CN114481260B - Preparation method and application of composite calcium-phosphorus micro-arc oxidation coating on surface of biological alloy - Google Patents
Preparation method and application of composite calcium-phosphorus micro-arc oxidation coating on surface of biological alloy Download PDFInfo
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Abstract
The invention relates to a preparation method of a composite calcium-phosphorus micro-arc oxidation coating on the surface of a biological alloyMethods and applications. The invention provides a preparation method of a titanium alloy surface graphene oxide modified micro-arc oxidation film. Firstly, titanium alloy is taken as a matrix and contains Na 3 PO 4 ·12H 2 And (3) performing micro-arc oxidation treatment in electrolyte of O, naOH and NaF. On the basis of the above, the method is carried out by using (CH 3 COO) 2 Ca is a calcium source, na 2 HPO 4 In the electrolyte of a phosphorus source, preparing a calcium-phosphorus film layer by secondary micro-arc oxidation, and adding graphene oxide with different contents into the electrolyte to modify the micro-arc calcium-phosphorus oxide film layer, so as to construct a novel composite coating with good comprehensive performance on the surface of the titanium alloy. According to the invention, the micro-arc oxidation process parameters are optimized by testing the film phase composition, microstructure, the binding force of the film and the matrix, corrosion resistance, biological activity and the like, so as to obtain the micro-arc oxidation film modified by graphene oxide on the surface of the titanium alloy.
Description
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to a preparation method of a composite calcium-phosphorus micro-arc oxidation coating on the surface of a biological alloy, the biological alloy with the composite coating prepared by the method, and application of the biological alloy with the composite coating as a biomedical material.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Titanium alloys are widely used in the manufacture of hard tissue implants because of their good biocompatibility and excellent corrosion resistance. However, titanium alloy implants remain foreign materials relative to human tissue and are not entirely acceptable to the human body. In addition, the mechanical properties, especially the elastic modulus, of the titanium alloy are greatly different from those of natural bones, under the action of stress, the stress bearing metal generates different strains with human bone tissues, the relative displacement occurs at the contact interface of the metal and the bones, and the long-term implantation can also generate stress shielding to influence the function of the implant. In order to enhance the biocompatibility of titanium alloy implants, surface modification techniques have become a focus of research on medical titanium alloys.
How to improve the osseointegration ability of the implant surface and the long-term in vivo stability make the implant more reliable and stable, and for metal-based implants the most common approach is to surface modify the implant. Micro-arc oxidation is one of the anodic oxidation techniques, and has been used for surface treatment of implants in recent years. By utilizing the technology, a layer of ceramic film can be generated on the metal surface in situ. The micro-arc oxidation film is of a porous structure, the specific surface area is large, and the uniform distribution of the holes provides more sites for cell attachment. The surface of the titanium alloy after micro-arc oxidation treatment can form a nano-scale and micro-scale microporous structure, and from the bionic point of view, the surface of the implant with the micro-nano structure can show better comprehensive performance due to being more similar to human bone tissue.
Disclosure of Invention
Based on the technical background, the invention aims to provide a biological alloy material with better biological performance and mechanical performance. The calcium-phosphorus film prepared by comparing the primary micro-arc oxidation and the secondary micro-arc oxidation has the advantages of high binding force between the secondary micro-arc oxidation film and the substrate and good corrosion resistance. In order to further improve the biocompatibility of the biological alloy material, the graphene oxide has the advantages of good hydrophilicity, dispersibility, easiness in modification and the like, and also has antibacterial property and biocompatibility which are required to be used as an excellent biomedical material. The present invention is therefore carried out on the mixture of calcium acetate (CH) 3 COO) 2 Ca) is a calcium source, disodium hydrogen phosphate (Na 2 HPO 4 ) Graphene oxide is added into the electrolyte of the phosphorus salt, and a micro-arc oxidation film layer is prepared on the surface of the titanium alloy by adopting a secondary micro-arc oxidation method. The prepared micro-arc oxidation film has the advantages of rough and porous surface, higher binding force with a matrix, good corrosion resistance and certain biological activity. The invention is expected to solve the problems of infection and loosening related to the titanium-based implant, and lays a certain practical foundation for research and development of the implant.
Based on the technical effects, the invention provides the following technical scheme:
the invention provides a preparation method of a composite calcium-phosphorus micro-arc oxidation coating on the surface of a biological alloy, which comprises the following steps: performing primary micro-arc oxidation treatment on the surface of the biological alloy, and placing the treated biological alloy in electrolyte containing calcium and phosphorus elements for secondary micro-arc oxidation treatment.
The biological alloy in the first aspect is one of gold, silver, platinum, stainless steel, cobalt-based and titanium alloy. In one possible embodiment of the present invention, the biological alloy is a titanium alloy; the titanium alloy is also provided with a pretreatment process before the preparation of the composite coating, wherein the pretreatment process comprises polishing and cleaning the surface of the titanium alloy; the polishing comprises the step-by-step polishing of the surface of the titanium alloy by adopting sand paper with different mesh numbers, and the cleaning comprises the ultrasonic cleaning by adopting absolute ethyl alcohol and water.
Preferably, the step of the primary micro-arc oxidation is as follows: titanium alloy is used as an anode, inert material is used as a cathode, and the titanium alloy is immersed into electrolyte for micro-arc oxidation.
Further, the electrolyte contains Na 3 PO 4 The mass ratio of NaOH to NaF is 7-9: 0.5 to 1.5:0.5 to 1.5; further, the ratio is 7 to 9:1:1. in a specific embodiment of the foregoing preferred technical solution, the composition of the electrolyte for primary micro-arc oxidation is as follows: 8g/L Na 3 PO 4 ·12H 2 O,1g/L NaOH and 1g/L NaF.
Further, the technological parameters of the primary micro-arc oxidation are as follows: the constant voltage mode is adopted, the positive voltage is 400V-500V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 500-700 Hz, and the time is 5-15min.
Preferably, the step of the secondary micro-arc oxidation is as follows:
taking the titanium alloy subjected to primary micro-arc oxidation treatment as an anode, taking an inert material as a cathode, and immersing the titanium alloy into electrolyte for micro-arc oxidation.
Further, the secondary micro-arc oxidation electrolyte Contains (CH) 3 COO) 2 Ca and Na 2 HPO 4 The mass ratio of the two is 24-27: 10 to 14.
Further, the technological parameters of the secondary micro-arc oxidation are as follows: the constant voltage mode is adopted, the positive voltage is 450V-500V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 500-700 Hz, and the time is 5-15min.
The invention researches find that the biological alloy after the secondary micro-arc oxidation is more tightly combined with the matrix, has better corrosion resistance on the surface, and is not easy to cause the problems of coating falling off and the like when being used in a body fluid environment. In order to further improve the biological activity of the biological coating, the invention also provides the following technical scheme that graphene oxide is doped in the coating subjected to the secondary micro-arc oxidation:
that is, in still another embodiment provided in the first aspect, graphene oxide is further included in the electrolyte solution of the secondary micro-arc oxidation treatment.
Further, in the above embodiment, the components of the electrolyte for the secondary micro-arc oxidation are as follows: (CH) 3 COO) 2 Ca、Na 2 HPO 4 And graphene oxide, wherein the ratio of the three is 24-27: 10 to 14:0-0.2g/L graphene oxide, wherein the content of the graphene oxide is not 0.
In a specific embodiment, the components of the electrolyte for the secondary micro-arc oxidation are as follows: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 0.112g/L graphene oxide.
In addition, in this embodiment, the technological parameters of the secondary micro-arc oxidation are as follows: the constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 500-700 Hz, and the time is 5-15min.
According to a second aspect of the invention, a biological alloy with a surface composite coating obtained by the preparation method of the composite calcium-phosphorus micro-arc oxidation coating on the surface of the biological alloy is provided.
In a third aspect of the invention, there is provided the use of a bio-alloy with a surface composite coating according to the second aspect as a biomedical material.
Preferably, the biomedical material means a material for diagnosing, treating, repairing or replacing a damaged tissue, organ or enhancing the function of an organism; further, bone-muscle system repair materials such as bones, teeth, joints, tendons, etc. are preferable, and artificial bones, artificial joints, etc. are specific examples.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a macroscopic morphology of calcium-phosphorus film prepared by micro-arc oxidation as described in examples 1-5;
wherein, (a) is example 1; (b) is example 2; (c) is example 3; (d) is example 4; (e) is example 5;
FIG. 2 is a macroscopic morphology of the calcium phosphate film prepared in examples 6-10;
wherein, (a) is example 6; (b) is example 7; (c) is example 8; (d) is example 9; (e) is example 10;
FIG. 3 is an X-ray diffraction pattern of the CaP film layers prepared in example 2 and example 9;
FIG. 4 shows the surface topography of the CaP film prepared in example 2 (a) and example 9 (b);
FIG. 5 shows the potentiodynamic polarization curve of the micro-arc oxide film layer of example 2 and example 9;
FIG. 6 shows the binding force detection results of example 2 and example 9;
FIG. 7 shows the bonding interface between the film and the substrate of example 2 (a) and example 9 (b) of FIG. 7
FIG. 8 is an X-ray diffraction pattern of samples prepared from different component electrolytes;
wherein, caP: example 9, cap-0.056GO: example 11, cap-0.112GO: example 12, cap-0.056GO: example 13;
FIG. 9 is a sample surface morphology prepared with different component electrolytes;
wherein a: example 9,b: examples 11, c: examples 12, d: example 13;
FIG. 10 is a graph of the potentiodynamic polarization of a membrane prepared from different component electrolytes;
wherein, caP: example 9, cap-0.056GO: example 11, cap-0.112GO: example 12, cap-0.056GO: example 13;
FIG. 11 shows the result of the film-to-substrate bonding force detection;
wherein, caP: example 9, cap-0.056GO: example 11, cap-0.112GO: example 12, cap-0.056GO: example 13;
FIG. 12 is an X-ray diffraction pattern of a sample prepared from electrolytes of different compositions after 72 hours of immersion in a simulated body fluid;
wherein, caP: example 9, cap-0.056GO: example 11, cap-0.112GO: example 12, cap-0.056GO: example 13;
FIG. 13 shows the surface morphology of samples prepared with different component electrolytes after 72h immersion in SBF;
wherein a: example 9,b: examples 11, c: examples 12, d: example 13.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
The titanium alloy steel sheet in each of the following examples was first pretreated as follows:
cutting the titanium alloy steel plate into 8X 10mm by using a wire cutting device 3 Is a sample of (a). The obtained sample was washed and then was subjected to a drilling machine to obtain a sample of 8X 8mm 2 A hole with a proper depth for inserting a wire is drilled on the surface of the steel wire. And then polishing step by using 180, 400, 600, 800, 1000-mesh metallographic sand paper. The ground sample was sequentially ultrasonically cleaned with alcohol and deionized water to obtain a titanium alloy sample in the following examples.
Example 1
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. The inert material is connected with the MAO power supply cathode. The electrolyte comprises the following components: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 . The constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 5min.
Example 2
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. The inert material is connected with the MAO power supply cathode. The electrolyte comprises the following components: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 . The constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Example 3
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. The inert material is connected with the MAO power supply cathode. The electrolyte comprises the following components: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 . The constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 15min.
Example 4
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. The inert material is connected with the MAO power supply cathode. The electrolyte comprises the following components: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 . The constant voltage mode is adopted, the positive voltage is 400V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Example 5
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. The inert material is connected with the MAO power supply cathode. The electrolyte comprises the following components: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 . The constant voltage mode is adopted, the positive voltage is 500V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Example 6
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. The inert material is connected with the MAO power supply cathode. The electrolyte comprises the following components: 8g/L Na 3 PO 4 ·12H 2 O,1g/L NaOH and 1g/L NaF. The constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Taking the micro-arc oxidation sample as a matrix, wherein the micro-arc oxidation sample comprises the following components in parts by weight: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 And (3) carrying out secondary micro-arc oxidation treatment on the electrolyte. The constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Example 7
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. Inert material connection MAOAnd a negative electrode of the power supply. The electrolyte comprises the following components: 8g/L Na 3 PO 4 ·12H 2 O,1g/L NaOH and 1g/L NaF. The constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Taking the micro-arc oxidation sample as a matrix, wherein the micro-arc oxidation sample comprises the following components in parts by weight: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 And (3) carrying out secondary micro-arc oxidation treatment on the electrolyte. The constant voltage mode is adopted, the positive voltage is 470V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 5min.
Example 8
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. The inert material is connected with the MAO power supply cathode. The electrolyte comprises the following components: 8g/L Na 3 PO 4 ·12H 2 O,1g/L NaOH and 1g/L NaF. The constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Taking the micro-arc oxidation sample as a matrix, wherein the micro-arc oxidation sample comprises the following components in parts by weight: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 And (3) carrying out secondary micro-arc oxidation treatment on the electrolyte. The constant voltage mode is adopted, the positive voltage is 470V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Example 9
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. The inert material is connected with the MAO power supply cathode. The electrolyte comprises the following components: 8g/L Na 3 PO 4 ·12H 2 O,1g/L NaOH and 1g/L NaF. Adopting constant voltage mode, positive voltage is 450V, negative voltage is 0, positive pulse number is 1, negative pulse number is 1, positive duty ratio is 30%, and negative duty ratio is20% frequency 600Hz for 10min.
Taking the micro-arc oxidation sample as a matrix, wherein the micro-arc oxidation sample comprises the following components in parts by weight: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 And (3) carrying out secondary micro-arc oxidation treatment on the electrolyte. The constant voltage mode is adopted, the positive voltage is 470V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 15min.
Example 10
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. The inert material is connected with the MAO power supply cathode. The electrolyte comprises the following components: 8g/L Na 3 PO 4 ·12H 2 O,1g/L NaOH and 1g/L NaF. The constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Taking the micro-arc oxidation sample as a matrix, wherein the micro-arc oxidation sample comprises the following components in parts by weight: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 And (3) carrying out secondary micro-arc oxidation treatment on the electrolyte. The constant voltage mode is adopted, the positive voltage is 500V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Example 11
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. The inert material is connected with the MAO power supply cathode. The electrolyte comprises the following components: 8g/L Na 3 PO 4 ·12H 2 O,1g/L NaOH and 1g/L NaF. The constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Taking the micro-arc oxidation sample as a matrix, wherein the micro-arc oxidation sample comprises the following components in parts by weight: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 0.056g/L graphene oxideAnd (3) carrying out secondary micro-arc oxidation treatment on the solution. The constant voltage mode is adopted, the positive voltage is 470V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 15min.
Example 12
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. The inert material is connected with the MAO power supply cathode. The electrolyte comprises the following components: 8g/L Na 3 PO 4 ·12H 2 O,1g/L NaOH and 1g/L NaF. The constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Taking the micro-arc oxidation sample as a matrix, wherein the micro-arc oxidation sample comprises the following components in parts by weight: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 And carrying out secondary micro-arc oxidation treatment on the graphene oxide in electrolyte of 0.112 g/L. The constant voltage mode is adopted, the positive voltage is 470V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 15min.
Example 13
The titanium alloy sample is rinsed with deionized water and then connected with the positive electrode of the MAO power supply, and is immersed into the electrolyte. The inert material is connected with the MAO power supply cathode. The electrolyte comprises the following components: 8g/L Na 3 PO 4 ·12H 2 O,1g/L NaOH and 1g/L NaF. The constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 600Hz, and the time is 10min.
Taking the micro-arc oxidation sample as a matrix, wherein the micro-arc oxidation sample comprises the following components in parts by weight: 26.427g/L (CH) 3 COO) 2 Ca，12.775g/L Na 2 HPO 4 And carrying out secondary micro-arc oxidation treatment on the graphene oxide in electrolyte of 0.168 g/L. Adopting constant voltage mode, positive voltage is 470V, negative voltage is 0, positive pulse number is 1, negative pulse number is 1, positive duty ratio is 30%, negative duty ratio is 20%,the frequency was 600Hz and the time was 15min.
The invention is researched aiming at the morphology and the performance of the composite calcium-phosphorus micro-arc oxidation coating on the surface of the titanium alloy in the above embodiment 1-embodiment 13, and can be seen from the graph:
the film layers prepared in examples 6-13 had rough and porous surfaces and had a phase composition of mainly rutile TiO 2 (Rutile), perovskite TiO 2 (Anatate) and Ca 2 P 2 O 7 . The binding force between the film prepared by adopting the two micro-arc oxidation methods and the substrate is higher than that between the film prepared by adopting the one-time micro-arc oxidation method and the substrate, and the corrosion resistance is slightly better than that of the film prepared by adopting the one-time micro-arc oxidation method. The addition of graphene oxide with a certain concentration improves the binding force between the film and the matrix, and improves the corrosion resistance and the bioactivity of the film. The invention is expected to solve the problems of infection and loosening related to the titanium-based implant, and lays a certain practical foundation for research and development of the implant.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the composite calcium-phosphorus micro-arc oxidation coating on the surface of the biological alloy is characterized by comprising the following steps: performing primary micro-arc oxidation treatment on the surface of the biological alloy, and placing the treated biological alloy in electrolyte containing calcium and phosphorus elements for secondary micro-arc oxidation treatment;
the secondary micro-arc oxidation comprises the following steps:
taking the titanium alloy subjected to primary micro-arc oxidation treatment as an anode, taking an inert material as a cathode, and immersing the titanium alloy into electrolyte for micro-arc oxidation;
the electrolyte of the primary micro-arc oxidation contains Na 3 PO 4 The mass ratio of NaOH to NaF is 7-9: 1:1, a step of;
electrolyte for secondary micro-arc oxidationThe component (C) is (CH) 3 COO) 2 Ca、Na 2 HPO 4 And graphene oxide, wherein the ratio of the three is 24-27: 10-14: 0-0.2g/L, wherein the graphene oxide content is not 0.
2. The method for preparing the composite calcium-phosphorus micro-arc oxidation coating on the surface of the biological alloy according to claim 1, wherein the biological alloy is titanium alloy; the titanium alloy is also provided with a pretreatment process before the preparation of the composite coating, wherein the pretreatment process comprises polishing and cleaning the surface of the titanium alloy; the polishing comprises the step-by-step polishing of the surface of the titanium alloy by adopting sand paper with different mesh numbers, and the cleaning comprises the ultrasonic cleaning by adopting absolute ethyl alcohol and water.
3. The method for preparing the composite calcium-phosphorus micro-arc oxidation coating on the surface of the biological alloy according to claim 1, wherein the technological parameters of the primary micro-arc oxidation are as follows: the constant voltage mode is adopted, the positive voltage is 400-500V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 500-700 Hz, and the time is 5-15min.
4. The method for preparing the composite calcium-phosphorus micro-arc oxidation coating on the surface of the biological alloy according to claim 1, wherein the technological parameters of the secondary micro-arc oxidation are as follows: the constant voltage mode is adopted, the positive voltage is 450V-500V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 500-700 Hz, and the time is 5-15min.
5. The method for preparing the composite calcium-phosphorus micro-arc oxidation coating on the surface of the biological alloy according to claim 4, wherein the technological parameters of the secondary micro-arc oxidation are as follows: the constant voltage mode is adopted, the positive voltage is 450V, the negative voltage is 0, the positive pulse number is 1, the negative pulse number is 1, the positive duty ratio is 30%, the negative duty ratio is 20%, the frequency is 500-700 Hz, and the time is 5-15min.
6. The biological alloy with the surface composite coating obtained by the preparation method of the biological alloy surface composite calcium-phosphorus micro-arc oxidation coating according to any one of claims 1 to 5.
7. Use of the bio-alloy with surface composite coating according to claim 6 as biomedical material.
8. Use of a bio-alloy with a surface composite coating according to claim 7 as biomedical material, characterized in that the biomedical material represents a material for diagnosing, treating, repairing or replacing diseased tissue, organs or enhancing the function of an organism.
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| CN103334145A (en) * | 2013-07-18 | 2013-10-02 | 哈尔滨工业大学 | Method for preparing biological activity micro-arc oxidation ceramic coating with macroscopic/microcosmic double-stage pore structure on surface of medical titanium through two-step method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103334145A (en) * | 2013-07-18 | 2013-10-02 | 哈尔滨工业大学 | Method for preparing biological activity micro-arc oxidation ceramic coating with macroscopic/microcosmic double-stage pore structure on surface of medical titanium through two-step method |
Non-Patent Citations (1)
| Title |
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| 张志莲 等.氧化石墨烯对Mg-Li 合金微弧氧化陶瓷层微观结构及耐蚀性的影响.《表面技术》.2019,第48卷(第48期),306-313、345. * |
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