阅读说明：本技术 一种氧化锆陶瓷表面原位生长蜂窝状纳米结构的制备方法及制备的改性氧化锆陶瓷 (Preparation method of in-situ growth honeycomb-shaped nano structure on surface of zirconia ceramic and prepared modified zirconia ceramic ) 是由 刘劲松 沈新坤 马萍萍 徐丽华 于 2020-03-27 设计创作，主要内容包括：本发明公开一种氧化锆陶瓷表面原位生长蜂窝状纳米结构的制备方法及制备的改性氧化锆陶瓷,首次通过简单高压水热处理途径,于氧化锆陶瓷表面成功制备了系列孔径可控的新型蜂巢状纳米结构,所获得的纳米结构为表面原位生长,主要成分为磷酸氢锆,可显著地提高材料表面饰瓷或树脂胶的粘接性能,分别提高约10或7MPa,且有效地促进了表面成骨细胞的增殖及成骨分化性能,具有良好的临床应用前景。(The invention discloses a preparation method of a honeycomb-shaped nano structure grown on the surface of zirconia ceramic in situ and a prepared modified zirconia ceramic, wherein a series of novel honeycomb-shaped nano structures with controllable pore diameters are successfully prepared on the surface of the zirconia ceramic by a simple high-pressure hydrothermal treatment way for the first time, the obtained nano structure is grown on the surface in situ, the main component is zirconium hydrogen phosphate, the bonding property of material surface decorative porcelain or resin adhesive can be obviously improved, the bonding property is respectively improved by about 10 or 7MPa, the proliferation and osteogenic differentiation properties of surface osteoblasts are effectively promoted, and the modified zirconia ceramic has good clinical application prospect.)

1. The preparation method of the zirconia ceramic surface in-situ growth honeycomb-shaped nano structure mainly comprises the following steps:

the zirconium oxide material after polishing treatment is placed in 1-2.5 wt% diluted phosphoric acid solution, treated for 12-36h at 80-160 ℃ in a high-pressure reaction kettle, or the zirconium oxide material after polishing treatment is placed in 0.5-1 wt% or more than or equal to 2.5 and less than 5 wt% diluted phosphoric acid solution, treated for 12-36h at 120-160 ℃ in the high-pressure reaction kettle, and then subjected to secondary calcination treatment, so as to obtain the zirconium oxide ceramic with the in-situ grown honeycomb nano structure.

2. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 1, which is characterized in that: the zirconia ceramics are subjected to surface grinding treatment by using 100-2000-mesh sandpaper.

3. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 2, which is characterized in that: the zirconium oxide material after polishing treatment is placed in 0.5-2.5 wt% diluted phosphoric acid solution and treated for 24 hours in a high-pressure reaction kettle at the temperature of 120-.

4. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 2, wherein the zirconia material after polishing treatment is placed in 2.5 wt% diluted phosphoric acid solution and treated for 24h at 160 ℃ in a high-pressure reaction kettle.

5. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 1, which is characterized in that: the high-pressure reaction kettle is made of a polytetrafluoroethylene inner container.

6. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 1, which is characterized in that: and ultrasonically cleaning a sample prepared by the reaction of the high-pressure reaction kettle in deionized water, and drying and then carrying out secondary calcination.

7. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 1, which is characterized in that: the calcination condition is calcination for 10-30min at 800-1100 ℃.

8. The method for preparing the zirconia ceramic surface in-situ growth cellular nanostructure according to claim 7, which is characterized in that: the calcination condition is calcination for 15min at 950 ℃.

9. A modified zirconia ceramic produced by the production method according to any one of claims 1 to 8.

Technical Field

The invention belongs to the field of biomedical materials, and relates to a preparation method of a honeycomb-shaped nano structure on the surface of zirconia ceramic and a prepared modified zirconia ceramic.

Background

The zirconia surface has strong chemical stability and difficult modification, so the bonding performance of the zirconia surface with surface decorative porcelain or resin adhesive is poor, and the zirconia surface also lacks the autonomous integration capability with surrounding bone tissues. At present, the modification method for zirconia surface morphology mainly comprises sand blasting, acid etching, sand blasting acid etching, laser, selective permeation acid etching and the like. The methods can change the surface appearance structure of the zirconia, but the preparation methods only adopt surface irregular etching, are difficult to consciously prepare some nanostructures which are beneficial to regulating and controlling functions of osteogenesis related cells, and are difficult to generate chemical groups required for later-stage functionalization. In addition, the construction of the surface functionalized coating is also a common modification strategy of the zirconia material, and the surface coating prepared by utilizing bioactive materials such as calcium phosphate and the like can enhance the bioactivity of the zirconia ceramic. The biggest problem of the coating is that the binding force between the coating and the substrate is not enough, and the coating is easy to peel off from the ceramic surface in long-term application, thereby limiting the clinical application of the coating. Therefore, how to realize the surface functional modification of the zirconia ceramics by a simple way is one of the key bottleneck problems for solving the clinical problems of the zirconia ceramics.

Disclosure of Invention

The patent aims at a preparation method for preparing a series of honeycomb-shaped nano structures on the surface of zirconia ceramic. The preparation method is simple and convenient to operate, good in repeatability and strong in controllability. The zirconia ceramics prepared by the method has good bioactivity, can obviously improve the adhesive property of surface decorative ceramics and resin adhesive, and has good clinical application prospect.

In order to achieve the above object, the present invention provides the following technical route:

the preparation method of the zirconia ceramic surface in-situ growth honeycomb-shaped nano structure mainly comprises the following steps:

placing the polished zirconia material in diluted phosphoric acid solution with the weight percent more than 1 percent and less than 2.5 percent, treating for 12-36 hours at the temperature of 80-160 ℃ in a high-pressure reaction kettle, or placing the polished zirconia material in diluted phosphoric acid solution with the weight percent more than or equal to 0.5-1 percent or less than or equal to 2.5 and less than 5 percent, treating for 12-36 hours at the temperature of 120-160 ℃ in the high-pressure reaction kettle, and then performing secondary calcination treatment to obtain the zirconia ceramic with the in-situ grown honeycomb nano structure.

Preferably, the zirconia ceramic is subjected to surface grinding treatment by using 100-2000-mesh sandpaper.

Preferably, the zirconium oxide material after polishing treatment is placed in 1-2.5 wt% diluted phosphoric acid solution and treated in a high-pressure reaction kettle at the temperature of 120 ℃ and 160 ℃ for 12-36 h.

Preferably, the polished zirconia material is placed in 2.5 wt% diluted phosphoric acid solution and treated in a high-pressure reaction kettle at 160 ℃ for 24 hours.

Preferably, the high-pressure reaction kettle is made of a polytetrafluoroethylene inner container.

Preferably, the sample prepared by the high-pressure reaction kettle is ultrasonically cleaned in deionized water, and is dried and then is calcined for the second time.

Preferably: the calcination condition is calcination for 10-30min at 800-1100 ℃.

Preferably: the calcination condition is calcination for 15min at 950 ℃.

The invention also provides the modified zirconia ceramic prepared by the preparation method in any protection.

The invention has the following remarkable advantages: the pressure is controlled by adjusting the temperature in a pressure-maintaining reaction vessel under the condition of high temperature through a simple high-pressure hydrothermal approach, acid etching is carried out by adopting dilute phosphoric acid under the double conditions of high temperature and high pressure, and honeycomb-shaped nano structures with different pore diameters are firstly constructed on the surface of the zirconia ceramic. The novel nano structures can obviously improve the bioactivity and the adhesive property of the decorative porcelain/resin adhesive of the zirconia, solve the problem that the zirconia ceramics are difficult to be biologically functionalized at present, and provide a new idea for the surface modification design of the zirconia ceramics. The preparation method is simple and convenient to operate, good in repeatability and strong in controllability; the zirconia implant prepared by the method has a regular honeycomb-shaped nano structure with controllable pore diameter on the surface, has good bioactivity and good porcelain/resin adhesive bonding performance, and has important research value and clinical significance in the field of dental implantation.

Description of the drawings:

FIG. 1: surface Scanning Electron Microscope (SEM) images (a) and aperture size statistics (B) of different samples.

FIG. 2: three-point bending strength (A) and Rockwell hardness (B) statistics for different samples.

FIG. 3: XPS characteristic peaks and fitting maps of Zr, 0 and P, Y elements on different sample surfaces.

FIG. 4: the bonding strength of the decorative porcelain (A) and the resin adhesive (B) on the surfaces of different samples; the confidence interval was 99.5% (. p < 0.05).

FIG. 5: cell activity (A) and mineralization level (B) of MC3T3-E1 osteoblasts on different sample surfaces; the confidence interval was 99.5% (. p < 0.05).

The specific implementation mode is as follows:

in order to make the technical solution and advantages of the present invention more clear, embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

The invention successfully prepares a series of novel honeycomb nano structures with controllable pore diameters on the surface of zirconia ceramics by a simple hydrothermal high-pressure treatment way. In the construction process, a plurality of factors can influence the construction of the honeycomb-shaped nano structure, the volume and concentration of phosphoric acid in the reaction kettle, the temperature and time of hydrothermal treatment, the temperature and time of secondary calcination and the like, and different control conditions can influence the preparation of target materials and the comprehensive biological performance of the target materials. The invention inspects the above influencing factors, and the result shows that: after the zirconia ceramics are polished step by using gradient sand paper of 100 meshes, 400 meshes, 1000 meshes and 2000 meshes, a sample is placed in 25mL of diluted phosphoric acid solution with the concentration of 1.0 or 2.5 wt%, the reaction is carried out for 24 hours at the temperature of 120 or 160 ℃ after the high-pressure reaction kettle is sealed, and the ideal honeycomb-shaped nano structure with different apertures in the range of 30-145nm can be obtained after the calcination is carried out for 15 minutes at the temperature of 950 ℃.