CN112251787B - Preparation method of zinc calcium silicate nano-array bioactive coating - Google Patents

Preparation method of zinc calcium silicate nano-array bioactive coating Download PDF

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CN112251787B
CN112251787B CN202010873901.7A CN202010873901A CN112251787B CN 112251787 B CN112251787 B CN 112251787B CN 202010873901 A CN202010873901 A CN 202010873901A CN 112251787 B CN112251787 B CN 112251787B
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张兰
朱胜波
袁海彦
憨勇
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Xian Jiaotong University
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Abstract

The invention discloses a preparation method of a zinc calcium silicate nano-array bioactive coating, which comprises the steps of firstly, preparing an anodic oxidation solution by taking deionized water as a solvent and sodium bicarbonate and sodium carbonate as solutes, and placing a polished zinc sheet in the solution to carry out anodic oxidation reaction to obtain a zinc oxide nanowire coating; then deionized water is used as a solvent, silicate is used as a solute, the zinc oxide nanowire coating obtained by anodic oxidation is placed in a solution for reaction by a solvothermal method, and Zn is obtained on the surface of the zinc alloy after the reaction is finished2SiO4Coating; finally, taking deionized water as a solvent and calcium hydroxide as a solute to react Zn2SiO4Placing the coated sample in a solution to react by a solvothermal method, and obtaining CaZn on the surface of the zinc alloy after the reaction is finished2Si2O7·H2O nanometer array bioactive coating. The invention prepares the zinc calcium silicate nanorod coating with good bioactivity on the surface of the zinc alloy by using an anodic oxidation-hydrothermal composite method, saves the manufacturing cost and obtains a regular nano array.

Description

Preparation method of zinc calcium silicate nano-array bioactive coating
Technical Field
The invention belongs to the field of surface modification of zinc and zinc alloy components, and particularly relates to CaZn2Si2O7·H2A preparation method of an O nano-array bioactive coating.
Background
Coronary artery disease is one of the leading causes of death in the global population, and has a serious impact on the economic condition and quality of life of people, and stent implantation is an effective method for treating coronary artery disease. The traditional bare metal stent, the drug eluting stent and the like can cause adverse reactions such as inflammation, late stent restenosis and the like, and the new generation of degradable stent can avoid and solve the problems and thus has attracted extensive attention of researchers. Zinc and zinc alloy have good tissue adaptability and proper degradation rate, but have larger cytotoxicity, so the surface of the zinc and zinc alloy needs to be modified, the release of zinc ions is reduced, the cytotoxicity is reduced, and the biocompatibility is improved. The zinc calcium silicate is a bioactive material, the components of calcium, silicon and zinc ions can improve the cell activity and promote the cell proliferation and differentiation, and the shape of the micro-nano structure has good bionic effect.
The preparation methods of the metal surface coating which are developed at present comprise the following steps: micro-arc oxidation, atomic beam deposition, chemical conversion, sol-gel, electrostatic spinning, and the like. CaZn reported in literature2Si2O7The preparation method of the coating comprises electrostatic atomization deposition, pulsed laser deposition, electrophoretic deposition and the like. However, the above methods have the defects of complex process, high cost, poor membrane-substrate bonding strength and the like, thereby limiting the application of the methods in the vascular stent.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a zinc calcium silicate nano-array bioactive coating to overcome the problems in the prior art, and the invention prepares CaZn with good bioactivity on the surface of a zinc alloy by using an anodic oxidation-hydrothermal composite method2Si2O7·H2And O, nano-array, so as to obtain the regular nano-array.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a zinc calcium silicate nano-array bioactive coating comprises the following steps:
the method comprises the following steps: forming an anodic oxidation solution by using deionized water as a solvent and sodium carbonate and sodium bicarbonate as solutes, and placing the polished zinc sheet in the anodic oxidation solution for anodic oxidation treatment to obtain a zinc oxide nanowire coating;
step two: deionized water is used as a solvent, silicate is used as a solute, then the zinc oxide nanowire coating is placed in the solution to react by a solvothermal method, and the zinc oxide nanowire coating is obtained after the reaction is finishedZn2SiO4A nano-coating;
step three: using deionized water as solvent, Ca (OH)2As a solute, Zn is then added2SiO4The nano coating is placed in a solution to react by a solvothermal method, and CaZn is obtained after the reaction is finished2Si2O7·H2O nanometer array bioactive coating.
Further, the concentration of the sodium bicarbonate in the anodic oxidation solution in the step one is 3.57-21.42mmol/L, and the concentration of the sodium carbonate is 2.83-16.98 mmol/L.
Further, the voltage of the anode oxidation treatment in the step one is 20-80V, and the time is 1-10 min.
Further, the silicate in the second step is sodium silicate, and the concentration of the sodium silicate in the solution obtained in the second step is 0.007-0.04 mol/L.
Further, the reaction temperature in the second step is 70-180 ℃ and the reaction time is 0.5-12 h.
Further, Ca (OH) in the solution obtained in the third step2The concentration is 0.005-0.02 mol/L.
Further, the reaction temperature in the third step is 70-110 ℃, and the reaction time is 0.5-12 h.
Compared with the prior art, the invention has the following beneficial technical effects:
the anodic oxidation-hydrothermal composite preparation method provided by the invention has a good technical effect, and the polished zinc sheet is placed in an anodic oxidation solution for anodic oxidation treatment by taking deionized water as a solvent and sodium carbonate and sodium bicarbonate as solutes, so as to obtain the zinc oxide nanowire coating. The experiment can be carried out by only one direct current power supply in the anodic oxidation process, and large-scale equipment such as micro-arc oxidation, atomic beam deposition and the like is not needed. And the maximum voltage required in the anodic oxidation process is not more than 80v, and the experimental process is safe and reliable. The zinc oxide nano-array obtained after anodic oxidation provides nucleation sites for hydrothermal reaction, so that the reaction can occur. Step two, taking deionized water as a solvent, silicate as a solute and zinc oxide nanowires as a zinc source, and carrying out a solvothermal reaction to obtain Zn2SiO4And (4) nano coating. The hydrothermal process is simple and easy to realize, and zinc ions react with silicate ions in the solution to generate zinc silicate. Step three, using deionized water as solvent, Ca (OH)2As a solute, Zn is added2SiO4The nano coating is put into solution to react by a solvothermal method to obtain CaZn2Si2O7·H2And (4) O nano array coating. The zinc silicate reacts with calcium ions and hydroxide ions in the solution to generate CaZn2Si2O7. The coating has a special nano structure and good bonding force and strength. In addition, CaZn2Si2O7·H2The O nano array slows down the release of zinc ions and reduces cytotoxicity, calcium ions and silicon ions can improve the biological activity of cells, and meanwhile, the coating has a unique micro-nano structure shape and good response to the cells, so that the O nano array has important significance in the application of the vascular stent.
Drawings
FIG. 1 is an SEM photograph of a ZnO nano-coating obtained in example 1 of the present invention;
FIG. 2 is an XRD spectrum of the ZnO nano-coating obtained in example 1 of the present invention;
FIG. 3 shows Zn obtained in example 1 of the present invention2SiO4SEM photograph of the nanocoating;
FIG. 4 shows Zn obtained in example 1 of the present invention2SiO4Nano coating XRD spectrogram;
FIG. 5 shows CaZn obtained in example 1 of the present invention2Si2O7H2SEM photograph of O;
FIG. 6 shows CaZn obtained in example 1 of the present invention2Si2O7H2XRD spectrum of O;
FIG. 7 shows CaZn obtained in example 1 of the present invention2Si2O7H2Film-to-substrate bond strength of O;
FIG. 8 shows CaZn obtained in example 1 of the present invention2Si2O7H2Cell viability of O at 7 d;
FIG. 9 shows CaZn obtained in example 4 of the present invention2Si2O7H2SEM photograph of O.
Detailed Description
Embodiments of the invention are described in further detail below:
CaZn2Si2O7·H2The preparation method of the O nano array bioactive coating comprises the following steps:
the method comprises the following steps: deionized water is used as a solvent, and sodium bicarbonate and sodium carbonate are used as solutes, wherein the concentration of the sodium bicarbonate is 3.57-21.42mmol/L, and the concentration of the sodium carbonate is 2.83-16.98mmol/L, so as to prepare an anodic oxidation solution. And (3) connecting the polished zinc sheet to the positive electrode of a power supply, connecting a carbon rod to the negative electrode, putting the zinc sheet and the carbon rod into a solution, and carrying out an anodic oxidation reaction, wherein the voltage of the anodic oxidation is 5-80V, and the time is 1-10 min. Obtaining the zinc oxide nanowire coating after the reaction is finished;
step two: a solvothermal method is utilized, deionized water is used as a solvent, silicate is used as a solute to prepare a solution, and the concentration of the silicate is 0.007-0.04 mol/L. Then placing the sample of the zinc oxide nanowire coating and the solution into a reaction kettle for reaction at the temperature of 70-180 ℃ for 0.5-12 h. Zn is obtained after the reaction is finished2SiO4And (4) nano coating.
Step three: a solvothermal method is utilized, deionized water is used as a solvent, calcium hydroxide is used as a solute to prepare a solution, and the concentration of the calcium hydroxide is 0.005-0.02 mol/L. Then Zn is added2SiO4And placing the sample of the nanowire coating and the solution into a reaction kettle for reaction at the temperature of 70-110 ℃ for 0.5-12 h. Obtaining CaZn with array structure after the reaction is finished2Si2O7·H2And (3) coating the O nanorod.
The present invention is described in further detail below with reference to examples:
example 1
The first step is as follows: deionized water is used as a solvent, and sodium carbonate and sodium bicarbonate are used as solutes to prepare electrolyte, wherein the concentration of the sodium carbonate is 2.83mmol/L, and the concentration of the sodium bicarbonate is 3.57 mmol/L. Connecting the polished zinc sheet to the positive electrode of a power supply, connecting a carbon rod to the negative electrode, placing the zinc sheet and the carbon rod into a solution, and carrying out an anodic oxidation reaction, wherein the voltage of the anodic oxidation is 80V, the time is 1min, and obtaining the zinc oxide nanowire coating after the reaction is finished;
the second step is that: 10ml of solution with sodium silicate as solute is prepared by a solvothermal method, wherein the concentration of sodium silicate is 0.02 mol/L. Transferring the solution into a 50mL high-temperature high-pressure reaction kettle, then placing a sample with a zinc oxide nanowire coating into the reaction kettle, preserving heat for 3h at the temperature of 110 ℃, and preparing Zn with the diameter of about 100nm2SiO4And (4) nano arrays.
The third step: 10ml of solution using calcium hydroxide as a solute was prepared by a solvothermal method, wherein the concentration of calcium hydroxide was 0.009 mol/L. Transferring the solution into a 50mL high-temperature high-pressure reaction kettle, and then carrying out reaction on the solution with Zn2SiO4Placing the sample of the nano-array coating in a reaction kettle, preserving heat for 12 hours at the temperature of 110 ℃, and obtaining CaZn with an array structure after the reaction is finished2Si2O7·H2And (4) O nanorods.
It can be seen from fig. 1 that the anodic oxidation reaction occurs to obtain a regular nano-array, and the XRD spectrum of fig. 2 shows that the phase of ZnO appears. As can be seen from FIG. 3, the hydrothermal reaction still provides regular nanoarrays, and from the XRD spectrum of FIG. 4, Zn appears2SiO4The phase of (1). As can be seen from fig. 5, the nanoarray is not changed after the hydrothermal reaction, and XRD of fig. 6 shows that the phase of CaZn2Si2O 7. H2O appears. It can be seen from fig. 7 that the coating has good film-to-substrate bond strength. From FIG. 8 we can see that CaZn is compared with pure zinc2Si2O7·H2The O-nanoarray coating still had good cellular activity at day seven.
Example 2
The first step is as follows: deionized water is used as a solvent, and sodium carbonate and sodium bicarbonate are used as solutes to prepare an electrolyte, wherein the concentration of the sodium carbonate is 5.66mmol/L, and the concentration of the sodium bicarbonate is 7.14 mmol/L. Connecting the polished zinc sheet to the positive electrode of a power supply, connecting a carbon rod to the negative electrode, placing the zinc sheet and the carbon rod into a solution, and carrying out an anodic oxidation reaction, wherein the voltage of the anodic oxidation is 50V, the time is 3min, and obtaining the zinc oxide nanowire coating after the reaction is finished;
the second step is that: 10ml of solution with sodium silicate as solute is prepared by a solvothermal method, wherein the concentration of sodium silicate is 0.04 mol/L. Transferring the solution into a 50mL high-temperature high-pressure reaction kettle, then placing a sample with a zinc oxide nanowire coating into the reaction kettle, and preserving heat for 12 hours at 70 ℃ to prepare Zn2SiO4And (4) nano arrays.
The third step: 10ml of solution with calcium hydroxide as solute is prepared by a solvothermal method, wherein the concentration of the calcium hydroxide is 0.02 mol/L. Transferring the solution into a 50mL high-temperature high-pressure reaction kettle, and then carrying out reaction on the solution with Zn2SiO4Placing the sample of the nano-array coating in a reaction kettle, preserving heat for 6 hours at 70 ℃, and obtaining CaZn with an array structure after the reaction is finished2Si2O7·H2And (4) O nanorods.
Example 3
The first step is as follows: deionized water is used as a solvent, and sodium carbonate and sodium bicarbonate are used as solutes to prepare an electrolyte, wherein the concentration of the sodium carbonate is 16.98mmol/L, and the concentration of the sodium bicarbonate is 21.42 mmol/L. Connecting the polished zinc sheet to the positive electrode of a power supply, connecting a carbon rod to the negative electrode, placing the zinc sheet and the carbon rod into a solution, and carrying out an anodic oxidation reaction, wherein the voltage of the anodic oxidation is 5V, the time is 10min, and obtaining the zinc oxide nanowire coating after the reaction is finished;
the second step is that: 10ml of solution with sodium silicate as solute is prepared by a solvothermal method, wherein the concentration of sodium silicate is 0.007 mol/L. Transferring the solution into a 50mL high-temperature high-pressure reaction kettle, then placing a sample with a zinc oxide nanowire coating into the reaction kettle, and preserving heat for 0.5h at 180 ℃ to prepare Zn2SiO4A nano-array;
the third step: 10ml of solution using calcium hydroxide as a solute was prepared by a solvothermal method, wherein the concentration of calcium hydroxide was 0.005 mol/L. Transferring the solution into a 50mL high-temperature high-pressure reaction kettle, and then carrying out reaction on the solution with Zn2SiO4Placing the sample of the nano-array coating in a reaction kettle, preserving heat for 12 hours at 70 ℃, and obtaining CaZn with an array structure after the reaction is finished2Si2O7·H2O nano rod。
Example 4
The first step is as follows: deionized water is used as a solvent, and sodium carbonate and sodium bicarbonate are used as solutes to prepare electrolyte, wherein the concentration of the sodium carbonate is 2.83mmol/L, and the concentration of the sodium bicarbonate is 3.57 mmol/L. Connecting the polished zinc sheet to the positive electrode of a power supply, connecting a carbon rod to the negative electrode, placing the zinc sheet and the carbon rod into a solution, and carrying out an anodic oxidation reaction, wherein the voltage of the anodic oxidation is 80V, the time is 1.5min, and obtaining the zinc oxide nanowire coating after the reaction is finished;
the second step is that: 10ml of solution with sodium silicate as solute is prepared by a solvothermal method, wherein the concentration of sodium silicate is 0.01 mol/L. Transferring the solution into a 50mL high-temperature high-pressure reaction kettle, then placing a sample with a zinc oxide nanowire coating into the reaction kettle, and preserving heat for 3h at the temperature of 110 ℃ to prepare Zn2SiO4A nano-array;
the third step: 10ml of solution with calcium hydroxide as solute is prepared by a solvothermal method, wherein the concentration of the calcium hydroxide is 0.02 mol/L. Transferring the solution into a 50mL high-temperature high-pressure reaction kettle, and then carrying out reaction on the solution with Zn2SiO4Placing the sample of the nano-array coating in a reaction kettle, preserving heat for 0.5h at the temperature of 110 ℃, and obtaining CaZn with an array structure after the reaction is finished2Si2O7·H2And (4) O nanorods.
As can be seen from FIG. 9, CaZn obtained in this example2Si2O7H2The O nano-rods are in a regular nano-array.
Example 5
The first step is as follows: deionized water is used as a solvent, and sodium carbonate and sodium bicarbonate are used as solutes to prepare an electrolyte, wherein the concentration of the sodium carbonate is 8.49mmol/L, and the concentration of the sodium bicarbonate is 10.71 mmol/L. Connecting the polished zinc sheet to the positive electrode of a power supply, connecting a carbon rod to the negative electrode, placing the zinc sheet and the carbon rod into a solution, and carrying out an anodic oxidation reaction, wherein the voltage of the anodic oxidation is 80V, the time is 1min, and obtaining the zinc oxide nanowire coating after the reaction is finished;
the second step is that: 10ml of solution with sodium silicate as solute is prepared by a solvothermal method, wherein the concentration of sodium silicate is 0.02 mol/L. The solution was transferred to 50mL high temperatureIn a high-pressure reaction kettle, placing a sample with the zinc oxide nanowire coating in the reaction kettle, and preserving heat for 3 hours at the temperature of 150 ℃ to prepare Zn2SiO4A nano-array;
the third step: 10ml of solution with calcium hydroxide as solute is prepared by a solvothermal method, wherein the concentration of the calcium hydroxide is 0.01 mol/L. Transferring the solution into a 50mL high-temperature high-pressure reaction kettle, and then carrying out reaction on the solution with Zn2SiO4Placing the sample of the nano-array coating in a reaction kettle, preserving heat for 6 hours at 100 ℃, and obtaining CaZn with an array structure after the reaction is finished2Si2O7·H2And (4) O nanorods.
Example 6
The first step is as follows: deionized water is used as a solvent, and sodium carbonate and sodium bicarbonate are used as solutes to prepare an electrolyte, wherein the concentration of the sodium carbonate is 8.49mmol/L, and the concentration of the sodium bicarbonate is 10.71 mmol/L. Connecting the polished zinc sheet to the positive electrode of a power supply, connecting a carbon rod to the negative electrode, placing the zinc sheet and the carbon rod into a solution, and carrying out an anodic oxidation reaction, wherein the voltage of the anodic oxidation is 30V, the time is 5min, and obtaining the zinc oxide nanowire coating after the reaction is finished;
the second step is that: 10ml of solution with sodium silicate as solute is prepared by a solvothermal method, wherein the concentration of sodium silicate is 0.02 mol/L. Transferring the solution into a 50mL high-temperature high-pressure reaction kettle, then placing a sample with a zinc oxide nanowire coating into the reaction kettle, and preserving heat for 3h at the temperature of 110 ℃ to prepare Zn2SiO4A nano-array;
the third step: 10ml of solution with calcium hydroxide as solute is prepared by a solvothermal method, wherein the concentration of the calcium hydroxide is 0.01 mol/L. Transferring the solution into a 50mL high-temperature high-pressure reaction kettle, and then carrying out reaction on the solution with Zn2SiO4Placing the sample of the nano-array coating in a reaction kettle, preserving heat for 12 hours at 90 ℃, and obtaining CaZn with an array structure after the reaction is finished2Si2O7·H2And (4) O nanorods.

Claims (5)

1. A preparation method of a zinc calcium silicate nano-array bioactive coating is characterized by comprising the following steps:
the method comprises the following steps: forming an anodic oxidation solution by using deionized water as a solvent and sodium carbonate and sodium bicarbonate as solutes, and placing the polished zinc sheet in the anodic oxidation solution for anodic oxidation treatment to obtain a zinc oxide nanowire coating;
step two: deionized water is used as a solvent, silicate is used as a solute, then the zinc oxide nanowire coating is placed in the solution to react by a solvothermal method, and Zn is obtained after the reaction is finished2SiO4A nano-coating;
wherein the silicate is sodium silicate, the concentration of sodium silicate in the obtained solution is 0.007-0.04mol/L, the reaction temperature is 70-180 ℃, and the reaction time is 0.5-12 h;
step three: using deionized water as solvent, Ca (OH)2As a solute, Zn is then added2SiO4The nano coating is placed in a solution to react by a solvothermal method, and CaZn is obtained after the reaction is finished2Si2O7·H2O nanometer array bioactive coating.
2. The method for preparing a zinc calcium silicate nano array bioactive coating according to claim 1, wherein in the first step, the concentration of sodium bicarbonate in the anodic oxidation solution is 3.57-21.42mmol/L, and the concentration of sodium carbonate is 2.83-16.98 mmol/L.
3. The method for preparing a zinc calcium silicate nano array bioactive coating according to claim 1, wherein the voltage of the anodic oxidation treatment in the first step is 20-80V, and the time is 1-10 min.
4. The method for preparing a zinc calcium silicate nano-array bioactive coating according to claim 1, wherein Ca (OH) in the solution obtained in step three2The concentration is 0.005-0.02 mol/L.
5. The method for preparing a zinc calcium silicate nano-array bioactive coating according to claim 1, wherein the reaction temperature in the third step is 70-110 ℃ and the reaction time is 0.5-12 h.
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