CN112226767A - Hydroxyapatite nanorod biological coating and preparation method thereof - Google Patents

Hydroxyapatite nanorod biological coating and preparation method thereof Download PDF

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CN112226767A
CN112226767A CN202011052797.1A CN202011052797A CN112226767A CN 112226767 A CN112226767 A CN 112226767A CN 202011052797 A CN202011052797 A CN 202011052797A CN 112226767 A CN112226767 A CN 112226767A
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zinc
nanorod
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aqueous solution
hydroxyapatite
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CN112226767B (en
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张兰
毛梦婷
袁海彦
憨勇
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Xian Jiaotong University
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Abstract

The invention relates to a hydroxyapatite nanorod biological coating and a preparation method thereof, wherein the method comprises the following steps of 1, placing zinc or zinc alloy into an aqueous solution of calcium acetate for hydrothermal reaction, placing the aqueous solution of calcium acetate into a reaction kettle, contacting the zinc or zinc alloy with the bottom of the reaction kettle, and forming a zinc oxide nanorod coating on one surface of the zinc or zinc alloy contacted with the bottom of the reaction kettle; adding an aqueous solution of NaOH into an aqueous solution of calcium salt and phosphate to form a mixed system A, wherein the mixed system A is alkaline, and the aqueous solution of the calcium salt and the phosphate is placed in a reaction kettle; and 2, placing the zinc or zinc alloy obtained in the step 1 in a mixed system A, placing the zinc oxide nanorod coating upwards, performing hydrothermal treatment at 70-180 ℃, and forming a hydroxyapatite nanorod biological coating with firm combination and good biological activity on the surface of the zinc oxide nanorod coating, thereby having important significance for developing the application of the zinc alloy in hard tissue repair and replacement and implants.

Description

Hydroxyapatite nanorod biological coating and preparation method thereof
Technical Field
The invention belongs to the technical field of zinc and zinc alloy surface treatment, and particularly relates to a hydroxyapatite nanorod biological coating and a preparation method thereof.
Background
The research shows that zinc as a trace element necessary for human bodies can promote the proliferation of osteoblasts, inhibit the generation of osteoclasts and stimulate the formation and mineralization of new bones. The zinc and the alloy thereof have good mechanical property and degradability, and have wide application prospect in the fields of orthopedic repair and cardiovascular stents. However, Zn in the degradation process of Zn2+Accumulate in the local environment, causing significant cytotoxicity. Thus, Zn is controlled2+The great release of the Zn implant is the key to reduce the toxicity of the Zn implant and improve the biocompatibility of the Zn implant. In order to realize the aim, a uniform hydroxyapatite nanorod biological coating can be prepared on the surface of zinc and zinc alloy, and the coating has stable chemical property, uniform surface appearance and good biocompatibility.
Hydroxyapatite (Ca)10(PO4)6(OH)2HA) is the main inorganic component of bones and teeth, HAs good biological activity, and is mostly used for the repair and replacement of human hard tissues (bones and teeth). The hydroxyapatite nanorod is a nano geometric configuration simulating human tissues, can promote osteogenesis related cell response and is beneficial to formation of new bones. The preparation method of the hydroxyapatite nanorod biological coating comprises various methods such as plasma spraying, sol-gel, biomimetic mineralization and micro-arc oxidation, however, the method is not suitable for surface treatment of zinc and zinc alloy with lower melting point due to too high process conditions such as plasma spraying temperature, or the HA coating obtained due to process characteristics such as micro-arc oxidation HAs weak bonding strength and cannot be appliedModifying the surface of zinc and zinc alloy.
The hydrothermal synthesis method is a method of dissolving and recrystallizing substances which are usually insoluble or insoluble in water in a specific closed reaction vessel (i.e. an autoclave) by using an aqueous solution as a reaction medium and heating the reaction vessel to create a high-temperature and high-pressure reaction environment. The hydrothermal method for preparing the nano-crystal has many advantages, the crystal nucleus growth speed is higher than that of other aqueous solution systems, and the preparation of products with high crystallinity and different crystal structures is facilitated.
So far, although a great deal of research on the preparation of HA nanorod biocoatings on other metal surfaces (such as titanium alloys) by a hydrothermal method HAs been reported, no report HAs been found on the preparation of HA nanorod biocoatings on zinc and zinc alloy surfaces.
Disclosure of Invention
The invention aims to provide a hydroxyapatite nanorod biological coating and a preparation method thereof, which have simple requirements and easy operation, and can prepare a uniformly distributed HA nanorod coating on the surface of a zinc alloy so that a matrix HAs good biocompatibility.
The purpose of the invention is solved by the following technical scheme:
a preparation method of a hydroxyapatite nanorod biological coating comprises the following steps:
step 1, placing zinc or zinc alloy into an aqueous solution of calcium acetate for hydrothermal reaction, placing the aqueous solution of calcium acetate into a reaction kettle, contacting the zinc or zinc alloy with the bottom of the reaction kettle, and forming a zinc oxide nanorod coating on one surface of the zinc or zinc alloy in contact with the bottom of the reaction kettle;
adding an aqueous solution of NaOH into an aqueous solution of calcium salt and phosphate to form a mixed system A, wherein the mixed system A is alkaline, the concentration of calcium ions in the aqueous solution of the calcium salt and the phosphate is 0.05-0.3mol/L, the concentration of phosphate ions is 0.03-0.18mol/L, and the aqueous solution of the calcium salt and the phosphate is placed in a reaction kettle;
and 2, placing the zinc or zinc alloy obtained in the step 1 in a mixed system A, placing the zinc oxide nanorod coating upwards, performing hydrothermal treatment at 70-180 ℃, and forming a hydroxyapatite nanorod biological coating on the surface of the zinc oxide nanorod coating.
Preferably, in the aqueous solution of calcium acetate in the step 1, the concentration of calcium acetate is 0.023-0.17 mol/L.
Preferably, the shape of the zinc or the zinc alloy in the step 1 is a cylinder, a circular truncated cone or a cuboid.
Preferably, the temperature of the hydrothermal reaction in the step 1 is 90-130 ℃ and the time is 60-240 min.
Preferably, the phosphate in step 1 is diammonium hydrogen phosphate, monoammonium phosphate or diammonium hydrogen phosphate and monoammonium phosphate.
Preferably, the calcium salt in step 1 is EDTA-Ca or calcium nitrate.
Preferably, the pH of the mixed system A in the step 1 is 12.5 to 12.8.
Preferably, the hydrothermal treatment in step 2 is carried out at said temperature for 15-360 min.
A hydroxyapatite nanorod biological coating obtained by the preparation method of the hydroxyapatite nanorod biological coating.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the preparation method of the hydroxyapatite nanorod biological coating, the hydroxyapatite nanorod coating which is firm in combination and good in biological activity is prepared on the surface of zinc or a zinc alloy by a two-step hydrothermal method, and the biocompatibility of the surface of the zinc alloy is improved. In the method, calcium acetate is used as a stabilizer to prevent the surface of zinc or zinc alloy from being corroded and keep the original appearance, ZnO nano-rods grow on the back surface, and Ca is used for adding the calcium acetate2+、PO4 4-The deposition of the zinc oxide nano-rod coating can form a Hydroxyapatite (HA) nano-rod biological coating on the surface of the zinc oxide nano-rod coating after the reaction is finished, the surface biocompatibility of zinc or zinc alloy can be improved, the prepared film HAs a special bionic nano-rod structure and good bonding strength, and Zn can be effectively slowed down2+The release rate of the zinc-zinc alloy is increased, the release of calcium and phosphorus is increased, the cytotoxicity of zinc and zinc alloy is reduced, and the biological activity is improved. For developing zinc alloy in hard stateTissue repair and replacement, and the use of implants are of great interest.
Drawings
FIG. 1 is an SEM image of the surface morphology of a ZnO film obtained by the first step of hydrothermal treatment in example 1 of the present invention.
Fig. 2 is a contact angle of the ZnO film layer obtained by the first hydrothermal treatment in example 1 of the present invention.
FIG. 3 is a surface topography SEM image of the HA film layer obtained after the second step of hydrothermal treatment in example 1 of the present invention.
FIG. 4 is a surface topography SEM image of an HA film layer obtained after the second step of hydrothermal treatment in example 2 of the present invention.
FIG. 5 is a SEM image of the surface morphology of the HA film layer obtained after the second hydrothermal treatment in example 3 of the present invention.
FIG. 6 is the contact angle of the HA film layer obtained after the second hydrothermal treatment in example 3 of the present invention.
FIG. 7 is a cell activity diagram of HA membrane obtained after the second hydrothermal treatment in example 3 of the present invention.
Fig. 8a is a scratch morphology of the HA film layer obtained after the second step of hydrothermal treatment in example 3 of the present invention and a bonding force between the film layer and the substrate calculated by combining the peeling position of the film layer.
Fig. 8b is an enlarged view of fig. 8a at the black box.
Fig. 8c is a diagram of elemental composition distribution at 1 and 2 in fig. 8 b.
FIG. 9 is a SEM image of the surface morphology of the HA film layer obtained after the second hydrothermal treatment in example 4 of the present invention.
Fig. 10 is XRD patterns of the ZnO film and HA film obtained in the present invention (examples 1, 2, 3, and 4).
Detailed Description
The invention relates to a preparation method of an HA nanorod biological coating on the surface of zinc and zinc alloy, which comprises the following steps:
the method comprises the following steps: deionized water is used as a solvent, calcium acetate is used as a solute, a solution with the concentration of 0.023-0.17mol/L of calcium acetate is formed, polished round zinc or zinc alloy with the thickness of 2mm and the diameter of 10mm is placed in the solution to be subjected to hydrothermal treatment at the temperature of 90-130 ℃ for 60-240min, for the convenience of description, the zinc or the zinc alloy is marked as a substrate, a zinc oxide nanorod coating is formed on the back surface of the substrate, the back surface of the substrate is the surface of the substrate, which is in contact with a reaction kettle, and the calcium acetate is used as a stabilizer, so that the upper surface of the substrate is not corroded, the original appearance of the substrate is still kept, and finally ZnO nanorods grow on the back surface.
Step two: deionized water is used as a solvent, calcium salt and phosphate are used as solutes, the calcium salt can be EDTA-Ca and calcium nitrate, the phosphate can be diammonium hydrogen phosphate, ammonium dihydrogen phosphate or diammonium hydrogen phosphate and ammonium dihydrogen phosphate with unlimited molar ratio, the concentration of the EDTA-Ca or the calcium nitrate is 0.05-0.3mol/L, the concentration of phosphate radical ions is 0.03-0.18mol/L, NaOH is used for adjusting the solution to be alkaline, the pH value is 12.5-12.8, a second-step aqueous solution is formed, a substrate with a zinc oxide nanorod coating on the surface is placed in the solution, the coating faces upwards, a second-step hydrothermal reaction is carried out, the reaction temperature is 70-180 ℃, the reaction time is 15-360min, and Ca is used for carrying out2+、PO4 4-After the reaction is finished, a Hydroxyapatite (HA) nanorod biological coating is formed on the surface of the zinc oxide nanorod coating, the original appearance of the Hydroxyapatite (HA) nanorod biological coating is kept unchanged, and the phase of the Hydroxyapatite (HA) nanorod biological coating is changed.
The invention is described in further detail below with reference to the following figures and examples:
example 1:
the method comprises the following steps: deionized water is used as a solvent, calcium acetate is used as a solute, wherein the concentration of calcium acetate is 0.034mol/L, a hydrothermal solution is formed, the polished zinc sheet is placed in the aqueous solution for hydrothermal treatment, the reaction temperature is 110 ℃, and the reaction time is 180min, so that the zinc oxide nanorod coating is obtained. Referring to fig. 1, the surface microstructure SEM photo shows that the surface of the material is a uniform nanorod structure, referring to fig. 2, the contact angle is calculated to be 18.3 °, the XRD pattern is referred to fig. 10, and the main phases of the material are Zn and ZnO.
Step two: deionized water is used as a solvent, EDTA-Ca and diammonium hydrogen phosphate are used as solutes, the concentration of the EDTA-Ca is 0.167mol/L, the concentration of the diammonium hydrogen phosphate is 0.1mol/L, a NaOH solution of 10 mol/L is used for adjusting the pH of the solution to 12.65 to form a second-step hydrothermal solution, a zinc alloy with a zinc oxide nanorod on the surface is placed in the solution for second-step hydrothermal reaction, the reaction temperature is 110 ℃, the reaction time is 15min, and an HA nanorod coating is obtained on the surface of the zinc alloy after the reaction is finished. The surface microstructure SEM picture is shown in figure 3, the XRD pattern is shown in figure 10, the microstructure is still a nano rod-shaped structure, and compared with a ZnO coating, hydroxyapatite is added into the phase.
Example 2:
the method comprises the following steps: deionized water is used as a solvent, calcium acetate is used as a solute, wherein the concentration of calcium acetate is 0.034mol/L, a hydrothermal solution is formed, the polished zinc sheet is placed in the aqueous solution for hydrothermal treatment, the reaction temperature is 110 ℃, and the reaction time is 180min, so that the zinc oxide nanorod coating is obtained.
Step two: deionized water is used as a solvent, EDTA-Ca and diammonium hydrogen phosphate are used as solutes, the concentration of the EDTA-Ca is 0.167mol/L, the concentration of the diammonium hydrogen phosphate is 0.1mol/L, a NaOH solution of 10 mol/L is used for adjusting the pH of the solution to 12.70 to form a second-step hydrothermal solution, a zinc alloy with a zinc oxide nanorod on the surface is placed in the solution for second-step hydrothermal reaction, the reaction temperature is 110 ℃, the reaction time is 60min, and an HA nanorod coating is obtained on the surface of the zinc alloy after the reaction is finished. The surface microstructure SEM picture is shown in figure 4, the XRD pattern is shown in figure 10, the microstructure is still a nano rod-shaped structure, and the XRD peak value is compared with the ZnO coating to increase the phase of hydroxyapatite.
Example 3:
the method comprises the following steps: deionized water is used as a solvent, calcium acetate is used as a solute, wherein the concentration of calcium acetate is 0.034mol/L, a hydrothermal solution is formed, the polished zinc sheet is placed in the aqueous solution for hydrothermal treatment, the reaction temperature is 110 ℃, and the reaction time is 180min, so that the zinc oxide nanorod coating is obtained.
Step two: deionized water is used as a solvent, EDTA-Ca and diammonium hydrogen phosphate are used as solutes, the concentration of the EDTA-Ca is 0.167mol/L, the concentration of the diammonium hydrogen phosphate is 0.1mol/L, a NaOH solution of 10 mol/L is used for adjusting the pH of the solution to 12.56 to form a hydrothermal solution of the second step, a zinc alloy with a zinc oxide nanorod on the surface is placed in the solution for hydrothermal reaction of the second step, the reaction temperature is 110 ℃, the reaction time is 180min, and an HA nanorod coating is obtained on the surface of the zinc alloy after the reaction is finished. Referring to fig. 5, a surface microstructure SEM photograph shows that the microstructure is still a nanorod, the contact angle picture refers to fig. 6, the contact angle is calculated to be 4.6 °, the hydrophilicity is greatly improved compared to the ZnO coating, the cell activity picture refers to fig. 7, the cell activity is significantly increased compared to the ZnO coating when the cells are cultured for 7 days, the scratch morphology of the film layer refers to fig. 8a, the film-substrate bonding strength is 11N, the enlarged view of the scratch of the film layer is shown in fig. 8b, it can be seen from fig. 8c that the scratch-free portion in fig. 8b HAs high Ca and phosphorus components, little oxygen and less Zn, the scratch portion in fig. 8b HAs the highest Zn and little Ca and phosphorus, and it is shown that there are some HA nanorod coatings at the scratch, and the bonding force is strong from another layer. And the XRD pattern, referring to fig. 10, shows that the phase structure increases hydroxyapatite compared to ZnO coating.
Example 4:
the method comprises the following steps: deionized water is used as a solvent, calcium acetate is used as a solute, wherein the concentration of calcium acetate is 0.034mol/L, a hydrothermal solution is formed, the polished zinc sheet is placed in the aqueous solution for hydrothermal treatment, the reaction temperature is 110 ℃, and the reaction time is 180min, so that the zinc oxide nanorod coating is obtained.
Step two: deionized water is used as a solvent, EDTA-Ca and diammonium hydrogen phosphate are used as solutes, the concentration of the EDTA-Ca is 0.167mol/L, the concentration of the diammonium hydrogen phosphate is 0.1mol/L, a NaOH solution of 10 mol/L is used for adjusting the pH of the solution to 12.53, a hydrothermal solution of the second step is formed, a zinc alloy with a zinc oxide nanorod on the surface is placed in the solution for hydrothermal reaction of the second step, the reaction temperature is 110 ℃, the reaction time is 360min, and an HA nanorod coating is obtained on the surface of the zinc alloy after the reaction is finished. Referring to fig. 9, the surface microstructure SEM photograph shows that the coating still has a nanorod structure.
Example 5:
the method comprises the following steps: and (2) taking deionized water as a solvent and calcium acetate as a solute, wherein the concentration of the calcium acetate is 0.023mol/L to form a hydrothermal solution, and placing the polished zinc alloy sheet into the aqueous solution for hydrothermal treatment at the reaction temperature of 130 ℃ for 60min to obtain the zinc oxide nanorod coating.
Step two: deionized water is used as a solvent, EDTA-Ca and diammonium hydrogen phosphate are used as solutes, wherein the concentration of the EDTA-Ca is 0.05mol/L, the concentration of the diammonium hydrogen phosphate is 0.03mol/L, 10 mol/LNaOH is adopted to adjust the pH of the solution to 12.8, a second-step hydrothermal solution is formed, a zinc alloy with a zinc oxide nanorod on the surface is placed in the solution, a second-step hydrothermal reaction is carried out, the reaction temperature is 70 ℃, the reaction time is 180min, and an HA nanorod coating is obtained on the surface of the zinc alloy after the reaction is finished.
Example 6:
the method comprises the following steps: and (2) taking deionized water as a solvent and calcium acetate as a solute, wherein the concentration of the calcium acetate is 0.17mol/L, forming a hydrothermal solution, and placing the polished zinc sheet into the aqueous solution for hydrothermal treatment at the reaction temperature of 90 ℃ for 240min to obtain the zinc oxide nanorod coating.
Step two: deionized water is used as a solvent, calcium nitrate and ammonium dihydrogen phosphate are used as solutes, wherein the concentration of the calcium nitrate is 0.3mol/L, the concentration of the ammonium dihydrogen phosphate is 0.18mol/L, 10 mol/LNaOH is adopted to adjust the pH of the solution to 12.5, a second-step hydrothermal solution is formed, a zinc alloy with a zinc oxide nanorod on the surface is placed in the solution, a second-step hydrothermal reaction is carried out, the reaction temperature is 180 ℃, the reaction time is 360min, and an HA nanorod coating is obtained on the surface of the zinc alloy after the reaction is finished.
Within the range provided by the invention, the HA film layer with good bioactivity, firm combination and super-hydrophilicity can be prepared on the surface of the zinc alloy, and the practical application of the zinc alloy material in the aspects of hard tissue implantation or cardiovascular stents and the like is greatly improved.

Claims (9)

1. A preparation method of a hydroxyapatite nanorod biological coating is characterized by comprising the following steps:
step 1, placing zinc or zinc alloy into an aqueous solution of calcium acetate for hydrothermal reaction, placing the aqueous solution of calcium acetate into a reaction kettle, contacting the zinc or zinc alloy with the bottom of the reaction kettle, and forming a zinc oxide nanorod coating on one surface of the zinc or zinc alloy in contact with the bottom of the reaction kettle;
adding an aqueous solution of NaOH into an aqueous solution of calcium salt and phosphate to form a mixed system A, wherein the mixed system A is alkaline, the concentration of calcium ions in the aqueous solution of the calcium salt and the phosphate is 0.05-0.3mol/L, the concentration of phosphate ions is 0.03-0.18mol/L, and the aqueous solution of the calcium salt and the phosphate is placed in a reaction kettle;
and 2, placing the zinc or zinc alloy obtained in the step 1 in a mixed system A, placing the zinc oxide nanorod coating upwards, performing hydrothermal treatment at 70-180 ℃, and forming a hydroxyapatite nanorod biological coating on the surface of the zinc oxide nanorod coating.
2. The method for preparing a hydroxyapatite nanorod bio-coating according to claim 1, wherein in the aqueous solution of calcium acetate in the step 1, the concentration of the calcium acetate is 0.023-0.17 mol/L.
3. The method for preparing a hydroxyapatite nanorod biological coating according to claim 1, wherein the zinc or the zinc alloy in the step 1 is cylindrical, truncated cone or rectangular parallelepiped in shape.
4. The method for preparing a hydroxyapatite nanorod biological coating according to claim 1, wherein the temperature of the hydrothermal reaction in step 1 is 90-130 ℃ and the time is 60-240 min.
5. The method for preparing a hydroxyapatite nanorod bio-coating according to claim 1, wherein the phosphate in step 1 is diammonium hydrogen phosphate, ammonium dihydrogen phosphate or diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
6. The method for preparing a hydroxyapatite nanorod biocoating according to claim 1, wherein the calcium salt in step 1 is EDTA-Ca or calcium nitrate.
7. The method for preparing a hydroxyapatite nanorod bio-coating according to claim 1, wherein the pH of the mixing system a in step 1 is 12.5-12.8.
8. The method for preparing a hydroxyapatite nanorod biocoating according to claim 1, wherein the hydrothermal treatment in step 2 is performed at the temperature for 15-360 min.
9. A hydroxyapatite nanorod bio-coating obtained by the method for preparing a hydroxyapatite nanorod bio-coating according to any one of claims 1 to 8.
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