッチ材料の製造方法、ガラス／セラミック／ガラス複合構造物、ガラス／セラミック／ガラス、医科あるいは歯科補綴、およびガラス／ジルコニア／ガラスサンドイッチ材料
EP2104654A2 (en) * 2006-12-29 2009-09-30 3M Innovative Properties Company Zirconia body and methods
EP2025659A1 (en) * 2007-07-23 2009-02-18 3M Innovative Properties Company Colouring solution for dental ceramic articles and related methods
CN101998939A (zh) * 2008-04-09 2011-03-30 东曹株式会社 透光性氧化锆烧结体、其生产方法及其用途
DE102008026980A1 (de) * 2008-05-29 2009-12-03 Wieland Dental + Technik Gmbh & Co. Kg Verfahren und Kit zur Dotierung oder Einfärbung von porösen Keramiken

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001181031A (ja) * 1999-12-20 2001-07-03 Kyocera Corp 光コネクタ用ジルコニア焼結体およびその製造方法
CN1810717A (zh) * 2006-03-03 2006-08-02 中国科学院上海硅酸盐研究所 氧化镱和氧化钇共稳定的氧化锆陶瓷材料及制备方法
CN101265088A (zh) * 2008-04-21 2008-09-17 天津大学 低温烧结氧化锆透明陶瓷材料及其制备方法
WO2010107678A1 (en) * 2009-03-20 2010-09-23 3M Innovative Properties Company Sintering support and methods
CN102028624A (zh) * 2010-12-24 2011-04-27 辽宁爱尔创生物材料有限公司 牙科用高透氧化锆材料及制备工艺

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US20130224454A1 (en) * 2012-02-23 2013-08-29 Yunoh Jung Non-Pre-Colored Multi-Layer Zirconia Dental Blank that has a Gradual Change in Chroma through a Thickness After Sintering
US9649179B2 (en) 2012-02-23 2017-05-16 B & D Dental Corporation Multi-layer zirconia dental blank that has a gradual change in chroma and translucency through a thickness after sintering
US10327875B2 (en) 2012-02-23 2019-06-25 Benjamin Y. Jung Creating a translucent effect within one half of a green body zirconia blank
US11654006B2 (en) 2012-02-23 2023-05-23 B & D Dental Corporation Multi-layer zirconia dental blank that has a gradual change in strength, translucency and chroma from one direction to the other after sintering
US10034728B2 (en) 2012-02-23 2018-07-31 B & D Dental Corporation Method of coloring a pre-sintered dental restoration
US10426583B2 (en) 2012-02-23 2019-10-01 Yunoh Jung High translucent colored dental zirconia blank
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US10226313B2 (en) 2012-02-23 2019-03-12 B & D Dental Corporation Method of coloring multi-layered pre-sintered dental restoration
US10463457B2 (en) 2012-02-23 2019-11-05 Yunoh Jung High translucent dental zirconia blank and sintered body
US10631961B2 (en) 2012-02-23 2020-04-28 B & D Dental Corporation High translucent dental zirconia blank and sintered body
US11051916B2 (en) 2012-02-23 2021-07-06 B & D Dental Corporation Dental zirconia system
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US9872746B2 (en) 2012-08-03 2018-01-23 3M Innovative Properties Company Translucency enhancing solution for zirconia ceramics

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EP2573060A1 (en) 2013-03-27
KR20140002801A (ko) 2014-01-08
US20130115365A1 (en) 2013-05-09
EP2573060B1 (en) 2019-01-09
US8697176B2 (en) 2014-04-15
KR101562610B1 (ko) 2015-10-22
EP2573060A4 (en) 2014-12-03
PT2573060T (pt) 2019-04-30
ES2719818T3 (es) 2019-07-16
CN102344285B (zh) 2013-04-17

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