阅读说明：本技术 一种用于齿科颜色可调的二硅酸锂微晶玻璃及其制备方法 (Lithium disilicate glass ceramics with adjustable dental color and preparation method thereof ) 是由 陈泽涛 单正杰 许洁芸 黄沛娜 史晓敏 陈卓凡 于 2021-09-08 设计创作，主要内容包括：本发明为一种用于齿科颜色可调的二硅酸锂微晶玻璃,其包括：玻璃基础组分为：SiO-(2)、Al-(2)O-(3)、Li-(2)O、K-(2)O、Na-(2)O、CaO；成核剂为：P-(2)O-(5)、ZrO-(2)、TiO-(2)；着色剂为Tb-(4)O-(7)％、CeO-(2)、V-(2)O-(5)、Er-(2)O-(3)、Fe-(3)O-(4)。本发明通过稀土及有色氧化物对二硅酸锂微晶玻璃进行颜色的调节,并且可以根据特定的颜色需求进行颜色的调节,不同的氧化物的引入均有特定的颜色调节性。本发明还提供了一种用于齿科颜色可调的二硅酸锂微晶玻璃的制备方法,该方法制备出来的二硅酸锂微晶玻璃具有和牙齿相匹配的色度与透明度,可以浇注成形和进行雕刻,特别适用于CAD/CAM进行机械精密雕刻和压铸成型,能节约人力物力,降低成本,减少污染,达到清洁生产的目的。(The invention relates to a lithium disilicate glass-ceramic with adjustable dental color, which comprises the following components: the basic components of the glass are as follows: SiO 2 2 、Al 2 O 3 、Li 2 O、K 2 O、Na 2 O, CaO, respectively; the nucleating agent is: p 2 O 5 、ZrO 2 、TiO 2 (ii) a The colorant is Tb 4 O 7 ％、CeO 2 、V 2 O 5 、Er 2 O 3 、Fe 3 O 4 . The invention adjusts the color of the lithium disilicate glass ceramics through the rare earth and the colored oxide, and can adjust the color according to the specific color requirement, and the introduction of different oxides has specific color adjustability. The invention also provides a preparation method of the lithium disilicate glass ceramics with adjustable dental colors, the lithium disilicate glass ceramics prepared by the method has the chromaticity and the transparency matched with teeth, can be cast and carved, is particularly suitable for CAD/CAM to carry out mechanical precision carving and die-casting forming, can save manpower and material resources, reduce cost, reduce pollution and achieve the aim of clean production.)

1. The lithium disilicate glass ceramics with adjustable dental color is characterized by comprising the following components in percentage by mass:

the basic components of the glass are as follows: SiO 2₂ 60～75％、Al₂O₃ 0.5～5％、Li₂O 5～17％、K₂O 1～8％、Na₂O 1～4％、CaO 0.1～3％；

The nucleating agent is: p₂O₅ 0.5～5％、ZrO₂ 0.5～5％、TiO₂ 0～5％；

The colorant is Tb₄O₇ 0.01～1.5％、CeO₂ 0.5～5％、V₂O₅ 0.01～1％、Er₂O₃0.5～3％、Fe₃O₄ 0～1％。

2. The lithium disilicate glass-ceramic for dental color adjustment according to claim 1, consisting of the following components in percentage by mass:

the basic components of the glass are as follows: SiO 2₂ 65～75％、Al₂O₃ 1～5％、Li₂O 10～17％、K₂O 2～5％、Na₂O 1～4％、CaO 0.1～2％；

The nucleating agent is: p₂O₅ 1～4.5％、ZrO₂ 0.5～3％、TiO₂ 0.1～3％；

The colorant is Tb₄O₇ 0.01～1％、CeO₂ 0.5～3％、V₂O₅ 0.1～1％、Er₂O₃ 0.5～3％、Fe₃O₄ 0～0.5％。

3. The lithium disilicate glass-ceramic for dental color adjustment according to claim 2, consisting of the following components in percentage by mass:

the basic components of the glass are as follows: SiO 2₂ 67～75％、Al₂O₃ 2～4％、Li₂O 13～17％、K₂O 2～4％、Na₂O 1～3％、CaO 0.1～1％；

The nucleating agent is: p₂O₅ 2～4％、ZrO₂ 0.5～2％、TiO₂ 0.1～1％；

The colorant is Tb₄O₇ 0.01～0.8％、CeO₂ 0.5～3％、V₂O₅ 0.1～0.5％、Er₂O₃0.5～3％、Fe₃O₄0～0.3％。

4. The microcrystalline glass of lithium disilicate according to claim 1, wherein the main crystal phase is lithium disilicate, and the secondary crystal phases are lithium metasilicate and quartz, wherein the mass fraction of lithium disilicate crystal is 60-80%.

5. A preparation method of lithium disilicate glass ceramics with adjustable dental color is characterized by comprising the following process steps:

s1, uniformly mixing all the raw materials of the glass basic component, the nucleating agent and the coloring agent into a batch, and pre-burning the batch at 800-900 ℃ for 0.5-4.5 h to obtain a pre-burned material;

s2, melting the pre-sintered material at 1450-1500 ℃ for 1-6 h to obtain glass liquid;

s3, stirring the molten glass, and clarifying and homogenizing at 1500 ℃ for 0.5-2 h; pouring and molding the clarified and homogenized molten glass to obtain a glass blank;

s4, preserving the temperature of the glass blank at 530 ℃ for 1-2 h, then annealing at 450 ℃ for 1-2 h, and naturally cooling to room temperature;

s5, carrying out primary heat treatment on the glass blank at 500-750 ℃, preserving heat for 10-120 min, and naturally cooling to room temperature to obtain purple opaque ceramic particles;

s6, carrying out CAD/CAM processing or die casting processing on the purple opaque ceramic particles obtained in the previous step, carrying out secondary heat treatment at 800-900 ℃ after the CAD/CAM processing, directly carrying out heat treatment at 890-920 ℃ during the die casting processing, and naturally cooling to room temperature to obtain a finished ceramic block, namely the lithium disilicate glass ceramics with adjustable dental color.

6. A preparation method of lithium disilicate glass ceramics with adjustable dental color is characterized in that the breaking strength of the prepared lithium disilicate glass ceramics with adjustable dental color is more than 346 MPa.

[ technical field ] A method for producing a semiconductor device

The invention relates to the technical field of microcrystalline glass, in particular to lithium disilicate microcrystalline glass with adjustable dental color and a preparation method thereof.

[ background of the invention ]

Dentition defect/loss repair is a great clinical problem in the oral cavity, and can cause partial chewing function loss of the oral cavity, certain influence on pronunciation and attractiveness, occlusion disorder and neuromuscular balance disorder of the oral and jaw systems, so that temporomandibular joint disorder is caused, and the life quality of patients is greatly influenced. With the increase of the life-span of people and the aging of the population in China, the incidence rate of dentition defects/loss caused by caries, periodontal diseases, physiological degenerative changes of the elderly, systemic diseases and the like gradually rises, the number of patients is continuously increased, and thus the demand for dental repair materials is continuously increased.

As a dental repair material, the ceramic has excellent biocompatibility, excellent corrosion resistance and abrasion resistance, and particularly, the unique aesthetic properties of the ceramic are incomparable with those of metal materials and other high polymer materials. In addition, the color of the all-ceramic prosthesis is close to that of natural teeth, so that the all-ceramic prosthesis has the characteristics of excellent aesthetic effect, high hardness, low heat conduction, non-conductivity, wear resistance and the like, is accepted by more and more patients, and becomes one of the main development trends of the fixed restoration of the oral cavity at present.

The lithium disilicate glass ceramics clinically applied at present have fewer colors and the color system is not completely consistent with the color of the teeth of the Chinese, so the domestic glass ceramics is developed according to the tooth condition of the Chinese, the color matching property of the restoration can be improved, and the cost of the tooth restoration material is reduced. In addition, the breaking strength of the lithium disilicate glass ceramics generated at home at present does not reach the level of imported products, so that the preparation of the lithium disilicate glass ceramics with high strength and controllable color has strong necessity. In order to solve the problems, a new technical scheme is provided.

[ summary of the invention ]

The lithium disilicate glass ceramics prepared by the method has the chromaticity and the transparency matched with teeth, can be cast and carved, is particularly suitable for mechanical precision carving and die-casting forming of CAD/CAM, can save manpower and material resources, reduce cost, reduce pollution and achieve the aim of clean production.

In order to solve the technical problems, the invention adopts the following technical scheme:

the lithium disilicate glass ceramics with adjustable dental color consists of the following components in percentage by mass:

the basic components of the glass are as follows: SiO 2₂ 60～75％、Al₂O₃ 0.5～5％、Li₂O 5～17％、K₂O 1～8％、Na₂O 1～4％、CaO 0.1～3％；

The nucleating agent is: p₂O₅ 0.5～5％、ZrO₂ 0.5～5％、TiO₂ 0～5％；

The colorant is Tb₄O₇ 0.01～1.5％、CeO₂ 0.5～5％、V₂O₅ 0.01～1％、Er₂O₃ 0.5～3％、Fe₃O₄ 0～1％。

In a further improvement, the lithium disilicate glass ceramics with adjustable dental color comprises the following components in percentage by mass:

the basic components of the glass are as follows: SiO 2₂ 65～75％、Al₂O₃ 1～5％、Li₂O 10～17％、K₂O 2～5％、Na₂O 1～4％、CaO 0.1～2％；

The nucleating agent is: p₂O₅ 1～4.5％、ZrO₂ 0.5～3％、TiO₂ 0.1～3％；

The colorant is Tb₄O₇ 0.01～1％、CeO₂ 0.5～3％、V₂O₅ 0.1～1％、Er₂O₃ 0.5～3％、Fe₃O₄0～0.5％。

In a further improvement, the lithium disilicate glass ceramics with adjustable dental color comprises the following components in percentage by mass:

the basic components of the glass are as follows: SiO 2₂ 67～75％、Al₂O₃ 2～4％、Li₂O 13～17％、K₂O 2～4％、Na₂O 1～3％、CaO 0.1～1％；

The nucleating agent is: p₂O₅ 2～4％、ZrO₂ 0.5～2％、TiO₂ 0.1～1％；

The colorant is Tb₄O₇ 0.01～0.8％、CeO₂ 0.5～3％、V₂O₅ 0.1～0.5％、Er₂O₃ 0.5～3％、Fe₃O₄ 0～0.3％。

In a further improvement, the lithium disilicate glass ceramics with adjustable dental color comprise a main crystal phase of lithium disilicate and a secondary crystal phase of lithium metasilicate and quartz, wherein the mass fraction of lithium disilicate crystals is 60-80%.

A preparation method of lithium disilicate glass ceramics with adjustable dental color comprises the following process steps:

s1, uniformly mixing all the raw materials of the glass basic component, the nucleating agent and the coloring agent into a batch, and pre-burning the batch at 800-900 ℃ for 0.5-4.5 h to obtain a pre-burned material;

s2, melting the pre-sintered material at 1450-1500 ℃ for 1-6 h to obtain glass liquid;

s3, stirring the molten glass, and clarifying and homogenizing at 1500 ℃ for 0.5-2 h; pouring and molding the clarified and homogenized molten glass to obtain a glass blank;

s4, preserving the temperature of the glass blank at 530 ℃ for 1-2 h, then annealing at 450 ℃ for 1-2 h, and naturally cooling to room temperature;

s5, carrying out primary heat treatment on the glass blank at 500-750 ℃, preserving heat for 10-120 min, and naturally cooling to room temperature to obtain purple opaque ceramic particles;

s6, carrying out CAD/CAM processing or die casting processing on the purple opaque ceramic particles obtained in the previous step, carrying out secondary heat treatment at 800-900 ℃ after the CAD/CAM processing, directly carrying out heat treatment at 890-920 ℃ during the die casting processing, and naturally cooling to room temperature to obtain a finished ceramic block, namely the lithium disilicate glass ceramics with adjustable dental color.

In a further development, the fracture strength of the produced lithium disilicate glass ceramics for dental color adjustment is more than 346 MPa.

Compared with the prior art, the invention has the following beneficial effects:

the invention has the innovativeness that the color of the lithium disilicate glass ceramics is adjusted through rare earth and colored oxides, and the color can be adjusted according to specific color requirements, and the introduction of different oxides has specific color adjustability, for example, the introduction of iron oxide can lead the final color of the lithium disilicate glass ceramics to be converted to red-black, mainly to black, the transmittance is reduced, the color is darker with the increase of the content of the iron oxide, the color is controllable, the addition of vanadium oxide can lead the color of the lithium disilicate glass ceramics to be converted to yellow, the color is darker with the increase of the content of the vanadium oxide, the color is controllable, the addition of the oxidation bait mainly leads the color of the lithium disilicate glass ceramics to be converted to red, the color is darker with the increase of the content of the oxidation bait, the color is controllable, the addition of terbium oxide mainly leads the color of the lithium disilicate glass ceramics to be converted to brown-black, the color of the lithium disilicate glass-ceramics is converted to yellow mainly by adding cerium oxide, and the color of the lithium disilicate glass-ceramics is converted to be darker as the content of the cerium oxide is increased, so that the lithium disilicate glass-ceramics has color controllability.

In the preparation process, the glass blank is annealed and then subjected to crystallization heat treatment, the glass has low hardness and is easy to cut and die-cast, and a microcrystalline glass product with lithium disilicate as a main crystal phase and high hardness and strength is formed through a crystallization step. Moreover, the novelty and the advancement of the invention lie in that the microcrystalline glass obtained after the crystallization heat treatment has higher breaking strength which is not lower than 346 MPa; the main crystal phase of the final product crystal is lithium disilicate, and the secondary crystal phase is lithium metasilicate, so that the lithium disilicate glass-ceramic product which is crystal white, has good transmittance and high breaking strength can be obtained; the invention controls the proportion of the lithium disilicate crystal phase, the mass fraction of the lithium disilicate crystal phase is 60-80%, and the lithium disilicate crystal is controlled to form a needle-shaped interlocking structure with the diameter of 1 mu m and the length of more than 5 mu m.

The invention is described in further detail below with reference to the following detailed description and accompanying drawings:

[ description of the drawings ]

FIG. 1 is a lithium disilicate glass-ceramic for dental color adjustment prepared by a formulation provided in an embodiment of the present invention;

FIG. 2 is a diagram of a microcrystalline glass of lithium disilicate with adjustable dental color prepared by the formulation provided by the second embodiment of the invention;

FIG. 3 is a microcrystalline glass of lithium disilicate with adjustable dental color prepared by the formulation provided by the third embodiment of the invention;

FIG. 4 shows a microcrystalline glass of lithium disilicate with adjustable dental color prepared by the formulation provided in the fourth embodiment of the present invention.

[ detailed description ] embodiments

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The lithium disilicate glass ceramics suitable for CAD/CAM processing are taken as an embodiment, and the specific preparation steps are as follows:

1. designing its basic chemical composition

Formulation calculations were made according to the chemical ingredients in the example formulation table (table 1);

2. sorting

The raw materials used in the chemical composition of the invention are

The basic components of the glass are as follows: SiO 2₂、Al₂O₃、Li₂O、K₂O、Na₂O、CaO；

The nucleating agent is: p₂O₅、ZrO₂、TiO₂；

The colorant is Tb₄O₇％、CeO₂、V₂O₅、Er₂O₃、Fe₃O₄；

3. Ingredients

Burdening according to the ingredient list, accurately calculating the amount of required ingredients, burdening, and fully ball-milling after burdening to ensure that the raw materials are uniformly mixed;

4. pre-firing

Presintering the prepared raw materials in a muffle furnace at 850 ℃ for 1 hour;

5. melting

After the presintered raw materials are ball-milled uniformly again, putting the raw materials into a melting furnace in batches, melting the raw materials at 1500 ℃, stirring and clarifying the raw materials for 1 hour, and controlling the melting time to ensure that the nucleating agent is uniformly distributed in the glass;

6. shaping of

The melted glass liquid can be molded by various glass molding devices to achieve the aim of facilitating subsequent processing, and the embodiment adopts casting molding (the melted glass liquid is directly poured into a mold;

7. nucleation and annealing

Quickly putting the formed glass body into a muffle furnace at 530 ℃ for nucleation for 1 hour, reducing the temperature to 450 ℃ for annealing after 1 hour, cooling the glass body along with the furnace for 1 hour, and taking out the glass body below 100 ℃;

8. pre-crystallization heat treatment

Putting the glass body into a high-temperature electric furnace, heating to 650 ℃ at a heating rate of 10 ℃/min, preserving heat for one hour, then cooling the glass body along with the furnace, wherein the main component of the obtained glass body is lithium silicate, the hardness of the glass is low, the glass is purple, and the cutting treatment can be carried out;

9. cutting, forming and crystallizing heat treatment

Grinding the surface part of the glass blank, then carrying out forming processing and polishing, putting the processed glass sample into a high-temperature electric furnace, heating to 850 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 30 minutes, then cooling along with the furnace to obtain a finished product,

the fracture strength of the obtained lithium disilicate glass ceramics with adjustable dental colors is more than 346MPa, and the colors of the lithium disilicate glass ceramics prepared by the embodiments are different, and the colors can be seen in the attached drawings.

TABLE 1 example formulation composition for dental color tunable lithium disilicate glass ceramics

	SiO2	Li2O	Al2O3	P2O5	TiO2	CeO2	Fe3O4	ZrO2	Na2O	K2O	V2O5	Er2O3	CaO	Tb4O7
															Example 1	73	13.9	3	3	0	0.4	0	2	0.7	3.1	0.2	0.1	0.3	0.2
Example 2	71.88	14.1	3	2.6	0.3	1	0	2	0.3	3	0.32	1	0.3	0.2
															Example 3	71.83	14.05	3.2	2.4	0.3	1.22	0	2	0.3	3	0.3	0.9	0.3	0.2
Example 4	71.73	14.03	3	2.4	0.3	1	0	2	1.79	2	0.28	1	0.3	0.17

Table 2: fracture strength of lithium disilicate glass ceramics prepared by each formula and with adjustable dental color

The above examples were tested as follows:

(1) breaking Strength test

The tested sample is prepared into a sheet shape (25 multiplied by 4 multiplied by 2mm) by using a low-speed cutting device and a grinding device, the surface of the glass sample is polished by using iron oxide, and the sample is subjected to a fracture strength test by using a three-point bending test method by using a universal strength tester. The loading speed of the instrument is 1mm/min, the span is 20mm, the maximum load can be obtained when the glass is broken, and the fracture strength of the sample can be calculated by using the following formula:

wherein M is the three-point bending strength (MPa), W is the maximum load (N), l is the span (mm), b is the sample width (mm), d is the sample thickness (mm), and the fracture strength of the sample can be obtained through calculation.

(2) Color comparison

The final colour of the lithium disilicate glass ceramics prepared according to the invention is determined by comparison with dental standard plates (3DVITA porcelain 29 colour) using a lithium disilicate glass ceramics prepared according to the invention.

The above preferred embodiments should be considered as examples of the embodiments of the present application, and technical deductions, substitutions, improvements and the like similar to, similar to or based on the embodiments of the present application should be considered as the protection scope of the present patent.

Although the present invention has been described in detail with reference to the above embodiments, it will be apparent to those skilled in the art from this disclosure that various changes or modifications can be made herein without departing from the principles and spirit of the invention as defined by the appended claims. Therefore, the detailed description of the embodiments of the present disclosure is to be construed as merely illustrative, and not limitative of the remainder of the disclosure, but rather to limit the scope of the disclosure to the full extent set forth in the appended claims.