CN115779143A - 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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CN115779143A
CN115779143A CN202211412160.8A CN202211412160A CN115779143A CN 115779143 A CN115779143 A CN 115779143A CN 202211412160 A CN202211412160 A CN 202211412160A CN 115779143 A CN115779143 A CN 115779143A
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titanium
treatment
preparation
zinc
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CN115779143B (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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Abstract

The invention provides a titanium-based implant and a preparation method and application thereof, belonging to the technical field of medical material manufacture. The preparation method comprises the following steps: carrying out acid etching treatment on the titanium substrate, carrying out anodic oxidation treatment, adding a zinc acetate solution, and then carrying out vacuum heating treatment, thereby constructing a micro-nano composite structure and a zinc oxide coating on the surface of the titanium substrate. According to the invention, researches show that 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 the zinc ions have a good antibacterial effect. Through design, the method provided by the invention can effectively combine the advantages of a micro-nano structure and zinc ions, improve the bone combining 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 double-acting surface of osteogenesis and antibacterial is realized, and the method has a 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 information in this background section is only for enhancement of 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 that is already known to a person of ordinary skill in the art.
At present, the bone tissue defect problem that the frequent emergence of population ageing and traffic accident caused needs to be solved urgently, simultaneously, there is the difference between different patient individuals, is difficult to carry out the mass production of titanium implant. 3D printing is being gradually applied in clinics as a flexible processing means. Among the numerous implant materials, titanium and its alloys have been widely used for the treatment of bone defects due to their good combination of properties.
However, the 3D printed titanium implant has a limited ability to bond with the surrounding bone tissue, and is prone to loosening after being implanted in vivo. Meanwhile, in the implantation process, the problems of bacterial infection and the like are easily caused, once the infection occurs, a patient needs to be treated by taking medicines and the like, and even needs to be implanted again in serious cases, so that great physiological and psychological pains are brought to the patient. Therefore, the surface of the implant needs to have a certain antibacterial ability to reduce the adhesion and proliferation of bacteria, thereby improving the success rate of implantation.
Disclosure of Invention
Based on the defects of the prior art, the invention provides a titanium-based implant and a preparation method and application thereof. According to the invention, researches show that 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 the zinc ions have a good antibacterial effect. Through design, the method provided by the invention can effectively combine the advantages of a micro-nano structure and zinc ions, improve the bone combining capability of the 3D printing titanium-based implant, and meanwhile, the zinc oxide can improve the antibacterial effect of the surface, thereby realizing the preparation of the double-acting surface of osteogenesis and antibacterial. The present invention has been completed based on the above results.
Specifically, the technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a method for preparing a titanium-based implant, the method comprising:
carrying out acid etching treatment on the titanium substrate, carrying out anodic oxidation treatment, adding a zinc acetate solution, and then carrying out vacuum heating treatment, thereby constructing a micro-nano composite structure and a zinc oxide coating on the surface of the titanium substrate; wherein the titanium substrate is obtained by 3D printing of titanium alloy Ti-6 Al-4V; wherein the concentration of zinc acetate is controlled to 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 between 360 and 400 ℃. By controlling the vacuum heating treatment conditions, the added 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 substrate can be rapidly 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-mentioned preparation method. Through the process treatment, the titanium-based implant prepared by the invention has a micro-nano structure, and the added zinc ion coating also has good osteogenesis promoting capability, and the zinc ion has an antibacterial effect, so that osteogenesis and antibacterial double effects are realized together.
It should be noted that, based on the above inventive concept, by adding other bioactive substances and the like in the preparation process, the corresponding performance of the implant is improved, and the protection scope of the present application is also included.
In a third aspect of the invention, the titanium-based implant is used for preparing a bone tissue defect repair material. The bone tissue defect repairing material obtained by the preparation method can improve the bone combination capability and has stronger antibacterial capability, thereby reducing the adhesion and proliferation of bacteria and improving the success rate of implantation.
The beneficial technical effects of one or more 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 has the advantages of low cost, strong operability and wide application prospect.
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The accompanying drawings, which 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 are not intended to limit the application.
FIG. 1 is a flow chart illustrating the preparation of a titanium-based implant according to example 1 of the present invention;
FIG. 2 is an SEM photograph of a 3D printed titanium-based implant made in example 1 of the present invention, wherein A is 5000 and B is 50000;
FIG. 3 is an EDS elemental surface total spectrum of a 3D printed titanium-based implant made in example 1 of the present invention;
FIG. 4 is a EDS elemental area distribution plot 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 example embodiments in accordance with the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In an exemplary embodiment of the present invention, there is provided a method for preparing a titanium-based implant, the method comprising:
carrying out acid etching treatment on the titanium substrate, carrying out anodic oxidation treatment, adding a zinc acetate solution, and then carrying out vacuum heating treatment, thereby constructing a micro-nano composite structure and a zinc oxide coating on the surface of the titanium substrate; wherein the titanium substrate is obtained by 3D printing of titanium alloy Ti-6 Al-4V; wherein the concentration of zinc acetate is controlled to 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 between 360 and 400 ℃. By controlling the vacuum heating treatment conditions, the added 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 attached to 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 substrate can be rapidly adjusted by adjusting the concentration of the zinc acetate solution.
In still another embodiment of the present invention, the concentration of zinc acetate is controlled to 5 mmol.L -1 The vacuum heat treatment condition is that the vacuum heat treatment is carried out for 1 hour at 370 ℃. The zinc acetate is preferably added dropwise. The titanium substrate surface formed after acid etching and anodic oxidation has good hydrophilicity, so that the zinc acetate solution can be rapidly developed on the surface and then is formed on the surfaceIn subsequent high-temperature and vacuum environments, simultaneously, the nanotube array is formed after anodic oxidation, and the nanotubes become good carriers for bearing zinc oxide nanoparticles, so that retention of a micro-nano structure and construction of a zinc oxide coating are realized.
In another embodiment of the present invention, the acid etching treatment is specifically an acid etching treatment in 1-5% hydrofluoric acid for 1-10 minutes, preferably an acid etching treatment in 2% hydrofluoric acid for 5 minutes; thereby removing residual titanium particles on the surface of the titanium substrate.
In another embodiment of the present invention, before the acid etching treatment, the titanium substrate is washed with acetone, ethanol and water in sequence; to make the cleaning more thorough, the cleaning may be ultrasonic cleaning.
The specific treatment method of the anodic oxidation treatment comprises the following steps: connecting the titanium substrate with the anode of a regulated power supply, connecting the cathode with a platinum sheet, and placing the sample and the platinum electrode in a container containing NH 4 Controlling the electrifying voltage to be 20-30V and the electrifying time to be 0.5-2 hours in the glycerol aqueous solution of F; the distance between the sample and the platinum electrode is 20-50mm, preferably 40mm.
The NH 4 The concentration of F is controlled to be 0.20-0.40M, preferably 0.27M; the volume ratio of glycerol to water in the glycerol aqueous solution is 0.5-5, preferably 1.
In another embodiment of the present invention, there is provided a titanium-based implant obtained by the above-mentioned preparation method. Through the process treatment, the titanium-based implant prepared by the invention has a micro-nano structure, and the added zinc ion coating also has good osteogenesis promoting capability, and the zinc ion has an antibacterial effect, so that osteogenesis and antibacterial double effects are realized together.
In another embodiment of the present invention, there is provided a use of the titanium-based implant as described above in the preparation of a bone tissue defect repair material. The bone tissue defect repairing material obtained by the preparation method can improve the bone combination capability and has stronger antibacterial capability, thereby reducing the adhesion and proliferation of bacteria and improving the success rate of implantation.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto. It should be understood that these examples are for illustrative purposes only 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:
ti-6Al-4V samples were prepared by SLM-molded 3D Printer DMP ProX 320 from 3D Systems, USA, using Ti-6Al-4V particles with a diameter of 10-53 μm, a laser power of 88W, and a scanning speed of 620mm · s, according to the manufacturer's instructions -1 Cutting a sample with the size of 10mm multiplied by 1mm by a linear cutting device, respectively ultrasonically cleaning the sample by using acetone, ethanol and deionized water for 15 minutes, then placing the sample in 2 percent hydrofluoric acid for acid etching for 5 minutes, then connecting the sample with a positive electrode of a regulated power supply, connecting a negative electrode with a platinum sheet with the size of 15mm multiplied by 0.1mm, wherein the distance between the sample and a platinum electrode is 40mm, and placing the sample and the platinum electrode in NH with the concentration of 0.27M 4 F (V: V = 1) was applied to an aqueous glycerol solution at an energization voltage of 25V for 1 hour, and then the obtained sample was ultrasonically cleaned in deionized water, and then the surface thereof was dropped with a pipette at a concentration of 5mmol · L using a pipette gun -1 And (3) putting the sample into a tubular vacuum furnace, heating the sample at 370 ℃ for 1 hour in vacuum, and cooling the sample along with the furnace to obtain the sample surface which retains the micro-nano structure and is added with the zinc oxide nano particles.
After vacuum heating treatment, the dropwise added zinc acetate solution can be decomposed into zinc oxide nanoparticles with the diameter of about 15 nm. The pyrolysis principle of zinc acetate is as follows:
Figure BDA0003939115040000061
wherein TiO with the diameter of about 80nm is formed on the surface by anodic oxidation 2 The nanotube array can observe that particles are gathered near the tube, but most of the particles enter the tube, so that the nanotube carries the nanoparticles; and the surface elements of the sample are analyzed through EDS (electronic discharge spectroscopy), so that the sample can be observedThe presence of zinc was observed and uniform adhesion of zinc on the surface was achieved, the relevant results are shown in fig. 2-4.
Example 2
A preparation method of a titanium-based implant specifically comprises the following steps:
ti-6Al-4V samples were prepared by an SLM-molded 3D printer DMP ProX 320 from 3D Systems, USA, using Ti-6Al-4V particles with a diameter of 10-53 μm, a laser power of 88W, and a scanning speed of 620mm s, according to the manufacturer's instructions -1 Cutting a sample with the size of 10mm multiplied by 1mm by a linear cutting device, respectively ultrasonically cleaning the sample by using acetone, ethanol and deionized water for 15 minutes, then placing the sample in 2 percent hydrofluoric acid for acid etching for 5 minutes, then connecting the sample with a positive electrode of a regulated power supply, connecting a negative electrode with a platinum sheet with the size of 15mm multiplied by 0.1mm, wherein the distance between the sample and a platinum electrode is 40mm, and placing the sample and the platinum electrode in NH with the concentration of 0.27M 4 In an aqueous glycerol solution (V: V = 1) of F, the energization voltage was 25V, the energization time was 1 hour, and then the obtained sample was ultrasonically cleaned in deionized water, and then a pipette was used to drop the sample onto the surface at a concentration of 3mmol · L -1 And (3) putting the sample into a tubular vacuum furnace, heating the sample at 380 ℃ for 1 hour in vacuum, and cooling the sample along with the furnace to obtain the sample surface with the micro-nano structure and the added zinc oxide nano particles.
Example 3
A preparation method of a titanium-based implant specifically comprises the following steps:
ti-6Al-4V samples were prepared by an SLM-molded 3D printer DMP ProX 320 from 3D Systems, USA, using Ti-6Al-4V particles with a diameter of 10-53 μm, a laser power of 88W, and a scanning speed of 620mm s, according to the manufacturer's instructions -1 Cutting a sample with the size of 10mm multiplied by 1mm by a linear cutting device, respectively ultrasonically cleaning the sample by using acetone, ethanol and deionized water for 15 minutes, then placing the sample in 3% hydrofluoric acid for acid etching for 5 minutes, then connecting the sample with a positive electrode of a regulated power supply, connecting a negative electrode with a platinum sheet with the size of 15mm multiplied by 0.1mm, and connecting the sample with a platinum electrodeThe distance between them was 40mm, and the sample and the platinum electrode were placed in NH at a concentration of 0.25M 4 In an aqueous glycerol solution (V: V = 1) of F, an energization voltage was 30V and an energization time was 0.5 hour, and then, after the obtained sample was ultrasonically cleaned in deionized water, a liquid transfer gun was used to drop a solution having a concentration of 6mmol · L onto the surface -1 And (3) putting the sample into a tubular vacuum furnace, heating the sample in vacuum at 360 ℃ for 2 hours, and cooling the sample along with the furnace to obtain the sample surface which retains the micro-nano structure and is added with the zinc oxide nano particles.
Finally, it should be noted that, although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing embodiments, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (10)

1. A method of making a titanium-based implant, the method comprising:
carrying out acid etching treatment on the titanium substrate, carrying out anodic oxidation treatment, adding a zinc acetate solution, and then carrying out vacuum heating treatment, thereby constructing a micro-nano composite structure and a zinc oxide coating on the surface of the titanium substrate; wherein the titanium substrate is obtained by 3D printing of titanium alloy Ti-6 Al-4V; wherein the concentration of zinc acetate is controlled to 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 between 360 and 400 ℃.
2. As claimed in claimThe process according to claim 1, wherein the concentration of zinc acetate is controlled to be 5 mmol.L -1 The vacuum heat treatment conditions are that vacuum heat treatment is carried out for 1 hour at 370 ℃.
3. The method of claim 1, wherein the zinc acetate is added dropwise.
4. The method according to claim 1, wherein the acid etching is performed in 1 to 5% hydrofluoric acid for 1 to 10 minutes.
5. The method of claim 1, wherein the titanium substrate is washed with acetone, ethanol, and water in sequence before the acid etching treatment; the cleaning is ultrasonic cleaning.
6. The method according to claim 1, wherein the specific treatment method of the anodic oxidation treatment comprises: connecting the titanium substrate with the anode of a regulated power supply, connecting the cathode with a platinum sheet, and placing the sample and the platinum electrode in a container containing NH 4 And F, in the glycerol aqueous solution, controlling the electrifying voltage to be 20-30V and the electrifying time to be 0.5-2 hours.
7. The method of claim 6, wherein the distance between the sample and the platinum electrode is 20 to 50mm.
8. The method of claim 6, wherein the NH is 4 The concentration of F is controlled to be 0.20-0.40M; the volume ratio of the glycerol to the water in the glycerol aqueous solution is 0.5-5.
9. Titanium-based implant obtainable by the method of preparation according to any one of claims 1 to 8.
10. Use of a titanium-based implant according to claim 9 for the preparation of a bone tissue defect repair material; in the application, the bone tissue defect repair material has stronger bone combination capability and antibacterial capability.
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Citations (5)

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Publication number Priority date Publication date Assignee Title
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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
US20210361786A1 (en) * 2018-05-14 2021-11-25 China Morefound Technology Ltd., Shenzhen Material with supercapacitance modified surface and preparation method and application thereof
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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Publication number Priority date Publication date Assignee Title
US20210361786A1 (en) * 2018-05-14 2021-11-25 China Morefound Technology Ltd., Shenzhen Material with supercapacitance modified surface and preparation method and application thereof
CN109234735A (en) * 2018-11-13 2019-01-18 山东大学 A kind of EBM molding titanium implants and its preparation method and application
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

Non-Patent Citations (1)

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Title
赵梓贺: "基于激光加工的Ti-6Al-4V微纳复合表面制备及其成骨抗菌性能研究", 万方学位论文库, pages 46 - 50 *

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