CN111320493B - Surface modification method of silicon nitride material and biological ceramic material - Google Patents
Surface modification method of silicon nitride material and biological ceramic material Download PDFInfo
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- CN111320493B CN111320493B CN202010165813.1A CN202010165813A CN111320493B CN 111320493 B CN111320493 B CN 111320493B CN 202010165813 A CN202010165813 A CN 202010165813A CN 111320493 B CN111320493 B CN 111320493B
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/53—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone involving the removal of at least part of the materials of the treated article, e.g. etching, drying of hardened concrete
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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Abstract
The invention relates to the technical field of silicon nitride ceramics, in particular to a surface modification method of a silicon nitride material and a biological ceramic material. The invention discloses a surface modification method of a silicon nitride material, which comprises the following steps: and (3) putting the silicon nitride ceramic into an alkaline solution for reaction. According to the invention, the surface of the silicon nitride ceramic is corroded by using an alkaline solvent, so that an oxide layer and a crystal boundary on the surface of the silicon nitride are removed, the surface of the silicon nitride ceramic has a micro-nano structure, and the stability of the silicon nitride is not damaged. The surface modification method improves the bioactivity of the surface of the silicon nitride ceramic material, so that the surface of the silicon nitride ceramic material is not required to be treated by a coating. The silicon nitride material can be used as a biological material for culturing cells, and can optimize and improve the adhesion, proliferation and differentiation capacities of the cells.
Description
Technical Field
The invention relates to the technical field of silicon nitride ceramics, in particular to a surface modification method of a silicon nitride material and a biological ceramic material.
Background
Silicon nitride (Si)3N4) As an important non-oxide engineering ceramic material, the material has good performances such as toughness, strength, corrosion resistance, abrasion resistance, high temperature resistance and the like, and has been widely noticed and applied for a long time. In recent years, it has been found through studies that Si3N4The material also has the characteristics of no cytotoxicity, good biocompatibility and the like, so the material is regarded as a new generation of biological ceramic material with great application and development potential. However, as a biological implant material, the surface chemistry and the microscopic morphology of the biological implant material have a significant influence on cell response behaviors such as cell adhesion, proliferation and differentiation, and therefore, the surface modification is performed by a physicochemical method to improve Si3N4The biological characteristics of the ceramic material further play the advantages thereof, expand the application range and have important significance.
At present, for increasing Si3N4The biological activity of the surface of the bioceramic is mostly studied by Si3N4The surface of the ceramic material is coated. However, this method also has a coating and Si3N4The interface bonding strength is low, thereby limiting the application of the interface bonding strength in the biomedical field.
Disclosure of Invention
The invention provides a surface modification method of a silicon nitride material and a biological ceramic material, and solves the problem that the bonding strength of a coating and a silicon nitride interface is low when the surface of the existing silicon nitride ceramic material is subjected to coating treatment.
The specific technical scheme is as follows:
the invention provides a surface modification method of a silicon nitride material, which comprises the following steps:
and putting the silicon nitride ceramic into an alkaline solution for reaction.
According to the invention, the alkaline solvent is used for corroding the surface of the silicon nitride ceramic, so that an oxide layer and a crystal boundary on the surface of the silicon nitride are removed, the surface of the silicon nitride ceramic has a micro-nano structure, the stability of the silicon nitride is not damaged, and the surface modification method optimizes and improves the cell adhesion, proliferation and differentiation capabilities of the silicon nitride ceramic.
The mechanism of the alkaline solution for corroding the surface of the silicon nitride ceramic is as follows:
Si3N4+6H2O＝3SiO2+4NH3；
6NaOH+3SiO2＝3H2O+3Na2SiO3
the silicon nitride ceramics used in the invention can be made by oneself or purchased in the market, and the invention does not limit the source of the silicon nitride in particular. The silicon nitride ceramic has a density of 98% or more and a size of 6 × 3 mm.
In the invention, before the silicon nitride ceramic is placed in an alkaline solution, the method further comprises the following steps: and (3) placing the silicon nitride ceramic in a solvent, carrying out ultrasonic cleaning, and drying.
After the silicon nitride ceramic is placed in a solvent for ultrasonic cleaning, impurities on the surface of the silicon nitride can be removed.
The solvent is acetone, methanol, ethanol or water.
The ultrasonic cleaning time is 10-30 min, and more preferably 10 min.
In the invention, the silicon nitride ceramic after ultrasonic cleaning and drying is placed in alkaline solution for reaction, so that the surface of the silicon nitride is corroded and becomes uneven.
The pH value of the alkaline solution is 10.5-13.5, and preferably 12.5-13.5; the alkaline solution is a sodium hydroxide solution.
The reaction adopts standing or ultrasonic treatment.
The standing time is 60-1200 min, the temperature is 10-100 ℃, and the standing time is preferably 600min at 60 ℃; the ultrasonic treatment time is 60-1200 min, the temperature is 10-100 ℃, and the ultrasonic treatment time is preferably 100min at 60 ℃.
According to the invention, the treatment of the surface morphology of the silicon nitride ceramic can be accurately controlled by regulating and controlling the pH value of the alkaline solution and the reaction temperature and time.
In the present invention, after the reaction is completed, it is preferable to rinse with deionized water and then dry.
Then, the sample obtained after drying is subjected to ultraviolet irradiation while being sterilized with ethanol, and then preferably washed with a phosphate buffer solution to obtain a surface-modified silicon nitride material.
The time of the ultraviolet irradiation is 0.5-3h, and preferably 1 h.
The invention also provides a biological ceramic material which is obtained by the surface modification method.
The biological ceramic material provided by the invention can effectively regulate and control cell response behaviors such as cell adhesion, proliferation, differentiation and the like.
According to the technical scheme, the invention has the following advantages:
the invention provides a surface modification method of a silicon nitride material, which comprises the following steps: and (3) putting the silicon nitride ceramic into an alkaline solution for reaction.
According to the invention, the surface of the silicon nitride ceramic is corroded by using an alkaline solvent, so that an oxide layer and a crystal boundary on the surface of the silicon nitride are removed, the surface of the silicon nitride ceramic has a micro-nano structure, and the stability of the silicon nitride is not damaged. The surface modification method improves the bioactivity of the surface of the silicon nitride ceramic material, so that the surface of the silicon nitride ceramic material is not required to be treated by a coating. The silicon nitride material can be used as a biological material for culturing cells, and can optimize and improve the adhesion, proliferation and differentiation capacities of the cells.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a scanning electron microscope image of a silicon nitride ceramic material and a biological ceramic material provided in example 1 of the present invention, wherein (a) is the silicon nitride ceramic material and (b) is the biological ceramic material;
FIG. 2 is a cell proliferation map of the silicon nitride ceramic material and the bio-ceramic material provided in example 1 of the present invention;
FIG. 3 is a fluorescence microscopic image of cultured cells of the silicon nitride ceramic material and the bio-ceramic material provided in example 1 of the present invention for 3 days, wherein (a) is the silicon nitride ceramic material and (b) is the bio-ceramic material.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below 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.
In the embodiment of the invention, the reagents and raw materials are all purchased from the market, and the human stem cells are obtained from the 4 th generation cells which are entrusted and cultured by the high-technology ceramic team of Guangdong university of industry.
Example 1
This example is the preparation of a bioceramic Material
(1) Mixing 6 x 3mm Si3N4Ultrasonically cleaning a ceramic sample (the density is more than or equal to 98%) by using ethanol every timeAnd washing for 10 minutes, and naturally drying for later use to obtain the silicon nitride ceramic material.
(2) Si to be cleaned3N4Placing the ceramic material in a 100ml tetrafluoro beaker, adding 20ml NaOH solution with pH value of 13, standing at 60 ℃ for reaction for 600 minutes, taking out, washing with a large amount of deionized water, drying at 60 ℃, then placing a sample in a pore plate, adding 75% alcohol, sterilizing for 1 hour under an ultraviolet lamp, and then washing with PBS to obtain the biological ceramic material.
Si which is not subjected to surface modification in the step (1)3N4And (3) observing the shapes of the ceramic material and the biological ceramic material obtained after the surface modification in the step (2), wherein the result is shown in figure 1.
Fig. 1 is a scanning electron microscope image of a silicon nitride ceramic material and a biological ceramic material provided in example 1, wherein (a) is the silicon nitride ceramic material and (b) is the biological ceramic material. As shown in fig. 1, after the surface of the silicon nitride ceramic material is modified, the surface is rough and has a micro-nano structure.
Example 2
In this example, a silicon nitride ceramic material and a bioceramic material are respectively placed in an orifice plate, sterilized with 75 vol% ethanol under an ultraviolet lamp for 1 hour, washed with PBS for three times, and subjected to a cell CCK8 test before and after the surfaces of the silicon nitride ceramic material and the bioceramic material. The cell proliferation culture time is 1, 3, 7 days, and the cell planting density is 5000/cm2After staining the cells, the cells were photographed using a fluorescence microscope to observe the cell density, and the in vitro biological activities of the silicon nitride ceramic material and the biological ceramic material were compared, and the results are shown in fig. 2 and 3.
FIG. 2 is a graph showing the cell proliferation of the silicon nitride ceramic material and the bio-ceramic material provided in example 1. As shown in fig. 2, the bioceramic material is not cytotoxic and has a biocompatibility and bioactivity significantly higher than that of silicon nitride ceramic material.
FIG. 3 is a fluorescence microscope photograph of the silicon nitride ceramic material and the bio-ceramic material provided in example 1, wherein (a) is the silicon nitride ceramic material and (b) is the bio-ceramic material, cultured for 3 days. As shown in fig. 3, after the human stem cells are cultured on the surface of the biological ceramic material for 3 days, the proliferation rate of the human stem cells is significantly higher than that of the silicon nitride ceramic material, which indicates that the surface of the biological ceramic material obtained by treating the biological ceramic material with the NaOH solution with the pH of 13 can enhance the adhesion and proliferation capacity of the human stem cells, and the biological compatibility is good, and indicates that the biological activity of the biological ceramic material obtained by treating the biological ceramic material with the NaOH solution with the pH of 13 is higher than that of the untreated silicon nitride ceramic material.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. A surface modification method of a silicon nitride material is characterized by comprising the following steps:
placing silicon nitride ceramics in alkaline solution for reaction;
the reaction adopts standing or ultrasonic treatment;
the standing time is 60-1200 min, and the temperature is 10-100 ℃;
the ultrasonic treatment time is 60-1200 min, and the temperature is 10-100 ℃;
the pH value of the alkaline solution is 10.5-13.5;
the alkaline solution is a sodium hydroxide solution.
2. The surface modification method of claim 1, further comprising, after the reacting: and carrying out ultraviolet irradiation on the reacted sample.
3. The surface modification method according to claim 2, wherein the ultraviolet irradiation is performed while sterilizing with ethanol;
the ultraviolet irradiation time is 0.5-3 h.
4. The method of claim 1, wherein prior to subjecting the silicon nitride ceramic to the alkaline solution, further comprising: and (3) placing the silicon nitride ceramic in a solvent, carrying out ultrasonic cleaning, and drying.
5. The surface modification method according to claim 4, wherein the solvent is acetone, methanol, ethanol or water.
6. The surface modification method according to claim 4, wherein the time for the ultrasonic cleaning is 10 to 30 min.
7. A bioceramic material, obtainable by the surface modification process of any one of claims 1 to 6.
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| ES2390971T3 (en) * | 2005-12-12 | 2012-11-20 | Eth Zurich | Foam and emulsions stabilized with ultrastable particles |
| CN100371296C (en) * | 2006-03-17 | 2008-02-27 | 中国科学院上海硅酸盐研究所 | Method increasing bioactivity of ceramic material contg. zirconium oxide |
| JP5485907B2 (en) * | 2007-12-20 | 2014-05-07 | トーメン メディカル アーゲー | Implant and method for producing the same, especially modification of its surface |
| CN103373863A (en) * | 2013-07-19 | 2013-10-30 | 河南安彩高科股份有限公司 | Surface oxide removal method for silicon nitride ceramic member |
| CN107693843B (en) * | 2017-04-01 | 2020-09-04 | 华东理工大学 | Surface modification method of biomedical active titanium and alloy implant material thereof |
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