CN112169023B - Nanorod arrayed coating with thermal control immunity and oxidation resistance functions as well as preparation method and application thereof - Google Patents

Nanorod arrayed coating with thermal control immunity and oxidation resistance functions as well as preparation method and application thereof Download PDF

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CN112169023B
CN112169023B CN202011062532.XA CN202011062532A CN112169023B CN 112169023 B CN112169023 B CN 112169023B CN 202011062532 A CN202011062532 A CN 202011062532A CN 112169023 B CN112169023 B CN 112169023B
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coating
nanorod
oxidation
titanium
thermal control
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CN112169023A (en
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李博
刘福立
憨勇
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Shaanxi Jianuo Boao Biotechnology Co ltd
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Xian Jiaotong University
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Abstract

The invention discloses a nanorod arrayed coating with thermal control immunity and antioxidant functions, and a preparation method and application thereof, and belongs to the technical field of biomedical materials. Firstly, preparing a porous titanium dioxide coating containing phosphorus and calcium on the surface layer of titanium or an alloy thereof by adopting a micro-arc oxidation process, then growing a hydroxyapatite nanorod-shaped coating on the porous titanium dioxide coating containing phosphorus and calcium in situ by using a hydrothermal treatment method, and finally preparing a polydopamine-coated hydroxyapatite nanorod array by using an oxidation self-polymerization method to finally obtain the nanorod-shaped coating with thermal control immunity and oxidation resistance. The process is stable and has strong controllability; the surface layer of the prepared biomedical material has dual effects of oxidation resistance and photo-thermal; the implant can be used for bone tissue healing and regeneration, and avoids the occurrence of side effects such as coating spalling induced by poor membrane/base binding force and osteolysis or excessive inflammation induced by the coating spalling.

Description

Nanorod arrayed coating with thermal control immunity and oxidation resistance functions as well as preparation method and application thereof
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to a nanorod arrayed coating with thermal control immunity and oxidation resistance functions as well as a preparation method and application thereof.
Background
Titanium and its alloy are widely used in bone, tooth, joint and other hard tissue substitute materials due to its good mechanical properties and biocompatibility, however, research shows that its failure rate after implantation is still high, and the reason for this is: (1) lack of antioxidant capacity: during the surgical implantation of titanium-based implants, excess Reactive Oxygen Species (ROS) containing superoxide anion O is induced by drilling2-OH, hydrogen peroxide H2O2Etc.) will destroy the microenvironment in the bone surrounding the implant, inducing excessive inflammation in the tissue, leading to failure of the osteointegration of the implant; (2) lack of immunomodulatory capacity: the M2 phenotype polarization which can not effectively and quickly regulate and control macrophages to inhibit inflammation and promote tissue repair and regeneration is caused, so that the osseointegration forming speed of the titanium-based implant is slow; (3) lack of osteoinductive capacity: cannot significantly promote osteogenesis such as adhesion, proliferation and differentiation of osteogenesis related cells (bone marrow stromal stem cells, osteoblasts, etc.). The above problems are solved by constructing and optimizing titanium-based surface coatings.
Research shows that the Hydroxyapatite (HA) nanorod array configured surface layer constructed by imitating bone matrix and components can remarkably promote the osteogenesis of osteogenesis related cells, but the arrayed coating still HAs no oxidation resistance and lacks immune modulation capability. In the aspect of immune modulation function enhancement, research has shown that macrophages can be polarized to M2 phenotype through thermal stimulation, namely, thermal control immunity, compared with modes such as drug loading, chemical grafting and the like, the thermal control immunity has the characteristics of safety, simplicity, economy and the like, however, heat generation in the research is generally generated through direct heating, and the mode is not suitable for clinical application.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a nanorod arrayed coating with thermal control immunity and antioxidant functions, a preparation method and application thereof, and the nanorod arrayed coating is stable in process and strong in controllability; the surface layer of the prepared biomedical material has dual effects of oxidation resistance and photo-thermal; the coating material as the implant can be used for the capability of healing and regenerating bone tissues, and avoids the occurrence of side reactions such as coating spalling induced by poor membrane/base binding force and osteolysis or excessive inflammation induced by the coating spalling.
The invention is realized by the following technical scheme:
the invention discloses a preparation method of a nanorod arrayed coating with thermal control immunity and antioxidant functions, which comprises the following steps:
step 1: carrying out micro-arc oxidation on a pure titanium or titanium alloy matrix in an electrolyte containing phosphorus ions and calcium ions to form a titanium dioxide coating on the surface of the titanium-based matrix;
step 2: preparing a hydroxyapatite nanorod-structured coating on the titanium dioxide coating obtained in the step 1 by adopting a hydrothermal treatment method;
and step 3: and (3) preparing a poly-dopamine-coated hydroxyapatite nanorod array on the hydroxyapatite nanorod-structured coating obtained in the step (2) by adopting an oxidation self-polymerization method to obtain the nanorod-arrayed coating with the thermal control immunity and the anti-oxidation function.
Preferably, step 1 is specifically:
the method comprises the steps of taking a pure titanium or titanium alloy matrix as an anode and a stainless steel electrolytic tank as a cathode, carrying out micro-arc oxidation in electrolyte containing phosphorus ions and calcium ions at the temperature of 300-310K, and cleaning and drying to form a titanium dioxide coating on the surface of the titanium matrix.
Further preferably, the parameters of the micro-arc oxidation are as follows: the arc frequency is 80-110 Hz, the voltage is 300-500V, and the duty ratio is 5-10%.
Further preferably, the electrolyte comprises: 0.001-0.01 mol/L of sodium hydroxide, 0.1-0.3 mol/L of calcium acetate and 0.01-0.03 mol/L of beta-phosphoglyceride disodium salt pentahydrate.
Preferably, step 2 specifically comprises:
step 2.1: putting the titanium substrate coated with the titanium dioxide coating obtained in the step 1 into 0.01-0.03 mol/L sodium hydroxide aqueous solution, and sealing for carrying out primary hydrothermal treatment for 1-2 hours;
step 2.2: adding calcium sodium ethylene diamine tetraacetate, a beta-phosphoglyceride disodium salt pentahydrate and sodium hydroxide into water, uniformly stirring, and sealing the product obtained in the step 2.1 for secondary hydrothermal treatment, wherein the concentration of the calcium sodium ethylene diamine tetraacetate is 0.05-0.1 mol/L, the concentration of the beta-phosphoglyceride disodium salt pentahydrate is 0.01-0.03 mol/L, and the concentration of the sodium hydroxide is 0.1-0.2 mol/L; and cleaning and drying the product for later use.
Further preferably, the temperature of the primary hydrothermal treatment is 360-380K, and the time is 1-2 h; the temperature of the secondary hydrothermal treatment is 380-400K, and the time is 18-22 h.
Preferably, step 3 is specifically: and (3) immersing the product obtained in the step (2) in a 1-5 mg/mL dopamine trihydroxymethyl aminomethane solution, stirring at normal temperature in a dark place, cleaning after stirring, and drying to obtain the nanorod arrayed coating with the thermal control immunity and the oxidation resistance.
Further preferably, the rotating speed of stirring is 400-800 r/min, and the stirring time is 10-15 h.
The invention also discloses the nanorod arrayed coating with the thermal control immunity and the oxidation resistance function, which is prepared by the preparation method.
The invention also discloses application of the nanorod arrayed coating with the thermal control immunity and the anti-oxidation function as an implant coating material.
Compared with the prior art, the invention has the following beneficial technical effects:
the preparation method of the nanorod arrayed coating with the thermal control immunity and the oxidation resistance comprises the steps of firstly preparing a porous titanium dioxide coating containing phosphorus and calcium on the surface layer of titanium or an alloy thereof by adopting a micro-arc oxidation process, then growing a Hydroxyapatite (HA) nanorod-configured coating on the porous titanium dioxide coating containing phosphorus and calcium in situ by using a hydrothermal treatment method, and finally preparing a Polydopamine (PDA) -coated hydroxyapatite nanorod array (PDA @ HA) by using an oxidation self-polymerization method to finally obtain the nanorod arrayed coating with the thermal control immunity and the oxidation resistance. In-situ preparation of microporous TiO by micro-arc oxidation2A layer providing a strong interfacial bond between the coating and the substrate; and the micro-arc oxidation electrolyte and the hydrothermal solution have simple components, do not contain easily decomposed components, and have stable and controllable process and strong repeatability. Selecting dopamine with reducing catechol group as antioxidant and photosensitizer, coating PDA film layer on HA nanorod surface by using oxidative autopolymerization behavior of dopamine in alkalescent environment, and constructing PDA @ HA with dual functions of antioxidation and photothermal regulation and immunizationAnd (4) a nanorod array surface layer. And the oxidative self-polymerization capability of the polydopamine is strong, the dipping and coating mode is very simple and convenient, and the process is stable, so that the process can be used for large-scale production and preparation.
Further, a 1-5 mg/mL dopamine trihydroxymethyl aminomethane solution is adopted, and the HA nanorod array coating is completely covered by polydopamine due to excessive concentration; too low a concentration may result in failure to form polydopamine on the HA nanorods, which is strongly and uniformly bonded.
Furthermore, the stirring speed is 400-800 r/min, and the excessive high speed can cause incomplete oxidative autopolymerization reaction of dopamine on the HA nanorods and insufficient firm bonding of polydopamine formed on the HA nanorods; too slow a rate may result in uneven polymeric coating of dopamine on the HA nanorods.
The nanorod array coating with the functions of thermal control immunity and oxidation resistance prepared by the preparation method has a double-layer structure, the surface layer is a nanorod array with a bone-like matrix configuration, and the inner layer (adjacent to a matrix) is microporous TiO containing phosphorus and calcium2And (4) coating. The surface layer of the HA nanorod array coated with the PDA HAs double effects of oxidation resistance and photo-thermal, and the coating is tightly combined with the titanium-based matrix. The adopted raw materials are nontoxic and safe, have no side effect on human bodies, are easy to obtain and are easy to popularize and apply.
When the nanorod array coating with the functions of thermal control immunity and oxidation resistance is used as an implant coating material, the surface layer can remarkably promote the function of osteoblast-related cells, has dual effects of oxidation resistance and photo-thermal, can effectively remove ROS induced by an operation, can utilize photo-thermal efficiency induced by near-infrared light to regulate immune response, and further greatly improves the capability of a titanium-based implant in promoting the healing and regeneration of bone tissues. In addition, the coating can be tightly combined with the titanium substrate, and the occurrence of side reactions such as coating stripping induced by poor membrane/base binding force and osteolysis or excessive inflammation induced by the coating stripping is avoided.
Drawings
FIG. 1 is a surface morphology SEM photograph, a cross-sectional morphology SEM photograph and a cross-sectional linear scanning spectral line of the HA nanorod-structured coating prepared in example 1 through micro-arc oxidation-hydrothermal treatment;
FIG. 2 shows the composition prepared in example 1 and having PDA @ HA/TiO2The surface appearance SEM photo, the cross section appearance SEM photo and the cross section line scanning spectral line of the titanium implant of the coating;
FIG. 3 shows the composition prepared in example 2 and having PDA @ HA/TiO2The surface appearance SEM photo, the cross section appearance SEM photo and the cross section appearance line scanning spectral line of the titanium implant of the coating;
FIG. 4 is a graph showing the results of example 3 with PDA @ HA/TiO2SEM photograph of the surface appearance of the titanium implant of the coating;
FIG. 5 shows the composition prepared in example 4 with PDA @ HA/TiO2SEM photograph of the surface appearance of the titanium implant of the coating;
FIG. 6 shows a graph having HA/TiO2Coated titanium implants and PDA @ HA/ TiO embodiment 1, 2, 3 and 42XRD characterization pattern of coated titanium implants;
FIG. 7 shows a structure having HA/TiO2Coated titanium implants and PDA @ HA/TiO embodiment 1, 2 and 32Raman characterization of coated titanium implants.
Detailed Description
The present invention will now be described in further detail with reference to the following figures and specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
A method for preparing a nanorod arrayed coating with thermal control immunity and anti-oxidation functions comprises the following steps:
step 1, performing micro-arc oxidation, wherein the micro-arc oxidation parameters are set as follows: the frequency of the micro-arc oxidation arc is set to be 100Hz, the power supply is positive voltage of 400V, and the duty ratio is 7.5%. In the micro-arc oxidation process, a titanium or alloy wafer is taken as an anode, a stainless steel electrolytic tank is taken as a cathode, and the components and the concentration of the electrolyte are as follows: 0.005mol/L of sodium hydroxide (NaOH), calcium acetate (Ca (CH)3COO)2)0.22mol/L, 0.02mol/L of beta-phosphoglyceride disodium salt pentahydrate (beta-GP). In the preparation process, a cooling system is adopted to control the temperature of the micro-arc oxidation electrolyte to be 303K. Micro-arc oxidationAnd then obtaining a sample coated with a titanium dioxide coating, and putting the prepared sample into a drying oven for later use after the sample is cleaned by alcohol and deionized water.
Step 2, carrying out hydrothermal treatment on the porous titanium dioxide coating containing phosphorus and calcium to obtain the HA nanorod structured coating:
step 2.1, primary hydrothermal treatment
Firstly, preparing a solution required by primary hydrothermal, preparing a sodium hydroxide aqueous solution with the concentration of 0.01mol/L by using mineral water, putting a titanium sheet coated with a titanium dioxide coating after micro-arc oxidation into reaction kettles, then adding 15mL of the sodium hydroxide aqueous solution into each reaction kettle, screwing down the reaction kettles, putting the reaction kettles into a drying oven, and finally setting temperature and time parameters. The temperature was adjusted to 360K and the time was set to 2 h.
Step 2.2, Secondary hydrothermal treatment
Firstly, mineral water is used for preparing a solution for secondary hydrothermal reaction, the solution contains 0.125mol/L of sodium hydroxide, 0.02mol/L of beta-GP and 0.09mol/L of LEDTA-Ca, the solution is evenly stirred, the solution for primary hydrothermal reaction in each reaction kettle is sucked out and discarded, then 15mL of secondary aqueous hot water solution is added, the reaction kettle is screwed down and put into an oven, and finally, the temperature and time parameters are set. The temperature was adjusted to 385K and the time was set to 20 h. After twice hydrothermal treatment, coated TiO is obtained2And taking the sample out of the reaction kettle, washing with deionized water, and putting into a drying box for later use. The coating with the HA nanorod structure containing phosphorus, calcium and oxygen is obtained, the surface SEM picture of the coating is shown in figure 1, and it can be seen from figure 1 that a regular and dense coating with the HA hexagonal prism-shaped nanorod structure is formed on the titanium dioxide coating. The cross-sectional SEM photograph and the spectral lines are shown in FIG. 1.
Step 3, preparing a poly-dopamine (PDA) -coated Hydroxyapatite (HA) nanorod array (PDA @ HA)
Firstly, preparing a dopamine solution in a weak alkali environment: preparing 1mg/mL dopamine-containing trihydroxymethylaminomethane solution (wherein the trihydroxymethylaminomethane concentration is 10mmol/L), placing the titanium sheet coated with the HA coating at the bottom of the solution, and keeping the titanium sheet at normal temperature and in a dark state at a speed of 600r/minStirring for 12 h. After the stirring is finished, the product with PDA @ HA/TiO is obtained2Coated titanium alloy samples. And finally, taking out the sample, washing with deionized water, and drying in an oven. Obtaining the product with PDA @ HA/TiO2SEM photographs and spectra of the surface and cross-section of the coated titanium alloy sample are shown in fig. 2.
Example 2
A method for preparing a nanorod arrayed coating with thermal control immunity and anti-oxidation functions comprises the following steps:
step 1, performing micro-arc oxidation, wherein the micro-arc oxidation parameters are set as follows: the frequency of the micro-arc oxidation arc is set to be 100Hz, the power supply is positive voltage of 400V, and the duty ratio is 7.5%. In the micro-arc oxidation process, a titanium or alloy wafer is taken as an anode, a stainless steel electrolytic tank is taken as a cathode, and the components and the concentration of the electrolyte are as follows: 0.005mol/L of sodium hydroxide (NaOH), calcium acetate (Ca (CH)3COO)2)0.22mol/L, 0.02mol/L of beta-phosphoglyceride disodium salt pentahydrate (beta-GP). In the preparation process, a cooling system is adopted to control the temperature of the micro-arc oxidation electrolyte to be 303K. And (3) obtaining a sample coated with the titanium dioxide coating after micro-arc oxidation, and putting the prepared sample into a drying oven for later use after the sample is cleaned by alcohol and deionized water.
Step 2, carrying out hydrothermal treatment on the porous titanium dioxide coating containing phosphorus and calcium to obtain the HA nanorod structured coating:
step 2.1, primary hydrothermal treatment
Preparing 0.01mol/L sodium hydroxide aqueous solution with mineral water, coating TiO on the micro-arc oxidized solution2And (3) putting the coated titanium sheet into reaction kettles, adding 15mL of sodium hydroxide aqueous solution into each reaction kettle, screwing down the reaction kettles, putting the reaction kettles into a baking oven, and finally setting temperature and time parameters. The temperature was adjusted to 360K and the time was set to 2 h.
Step 2.2, Secondary hydrothermal treatment
Firstly, mineral water is used for preparing a solution for secondary hydrothermal reaction, the solution contains 0.125mol/L of sodium hydroxide, 0.02mol/L of beta-GP and 0.09mol/L of LEDTA-Ca, the solution is evenly stirred, the solution for primary hydrothermal reaction in each reaction kettle is sucked out and discarded, then 15mL of secondary aqueous hot water solution is added, the reaction kettle is screwed down and put into an oven, and finally, the temperature and time parameters are set. The temperature was adjusted to 385K and the time was set to 20 h. And (3) obtaining a titanium sheet coated with the HA nanorod-structured coating after two times of hydrothermal treatment, taking the sample out of the reaction kettle, washing the sample with deionized water, and putting the sample into a drying oven for later use. Obtaining the HA nano rod-shaped configuration coating containing phosphorus, calcium and oxygen.
Step 3, preparing a poly-dopamine (PDA) -coated Hydroxyapatite (HA) nanorod array (PDA @ HA)
Firstly, preparing a dopamine solution in a weak alkali environment: preparing a dopamine trihydroxymethylaminomethane solution with the concentration of 2mg/mL (wherein the trihydroxymethylaminomethane concentration is 10mmol/L), then placing the titanium sheet coated with the HA coating at the bottom of the solution, and stirring for 12 hours at the speed of 600r/min under the normal temperature and light-proof state. After the stirring is finished, the product with PDA @ HA/TiO is obtained2Coated titanium alloy samples. And finally, taking out the sample, washing with deionized water, and drying in an oven. Obtaining the product with PDA @ HA/TiO2SEM photographs and spectra of the surface and cross-section of the coated titanium alloy sample are shown in fig. 3.
Example 3
A method for preparing a nanorod arrayed coating with thermal control immunity and anti-oxidation functions comprises the following steps:
step 1, performing micro-arc oxidation, wherein the micro-arc oxidation parameters are set as follows: the frequency of the micro-arc oxidation arc is set to be 100Hz, the power supply is positive voltage of 400V, and the duty ratio is 7.5%. In the micro-arc oxidation process, a titanium or alloy wafer is taken as an anode, a stainless steel electrolytic tank is taken as a cathode, and the components and the concentration of the electrolyte are as follows: 0.005mol/L of sodium hydroxide (NaOH), calcium acetate (Ca (CH)3COO)2)0.22mol/L, 0.02mol/L of beta-phosphoglyceride disodium salt pentahydrate (beta-GP). In the preparation process, a cooling system is adopted to control the temperature of the micro-arc oxidation electrolyte to be 303K. And (3) obtaining a sample coated with the titanium dioxide coating after micro-arc oxidation, and putting the prepared sample into a drying oven for later use after the sample is cleaned by alcohol and deionized water.
Step 2, carrying out hydrothermal treatment on the porous titanium dioxide coating containing phosphorus and calcium to obtain the HA nanorod structured coating:
step 2.1, primary hydrothermal treatment
Preparing 0.01mol/L sodium hydroxide aqueous solution by using mineral water, putting the titanium sheet coated with the titanium dioxide coating after micro-arc oxidation into reaction kettles, then adding 15mL sodium hydroxide aqueous solution into each reaction kettle, screwing down the reaction kettles, putting the reaction kettles into a baking oven, and finally setting temperature and time parameters. The temperature was adjusted to 360K and the time was set to 2 h.
Step 2.2, Secondary hydrothermal treatment
Firstly, mineral water is used for preparing a solution for secondary hydrothermal reaction, the solution contains 0.125mol/L of sodium hydroxide, 0.02mol/L of beta-GP and 0.09mol/L of LEDTA-Ca, the solution is evenly stirred, the solution for primary hydrothermal reaction in each reaction kettle is sucked out and discarded, then 15mL of secondary aqueous hot water solution is added, the reaction kettle is screwed down and put into an oven, and finally, the temperature and time parameters are set. The temperature was adjusted to 385K and the time was set to 20 h. And (3) obtaining a titanium sheet coated with the HA nanorod-structured coating after two times of hydrothermal treatment, taking the sample out of the reaction kettle, washing the sample with deionized water, and putting the sample into a drying oven for later use. Obtaining the titanium dioxide/HA nano rod-shaped configuration coating containing phosphorus, calcium and oxygen.
Step 3, preparing a poly-dopamine (PDA) -coated Hydroxyapatite (HA) nanorod array (PDA @ HA)
Firstly, preparing a dopamine solution in a weak alkali environment: preparing a dopamine trihydroxymethylaminomethane solution with the concentration of 3mg/mL (wherein the trihydroxymethylaminomethane concentration is 10mmol/L), then placing the titanium sheet coated with the HA coating at the bottom of the solution, and stirring for 12 hours at the speed of 600r/min under the normal temperature and light-proof state. After the stirring is finished, the product with PDA @ HA/TiO is obtained2Coated titanium alloy samples. And finally, taking out the sample, washing with deionized water, and drying in an oven. Obtaining the product with PDA @ HA/TiO2A surface SEM photograph of a coated titanium alloy sample is shown in figure 4.
Example 4
A method for preparing a nanorod arrayed coating with thermal control immunity and anti-oxidation functions comprises the following steps:
step 1, micro-arc oxidation is carried out, and micro-arc oxidation is carried outThe number is set as: the frequency of the micro-arc oxidation arc is set to be 80Hz, the power supply is positive pressure of 300V, and the duty ratio is 5%. In the micro-arc oxidation process, a titanium or alloy wafer is taken as an anode, a stainless steel electrolytic tank is taken as a cathode, and the components and the concentration of the electrolyte are as follows: 0.001mol/L of sodium hydroxide (NaOH), calcium acetate (Ca (CH)3COO)2)0.1mol/L, 0.01mol/L of beta-phosphoglyceride disodium salt pentahydrate (beta-GP). In the preparation process, a cooling system is adopted to control the temperature of the micro-arc oxidation electrolyte to be 300K. And (3) obtaining a sample coated with the titanium dioxide coating after micro-arc oxidation, and putting the prepared sample into a drying oven for later use after the sample is cleaned by alcohol and deionized water.
Step 2, carrying out hydrothermal treatment on the porous titanium dioxide coating containing phosphorus and calcium to obtain the HA nanorod structured coating:
step 2.1, primary hydrothermal treatment
Preparing 0.02mol/L sodium hydroxide aqueous solution by using mineral water, putting the titanium sheet coated with the titanium dioxide coating after micro-arc oxidation into reaction kettles, then adding 15mL sodium hydroxide aqueous solution into each reaction kettle, screwing down the reaction kettles, putting the reaction kettles into a baking oven, and finally setting temperature and time parameters. The temperature was adjusted to 370K and the time was set to 1 h.
Step 2.2, Secondary hydrothermal treatment
Firstly, mineral water is used for preparing a solution for secondary hydrothermal reaction, the solution contains 0.1mol/L of sodium hydroxide, 0.01mol/L of beta-GP and 0.05mol/L of LEDTA-Ca, the solution is evenly stirred, the solution which is subjected to primary hydrothermal reaction in each reaction kettle is sucked out and discarded, then 15mL of secondary aqueous hot water solution is added, the reaction kettles are screwed down and put into an oven, and finally, the temperature and time parameters are set. The temperature was adjusted to 380K and the time was set to 18 h. And (3) obtaining a titanium sheet coated with the HA nanorod-structured coating after two times of hydrothermal treatment, taking the sample out of the reaction kettle, washing the sample with deionized water, and putting the sample into a drying oven for later use. Obtaining the HA nano rod-shaped configuration coating containing phosphorus, calcium and oxygen.
Step 3, preparing a poly-dopamine (PDA) -coated Hydroxyapatite (HA) nanorod array (PDA @ HA)
Firstly, preparing a dopamine solution in a weak alkali environment: preparing concentrateAdding dopamine with the concentration of 4mg/mL into a trihydroxymethylaminomethane solution (wherein the trihydroxymethylaminomethane concentration is 10mmol/L), then placing the titanium sheet coated with the HA coating at the bottom of the solution, and stirring for 10 hours at the speed of 400r/min under the state of normal temperature and light shielding. After the stirring is finished, the product with PDA @ HA/TiO is obtained2Coated titanium alloy samples. And finally, taking out the sample, washing with deionized water, and drying in an oven. Obtaining the product with PDA @ HA/TiO2A surface SEM photograph of a coated titanium alloy sample is shown in figure 5.
Example 5
A method for preparing a nanorod arrayed coating with thermal control immunity and anti-oxidation functions comprises the following steps:
step 1, performing micro-arc oxidation, wherein the micro-arc oxidation parameters are set as follows: the frequency of the micro-arc oxidation arc is set to be 110Hz, the power supply is positive voltage of 500V, and the duty ratio is 10%. In the micro-arc oxidation process, a titanium or alloy wafer is taken as an anode, a stainless steel electrolytic tank is taken as a cathode, and the components and the concentration of the electrolyte are as follows: 0.01mol/L of sodium hydroxide (NaOH), calcium acetate (Ca (CH)3COO)2)0.3mol/L, 0.03mol/L of beta-phosphoglyceride disodium salt pentahydrate (beta-GP). In the preparation process, a cooling system is adopted to control the temperature of the micro-arc oxidation electrolyte to be 310K. And (3) obtaining a sample coated with the titanium dioxide coating after micro-arc oxidation, and putting the prepared sample into a drying oven for later use after the sample is cleaned by alcohol and deionized water.
Step 2, carrying out hydrothermal treatment on the porous titanium dioxide coating containing phosphorus and calcium to obtain the HA nanorod structured coating:
step 2.1, primary hydrothermal treatment
Deionized water is used for preparing a sodium hydroxide aqueous solution with the concentration of 0.03mol/L, the titanium sheet coated with the titanium dioxide coating after micro-arc oxidation is placed into reaction kettles, then 15mL of the sodium hydroxide aqueous solution is added into each reaction kettle, the reaction kettles are screwed down and placed into a baking oven, and finally, the temperature and time parameters are set. The temperature was adjusted to 380K and the time was set to 1 h.
Step 2.2, Secondary hydrothermal treatment
Firstly, preparing a solution of a secondary hydrothermal reaction by using deionized water, wherein the solution contains 0.2mol/L of sodium hydroxide, 0.03mol/L of beta-GP and 0.1mol/L of LEDTA-Ca, uniformly stirring the solution, sucking out and discarding the solution of the primary hydrothermal reaction in each reaction kettle, adding 15mL of secondary aqueous hot water solution, screwing down the reaction kettles, putting the reaction kettles into an oven, and finally setting temperature and time parameters. The temperature was adjusted to 400K and the time was set to 22 h. And (3) obtaining a titanium sheet coated with the HA nanorod-structured coating after two times of hydrothermal treatment, taking the sample out of the reaction kettle, washing the sample with deionized water, and putting the sample into a drying oven for later use.
Step 3, preparing a poly-dopamine (PDA) -coated Hydroxyapatite (HA) nanorod array (PDA @ HA)
Firstly, preparing a dopamine solution in a weak alkali environment: preparing 5mg/mL dopamine-containing trihydroxymethylaminomethane solution (wherein the trihydroxymethylaminomethane concentration is 10mmol/L), placing the titanium sheet coated with the HA coating at the bottom of the solution, and stirring at the normal temperature and in a dark state at the speed of 800r/min for 15 h. After the stirring is finished, the product with PDA @ HA/TiO is obtained2Coated titanium alloy samples. And finally, taking out the sample, washing with deionized water, and drying in an oven. Obtaining the product with PDA @ HA/TiO2Coated titanium alloy samples.
When the primary hydrothermal reaction solution and the secondary hydrothermal reaction solution are prepared in step 2, mineral water or deionized water is preferably used.
Examples prepared with PDA @ HA/TiO2The titanium alloy sample of the coating comprises TiO which are sequentially arranged from the surface of the substrate to the outside2The coating and the PDA @ HA coating are shown in figure 6, and the titanium alloy with the HA coating is obtained after micro-arc oxidation and hydrothermal treatment in an XRD representation diagram. As shown in fig. 7, the raman characterization chart has similar rules, except that after dopamine oxidative autopolymerization deposition, the relevant characteristic peaks of polydopamine can be obtained, which respectively correspond to the stretching and deformation of the catechol group, and the strength of the PDA characteristic peak becomes stronger with the increase of the concentration. Combining the surface SEM and cross-sectional SEM photographs,it can be said that the coating HAs PDA @ HA/TiO2The titanium alloy implant with the bioactive coating is successfully prepared.

Claims (5)

1. A preparation method of a nanorod arrayed coating with thermal control immunity and anti-oxidation functions is characterized by comprising the following steps:
step 1: carrying out micro-arc oxidation on a pure titanium or titanium alloy matrix in an electrolyte containing phosphorus ions and calcium ions to form a titanium dioxide coating on the surface of the titanium-based matrix; the step 1 specifically comprises the following steps: taking a pure titanium or titanium alloy matrix as an anode and a stainless steel electrolytic tank as a cathode, carrying out micro-arc oxidation in an electrolyte containing phosphorus ions and calcium ions at the temperature of 300-310K, and cleaning and drying to form a titanium dioxide coating on the surface of the titanium matrix; the parameters of the micro-arc oxidation are as follows: the arc frequency is 80-110 Hz, the voltage is positive voltage 300-500V, and the duty ratio is 5% -10%;
step 2: preparing a hydroxyapatite nanorod-structured coating on the titanium dioxide coating obtained in the step 1 by adopting a hydrothermal treatment method; the step 2 specifically comprises the following steps:
step 2.1: putting the titanium substrate coated with the titanium dioxide coating obtained in the step 1 into 0.01-0.03 mol/L sodium hydroxide aqueous solution, and sealing for carrying out primary hydrothermal treatment for 1-2 hours;
step 2.2: adding calcium sodium ethylene diamine tetraacetate, a beta-phosphoglyceride disodium salt pentahydrate and sodium hydroxide into water, uniformly stirring, and sealing the product obtained in the step 2.1 for secondary hydrothermal treatment, wherein the concentration of the calcium sodium ethylene diamine tetraacetate is 0.05-0.1 mol/L, the concentration of the beta-phosphoglyceride disodium salt pentahydrate is 0.01-0.03 mol/L, and the concentration of the sodium hydroxide is 0.1-0.2 mol/L; cleaning and drying the product for later use; the temperature of the primary hydrothermal treatment is 360-380K, and the time is 1-2 h; the temperature of the secondary hydrothermal treatment is 380-400K, and the time is 18-22 h;
and step 3: preparing a poly-dopamine-coated hydroxyapatite nanorod array on the hydroxyapatite nanorod-structured coating obtained in the step 2 by adopting an oxidation self-polymerization method to obtain a nanorod-arrayed coating with thermal control immunity and anti-oxidation functions; the step 3 specifically comprises the following steps: and (3) immersing the product obtained in the step (2) in a 1-5 mg/mL dopamine trihydroxymethyl aminomethane solution, stirring at normal temperature in a dark place, cleaning after stirring, and drying to obtain the nanorod arrayed coating with the thermal control immunity and the oxidation resistance.
2. The method for preparing the nanorod arrayed coating with the thermal control immunity and the anti-oxidation function according to claim 1, wherein the electrolyte comprises: 0.001-0.01 mol/L of sodium hydroxide, 0.1-0.3 mol/L of calcium acetate and 0.01-0.03 mol/L of beta-phosphoglyceride disodium salt pentahydrate.
3. The method for preparing the nanorod array coating with the thermal control immunity and the anti-oxidation function according to claim 1, wherein the stirring speed is 400-800 r/min and the stirring time is 10-15 h.
4. The nanorod array coating prepared by the preparation method of any one of claims 1-3 and having thermal control immunity and oxidation resistance functions.
5. The use of the nanorod arrayed coating of claim 4 with thermal control immunity and oxidation resistance as an implant coating material.
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