CN111454057A

CN111454057A - Dental zirconia all-ceramic material and preparation method thereof

Info

Publication number: CN111454057A
Application number: CN202010532464.2A
Authority: CN
Inventors: 孔令兵; 张天舒; 刘银; 董强
Original assignee: Nanjing Sanotes Material Technology Co ltd
Current assignee: Nanjing Sanotes Material Technology Co ltd
Priority date: 2019-06-12
Filing date: 2020-06-11
Publication date: 2020-07-28
Also published as: CN110078500A

Abstract

The invention discloses a dental zirconia all-ceramic material, which is prepared from nano ZrO by adopting a polyacrylamide gel method₂Powder dry pressing synthesis, the nano ZrO₂The powder is prepared from ZrOCl₂·8H₂O and ZrO (NO)₃)₂·2H₂The gel precursor prepared from the composite zirconium source consisting of O is subjected to a gel thermal decomposition step and a crystallization step to obtain powder particle sizes distributed in the range of 60.4-82.6 nm; wherein, before gelationThe precursor is decomposed at a decomposition rate of 85 to 95% in the gel thermal decomposition step and ZrO at a decomposition rate of 90 to 95% in the crystallization step₂From tetragonal phase to monoclinic phase.

Description

Dental zirconia all-ceramic material and preparation method thereof

Technical Field

The invention relates to the technical field of biological materials, in particular to a dental zirconia all-ceramic material and a preparation method thereof.

Background

With the development of the research of oral cavity repairing materials, All-ceramic repairing technology (All-ceramic repairing technology) with good biocompatibility and aesthetic effect is widely considered as a more ideal repairing mode. In known all-ceramic material systems, zirconium oxide (ZrO)₂) Ceramics have obvious advantages in mechanical properties such as strength and toughness compared with other materials, and therefore, the ceramics become the focus of attention and research of the current oral cavity materials.

The zirconia crystal has three structures of monoclinic phase (m), tetragonal phase (t) and cubic phase (c). The critical temperatures for the phase transitions between these three phases are 1170 ℃ and 2370 ℃ respectively. In the oral environment, zirconia ceramics have a Fatigue phenomenon (Fatigue). Tetragonal zirconia (t-ZrO) in a low temperature humid environment₂) Can generate monoclinic phase (m-ZrO)₂) The phase change of the zirconium oxide ceramic is called low-temperature aging effect (L TD). The humid environment, temperature and cyclic stress in the oral cavity can cause the reduction of the mechanical property of the all-ceramic material, and cause a plurality of complications such as the fracture of the repair material.

The mechanical properties of zirconia ceramics are affected by their microstructure, which depends mainly on their grain size. Generally speaking, the smaller the grain size, the narrower the grain size distribution, and the higher the stability of the crystal phase, the higher the fatigue strength of the material. In the prior art, the mechanical properties of zirconia ceramic materials are usually controlled by modifying the zirconia powder raw material.

For example, chinese invention CN106747432A discloses a raw material powder of a high wear-resistant zirconia ceramic part and a preparation method thereof. The raw material powder comprises, by weight, 80-90 parts of a material A, 1-4 parts of PVA, 0.5-2.5 parts of Arabic gum, 0.1-1.5 parts of glycerol and 130-150 parts of deionized water; the material A comprises the following components in parts by weight: 60-80 parts of yttrium-stabilized zirconia, 5-10 parts of lanthanum oxide, 2-6 parts of high clay, 2-5 parts of graphite and 0.1-0.5 part of calcium oxide; wherein, the graphite needs to be soaked by dilute nitric acid and then subjected to solid-liquid separation. The graphite soaked by dilute nitric acid replaces the traditional lubricating additives such as molybdate, magnesia and the like, so that the friction coefficient of the zirconia ceramic at high temperature (1200-1400 ℃) is reduced, the porosity of the material is reduced, the density of the material is improved, the sintering temperature of the zirconia material is reduced, and the wear resistance of the ceramic body prepared from the powder is improved.

The method only improves macroscopic properties such as a friction system of the powder from the sintering temperature, but does not improve microstructures such as the particle size and the particle size distribution of the powder, and has limited improvement on the phase stability and the fatigue resistance of a ceramic body made of the powder.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a dental zirconia all-ceramic material, which is prepared from nano ZrO by adopting a polyacrylamide gel method₂Powder is synthesized by dry pressing. The nano ZrO₂The powder is prepared from ZrOCl₂·8H₂O and ZrO (NO)₃)₂·2H₂The gel precursor prepared from the composite zirconium source consisting of O is prepared through a gel thermal decomposition step and a crystallization step so as to obtain powder particle sizes distributed in the range of 60.4-82.6 nm. Wherein the gel precursor has a decomposition rate of 85 to 95% in the gel thermal decomposition step and 90 to 95% of ZrO in the crystallization step₂From tetragonal phase to monoclinic phase.

According to a preferred embodiment, ZrOCl is present in the composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂The molar ratio of O is 0.5:1 to 2: 1.

According to a preferred embodiment, the gel pyrolysis step is carried out at a temperature of 550 ℃ to 570 ℃.

According to a preferred embodiment, the crystallization step is carried out at a temperature of 860 ℃ to 880 ℃.

According to a preferred embodiment, the nano-ZrO₂After the powder is dry-pressed and molded, the surface of the powder is modified by the oxidized graphene and the oxidized fullerene to improve the biocompatibility.

According to a preferred embodiment, the surface modification is carried out by: nano ZrO is mixed with₂Immersing the substrate obtained by dry pressing and molding the powder into a 3.5 percent G L YMO/ethanol solution for 1 hour, taking out and drying the substrate to carry out silanization, immersing the silanized substrate into deionized water ultrasonic dispersion liquid containing 1.2mg/ml of graphene oxide and fullerene oxide with the molar ratio of 1:1, reacting for 1.5 hours at 40 ℃, taking out and drying.

According to a preferred embodiment, after surface modification, the surface of the substrate forms an agglomerated stack of spaced graphene oxide and fullerene oxide.

The invention also discloses a preparation method of the dental zirconia all-ceramic material, which comprises the step of preparing the nano ZrO by adopting a polyacrylamide gel method₂And carrying out dry pressing on the powder. The nano ZrO₂The powder is prepared from ZrOCl₂·8H₂O and ZrO (NO)₃)₂·2H₂The gel precursor prepared from the composite zirconium source consisting of O is prepared through a gel thermal decomposition step and a crystallization step so as to obtain powder particle sizes distributed in the range of 60.4-82.6 nm. Wherein the gel precursor has a decomposition rate of 85 to 95% in the gel thermal decomposition step and 90 to 95% of ZrO in the crystallization step₂From tetragonal phase to monoclinic phase.

According to a preferred embodiment, ZrOCl is present in the composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂The molar ratio of O is 0.5:1 to 2: 1. The gel thermal decomposition step is carried out at 550 ℃ to 570 ℃. The crystallization step is carried out at 860 ℃ to 88 DEG CAt 0 ℃.

According to a preferred embodiment, the nano-ZrO₂After the powder is dry-pressed and molded, the surface of the powder is modified by the oxidized graphene and the oxidized fullerene to improve the biocompatibility. Wherein the surface modification is performed by: nano ZrO is mixed with₂Immersing the substrate obtained by dry pressing and molding the powder into a 3.5 percent G L YMO/ethanol solution for 1 hour, taking out and drying the substrate to carry out silanization, immersing the silanized substrate into deionized water ultrasonic dispersion liquid containing 1.2mg/ml of graphene oxide and fullerene oxide with the molar ratio of 1:1, reacting for 1.5 hours at 40 ℃, taking out and drying.

According to a preferred embodiment, the ZrOCl in the composite zirconium source is controlled₂·8H₂O and ZrO (NO)₃)₂·2H₂Nano ZrO prepared by adjusting proportion of O₂Average particle size and particle size distribution range of the powder.

The beneficial technical effects of the invention comprise one or more of the following:

1. the invention adopts ZrOCl₂·8H₂O and ZrO (NO)₃)₂·2H₂O, by controlling the thermal decomposition condition and crystallization condition, the prepared nano ZrO₂The particle size distribution of the powder is obviously narrow, and the agglomeration degree is reduced.

2. Using nano ZrO of uniform particle size₂The dental all-ceramic material obtained by powder dry-pressing molding has the advantages that due to the reduction of internal stress and the improvement of toughness, the anti-fatigue strength is improved in a low-temperature and humid oral environment, and the occurrence probability of fatigue complications such as fracture is obviously reduced.

3. The surface modification is carried out by utilizing the oxidized graphene and the oxidized fullerene, so that the surface of the ceramic material has rich oxygen-containing groups, the hydrophilicity is increased, and the hydrophilic surface is favorable for early cell adhesion. The folded surface formed by the oxidized graphene and the oxidized fullerene can further provide stronger adhesion, prevent the cell from falling off and is beneficial to cell proliferation, so that the biocompatibility of the dental all-ceramic material is improved.

Drawings

FIG. 1 shows ZrO produced in example 1 of the present invention₂The particle size distribution diagram of the powder;

FIG. 2 shows ZrO produced in example 1 of the present invention₂XRD spectrum of the powder; and

FIG. 3 shows ZrO produced in example 1 of the present invention₂SEM appearance of the powder.

Detailed Description

The following detailed description is made with reference to fig. 1 to 3.

Example 1

The embodiment discloses a dental zirconia all-ceramic material, which is prepared from nano ZrO by adopting a polyacrylamide gel method₂Powder is synthesized by dry pressing. Conventional preparation of ZrO₂The powder method comprises a hydrothermal synthesis method, a micro-emulsion method, a coprecipitation method, a sol-gel method and the like. The polyacrylamide gel method is an improved sol-gel method, and has the advantages of low cost, simple operation, adjustable powder components and the like. Nano ZrO₂The powder is prepared from ZrOCl₂·8H₂O and ZrO (NO)₃)₂·2H₂The gel precursor prepared from the composite zirconium source consisting of O is prepared through a gel thermal decomposition step and a crystallization step so as to obtain powder particle sizes distributed in the range of 60.4-82.6 nm. Concretely, ZrOCl₂·8H₂O and ZrO (NO)₃)₂·2H₂Preparing 0.4 mol/L aqueous solution from O according to the molar ratio of 1:1, adding Acrylamide (AM) and methylene bisacryloyl (N, N' -methylene bis (acrylamide, MBAM) with the molar ratio of 20:1 into the solution, stirring uniformly at room temperature, heating the aqueous solution to 60 ℃ and keeping the heated solution for 1 hour to obtain a gel precursor, drying the gel precursor at 80 ℃ for 24 hours, grinding the gel precursor into powder, heating the dry gel powder in a muffle furnace, heating the dry gel powder to 550-570 ℃, preferably 560 ℃ for thermal decomposition, monitoring the mass change of the dry gel powder, calculating the decomposition rate of the gel precursor through the mass loss of the dry gel powder, and mainly dividing the thermal weight loss of the dry gel powder into three stages, wherein the first stage is from room temperature to 210 ℃ to 230 ℃, and the weight loss of the stage is a main source of weight lossLoss of water molecules. The second stage weight loss is in the range of 230 ℃ to 470 ℃, and the stage weight loss is the gasification or oxidative decomposition of small organic molecules, namely the cross-linking agent, in this embodiment, AM and MBAM. The third-stage weight loss occurs above 500 ℃, and is mainly ZrOCl₂And ZrO (NO)₃)₂Decomposition to form ZrO₂Weight loss due to nanopowder. The decomposition rate of the gel precursor can be calculated by monitoring the weight loss. ZrOCl needs to be considered for the calculation₂And ZrO (NO)₃)₂In a molar ratio of (a). Calculated according to dynamics, ZrOCl₂And ZrO (NO)₃)₂Are comparable in thermal decomposition kinetics, so that, in this thermal decomposition phase, both decompose to form ZrO at substantially the same rate₂Thus, the total decomposition rate can be calculated by detecting the total weight loss. Wherein, the temperature of the gel precursor is increased to 860 ℃ to 880 ℃ when the decomposition rate of the gel precursor reaches 85% to 95% in the thermal decomposition step of the gel, and the crystallization step is preferably carried out at 870 ℃. 90 to 95% ZrO in the crystallization step₂From tetragonal phase to monoclinic phase.

In the process of preparing the nano powder by adopting the polyacrylamide gel method, the slightly soluble solution containing the zirconium salt is separated in gel network cavities formed by AM and MBAM, so that zirconium salt particles formed after sintering are also separated in the gel network cavities formed by AM and MBAM, and ZrO₂The particle size of the nano powder is reduced. The inventors have found that the kind of the zirconium source used is specific to ZrO₂Crystallization temperature of nano powder, ZrO obtained after heat treatment₂The size and surface energy of the nano powder have great influence, and further the ZrO₂The mechanical properties of the ceramic material prepared from the nano powder, such as fatigue resistance and phase stability. ZrO due to Cl-in the gel₂Can reduce the critical grain size of ZrO₂The crystallization temperature of (a). And NO in the gel₃Presence of-can inhibit ZrO₂Grain nucleation of and m-ZrO₂The growth of (2). NO in gel₃Can further reduce ZrO₂Average grain size of nano powder and relative increase of ZrO₂The crystallization temperature of (a).

Surprisingly, the combinationUsing a catalyst consisting of ZrOCl₂·8H₂O and ZrO (NO)₃)₂·2H₂O, and further adjusting the thermal decomposition process and the crystallization process of the gel precursor obtained from the composite zirconium source, including parameters such as thermal decomposition temperature, decomposition rate, thermal decomposition time, crystallization temperature, crystallization time, phase transformation rate and the like, so that the finally obtained ZrO can be effectively optimized₂Particle size of the powder including ZrO₂The particle size of the powder is reduced and the particle size distribution range is narrower, thereby preparing ZrO with more uniform particle size₂And (3) powder. By using a composite zirconium source, NO is present in the gel precursor at the same time₃-and Cl-, NO₃ ^-And Cl^-Simultaneously as point defects to inhibit the grain nucleation of the zirconia, so that the ZrO₂The particle size of the powder is more uniform.

ZrO₂The grain size of the powder is more uniform, so that ZrO prepared by dry pressing₂When the all-ceramic material is used, particularly a dental all-ceramic material, the internal stress of the ceramic body is obviously reduced, the toughness and the fatigue resistance of the ceramic body are improved, and the probability of fatigue complications such as fracture and the like is obviously reduced particularly in a low-temperature and humid environment of an oral cavity.

ZrO prepared in this example₂The powder has fine particles, uniform particle size distribution and high phase purity, and has remarkable improvement effect on the sintering performance and the application performance of the finally formed dental zirconia all-ceramic material, especially on the phase stability and the fatigue resistance.

It is to be noted that, in the context of the present invention, ZrO₂The particle size of the powder is not the particle size of the powder obtained by preparing a gel precursor by a polyacrylamide gel method, and performing thermal decomposition and crystallization, but is not the particle size of the ZrO just formed₂Particle size of gel precursor. It is known in the art that ZrO having a particle size of about 10nm can be obtained by a precipitation method or the like₂However, such ZrO₂Has extremely high surface energy, and can be seriously agglomerated in the heating or sintering process, so that the grain diameter of the obtained powder or ceramic material is remarkably increased to more than 100nm, and the grain diameter distribution range is wide (the grain diameter distribution interval is also more than 100 nm), and is not uniformEven, voids can also be formed, affecting the mechanical properties of the ceramic.

Preferably, ZrOCl in the composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂The molar ratio of O is 0.5:1 to 2: 1. FIG. 1 shows nano-ZrO produced in the present example₂Particle size distribution data of the powder. According to a preferred embodiment, ZrOCl in the composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂The molar ratio of O is 1:1, and the nano ZrO finally obtained by using the zirconium source proportion₂The particle size distribution of the powder particles ranged from 60.4 to 82.6nm, as shown in fig. 1 (b). According to another preferred embodiment, ZrOCl in the composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂The molar ratio of O is 0.5:1, and the nano ZrO finally obtained by using the zirconium source ratio₂The particle size distribution of the powder particles ranged from 53.2 to 73.6nm, as shown in FIG. 1 (a). According to another preferred embodiment, ZrOCl in the composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂The molar ratio of O is 2:1, and the nano ZrO finally obtained by using the zirconium source proportion₂The particle size distribution of the powder particles ranged from 70.8 to 93.7nm, as shown in fig. 1 (c).

The inventors analyzed the above experimental data and found that the nano ZrO produced₂Particle size distribution range of powder particles and ZrOCl in composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂The proportion of O has a high degree of relevance. Nano ZrO₂The particle size distribution range and the particle size data interval of the powder particles, or the average particle size of the powder particles, are determined according to the ZrOCl in the composite zirconium source₂·8H₂The proportion of O is reduced along with the reduction of ZrOCl in the composite zirconium source₂·8H₂The proportion of O increases.

Therefore, the invention also provides a method for adjusting ZrOCl in the composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂O ratio to adjust the prepared nano ZrO₂Of the mean particle diameter, or range of particle diameter distributions, of the powder particlesA method. Preferably, in the composite zirconium source, ZrOCl₂·8H₂O and ZrO (NO)₃)₂·2H₂When the molar ratio of O is between 0.5:1 and 2:1, ZrOCl in the composite zirconium source is adjusted₂·8H₂O and ZrO (NO)₃)₂·2H₂Molar ratio of O is adjusted to obtain nano ZrO₂The average particle size of the powder particles, or the particle size distribution range. Preferably, by reducing ZrOCl in the composite zirconium source₂·8H₂The content of O is such that nano ZrO is obtained₂The average particle size of the powder particles or the particle size distribution interval is reduced; by increasing ZrOCl in a composite zirconium source₂·8H₂The content of O is such that nano ZrO is obtained₂The average particle diameter or the particle diameter distribution interval of the powder particles is increased.

FIG. 3 shows nano-ZrO prepared in this example₂SEM morphology of powder, wherein FIG. 3(a) shows ZrOCl in the composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂Nano ZrO obtained with molar ratio of O0.5: 1₂SEM appearance of the powder. FIG. 3(b) shows ZrOCl in a composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂Nano ZrO obtained with molar ratio of O1: 1₂SEM appearance of the powder. FIG. 3(c) shows ZrOCl in a composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂Nano ZrO with O molar ratio of 2:1₂SEM appearance of the powder.

Preferably, the gel pyrolysis step is carried out at 550 ℃ to 570 ℃. In general, xerogels synthesized by polyacrylamide gel processes decompose completely at temperatures above 580 ℃. The embodiment adopts the heat treatment temperature which is slightly lower than the complete decomposition temperature, so that the decomposition speed of the xerogel is convenient to reduce, the decomposition degree of the xerogel is convenient to regulate and control, and particularly the agglomeration and size increase of the nanoparticles after the xerogel is completely decomposed are inhibited. Preferably, in the thermal decomposition step, the heating rate is 20 ℃/min, and the heating is maintained for 1 to 4 hours at the maximum temperature. And (3) monitoring the decomposition rate of the xerogel in the thermal decomposition process, stopping the thermal decomposition step when the decomposition rate reaches 85-95%, and continuing heating for crystallization.

Preferably, the crystallization step is carried out at 860 ℃ to 880 ℃. Preferably, the temperature is raised from the thermal decomposition temperature to the crystallization temperature at a rate of 20 to 30 ℃/min. As shown in FIG. 2, tetragonal ZrO was found at about 400 deg.C₂The diffraction peak of (1). When the temperature is raised to 600 ℃, monoclinic phase ZrO appears₂The diffraction peak of (1). When the temperature is further raised to above 900 ℃, all of the ZrO is converted into monoclinic phase₂. In this example, the crystallization temperature was controlled to be less than 900 ℃ to 90 to 95% ZrO₂The tetragonal phase is changed into the monoclinic phase, and a biphase structure exists in a finished product, so that ZrO can be prevented₂The particle size is increased due to further agglomeration of the nano particles at high temperature, and on the other hand, a biphase structure is reserved in the powder, so that the internal stress of the ceramic material after dry pressing forming when the temperature changes can be reduced, and cracking and falling off in the using process can be prevented.

Preferably, the crystallized nano ZrO₂And dry pressing the powder to prepare the ceramic part. The double-sided pressing mode is adopted, the dry pressing forming pressure is 70 to 90Mpa, and the dry pressing forming temperature is 25 to 35 ℃.

Preferably, nano ZrO₂After the powder is dry-pressed and molded, the surface of the powder is modified by the oxidized graphene and the oxidized fullerene to improve the biocompatibility. The surface modification is carried out by the following steps: nano ZrO is mixed with₂Immersing a matrix obtained by dry pressing and molding the powder into a 3.5 percent G L YMO/ethanol solution for 1 hour, taking out and drying the matrix to silanize the matrix, immersing the silanized matrix into deionized water ultrasonic dispersion containing 1.2mg/ml of graphene oxide and fullerene oxide with the total mass percent and the molar ratio of 1:1, reacting for 1.5 hours at 40 ℃, taking out and drying.

Preferably, after the surface modification, the surface of the substrate forms an agglomerated stack with the graphene oxide and the fullerene oxide arranged at intervals. Preferably, the ceramic substrate chemically modified by graphene oxide and fullerene oxide is subjected to XPS analysis after being ultrasonically cleaned and dried by ethanol or acetone, and a C-C peak of 284.8eV, a C-O peak of 288.5eV, a C-O peak of 286.7eV, and a C-O peak of 289.4eV are observed in XPS spectra, indicating the presence of graphene oxide and fullerene oxide on the surface of the ceramic. Under SEM, the surface of the matrix can be observed to form an agglomerated stack with graphene oxide and fullerene oxide arranged at intervals. The binding sites of the graphene oxide and the fullerene oxide with the ceramic surface are related to the defects of the ceramic surface, particularly the matching degree of the particle size of the modifier with the defect size of the surface of the ceramic matrix. The oxidized fullerene is highly aggregated at a defect site such as a crack having a large size, and the oxidized graphene is highly aggregated at a site having a small defect size or having few defects.

Preferably, the present embodiment uses a mixture of graphene oxide and fullerene oxide for surface modification, wherein graphene oxide is a two-dimensional structure, and fullerene oxide is a three-dimensional structure, and compared with surface modification using a single component, the combination of the two-dimensional structure and the three-dimensional structure is used, especially because the respective adaptive capacities of graphene oxide and the ceramic material surface microstructure, especially the surface defect, complement each other, so that the reactivity, i.e. the modification rate, of the ceramic surface after modification treatment can be improved, the concentration of the active oxygen-containing group on the ceramic material surface can be increased, the hydrophilicity of the ceramic material can be enhanced, the cell adhesion can be facilitated, the tension and the adhesion of the dental implant made of the ceramic material can be enhanced, the proliferation capacity of cells near the implant can be improved, and the application of the dental implant in dental restoration can be facilitated. The bioaffinity test of the chemically modified ceramic matrix of this example shows that cell proliferation on the surface modified ceramic matrix is more active than on the non-surface modified ceramic matrix. The ceramic matrix sample after surface modification can be more densely adhered to the ceramic surface, and shows a more active cell proliferation state.

Preferably, the bioaffinity test method is as follows: inoculating the surface-modified ceramic matrix and unmodified ceramic matrix and human dental pulp stem cells by a static surface inoculation method, and then co-culturing. First, the ceramic matrix was completely put into complete medium and incubated in a carbon dioxide incubator at 37 ℃ for 24 hours. Removing culture medium, and adding the stem cells into two pottery drop by dropIn a ceramic substrate, wherein the cell density is 10⁶Incubating the cell/100 mu L cell suspension in a constant-temperature incubator with 5% carbon dioxide at 37 ℃ for 4 hours, then continuing to incubate for 1 day, 3 days and 5 days, taking out the cell suspension, rinsing the cell suspension by using PBS (phosphate buffer solution) at 37 ℃, fixing the cell suspension by using 4% paraformaldehyde for 15 minutes at room temperature, carrying out permeabilization treatment on 0.5% Triton X-100 solution for 5 minutes, adding TRITC-labeled phalloidin working solution to submerge the cell suspension on a ceramic matrix, incubating the cell suspension in a dark place at room temperature for 1 hour, adding 1 mu g/m L DAPI staining solution to incubate the cell suspension in a dark place for 5 minutes, and observing the adhesion forms of the cells on the two ceramic matrices.

Example 2

According to a preferred embodiment, ZrOCl is present in the composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂The molar ratio of O is 0.5:1 to 2: 1. The gel thermal decomposition step is carried out at 550 ℃ to 570 ℃. The crystallization step is carried out at 860 ℃ to 880 ℃.

According to a preferred embodiment, the nano-ZrO₂After the powder is dry-pressed and molded, the surface of the powder is modified by the oxidized graphene and the oxidized fullerene to improve the biocompatibility. Wherein the surface modification is performed by: nano ZrO is mixed with₂Immersing the substrate obtained by dry pressing the powder into 3.5 percent G L YMO/ethanol solution for 1 hour, taking out and drying to silanize the substrate, immersing the silanized substrate into the separation solution containing 1.2mg/ml of graphene oxide and fullerene oxide with the molar ratio of 1:1Reacting in the sub-water ultrasonic dispersion liquid at 40 ℃ for 1.5 hours, taking out and drying.

It should be noted that the above-mentioned embodiments are exemplary, and that those skilled in the art, having benefit of the present disclosure, may devise various arrangements that are within the scope of the present disclosure and that fall within the scope of the invention. It should be understood by those skilled in the art that the present specification and figures are illustrative only and are not limiting upon the claims. The scope of the invention is defined by the claims and their equivalents.

Claims

1. A dental zirconia all-ceramic material is nano ZrO prepared by a polyacrylamide gel method₂The powder dry pressing synthesis is characterized in that,

the nano ZrO₂The powder is prepared from ZrOCl₂·8H₂O and ZrO (NO)₃)₂·2H₂The gel precursor prepared from the composite zirconium source consisting of O is subjected to a gel thermal decomposition step and a crystallization step to obtain powder particle sizes distributed in the range of 60.4-82.6 nm;

wherein the gel precursor has a decomposition rate of 85 to 95% in the gel thermal decomposition step and 90 to 95% of ZrO in the crystallization step₂From tetragonal phase to monoclinic phase.

2. The dental zirconia all-ceramic material of claim 1 wherein ZrOCl is ZrOCl in the composite zirconium source₂·8H₂O and ZrO (NO)₃)₂·2H₂The molar ratio of O is 0.5:1 to 2: 1.

3. The dental zirconia all-ceramic material according to claim 2, wherein the gel thermal decomposition step is performed at 550 ℃ to 570 ℃.

4. The dental zirconia all-ceramic material of claim 3, wherein the crystallization step is performed at 860 ℃ to 880 ℃.

5. The dental zirconia all-ceramic material of claim 4, wherein the nano ZrO 2 is₂After the powder is dry-pressed and molded, the surface of the powder is modified by the oxidized graphene and the oxidized fullerene to improve the biocompatibility.

6. The dental zirconia all-ceramic material of claim 5, wherein the surface modification is performed by:

nano ZrO is mixed with₂Immersing the matrix obtained by dry pressing and molding the powder into a 3.5% G L YMO/ethanol solution for 1 hour, taking out and drying to silanize the matrix;

immersing the silanized substrate into deionized water ultrasonic dispersion containing 1.2mg/ml of total mass percent and 1:1 of graphene oxide and fullerene oxide, reacting for 1.5 hours at 40 ℃, taking out and drying.

7. The dental zirconia all-ceramic material of claim 6, wherein after surface modification, the matrix surface forms an agglomerated stack of spaced graphene oxide and fullerene oxide.

8. A process for preparing the full-ceramic dental zirconia material includes preparing the nano ZrO by polyacrylamide gel method₂The powder is dry-pressed and molded, which is characterized in that,

9. The method of claim 8, wherein the zirconium source is combinedZrOCl₂·8H₂O and ZrO (NO)₃)₂·2H₂The molar ratio of O is 0.5:1 to 2: 1; the gel thermal decomposition step is carried out at the temperature of 550-570 ℃; the crystallization step is carried out at 860 to 880 deg.C, nano ZrO₂After the powder is dry-pressed and molded, the surface of the powder is modified by the oxidized graphene and the oxidized fullerene to improve the biocompatibility,

wherein the surface modification is performed by:

10. The method of claim 9, wherein ZrOCl in the composite zirconium source is controlled₂·8H₂O and ZrO (NO)₃)₂·2H₂Nano ZrO prepared by adjusting proportion of O₂Average particle size and particle size distribution range of the powder.