CN113956036A

CN113956036A - Composite all-ceramic material applied to posterior dental crowns and preparation method thereof

Info

Publication number: CN113956036A
Application number: CN202111418319.2A
Authority: CN
Inventors: 刘奕路; 黎永华
Original assignee: Nanjing Ousaier Tooth Industry Co ltd
Current assignee: Nanjing Ousaier Tooth Industry Co ltd
Priority date: 2021-11-26
Filing date: 2021-11-26
Publication date: 2022-01-21
Anticipated expiration: 2041-11-26
Also published as: CN113956036B

Abstract

The invention belongs to the field of ceramic materials, and particularly relates to a composite all-ceramic material applied to a back tooth crown and a preparation method thereof, which solve the problems of easy abrasion and damage and poor machinability caused by the brittleness of the traditional Y-TZP, and the composite all-ceramic material applied to the back tooth crown comprises the following raw materials in parts by mass: 90-100 parts of TiC-Y-TZP powder and 5-10 parts of Co-Ge-Zr alloy-carbon nano tube. According to the technical scheme, the toughness is improved and the mechanical strength of the composite all-ceramic material is improved through the introduction of the carbon nano tubes, TiC and alloy, the carbon nano tubes are introduced through the alloy as an adhesive, the problem of agglomeration of the carbon nano tubes in the sintering process of the composite all-ceramic material is solved due to the existence of the alloy, the carbon nano tube pieces are uniformly distributed in the TiC-Y-TZP ceramic, the good interface combination is achieved, the mechanical property of the composite ceramic material is improved, and meanwhile, the introduction of the alloy is also beneficial to the improvement of the mechanical property.

Description

Composite all-ceramic material applied to posterior dental crowns and preparation method thereof

Technical Field

The invention belongs to the field of ceramic materials, and particularly relates to a composite all-ceramic material applied to a posterior tooth crown and a preparation method thereof.

Technical Field

The ceramic material has good biocompatibility and structure, color and texture similar to human teeth, so the ceramic material is known as a main tooth dentition defect repairing material in the 21 st century. Although cast ceramics, glass-infiltrated alumina ceramics, compact polycrystalline alumina ceramics and zirconia ceramics are available at present and are used clinically, the traditional ceramic materials are mainly suitable for anterior teeth and have a large difference with the requirement on the strength of a dental crown bridge prosthesis (600-900 MPa).

Yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) plays an important role in various dental restorative materials due to its high hardness and rigidity, excellent biocompatibility, and satisfactory aesthetic properties. However, these bioceramics are very hard compared to human teeth; for example, Y-TZP is ≈ 4 and ≈ 24 times harder than human enamel and dentin, respectively (the hardness of Y-TZP ≈ 12GPa), however, ZrO₂Phase changes in the base ceramic can shorten its useful life in the dental field, especially under complex biochemical conditions. Brittleness of still ZrO₂One obstacle of base ceramics is that more effort is required to increase ZrO₂Mechanical properties of the base ceramic.

As one of the highest strength materials, having excellent mechanical properties of a breaking strength of 125GPa and a young's modulus of up to 1GPa, carbon nanotubes may be used as a reinforcing phase to improve the mechanical and electrical properties of the ceramic. However, the hydrophobic nature and agglomeration caused by van der waals forces limit their application in the medical field.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a composite all-ceramic material applied to a posterior dental crown and a preparation method thereof, and solves the problems of easy abrasion and damage and poor machinability caused by the brittleness of the traditional Y-TZP.

In order to achieve the purpose, the invention is realized by the following scheme:

a preparation method of a composite all-ceramic material applied to a posterior dental crown comprises the following steps:

s1, ZrOCl₂·8H₂O、Y(NO₃)₃·6H₂O and Ti (SO)₄)₂Dissolving in deionized water to obtain a solution, and adding the solution to NH with pH of 9₄Maintaining pH at 9 in OH solution, filtering, washing the filtered precipitate with deionized water for 5 times, washing the precipitate with ethanol for 2 times, drying the precipitate at 80 deg.C, and calcining at 800 deg.C for 1 hr to obtain ZrO₂–TiO₂–Y₂O₃A solid solution;

s2 ZrO prepared₂–TiO₂–Y₂O₃Mixing the solid solution and polyacrylonitrile, grinding, then putting the mixture into a furnace for carbonization at 1550-;

s3, mixing the dried carbon nanotube powder with a solution in which Co-Ge-Zr is dispersed in acetone, grinding the mixture in a solvent, depositing the mixture for 4 hours, and evaporating the solvent to obtain a Co-Ge-Zr alloy-carbon nanotube;

s4, mixing 90-100 parts of TiC-Y-TZP powder obtained in the step S2 and 5-10 parts of Co-Ge-Zr alloy-carbon nano tube obtained in the step S3, adding the mixture into a ball mill filled with ethanol solution, mixing for 15 hours at the rotating speed of 150r/min, filtering to obtain mixed powder, drying the mixed powder at 70 ℃, passing through a 100-mesh sieve, and calcining in vacuum at the temperature of 1450-.

Preferably, said ZrOCl₂·8H₂O、Y(NO₃)₃·6H₂O、Ti(SO₄)₂Deionized water and NH₄The mass ratio of OH is 70-80: 3-6: 15-20: 200-300: 100-150.

Preferably, the ZrO₂–TiO₂–Y₂O₃The mass ratio of the solid solution to the polyacrylonitrile is 100: 1-1.5.

Preferably, the mass ratio of the carbon nanotube powder to the solution in which Co-Ge-Zr is dispersed in acetone is 5 to 10: 1-5, wherein the mass ratio of acetone to Co-Ge-Zr alloy in the solution with Co-Ge-Zr dispersed in acetone is 100-: 5-10, wherein the mass ratio of Co, Ge and Zr in the Co-Ge-Zr alloy is 1: 1: 1.

the composite all-ceramic material applied to the posterior dental crown comprises the following raw materials in parts by mass: 90-100 parts of TiC-Y-TZP powder and 5-10 parts of Co-Ge-Zr alloy-carbon nano tube.

Compared with the prior art, the method has the beneficial effects that:

(1) in the technical scheme of the invention, the toughness is improved and the mechanical strength of the composite all-ceramic material is improved by introducing the carbon nano tube, TiC and alloy, the TiC and the Y-TZP form the composite ceramic, the existence of the TiC crystallized in situ leads to the reduction of the grain growth and the improvement of the mechanical property of the zirconia material, the carbon nano tube is introduced by taking the alloy as a bonding agent, the existence of the alloy solves the agglomeration problem of the carbon nano tube in the sintering process of the composite all-ceramic material, the carbon nano tube pieces are uniformly distributed in the TiC-Y-TZP ceramic, the good interface combination is realized, the mechanical property of the composite ceramic material is improved, meanwhile, the introduction of the alloy is also beneficial to the improvement of the mechanical property, and the introduction of polyacrylonitrile in the ZrO₂–TiO₂–Y₂O₃In the solid solution, higher carbon formation rate can be realized, and the polyacrylonitrile can complex metal ions, induce the metal ions to be uniformly distributed and also improve the mechanical strength of the ceramic material.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.

Example 1

ZrOCl₂·8H₂O、Y(NO₃)₃·6H₂O、Ti(SO₄)₂deionized water and NH₄The mass ratio of OH is 70: 3: 15: 200: 100.

s2 ZrO prepared₂–TiO₂–Y₂O₃Mixing the solid solution and polyacrylonitrile, grinding, then putting the mixture into a furnace for carbonization at 1550 ℃ under the atmosphere of argon, and grinding to obtain TiC-Y-TZP powder;

ZrO₂–TiO₂–Y₂O₃the mass ratio of the solid solution to the polyacrylonitrile is 100: 1.

s3, mixing the dried carbon nanotube powder with a solution in which Co-Ge-Zr is dispersed in acetone, grinding the mixture in a solvent, depositing the mixture for 4 hours, and evaporating the solvent to obtain a Co-Ge-Zr alloy-carbon nanotube; the mass ratio of the carbon nanotube powder to the solution with Co-Ge-Zr dispersed in acetone is 5: 1, the mass ratio of acetone to Co-Ge-Zr alloy in the solution with Co-Ge-Zr dispersed in acetone is 100: 5, the mass ratio of Co, Ge and Zr in the Co-Ge-Zr alloy is 1: 1.

s4, mixing 90 parts of TiC-Y-TZP powder obtained in the step S2 and 5 parts of Co-Ge-Zr alloy-carbon nano tube obtained in the step S3, adding the mixture into a ball mill filled with ethanol solution, mixing for 15 hours at the rotating speed of 150r/min, filtering to obtain mixed powder, drying the mixed powder at 70 ℃, passing through a 100-mesh sieve, and calcining in vacuum at the temperature of 1450 ℃, thus obtaining the finished product.

Example 2

ZrOCl₂·8H₂O、Y(NO₃)₃·6H₂O、Ti(SO₄)₂deionized water and NH₄The mass ratio of OH is 75: 5: 17: 250: 120.

ZrO₂–TiO₂–Y₂O₃the mass ratio of the solid solution to the polyacrylonitrile is 100: 1.3.

s3, mixing the dried carbon nanotube powder with a solution in which Co-Ge-Zr is dispersed in acetone, grinding the mixture in a solvent, depositing the mixture for 4 hours, and evaporating the solvent to obtain a Co-Ge-Zr alloy-carbon nanotube; the mass ratio of the carbon nanotube powder to the solution with Co-Ge-Zr dispersed in acetone is 7: 3, the mass ratio of the acetone to the Co-Ge-Zr alloy in the solution with the Co-Ge-Zr dispersed in the acetone is 130: 7, the mass ratio of Co, Ge and Zr in the Co-Ge-Zr alloy is 1: 1.

s4, mixing 95 parts of TiC-Y-TZP powder obtained in the step S2 and 7 parts of Co-Ge-Zr alloy-carbon nano tube obtained in the step S3, adding the mixture into a ball mill filled with ethanol solution, mixing for 15 hours at the rotating speed of 150r/min, filtering to obtain mixed powder, drying the mixed powder at 70 ℃, passing through a 100-mesh sieve, and calcining in vacuum at the temperature of 1500 ℃ to obtain the finished product.

Example 3

ZrOCl₂·8H₂O、Y(NO₃)₃·6H₂O、Ti(SO₄)₂deionized water and NH₄The mass ratio of OH is 80: 6: 20: 300: 150.

s2 ZrO prepared₂–TiO₂–Y₂O₃Mixing the solid solution and polyacrylonitrile, grinding, then putting the mixture into a furnace for carbonization at 1650 ℃ under the argon atmosphere, and grinding to obtain TiC-Y-TZP powder;

ZrO₂–TiO₂–Y₂O₃the mass ratio of the solid solution to the polyacrylonitrile is 100: 1.5.

s3, mixing the dried carbon nanotube powder with a solution in which Co-Ge-Zr is dispersed in acetone, grinding the mixture in a solvent, depositing the mixture for 4 hours, and evaporating the solvent to obtain a Co-Ge-Zr alloy-carbon nanotube; the mass ratio of the carbon nanotube powder to the solution with Co-Ge-Zr dispersed in acetone is 10: 5, the mass ratio of the acetone to the Co-Ge-Zr alloy in the solution in which the Co-Ge-Zr is dispersed in the acetone is 150: 10, the mass ratio of Co, Ge and Zr in the Co-Ge-Zr alloy is 1: 1.

s4, mixing 100 parts of TiC-Y-TZP powder obtained in the step S2 and 10 parts of Co-Ge-Zr alloy-carbon nano tube obtained in the step S3, adding the mixture into a ball mill filled with ethanol solution, mixing for 15 hours at the rotating speed of 150r/min, filtering to obtain mixed powder, drying the mixed powder at 70 ℃, passing through a 100-mesh sieve, and calcining in vacuum at the temperature of 1650 ℃ to obtain the finished product.

Comparative example

The comparative example used a commercially available composite all-ceramic material for the posterior crown.

The composite all-ceramic materials prepared in the examples and the composite all-ceramic materials in the comparative examples were subjected to mechanical strength tests.

And (3) determination of the compressive strength of the composite all-ceramic material:

1. sample preparation

(1) And (3) firing 10 regular samples with the diameter (D) of (20 +/-2) mm and the height (H) of (20 +/-2) mm according to the production process conditions. The upper and lower surfaces of the sample are ground and leveled by a No. 100 carborundum abrasive material on a grinding machine, the non-parallelism of the upper and lower surfaces of the sample is less than 0.010mm/cm, and the verticality of the central line and the bottom surface of the sample is not less than 0.0220 mm/cm.

(2) Cleaning the sample, removing the sample with visible defects, and drying for later use.

2. Experimental procedure

(1) And (4) measuring the size of the pressure surface of the sample, and calculating the area, wherein each group of samples is not less than 5.

(2) The sample was placed at the center of the platen of the testing machine, and a load was applied at a speed of 2X 10N/S until the sample was broken, and the maximum load at the time of breaking the sample was read. When the high porosity sample has no obvious destruction phenomenon, the sample with the height change of 10% is taken as a sample destruction point.

(3) Substituting the test result into the following formula to calculate the pressure

Shrinkage strength:

Rc＝P/S

wherein Rc- -compressive strength, MPa;

p- -breaking load, N;

s- -the stress area of the sample.

The results of the compressive strength test are shown in table 1 below:

TABLE 1

As can be seen from table 1 above, the composite all-ceramic material prepared in the example of the present invention has higher compressive strength than the commercially available composite all-ceramic material.

And (3) determining the flexural strength of the composite all-ceramic material:

the flexural strength calculation formula is as follows:

R＝3PL/2bh2

in the formula:

r-bending strength of the sample, MPa;

p- -sample failure load, N;

l-fulcrum span, mm;

b- -sample width, mm;

h- -specimen thickness, mm.

The size of the sample of the composite all-ceramic material affects the flexural strength, the thickness of the product is 10 +/-1 mm, and the width of the product is 10 +/-1 mm.

The experimental steps are as follows:

(1) the preparation of the sample comprises the steps of cutting a flat part of three composite ceramic material products to obtain a sample with the width-thickness ratio of 1:1, the length of the sample of 120mm, the width of 25 +/-1 mm, the thickness of 25 +/-1 mm and 5-10 samples, wherein the sample must be ground flat without allowing obvious edges or cracks caused by sample preparation, and impurities on the surface of the sample must be removed completely before the test.

(2) The qualified samples were numbered and the widths and thicknesses of three sections near the center of the span of the test specimen were measured, and the arithmetic mean was taken.

(3) The span between the supports is adjusted to be 100mm (or 50mm), the sample is placed on the supports, the load is applied at the speed of 2 +/-0.5N/s until the sample is destroyed, and the load value at the time of the destruction is read.

(4) The bending strength was calculated by substituting the experimental results into the above formula.

The flexural strength test results of the composite all-ceramic material are shown in the following table 2:

TABLE 2

As can be seen from table 2 above, compared with the conventional composite all-ceramic material, the composite all-ceramic material prepared in the embodiment of the present invention greatly improves the flexural strength of the composite all-ceramic material by adding the carbon nanotube, TiC, and the alloy.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims

1. A preparation method of a composite all-ceramic material applied to a posterior dental crown is characterized by comprising the following steps:

s4, adding the TiC-Y-TZP powder obtained in the step S2 and the Co-Ge-Zr alloy-carbon nano tube obtained in the step S3 into a ball mill filled with ethanol solution for mixing for 15 hours at the rotating speed of 150r/min, filtering to obtain mixed powder, drying the mixed powder at 70 ℃, passing through a 100-mesh sieve, and calcining in vacuum at the temperature of 1450-.

2. The method of claim 1, wherein the ZrOCl is₂·8H₂O、Y(NO₃)₃·6H₂O、Ti(SO₄)₂Deionized water and NH₄The mass ratio of OH is 70-80: 3-6: 15-20: 200-300: 100-150.

3. The production method according to claim 1, wherein the ZrO₂–TiO₂–Y₂O₃The mass ratio of the solid solution to the polyacrylonitrile is 100: 1-1.5.

4. The method according to claim 1, wherein the mass ratio of the carbon nanotube powder to the solution in which Co-Ge-Zr is dispersed in acetone is 5 to 10: 1-5, wherein the mass ratio of acetone to Co-Ge-Zr alloy in the solution with Co-Ge-Zr dispersed in acetone is 100-: 5-10, wherein the mass ratio of Co, Ge and Z in the Co-Ge-Zr alloy is 1: 1: 1.

5. the composite all-ceramic material for the posterior dental crown prepared by the preparation method according to any one of claims 1 to 4, which is characterized by comprising the following raw materials in parts by mass: 90-100 parts of TiC-Y-TZP powder and 5-10 parts of Co-Ge-Zr alloy-carbon nano tube.