Antibacterial and corrosion-resistant ultrathin titanium oxide prepared on medical titanium surface and method and application of antibacterial and corrosion-resistant ultrathin titanium oxide
Through physical room temperature discharge method, titanium oxide film with a thickness of 30-50 nanometers is formed on the surface of medical titanium, which solves the problem of capillary blockage caused by excessive antibacterial film thickness in the prior art, and achieves efficient, environmentally friendly and low-cost antibacterial and corrosion resistance.
Patent Information
- Application Number
- CN202411543388.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-31
- Publication Date
- 2025-02-07
AI Technical Summary
In the existing medical titanium surface modification technology, the antibacterial membrane layer is thicker, which can easily lead to the membrane layer falling off and causing capillary blockage.
Using physical room temperature discharge method, air molecules are plasmaized by high-frequency discharge on the surface of medical titanium, combined with electric field, the reactive oxygen molecules undergo low-temperature oxidation reaction with metal surface, forming an antibacterial and corrosion-resistant titanium oxide film with a thickness of about 30-50 nanometers. .
It has achieved the in-situ growth of ultra-thin titanium oxide film on the titanium surface, which has good antibacterial properties and excellent corrosion resistance, avoiding the risk of blood vessel blockage caused by the film layer falling off. At the same time, the process does not use toxic chemical components, which is low in cost and environmentally friendly.
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Abstract
Description
Technical Field
[0001] The invention belongs to the field of medical materials, and specifically relates to an antibacterial and anti-corrosion ultra-thin titanium oxide prepared on the surface of medical titanium, a method and an application thereof. Background Art
[0002] Titanium and titanium alloys are widely used in the biomedical field due to their excellent mechanical properties, corrosion resistance and biocompatibility. As a replacement material for hard tissue in the body, titanium or titanium alloys still have problems such as high recurrence rate of inflammation, reduced mechanical properties caused by long-term corrosion, and subsequent dissolution of slightly toxic metals in the alloy that cause harm to the human body after implantation.
[0003] To solve the above problems, the most commonly used method is to perform surface treatment on titanium and titanium alloys. Common physical modification methods include physical vapor deposition, spraying, 3D printing, etc.; common chemical modification methods mainly include chemical vapor deposition, hydrothermal method, anodizing, etc. The modified film layer prepared by physical methods generally has the problem of weak membrane-base bonding and high preparation cost; while chemical methods are mostly based on the in-situ growth of metals, with good bonding but the film thickness is generally at the micron level. If the film layer falls off, there will be a risk of capillary blockage in the body. Therefore, it is of great biomedical value to prepare an antibacterial, corrosion-resistant, non-toxic ultra-thin in-situ modified film layer on the surface of medical titanium and titanium alloys. Summary of the invention
[0004] The purpose of the present invention is to provide an antibacterial and corrosion-resistant ultra-thin titanium oxide prepared on the surface of medical titanium, as well as a method and application, so as to overcome the shortcomings of existing surface modification technology in the biomedical field. The present invention can in situ grow a layer of 30-50 nanometer thick titanium oxide film on the titanium surface, and the titanium oxide film has excellent antibacterial and corrosion resistance.
[0005] The present invention is achieved through the following technical solutions: A method for preparing antibacterial and anti-corrosion ultrathin titanium oxide on the surface of medical titanium, comprising: Cutting medical titanium into blocks, grinding, polishing, cleaning and drying to obtain samples to be used; In a preset environment, the sample to be used is placed between two parallel silicon oxide electrode plates; Turn on the external high-voltage power supply between the two silicon oxide electrode plates, and control the voltage input between the two silicon oxide electrode plates to be within a preset voltage range; The AC frequency of the external power supply is adjusted to a preset frequency range, the input current is controlled within a preset current range, and after processing for a preset time, antibacterial and corrosion-resistant ultra-thin titanium oxide is prepared on the surface of the medical titanium.
[0006] Furthermore, the medical titanium is medical pure titanium.
[0007] Furthermore, the height of the sample to be used is 0.1-6 mm, and the area of the sample to be used is 0.25-10 cm 2 .
[0008] Furthermore, the temperature of the preset environment is 10-35°C, and the humidity is less than 40%.
[0009] Furthermore, the sample to be used is placed between two parallel silicon oxide electrode plates, and the distance between the electrode plates is adjusted to 0.2-8 mm.
[0010] Furthermore, the preset voltage range is 30-55V.
[0011] Furthermore, the preset frequency range is 8-13 KHz, and the preset current range is 1.5-2.0 A.
[0012] Furthermore, the preset processing time is 10-180 min.
[0013] An antibacterial and anti-corrosion ultra-thin titanium oxide prepared on the surface of medical titanium is prepared by the above method, and the thickness of the antibacterial and anti-corrosion ultra-thin titanium oxide is 30-50 nm.
[0014] The invention discloses an application of antibacterial and corrosion-resistant ultrathin titanium oxide prepared on the surface of medical titanium in preparing a replacement material for hard tissue in a living body.
[0015] Compared with the prior art, the present invention has the following beneficial technical effects: The present invention relates to a surface modification method for medical titanium. In view of the problem that the thickness of the traditional antibacterial film layer is relatively thick (at the micron level), and the capillary blockage is easily caused when the film layer falls off, the present invention adopts a physical room temperature discharge method, and the air molecules are plasmatized by high-frequency discharge, and the electric field formed between the metal surface and the electrode prompts these charged plasmas (mainly active oxygen molecules) to react with the metal surface at a low temperature, and the metal surface is uniformly oxidized into titanium oxide with a thickness of about 30-50 nanometers. The low-temperature oxidation process involving this electric field makes the film layer grow to a thickness of only tens of nanometers, and its performance is also different from the titanium oxide film prepared by the conventional method. The experimental results show that the film shows good antibacterial and excellent corrosion resistance. The method has a stable effect, and the entire process does not use any toxic and harmful chemical components. It is a method that is efficient, environmentally friendly, low-cost and different from the traditional metal antibacterial surface technology. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1The surface roughness of medical pure titanium changes with the antibacterial treatment time, where a is untreated, b is treated for 10 min, c is treated for 60 min, d is treated for 180 min, and e is the statistical result of the surface morphology changes of the above samples; Figure 2 Low-magnification and high-resolution transmission electron micrographs (HRTEM) of the surface film cross-section of the sample treated for 60 min; Figure 3a This is the full XPS spectrum of pure titanium surface before and after treatment; Figure 3b XPS fine spectra of Ti 2p on pure titanium surface before and after treatment; Figure 4 The absorbance at 600 nm after Staphylococcus aureus was incubated with samples treated with antimicrobial agents for different periods of time for 24 h; Figure 5 The antibacterial effect of the sample surface on different concentrations of bacterial solution increases with the antibacterial treatment time. a is the dilution of the adherent bacterial solution 100 times; b is the dilution of the adherent bacterial solution 1000 times; Figure 6 This is the electrochemical polarization behavior of medical pure titanium in simulated body fluids after different treatment times. DETAILED DESCRIPTION
[0017] The present invention is further described in detail below, which is intended to explain the present invention rather than to limit it.
[0018] A method for preparing antibacterial and anti-corrosion ultra-thin titanium oxide on the surface of medical titanium, wherein medical pure titanium is cut into blocks, sanded and polished, cleaned with acetone and alcohol in sequence, and dried for standby use, wherein the standby sample has a height of 0.1-6 mm and an area of 0.25-10 cm 2 , the thickness of a single specimen to be used is uniform.
[0019] The ambient temperature is adjusted to 10-35°C and the humidity is less than 40%, and the above-mentioned sample to be used is placed between two parallel silicon oxide electrode plates, and the distance between the electrode plates is adjusted to 0.2-8 mm.
[0020] Turn on the high voltage power supply and control the voltage across the input plate to between 30-55 V.
[0021] The frequency of the AC power supply is adjusted to 8-13 KHz, the input current is controlled to 1.5-2.0 A, and the processing time is 10-180 minutes to prepare antibacterial and corrosion-resistant ultra-thin titanium oxide on the surface of medical titanium.
[0022] The antibacterial and anti-corrosion ultra-thin titanium oxide prepared by the invention has a thickness of 30-50 nm.
[0023] The antibacterial and anti-corrosion ultra-thin titanium oxide prepared by the invention is used in preparing a replacement material for hard tissue in a living body.
[0024] The present invention relates to a surface modification method for medical titanium. In view of the problem that the thickness of the traditional antibacterial film layer is relatively thick (at the micron level), and the capillary blockage is easily caused when the film layer falls off, the present invention adopts a physical room temperature discharge method to uniformly oxidize the metal surface into titanium oxide with a thickness of about 30-50 nanometers, thereby obtaining good antibacterial properties and excellent corrosion resistance. The method has a stable effect, and the entire process does not use any toxic or harmful chemical components. It is an efficient, environmentally friendly, low-cost method that is different from traditional metal antibacterial surface technology.
[0025] The embodiments of the present invention will be described in detail below in conjunction with the examples. The implementation cases are preferred embodiments of the present invention and should not be used to limit the scope of the present invention. In the following examples, the methods and experimental equipment used are all conventional methods and instruments unless otherwise specified.
[0026] Example 1 A method for preparing antibacterial and anti-corrosion ultrathin titanium oxide on the surface of medical titanium, wherein the medical pure titanium is cut into blocks, sanded and polished, cleaned with acetone and alcohol in sequence, and dried for standby use, wherein the standby sample has a height of 0.1 mm and an area of 0.25 cm 2 , the thickness of a single specimen to be used is uniform.
[0027] The ambient temperature was adjusted to 10°C and the humidity was less than 40%, and the sample to be used was placed between two parallel silicon oxide electrode plates, and the distance between the electrode plates was adjusted to 0.2 mm.
[0028] Turn on the high voltage power supply and control the voltage across the input plate to 30 V.
[0029] The frequency of the AC power supply was adjusted to 8 kHz, the input current was controlled at 1.5 A, and the processing time was 10 min. An antibacterial and corrosion-resistant ultrathin titanium oxide with a thickness of 30 nm was prepared on the surface of medical titanium.
[0030] Example 2 A method for preparing antibacterial and anti-corrosion ultra-thin titanium oxide on the surface of medical titanium, wherein the medical pure titanium is cut into blocks, sanded and polished, cleaned with acetone and alcohol in sequence, and dried for standby use. The standby sample has a height of 6 mm and an area of 10 cm 2 , the thickness of a single specimen to be used is uniform.
[0031] The ambient temperature was adjusted to 35°C and the humidity was less than 40%. The sample to be used was placed between two parallel silicon oxide electrode plates, and the distance between the electrode plates was adjusted to 8 mm.
[0032] Turn on the high voltage power supply and control the voltage across the input plate to 55 V.
[0033] The frequency of the AC power supply was adjusted to 13 KHz, the input current was controlled at 2.0 A, and the processing time was 180 min. An antibacterial and corrosion-resistant ultrathin titanium oxide with a thickness of 50 nm was prepared on the surface of medical titanium.
[0034] Example 3 A method for preparing antibacterial and anti-corrosion ultra-thin titanium oxide on the surface of medical titanium, wherein the medical pure titanium is cut into blocks, sanded and polished, cleaned with acetone and alcohol in sequence, and dried for standby use. The standby sample has a height of 3 mm and an area of 7 cm 2 , the thickness of a single specimen to be used is uniform.
[0035] The ambient temperature was adjusted to 25°C and the humidity was less than 40%, and the sample to be used was placed between two parallel silicon oxide electrode plates, and the distance between the electrode plates was adjusted to 4 mm.
[0036] Turn on the high voltage power supply and control the voltage across the input plate to 40 V.
[0037] The frequency of the AC power supply was adjusted to 10 kHz, the input current was controlled at 1.8 A, and the processing time was 60 min. An antibacterial and corrosion-resistant ultrathin titanium oxide with a thickness of 40 nm was prepared on the surface of medical titanium.
[0038] Compared with the currently reported methods for the antibacterial properties of medical titanium surfaces, the titanium oxide film layer grown in situ on the titanium and titanium alloy surfaces by this method has the characteristics of ultra-thin thickness (30-50 nm), uniform film thickness, stable composition and performance, and simple preparation process. First, as the treatment time increases, the titanium oxide film layer grows on the titanium surface, but the increase in treatment time does not increase the roughness of the metal surface, as shown below Figure 1 As shown in Figure 2, atomic force microscopy (AFM) shows that within the range of 10*10µm, when the average surface roughness of pure titanium metal is about 7 nm, as the processing time increases, it remains within the range of 7±1nm, and the average surface roughness does not fluctuate greatly. This shows that this method can obtain a uniform nanoscale growth rate within a large sample area and is not affected by the processing time. Figure 2 The transmission electron spectroscopy (TEM) microscopic morphology of the film cross section after treatment for 60 min (Example 3) shows that the film thickness is uniform within a range of at least 500 nm, which is consistent with the above Figure 1The results are consistent. High-resolution microscopy (HRTEM) shows that the thickness of the film is about 40nm. The titanium oxide film is mainly amorphous, and a small amount of nanocrystalline titanium oxide is formed on the outer layer. This result shows that for human capillaries with a diameter of about 5 microns, the thin film obtained by this method will not cause blood vessel blockage even if it falls off. The surface composition of the treated medical pure titanium was analyzed by X-ray photoelectron spectroscopy (XPS), such as Figure 3a and Figure 3b The XPS spectrum results show that no other elements are introduced on the surface of the sample after any treatment time, which ensures the safety of this method in the surface modification of medical pure titanium. By further analyzing the Ti2p fine spectrum, it is found that Ti 0 The peak position disappears, and the peak position of titanium is similar to that of Ti 4+ consistent, indicating that the metal surface is oxidized to Ti 4+ , so the titanium oxide obtained after antibacterial treatment is non-toxic.
[0039] Taking Staphylococcus aureus as an example, the absorbance at 600 nm (OD600 value) of the test sample after incubation with bacteria for 24 hours is as follows: Figure 4 As shown. Compared with untreated medical pure titanium, the number of Staphylococcus aureus on the sample surface decreased by 31% and 56% after 10 min and 60 min treatment, respectively. However, when the treatment time reached 180 min, the number of bacteria increased. This result shows that the optimal treatment time for the antibacterial property of the film layer is about 60 min. Figure 5 The figure shows the change of colony count with treatment time when the bacterial solution concentration was diluted to 100 times and 1000 times. The colony count at both concentrations was the lowest when the treatment time reached 60 min, indicating good antibacterial activity. Figure 6 To evaluate the corrosion resistance of medical pure titanium in simulated body fluids, with the increase of treatment time, the corrosion current density rapidly decreased by two orders of magnitude, and the passivation potential increased significantly, indicating that the sample's resistance to uniform corrosion and pitting corrosion has been significantly improved.
[0040] Although the present invention has been disclosed as above in the form of a preferred embodiment, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.
Claims
1. A method for preparing antibacterial and anti-corrosion ultra-thin titanium oxide on the surface of medical titanium, characterized in that: include: Cutting medical titanium into blocks, grinding, polishing, cleaning and drying to obtain samples to be used; In a preset environment, the sample to be used is placed between two parallel silicon oxide electrode plates; Turn on the external high-voltage power supply between the two silicon oxide electrode plates, and control the voltage input between the two silicon oxide electrode plates to be within a preset voltage range; The AC frequency of the external power supply is adjusted to a preset frequency range, the input current is controlled within a preset current range, and after processing for a preset time, antibacterial and corrosion-resistant ultra-thin titanium oxide is prepared on the surface of the medical titanium.
2. The method for preparing antibacterial and anticorrosive ultrathin titanium oxide on the surface of medical titanium according to claim 1, characterized in that: The medical titanium is medical pure titanium.
3. The method for preparing antibacterial and anticorrosive ultrathin titanium oxide on the surface of medical titanium according to claim 1, characterized in that: The height of the sample to be used is 0.1-6 mm, and the area of the sample to be used is 0.25-10 cm 2 .
4. The method for preparing antibacterial and anticorrosive ultrathin titanium oxide on the surface of medical titanium according to claim 1, characterized in that: The temperature of the preset environment is 10-35°C, and the humidity is less than 40%.
5. The method for preparing antibacterial and anticorrosive ultrathin titanium oxide on the surface of medical titanium according to claim 1, characterized in that: The sample to be used is placed between two parallel silicon oxide electrode plates, and the distance between the electrode plates is adjusted to 0.2-8 mm.
6. The method for preparing antibacterial and anticorrosive ultrathin titanium oxide on the surface of medical titanium according to claim 1, characterized in that: The preset voltage range is 30-55 V.
7. The method for preparing antibacterial and anticorrosive ultrathin titanium oxide on the surface of medical titanium according to claim 1, characterized in that: The preset frequency range is 8-13 KHz, and the preset current range is 1.5-2.0 A.
8. The method for preparing antibacterial and anticorrosive ultrathin titanium oxide on the surface of medical titanium according to claim 1, characterized in that: The preset processing time is 10-180 min.
9. An antibacterial and anti-corrosion ultra-thin titanium oxide prepared on the surface of medical titanium, prepared by the method according to any one of claims 1 to 8, characterized in that: The thickness of the antibacterial and anti-corrosion ultra-thin titanium oxide is 30-50 nm.
10. Use of the antibacterial and anti-corrosion ultra-thin titanium oxide prepared on the surface of medical titanium as claimed in claim 9 in preparing a replacement material for hard tissue in a living body.