CN112142462A - A kind of manufacturing method of anti-inflammatory dental restoration material with layer-by-layer self-assembled coating - Google Patents

Abstract

A method for manufacturing an anti-inflammatory dental restoration material with layers of self-assembled coatings relates to a manufacturing method for a dental restoration material. The purpose of the present invention is to solve the problems that the existing zirconia ceramics have high brittleness and low fracture toughness, and are prone to fracture, chipping and no anti-inflammatory properties as tooth restoration materials. Methods: 1. Prepare solution A; 2. Prepare slurry; 3. Prepare ceramic block; 4. Sinter; The fracture toughness of the anti-inflammatory tooth repair material with layers of self-assembled coatings prepared by the invention is improved by 1 to 1.5 times compared with zirconia ceramics. The present invention can obtain an anti-inflammatory dental restoration material with layers of self-assembled coatings.

Description

A kind of manufacturing method of anti-inflammatory dental restoration material with layer-by-layer self-assembled coating

technical field

The present invention relates to a method of manufacturing a dental restoration material.

Background technique

Teeth are structures found in many vertebrates, humans and higher animals for chewing food. Teeth are the hardest organs in the human body. Generally speaking, teeth are white and hard in texture. Teeth come in a variety of shapes for a variety of purposes, including tearing and grinding food. Once the tooth is damaged, it needs to be repaired. Therefore, the restoration material is one of the key contents of the research in the field of dentistry.

At present, dental restoration materials have gradually developed from initial resins to metals, and finally to zirconia denture materials. Zirconia ceramic materials have good comprehensive properties such as high melting point, high hardness, high wear resistance, and oxidation resistance. With sufficient sources and low manufacturing cost, it is suitable for large-scale industrial production. Therefore, zirconia has gradually become a popular dental restoration material. In addition, zirconia ceramics have good biocompatibility and are close to the natural teeth of the human body. Glaze texture and transparency. However, due to the natural brittleness of zirconia ceramics, the further wide application of such products is hindered. Therefore, the lower fracture toughness and higher brittleness of zirconia ceramics limit its application.

Therefore, there is an urgent need to develop a tooth restoration material with high flexural strength, high fracture toughness, anti-inflammatory and biocompatibility, which has not been reported so far.

SUMMARY OF THE INVENTION

The purpose of the present invention is to solve the problems of high brittleness and low fracture toughness of the existing zirconia ceramics, which are prone to fracture, chipping and no anti-inflammatory properties as tooth restoration materials, and provide a self-assembled coating with layers of layers. A method of manufacturing an anti-inflammatory dental restorative material.

A manufacturing method of an anti-inflammatory dental restoration material with layers of self-assembled coatings, which is completed according to the following steps:

1. Mix the deionized water, sodium oleate, sodium carboxymethyl cellulose and polyvinyl alcohol uniformly, and then stir to obtain solution A;

The mass ratio of deionized water described in step 1 and sodium carboxymethyl cellulose is 100: (0.3～1);

The mass ratio of deionized water and polyvinyl alcohol described in step 1 is 100: (0.5～2);

The mass ratio of deionized water described in step 1 and sodium oleate is 100: (1.5～2);

2. Add nano-zirconia powder, nano-alumina powder and nano-ceria powder to solution A, and then stir to obtain slurry;

The mass ratio of the nano-zirconia powder, nano-alumina powder and nano-ceria powder described in step 2 is 100:(4-8):(8-15);

The mass ratio of solution A described in step 2 to nano-zirconia powder is 100:(10～20);

3. The slurry is spray granulated in a spray granulator, and the obtained granules are pressed again to obtain a porcelain block;

The thickness of the porcelain block described in step 3 is 15mm～30mm;

The pressing pressure described in step 3 is 80MPa～150MPa;

4. Put the porcelain block into the muffle furnace, heat it up to 250℃～300℃ at a heating rate of 2℃/min～4℃/min, then keep it at 250℃～300℃ for 2h～4h, and then heat it at 2℃ The heating rate of /min～4℃/min is raised from 250℃～300℃ to 750℃～800℃, then kept at 750℃～800℃ for 2h～3h, and then heated at 2℃/min～4℃/min The rate is increased from 750°C to 800°C to 1500°C to 1560°C, and then kept at 1500°C to 1560°C for 1h to 2h; a composite ceramic block toughened by alumina and ceria is obtained;

5. Layer-by-layer self-assembly:

1. Immerse the alumina and ceria toughened composite ceramic block in polyvinyl alcohol solution for 5min-10min, take it out and blow dry; then place it in tannic acid solution for 5min-10min, take it out and blow dry;

The volume ratio of the mass of polyvinyl alcohol and deionized water in the polyvinyl alcohol solution described in step 5 1. is (1g～2g): 100mL;

The mass ratio of the tannic acid in the tannic acid solution described in step 5. to the deionized water is (1g～2g): 100mL;

②, repeat step 5 ① 20 to 40 times to obtain a composite ceramic block coated with a coating;

3. Put the coated composite ceramic block in the epigallocatechin gallate solution for 5min-10min, take it out and blow dry, then place it in the tannic acid solution to soak for 5min-10min, take it out and blow dry ;

In the tannic acid solution described in step 3., the mass ratio of tannic acid to deionized water is (1g～2g): 100mL;

The mass ratio of epigallocatechin gallate and deionized water in the epigallocatechin gallate solution described in step 5 3. is (0.001g～0.01g): 1mL;

④. Repeat step ③ for 20 to 40 times to obtain an anti-inflammatory dental restoration material with layers of self-assembled coatings.

The principle and advantages of the present invention:

1. In the present invention, sodium oleate is used as dispersant, sodium carboxymethyl cellulose and polyvinyl alcohol are used as binder, nano-zirconia powder is used as raw material, and nano-alumina powder and nano-ceria powder are used as toughening agent Alumina and cerium dioxide toughened composite ceramic blocks were prepared by using polyvinyl alcohol, tannic acid and epigallocatechin gallate as raw materials. A high hardness coating is prepared on the surface of the toughened composite ceramic block, which can prevent the penetration of body fluids, and because it contains epigallocatechin gallate, it has anti-inflammatory properties and is not easy to cause inflammation;

2. The fracture toughness of zirconia ceramics is 8MPa·m ^1/2 , while the fracture toughness of the anti-inflammatory dental restoration material with layers of self-assembled coatings prepared by the invention can reach 16MPa·m ^1/2 to 20MPa·m Therefore, the fracture toughness of the anti-inflammatory dental restoration material with layers of self-assembled coatings prepared by the present invention is ¹ to 1.5 times higher than that of zirconia ceramics.

Description of drawings

FIG. 1 is a digital photograph of the anti-inflammatory dental restoration material with layers of self-assembled coatings prepared in Example 1. FIG.

Detailed ways

Embodiment 1: The manufacturing method of an anti-inflammatory dental restoration material with layers of self-assembled coatings in this embodiment is completed according to the following steps:

1. Mix the deionized water, sodium oleate, sodium carboxymethyl cellulose and polyvinyl alcohol uniformly, and then stir to obtain solution A;

The mass ratio of deionized water described in step 1 and sodium carboxymethyl cellulose is 100: (0.3～1);

The mass ratio of deionized water and polyvinyl alcohol described in step 1 is 100: (0.5～2);

The mass ratio of deionized water described in step 1 and sodium oleate is 100: (1.5～2);

2. Add nano-zirconia powder, nano-alumina powder and nano-ceria powder to solution A, and then stir to obtain slurry;

The mass ratio of the nano-zirconia powder, nano-alumina powder and nano-ceria powder described in step 2 is 100:(4-8):(8-15);

The mass ratio of solution A described in step 2 to nano-zirconia powder is 100:(10～20);

3. The slurry is spray granulated in a spray granulator, and the obtained granules are pressed again to obtain a porcelain block;

The thickness of the porcelain block described in step 3 is 15mm～30mm;

The pressing pressure described in step 3 is 80MPa～150MPa;

4. Put the porcelain block into the muffle furnace, heat it up to 250℃～300℃ at a heating rate of 2℃/min～4℃/min, then keep it at 250℃～300℃ for 2h～4h, and then heat it at 2℃ The heating rate of /min～4℃/min is raised from 250℃～300℃ to 750℃～800℃, then kept at 750℃～800℃ for 2h～3h, and then heated at 2℃/min～4℃/min The rate is increased from 750°C to 800°C to 1500°C to 1560°C, and then kept at 1500°C to 1560°C for 1h to 2h; a composite ceramic block toughened by alumina and ceria is obtained;

5. Layer-by-layer self-assembly:

1. Immerse the alumina and ceria toughened composite ceramic block in polyvinyl alcohol solution for 5min-10min, take it out and blow dry; then place it in tannic acid solution for 5min-10min, take it out and blow dry;

The volume ratio of the mass of polyvinyl alcohol and deionized water in the polyvinyl alcohol solution described in step 5 1. is (1g～2g): 100mL;

The mass ratio of the tannic acid in the tannic acid solution described in step 5. to the deionized water is (1g～2g): 100mL;

②, repeat step 5 ① 20 to 40 times to obtain a composite ceramic block coated with a coating;

3. Put the coated composite ceramic block in the epigallocatechin gallate solution for 5min-10min, take it out and blow dry, then place it in the tannic acid solution to soak for 5min-10min, take it out and blow dry ;

In the tannic acid solution described in step 3., the mass ratio of tannic acid to deionized water is (1g～2g): 100mL;

The mass ratio of epigallocatechin gallate and deionized water in the epigallocatechin gallate solution described in step 5 3. is (0.001g～0.01g): 1mL;

④. Repeat step ③ for 20 to 40 times to obtain an anti-inflammatory dental restoration material with layers of self-assembled coatings.

Embodiment 2: The difference between this embodiment and Embodiment 1 is that the particle size of the nano-zirconia powder described in step 2 is 20 nm to 40 nm. Other steps are the same as in the first embodiment.

Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that the particle size of the nano-alumina powder described in Step 2 is 40 nm to 60 nm. Other steps are the same as in the first or second embodiment.

Embodiment 4: One of the differences between this embodiment and Embodiments 1 to 3 is that the particle size of the nano-ceria powder described in Step 2 is 40 nm to 60 nm. Other steps are the same as those of the specific embodiments 1 to 3.

Embodiment 5: One of the differences between this embodiment and Embodiments 1 to 4 is that the particle size of the particles obtained by spray granulation in step 3 is 10 μm to 30 μm. The other steps are the same as those in the first to fourth embodiments.

Embodiment 6: The difference between this embodiment and Embodiments 1 to 5 is that the atomization frequency of the spray granulation described in step 3 is 200 Hz, the rotational speed of the feed pump is 30 r/min, and the drying temperature is 220 ° C ~300°C. Other steps are the same as those of the specific embodiments 1 to 5.

Embodiment 7: One of the differences between this embodiment and Embodiments 1 to 6 is that the pressing pressure in step 3 is 80 MPa to 100 MPa. Other steps are the same as those of the specific embodiments 1 to 6.

Embodiment 8: The difference between this embodiment and Embodiments 1 to 7 is that: in step 4, the ceramic block is put into a muffle furnace, and the temperature is raised to 280°C at a heating rate of 3°C/min, and then at 280°C. Incubate for 3 h, then heat up from 280 °C to 800 °C at a heating rate of 3 °C/min, then hold at 800 °C for 2 h, and then heat up from 800 °C to 1550 °C at a heating rate of 3 °C/min, and then at 1550 °C Under heat preservation for 1.5h; a composite ceramic block is obtained. Other steps are the same as those of the specific embodiments 1 to 7.

Embodiment 9: The difference between this embodiment and Embodiments 1 to 8 is that: in step 5 (2), repeat step 5 (1) 30 to 40 times to obtain a composite ceramic block coated with a coating; repeat step (4) in step 5 5. 30 to 40 times to obtain an anti-inflammatory dental restoration material with layers of self-assembled coatings. Other steps are the same as those of the specific embodiments 1 to 8.

Embodiment 10: The difference between this embodiment and Embodiments 1 to 9 is: the quality and deionization of epigallocatechin gallate in the epigallocatechin gallate solution described in step 3. The volume ratio of water is (0.005g～0.008g):1mL. Other steps are the same as those of the specific embodiments 1 to 9.

Adopt the following examples to verify the beneficial effects of the present invention:

Embodiment 1: A manufacturing method of an anti-inflammatory dental restoration material with layers of self-assembled coatings, which is completed according to the following steps:

1. Mix the deionized water, sodium oleate, sodium carboxymethyl cellulose and polyvinyl alcohol uniformly, and then stir to obtain solution A;

The mass ratio of deionized water described in step 1 and sodium carboxymethyl cellulose is 100:0.6;

The mass ratio of deionized water described in step 1 and polyvinyl alcohol is 100:1.2;

The mass ratio of deionized water described in step 1 and sodium oleate is 100:1.8;

2. Add nano-zirconia powder, nano-alumina powder and nano-ceria powder to solution A, and then stir to obtain slurry;

The particle size of the nano-zirconia powder described in step 2 is 20nm～40nm;

The particle size of the nano-alumina powder described in step 2 is 40nm～60nm;

The particle size of the nano-ceria powder described in step 2 is 40nm～60nm;

The mass ratio of the nano-zirconia powder, nano-alumina powder and nano-ceria powder described in step 2 is 100:6:10;

The mass ratio of solution A described in step 2 and nano-zirconia powder is 100:15;

3. The slurry is spray granulated in a spray granulator, and the obtained granules are pressed again to obtain a porcelain block;

The particle size obtained by spray granulation in step 3 is 10 μm～15 μm;

The thickness of the porcelain block described in step 3 is 20mm;

The atomization frequency of the spray granulation described in step 3 is 200Hz, the rotational speed of the feed pump is 30r/min, and the drying temperature is 300°C;

The pressure of pressing described in the step 3 is 90MPa;

4. Put the porcelain block into the muffle furnace, heat it up to 280°C at a heating rate of 3°C/min, keep it at 280°C for 3 hours, and then heat it up from 280°C to 800°C at a heating rate of 3°C/min. The temperature was kept at 800 °C for 2 h, then increased from 800 °C to 1550 °C at a heating rate of 3 °C/min, and then kept at 1550 °C for 1.5 h; the composite ceramic block toughened by alumina and ceria was obtained;

5. Layer-by-layer self-assembly:

1. Immerse the alumina and ceria toughened composite ceramic block in polyvinyl alcohol solution for 10min, take it out and blow dry; then place it in tannic acid solution for 10 minutes, take out and blow dry;

The mass ratio of polyvinyl alcohol to deionized water in the polyvinyl alcohol solution described in step 5. is 1.5g:100mL;

The mass ratio of tannic acid in the tannic acid solution described in step 5. to deionized water is 1.5g:100mL;

②, repeat step 5 ① 30 times to obtain a composite ceramic block coated with a coating;

3. Place the coated composite ceramic block in the epigallocatechin gallate solution for 10min, take it out and dry it, then place it in the tannic acid solution and soak it for 10min, take it out and dry it;

The mass ratio of epigallocatechin gallate and deionized water in the epigallocatechin gallate solution described in step 5 3. is 0.006g:1mL;

In the tannic acid solution described in step 5., the mass ratio of tannic acid and deionized water is 1.5g:100mL;

④. Repeat step 5 and ③ 30 times to obtain an anti-inflammatory dental restoration material with layers of self-assembled coatings.

The fracture toughness of the anti-inflammatory dental restoration material with layers of self-assembled coatings prepared in Example 1 can reach 20 MPa·m ^1/2 .

Embodiment 2: The difference between this embodiment and Embodiment 1 is that the mass ratio of the nano-zirconia powder, the nano-alumina powder and the nano-ceria powder described in the second step is 100:4:8. Other steps and parameters are the same as in the first embodiment.

The fracture toughness of the anti-inflammatory dental restoration material with layers of self-assembled coatings prepared in Example 2 can reach 16.9 MPa·m ^1/2 .

Embodiment 3: The difference between this embodiment and Embodiment 1 is: in step 4, the ceramic block is put into the muffle furnace, and the temperature is raised to 250°C at a heating rate of 4°C/min, and then kept at 250°C for 2h. Then, the temperature was increased from 250 °C to 780 °C at a heating rate of 4 °C/min, then kept at 780 °C for 3 h, and then heated from 780 °C to 1500 °C at a heating rate of 4 °C/min, and then kept at 1500 °C for 2 h. A composite ceramic block toughened by alumina and ceria is obtained. Other steps and parameters are the same as in the first embodiment.

The fracture toughness of the anti-inflammatory dental restoration material with layers of self-assembled coatings prepared in Example 3 can reach 18.3 MPa·m ^1/2 .

Comparative example: zirconia ceramics are completed according to the following steps:

1. Add nano-zirconia powder to deionized water, and then stir to obtain slurry;

The particle size of the nano-zirconia powder described in step 1 is 20nm～40nm;

The mass ratio of the deionized water described in the step 1 to the nano-zirconia powder is 100:15;

2. The slurry is sprayed and granulated in a spray granulator, and the obtained particles are then pressed to obtain a porcelain block;

In step 2, the particle size of the particles obtained by spray granulation is 10 μm to 15 μm;

The thickness of the porcelain block described in step 2 is 20mm;

The atomization frequency of the spray granulation described in step 2 is 200Hz, the rotational speed of the feed pump is 30r/min, and the drying temperature is 300°C;

The pressure of the pressing described in the step 2 is 90MPa;

3. Put the porcelain block into the muffle furnace, heat it up to 280°C at a heating rate of 3°C/min, keep it at 280°C for 3 hours, and then heat it up from 280°C to 800°C at a heating rate of 3°C/min. The temperature is then kept at 800°C for 2 hours, then heated from 800°C to 1550°C at a heating rate of 3°C/min, and then kept at 1550°C for 1.5 hours to obtain zirconia ceramics.

The fracture toughness of the zirconia ceramics prepared in the comparative example can reach 8 MPa·m ^1/2 .

FIG. 1 is a digital photograph of the anti-inflammatory dental restoration material with layers of self-assembled coatings prepared in Example 1. FIG.

The anti-inflammatory dental restoration materials with layers of self-assembled coatings prepared in Example 1, Example 2 and Example 3 did not cause inflammation in the oral cavity as dental restoration materials.

The thicknesses of the anti-inflammatory dental restoration materials with layers of self-assembled coatings prepared in Example 1, Example 2 and Example 3 are listed in Table 1 as dental restorations.

Table 1

Example Thickness/mm Example 1 0.29mm～0.64mm Embodiment 2 0.33mm～0.82mm Embodiment 3 0.32mm～0.79mm

Claims (10)

1. A method for manufacturing an anti-inflammatory tooth restoration material with a layer-by-layer self-assembly coating is characterized in that the method for manufacturing the anti-inflammatory tooth restoration material with the layer-by-layer self-assembly coating is completed according to the following steps:

firstly, uniformly mixing deionized water, sodium oleate, sodium carboxymethylcellulose and polyvinyl alcohol, and stirring to obtain a solution A;

the mass ratio of the deionized water to the sodium carboxymethyl cellulose in the first step is 100 (0.3-1);

the mass ratio of the deionized water to the polyvinyl alcohol in the first step is 100 (0.5-2);

the mass ratio of the deionized water to the sodium oleate in the first step is 100 (1.5-2);

secondly, adding nano zirconia powder, nano alumina powder and nano cerium dioxide powder into the solution A, and stirring to obtain slurry;

the mass ratio of the nano zirconia powder, the nano alumina powder and the nano ceria powder in the second step is 100 (4-8) to (8-15);

the mass ratio of the solution A to the nano zirconia powder in the step two is 100 (10-20);

thirdly, carrying out spray granulation on the slurry in a spray granulator, and pressing the obtained particles to obtain a ceramic block;

the thickness of the porcelain block in the third step is 15 mm-30 mm;

the pressing pressure in the third step is 80MPa to 150 MPa;

fourthly, placing the porcelain block into a muffle furnace, heating to 250-300 ℃ at a heating rate of 2-4 ℃/min, then preserving heat at 250-300 ℃ for 2-4 h, heating from 250-300 ℃ to 750-800 ℃ at a heating rate of 2-4 ℃/min, then preserving heat at 750-800 ℃ for 2-3 h, heating from 750-800 ℃ to 1500-1560 ℃ at a heating rate of 2-4 ℃/min, and then preserving heat at 1500-1560 ℃ for 1-2 h; obtaining a composite ceramic block toughened by alumina and cerium dioxide;

fifthly, self-assembling layer by layer:

firstly, immersing the composite ceramic block toughened by the alumina and the cerium dioxide into a polyvinyl alcohol solution for 5-10 min, taking out and drying; then placing the mixture into a tannic acid solution for soaking for 5min to 10min, taking out and drying;

the volume ratio of the mass of the polyvinyl alcohol in the polyvinyl alcohol solution in the step V to the deionized water is (1 g-2 g) to 100 mL;

the volume ratio of the mass of the tannic acid in the tannic acid solution to the deionized water in the step V is (1 g-2 g) to 100 mL;

fifthly, repeating the fifth step for 20-40 times to obtain a composite ceramic block coated with the coating;

thirdly, placing the composite ceramic block coated with the coating in epigallocatechin gallate solution for 5-10 min, taking out and drying, then placing the ceramic block in tannic acid solution for soaking for 5-10 min, taking out and drying;

the volume ratio of the mass of the tannic acid in the tannic acid solution to the deionized water in the step five (1 g-2 g) is 100 mL;

the volume ratio of the mass of the epigallocatechin gallate in the epigallocatechin gallate solution to the deionized water is (0.001 g-0.01 g) 1 mL;

fourthly, repeating the fifth step and the third step for 20 to 40 times to obtain the anti-inflammatory tooth restoration material with the layer-by-layer self-assembly coating.

2. The method for preparing an anti-inflammatory dental restoration material having a layer-by-layer self-assembled coating as claimed in claim 1, wherein the nano zirconia powder in step two has a particle size of 20nm to 40 nm.

3. The method for producing an anti-inflammatory dental restoration material having a layer-by-layer self-assembled coating as claimed in claim 1, wherein the nano alumina powder in step two has a particle size of 40nm to 60 nm.

4. The method for preparing an anti-inflammatory dental restoration material having a layer-by-layer self-assembled coating as claimed in claim 1, wherein the nano-ceria powder in step two has a particle size of 40nm to 60 nm.

5. The method for preparing an anti-inflammatory dental restoration material having a layer-by-layer self-assembled coating according to claim 1, wherein the spray granulation in step three is carried out to obtain particles having a particle size of 10 μm to 30 μm.

6. The method for preparing an anti-inflammatory dental restoration material having a layer-by-layer self-assembled coating according to claim 1, wherein the spray granulation in step three has an atomization frequency of 200Hz, a feed pump rotation speed of 30r/min, and a drying temperature of 220 ℃ to 300 ℃.

7. The method for preparing an anti-inflammatory dental restoration material having a layer-by-layer self-assembled coating according to claim 1, wherein the pressing pressure in step three is 80MPa to 100 MPa.

8. The method for preparing an anti-inflammatory dental restoration material with a layer-by-layer self-assembled coating according to claim 1, wherein the fourth step comprises placing the ceramic block in a muffle furnace, heating to 280 ℃ at a heating rate of 3 ℃/min, maintaining the temperature at 280 ℃ for 3 hours, heating from 280 ℃ to 800 ℃ at a heating rate of 3 ℃/min, maintaining the temperature at 800 ℃ for 2 hours, heating from 800 ℃ to 1550 ℃ at a heating rate of 3 ℃/min, and maintaining the temperature at 1550 ℃ for 1.5 hours to obtain the alumina and ceria toughened composite ceramic block.

9. The method for producing an anti-inflammatory dental restoration material having a layer-by-layer self-assembled coating according to claim 1, wherein the step five (c) is repeated 30 to 40 times to obtain a composite ceramic block coated with a coating; and in the step V, repeating the step V and the step V for 30 to 40 times to obtain the anti-inflammatory tooth restoration material with the layer-by-layer self-assembly coating.

10. The method for preparing an anti-inflammatory tooth restoration material with a layer-by-layer self-assembly coating according to claim 1, wherein the volume ratio of the weight of epigallocatechin gallate in the epigallocatechin gallate solution in the step (fifty) to deionized water is (0.005 g-0.008 g):1 mL.

Images