CN115779143B - Titanium-based implant, and preparation method and application thereof - Google Patents

Titanium-based implant, and preparation method and application thereof Download PDF

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CN115779143B
CN115779143B CN202211412160.8A CN202211412160A CN115779143B CN 115779143 B CN115779143 B CN 115779143B CN 202211412160 A CN202211412160 A CN 202211412160A CN 115779143 B CN115779143 B CN 115779143B
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titanium
preparation
treatment
sample
zinc
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CN115779143A (en
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万熠
纪振冰
赵梓贺
于明志
王宏卫
王滕
范世缘
邹宇锦
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Shandong University
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Shandong University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

Abstract

The invention provides a titanium-based implant, a preparation method and application thereof, and belongs to the technical field of medical material manufacturing. The preparation method comprises the following steps: and (3) carrying out acid etching treatment on the titanium substrate, then carrying out anodic oxidation treatment, adding zinc acetate solution into the titanium substrate, and then carrying out vacuum heating treatment, so as to construct the micro-nano composite structure and the zinc oxide coating on the surface of the titanium substrate. According to the invention, the micro-nano structure processed on the surface of the titanium implant and the added zinc ion coating have good capability of promoting osteogenesis, and zinc ions have good antibacterial effect. Through design, the method can effectively combine the advantages of the micro-nano structure and zinc ions, improve the bone-bonding capability of the 3D printing titanium-based implant, and meanwhile, the zinc oxide can improve the antibacterial effect of the surface, so that the preparation of the osteogenesis and antibacterial double-acting surface is realized, and the method has good practical application value.

Description

Titanium-based implant, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of medical material manufacturing, and particularly relates to a titanium-based implant, and a preparation method and application thereof.
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.
Currently, the problem of bone tissue defect caused by aging population and frequent traffic accidents is urgent to be solved, meanwhile, differences exist among different patients, and mass production of titanium implants is difficult. 3D printing is increasingly being used in clinic as a flexible way of processing. Among the numerous implant materials, titanium and its alloys have been widely used for the treatment of bone tissue defects due to their good combination of properties.
However, the 3D printed titanium implant has limited binding ability to surrounding bone tissue, and is prone to loosening after implantation. Meanwhile, in the implantation process, the problems of bacterial infection and the like are easy to occur, once the infection occurs, a patient must be treated by taking medicines and the like, and even the patient needs to be re-implanted when serious, and great physiological and psychological pains are brought to the patient. Therefore, the surface of the implant should have a certain antibacterial ability to reduce adhesion and proliferation of bacteria, thereby improving the success rate of implantation.
Disclosure of Invention
Based on the defects in the prior art, the invention provides a titanium-based implant, and a preparation method and application thereof. According to the invention, the micro-nano structure processed on the surface of the titanium implant and the added zinc ion coating have good capability of promoting osteogenesis, and zinc ions have good antibacterial effect. Through design, the method can effectively combine the advantages of the micro-nano structure and zinc ions, improve the bone-bonding capability of the 3D printing titanium-based implant, and meanwhile, the zinc oxide can improve the antibacterial effect of the surface, so that the preparation of the osteogenesis and antibacterial double-acting surface is realized. Based on the above results, the present invention has been completed.
Specifically, the technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a method of preparing a titanium-based implant, the method comprising:
performing acid etching treatment on a titanium substrate, performing anodic oxidation treatment, adding zinc acetate solution into the titanium substrate, and performing vacuum heating treatment to construct a micro-nano composite structure and a zinc oxide coating on the surface of the titanium substrate; wherein the titanium matrix is obtained by 3D printing of titanium alloy Ti-6 Al-4V; wherein the concentration of zinc acetate is controlled to be 3-8 mmol.L -1 The vacuum heating treatment condition is that the vacuum heating treatment is carried out for 0.5-2 hours at 360-400 ℃. By controlling the vacuum heating treatment condition, the zinc acetate solution with proper concentration can be decomposed into zinc oxide nano particles with the diameter of about 15nm, and the zinc oxide nano particles are attached to the surface of the titanium-based implant, so that the antibacterial effect of the implant is improved. And the content of zinc element on the surface of the titanium matrix can be quickly adjusted by adjusting the concentration of the zinc acetate solution.
In a second aspect of the present invention, there is provided a titanium-based implant obtained by the above-described production method. The titanium-based implant prepared by the process has a micro-nano structure, the added zinc ion coating has good bone-promoting capability, and the antibacterial effect of zinc ions is achieved together to realize bone and antibacterial double functions.
It should be noted that, based on the above inventive concept, by adding other bioactive substances in the preparation process, the corresponding performance of the implant is improved, which is also within the scope of protection of the present application.
In a third aspect of the invention, there is provided the use of the titanium-based implant described above for the preparation of a bone tissue defect repair material. The bone tissue defect repair material obtained by the preparation method can improve the bone combining capacity and has stronger antibacterial capacity, thereby reducing the adhesion and proliferation of bacteria and improving the implantation success rate.
The beneficial technical effects of one or more of the technical schemes are as follows:
the technical scheme provides a method for constructing a micro-nano composite structure and a zinc oxide coating on the surface of a 3D printing titanium-based implant, and the prepared 3D printing titanium-based implant can be added with the zinc oxide coating on the basis of keeping the original micro-nano structure. Meanwhile, the preparation method of the technical scheme is low in cost, strong in operability and wide in application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute an undue limitation to the application.
FIG. 1 is a flow chart showing the preparation of a titanium-based implant according to example 1 of the present invention;
FIG. 2 is an SEM image of a 3D printed titanium-based implant made in example 1 of the present invention, where A is 5000 and B is 50000;
FIG. 3 is a total EDS elemental surface spectrum of a 3D printed titanium-based implant made in example 1 of the present invention;
fig. 4 is an EDS elemental profile of a 3D printed titanium-based implant made in example 1 of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary 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 in accordance with the present application. 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 one exemplary embodiment of the present invention, there is provided a method of preparing a titanium-based implant, the method comprising:
performing acid etching treatment on a titanium substrate, performing anodic oxidation treatment, adding zinc acetate solution into the titanium substrate, and performing vacuum heating treatment to construct a micro-nano composite structure and a zinc oxide coating on the surface of the titanium substrate; wherein the titanium matrix is obtained by 3D printing of titanium alloy Ti-6 Al-4V; wherein the concentration of zinc acetate is controlled to be 3-8 mmol.L -1 The vacuum heating treatment condition is that the vacuum heating treatment is carried out for 0.5-2 hours at 360-400 ℃. By controlling the vacuum heating treatment condition, the zinc acetate solution with proper concentration can be decomposed into zinc oxide nano particles with the diameter of about 15nm, and the zinc oxide nano particles are uniformly adhered and distributed on the surface of the titanium-based implant, so that the antibacterial effect of the implant is improved. And the content of zinc element on the surface of the titanium matrix can be quickly adjusted by adjusting the concentration of the zinc acetate solution.
In still another embodiment of the present invention, the zinc acetate concentration is controlled to be 5 mmol.L -1 The vacuum heating treatment condition is that vacuum heating treatment is carried out at 370 ℃ for 1 hour. The zinc acetate is preferably added in a dropwise manner. The surface of the titanium matrix formed after acid etching and anodic oxidation has good hydrophilicity, so that zinc acetate solution can be rapidly spread on the surface of the titanium matrix, and then a nanotube array is formed after anodic oxidation in a subsequent high-temperature and vacuum environment, and meanwhile, the nanotubes become good carriers for bearing zinc oxide nano particles, so that the reservation of a micro-nano structure and the construction of a zinc oxide coating are realized.
In a further embodiment of the invention, the acid etch treatment is specifically an acid etch treatment in 1-5% hydrofluoric acid for 1-10 minutes, preferably in 2% hydrofluoric acid for 5 minutes; thereby being used for removing the residual titanium particles on the surface of the titanium matrix.
In yet another embodiment of the present invention, acetone, ethanol and water are sequentially used to clean the titanium substrate prior to the acid etching treatment; to make the cleaning more thorough, the cleaning may be ultrasonic cleaning.
The specific treatment method for the anodic oxidation treatment comprises the following steps: the titanium baseThe body is connected with the positive pole of the regulated power supply, the negative pole is connected with the platinum sheet, and the sample and the platinum electrode are placed in a reactor containing NH 4 F, in glycerol aqueous solution, controlling the electrifying voltage to be 20-30V and the electrifying time to be 0.5-2 hours; the distance between the sample and the platinum electrode is 20-50mm, preferably 40mm.
The NH is 4 F concentration is controlled to be 0.20-0.40M, preferably 0.27M; the volume ratio of glycerol to water in the aqueous glycerol solution is 0.5-5:1, preferably 1:1.
In yet another embodiment of the present invention, there is provided a titanium-based implant obtained by the above-described preparation method. The titanium-based implant prepared by the process has a micro-nano structure, the added zinc ion coating has good bone-promoting capability, and the antibacterial effect of zinc ions is achieved together to realize bone and antibacterial double functions.
In yet another embodiment of the present invention, there is provided the use of the titanium-based implant described above for the preparation of a bone tissue defect repair material. The bone tissue defect repair material obtained by the preparation method can improve the bone combining capacity and has stronger antibacterial capacity, thereby reducing the adhesion and proliferation of bacteria and improving the implantation success rate.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
A preparation method of a titanium-based implant specifically comprises the following steps:
a sample of Ti-6Al-4V was prepared by a 3D printer DMP ProX 320 formed by SLM of 3D Systems, the diameter of the Ti-6Al-4V particles used was 10-53 μm, the laser power was 88W, and the scanning speed was 620 mm.s, according to the manufacturer's instructions -1 The sample size is 10mm x 1mm, after the sample is cut off by a wire cutting device, the sample is respectively ultrasonically cleaned for 15 minutes by using acetone, ethanol and deionized water, then the sample is placed in 2% hydrofluoric acid for acid etching for 5 minutes, and then the sample is connected with the positive electrode of a stabilized voltage power supply, and the negative electrode is connected with the positive electrode of the stabilized voltage power supply with the size of 15mm x 0.The 1mm platinum sheet was attached, the distance between the sample and the platinum electrode was 40mm, and the sample and the platinum electrode were placed in NH at a concentration of 0.27M 4 F, in glycerol aqueous solution (V: V=1:1), the electrifying voltage is 25V, the electrifying time is 1 hour, then the obtained sample is ultrasonically cleaned in deionized water, and a pipetting gun is used for dripping the 5 mmol.L concentration on the surface -1 Placing the sample in a tubular vacuum furnace, heating in vacuum at 370 ℃ for 1 hour, and cooling the sample along with the furnace to obtain the surface of the sample with the micro-nano structure reserved and the zinc oxide nano particles added.
The zinc acetate solution added dropwise can be decomposed into zinc oxide nanoparticles with the diameter of about 15nm through vacuum heating treatment. The principle of zinc acetate pyrolysis is as follows:
wherein, through anodic oxidation, tiO with the diameter of about 80nm is formed on the surface 2 The nanotube array can observe that particles are gathered near the tube, but most of the particles enter the tube, so that the nano-tube can bear nano-particles; and the surface elements of the sample are analyzed by EDS, so that the existence of zinc element can be observed, the zinc element is uniformly attached on the surface, and the related results are shown in figures 2-4.
Example 2
A preparation method of a titanium-based implant specifically comprises the following steps:
a sample of Ti-6Al-4V was prepared by a 3D printer DMP ProX 320 formed by SLM of 3D Systems, the diameter of the Ti-6Al-4V particles used was 10-53 μm, the laser power was 88W, and the scanning speed was 620 mm.s, according to the manufacturer's instructions -1 The size of the sample is 10mm multiplied by 1mm, the sample is cut by a linear cutting device, then the sample is respectively ultrasonically cleaned for 15 minutes by using acetone, ethanol and deionized water, then the sample is placed in 2% hydrofluoric acid for 5 minutes, then the sample is connected with the positive electrode of a stabilized voltage power supply, the negative electrode is connected with a platinum sheet with the size of 15mm multiplied by 0.1mm, and the sampleA distance from the platinum electrode was 40mm, and the sample and the platinum electrode were placed in NH at a concentration of 0.27M 4 F, in glycerol aqueous solution (V: V=1:1), the electrifying voltage is 25V, the electrifying time is 1 hour, then the obtained sample is ultrasonically cleaned in deionized water, and a pipetting gun is used for dripping the concentration of 3 mmol.L on the surface -1 Placing the sample in a tubular vacuum furnace, heating in vacuum at 380 ℃ for 1 hour, and cooling the sample along with the furnace to obtain the surface of the sample which retains the micro-nano structure and is added with zinc oxide nano particles.
Example 3
A preparation method of a titanium-based implant specifically comprises the following steps:
a sample of Ti-6Al-4V was prepared by a 3D printer DMP ProX 320 formed by SLM of 3D Systems, the diameter of the Ti-6Al-4V particles used was 10-53 μm, the laser power was 88W, and the scanning speed was 620 mm.s, according to the manufacturer's instructions -1 The sample size is 10mm x 1mm, the sample is cut by a wire cutting device, then the sample is respectively ultrasonically cleaned for 15 minutes by using acetone, ethanol and deionized water, then the sample is placed in 3% hydrofluoric acid for 5 minutes, then the sample is connected with the positive electrode of a stabilized voltage power supply, the negative electrode is connected with a platinum sheet with the size of 15mm x 0.1mm, the distance between the sample and a platinum electrode is 40mm, and the sample and the platinum electrode are placed in NH with the concentration of 0.25M 4 F, in glycerol aqueous solution (V: V=1:1), the electrifying voltage is 30V, the electrifying time is 0.5 hour, then the obtained sample is ultrasonically cleaned in deionized water, and a pipetting gun is used for dripping the 6 mmol.L concentration on the surface -1 Placing the sample in a tubular vacuum furnace, heating in vacuum at 360 ℃ for 2 hours, and cooling the sample along with the furnace to obtain the surface of the sample which retains the micro-nano structure and is added with zinc oxide nano particles.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited to the above-mentioned embodiments, but may be modified or substituted for some of them 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. While the foregoing describes the embodiments of the present invention, it should be understood that the present invention is not limited to the embodiments, and that various modifications and changes can be made by those skilled in the art without any inventive effort.

Claims (8)

1. A method of preparing a titanium-based implant, the method comprising:
performing acid etching treatment on a titanium substrate, performing anodic oxidation treatment, adding zinc acetate solution into the titanium substrate, and performing vacuum heating treatment to construct a micro-nano composite structure and a zinc oxide coating on the surface of the titanium substrate; wherein the titanium matrix is obtained by 3D printing of titanium alloy Ti-6 Al-4V; wherein the concentration of zinc acetate is controlled to be 3-8 mmol.L -1 The vacuum heating treatment condition is that the vacuum heating treatment is carried out for 0.5 to 2 hours at the temperature of 360 to 400 ℃;
the acid etching treatment is specifically carried out in 1-5% hydrofluoric acid for 1-10 minutes;
the specific treatment method for the anodic oxidation treatment comprises the following steps: connecting the titanium matrix with the positive electrode of a regulated power supply, connecting the negative electrode with a platinum sheet, and placing the sample and the platinum electrode in a reactor containing NH 4 F, controlling the electrifying voltage to be 20-30V and electrifying time to be 0.5-2 hours in glycerol aqueous solution.
2. The preparation method according to claim 1, wherein the zinc acetate concentration is controlled to be 5 mmol.L -1 The vacuum heating treatment condition is that vacuum heating treatment is carried out at 370 ℃ for 1 hour.
3. The preparation method of claim 1, wherein the zinc acetate is added dropwise.
4. The method according to claim 1, wherein the titanium substrate is washed with acetone, ethanol and water in this order before the acid etching treatment; the cleaning is ultrasonic cleaning.
5. The method of claim 1, wherein the distance between the sample and the platinum electrode is 20-50mm.
6. The method of claim 1, wherein the NH is 4 F concentration is controlled to be 0.20-0.40M; the volume ratio of glycerol to water in the glycerol aqueous solution is 0.5-5:1.
7. A titanium-based implant obtainable by the process of any one of claims 1 to 6.
8. Use of the titanium-based implant of claim 7 for the preparation of a bone tissue defect repair material; in the application, the bone tissue defect repair material has stronger bone combining capability and antibacterial capability.
CN202211412160.8A 2022-11-11 2022-11-11 Titanium-based implant, and preparation method and application thereof Active CN115779143B (en)

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CN110152056A (en) * 2019-05-27 2019-08-23 吉林大学 A method of functional ionic is rapidly introduced into titanium alloy surface
CN110354304A (en) * 2019-07-29 2019-10-22 湖州市中心医院 Substrate and its preparation process for prosthese after artificial joint replacement
CN114908314A (en) * 2022-05-16 2022-08-16 浙江飞剑工贸有限公司 Antibacterial coating capable of releasing metal ions in micro-scale and preparation method thereof

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