CN111020669A

CN111020669A - Medical S-TiO on titanium metal surface2-xMethod for producing thin film

Info

Publication number: CN111020669A
Application number: CN201911238653.2A
Authority: CN
Inventors: 吴水林; 苏昆; 刘想梅
Original assignee: Hubei University
Current assignee: Hubei University
Priority date: 2019-12-06
Filing date: 2019-12-06
Publication date: 2020-04-17
Anticipated expiration: 2039-12-06
Also published as: CN111020669B

Abstract

The invention discloses medical S-TiO on the surface of titanium metal_2‑xThe preparation method of the film comprises the following steps: cleaning and drying a medical titanium metal substrate for later use; placing the porcelain boat respectively filled with sulfur powder and substrate in a tube furnace, vacuumizing, introducing argon, heating for reaction, and naturally cooling to obtain S-TiO_2‑xA film. The preparation method is simple and easy to implement, low in cost, good in repeatability and easy to popularize, the prepared film grows in situ on the surface of the medical titanium metal, the film has extremely high binding force and good stability, has good photoacoustic response capability, high sterilization rate and excellent biocompatibility, and has great application potential in the aspect of surface modification of medical implants.

Description

Medical S-TiO on titanium metal surface2-xMethod for producing thin film

Technical Field

The invention belongs to the technical field of surface modification of metal materials, and particularly relates to a photoacoustic response energy S-TiO with oxygen defects, which is grown in situ on the surface of medical titanium metal by doping sulfur_2-xA method for preparing a film.

Background

Among medical metal materials, titanium metal has excellent properties of good mechanical property, strong corrosion resistance, good biocompatibility, elastic modulus close to human skeleton and the like, is an implant material commonly used in orthopedics at present, and is widely applied to a load part in internal fixation surgery of orthopedics in particular. However, titanium itself has no antibacterial ability, and is easily infected with bacteria when implanted into a human body in clinical use, thereby causing implant failure. In addition, titanium, as a bio-inert metal, has the problems of poor bioactivity, poor osseointegration of the implant, long healing time and the like when being implanted into a human body.

At present, recurrence of implant infection is still common. To address the problem of implant infection, clinical treatment of patients still relies on systemic antibiotics. However, abuse of antibiotics has led to the worldwide spread of multidrug resistant (MDR) bacteria. Therefore, many researchers have focused on the use of antimicrobial coatings on implant surfaces that can actively kill bacteria or passively prevent bacterial attachment. The antimicrobial coating may inhibit bacterial infection by releasing an antimicrobial agent (e.g., an antibiotic, Ag ions, Cu ions, chlorhexidine, or an antimicrobial peptide). Implant coatings with photodynamic and photothermal antimicrobial properties have been reported to require the incorporation of organic photosensitizers, semiconductors or photothermal agents in the implant coating to generate Reactive Oxygen Species (ROS) or heat, as has been the design of photosensitive nanoparticles in photodynamic and photothermal tumor therapy. However, the potential toxicity of the antimicrobial agent is not negligible and over time the antimicrobial ability of the coating will gradually fail, also at risk of flaking. To avoid the introduction of an external coating, the Ti-doped heavy metal element matrix alloy may also impart self-antimicrobial properties to the implant, for example, Ti-Cu or Ti-Ag alloys have been prepared without an external coating to achieve antimicrobial properties. However, the long-term uncontrolled release of heavy metal ions may be potentially toxic to the patient and even inhibit osteointegration.

Disclosure of Invention

In order to solve the problems, the invention provides S-doped S-TiO on the surface of medical titanium metal_2-xA method for preparing a film. The non-metal element is doped for the first time, and the photoacoustic response capability film with oxygen defect in-situ growth is prepared on the surface of medical titanium metal, has good acoustic catalysis photothermal performance, excellent antibacterial capability andexcellent osseointegration effect.

In order to achieve the purpose, the technical scheme provided by the invention is as follows:

step one, pretreating a medical titanium metal substrate

Ultrasonically cleaning a substrate by using acetone, ethanol and deionized water in sequence, drying the substrate in vacuum at room temperature, and placing the substrate in a porcelain boat for later use;

step two, preparing the film

Uniformly placing a proper amount of sulfur powder in a porcelain boat, then respectively placing the porcelain boats filled with the sulfur powder and a substrate in a reaction furnace, vacuumizing the furnace, filling argon to replace the air in the furnace, introducing high-purity argon into the furnace, heating the sulfur powder to 200-250 ℃, heating the substrate to 700-800 ℃, preserving heat, reacting for 1-2 h, and cooling to obtain S-TiO_2-xA film.

Further, in the first step, the surface of the medical titanium metal is subjected to micro-arc oxidation treatment.

Furthermore, in the second step, the porcelain boat for loading samples is made of corundum materials, and a corundum cover is not used in the preparation process.

Further, in the second step, the reaction furnace is a dual-temperature-zone atmosphere furnace, and the heating rate is 1-20 ℃/min.

According to the preferable scheme of the invention, the sulfur powder is heated to 230 ℃, the substrate is heated to 750 ℃, and the reaction time is kept at 1 h.

Further, in the second step, the argon is filled from the low-temperature area to the high-temperature area in the filling direction, and the filling rate is 20-40 cm³/min。

S-doped S-TiO prepared by adopting method_2-xCompared with the prior art, the film has the following beneficial effects:

1. the method adopts a simple chemical vapor deposition method, takes sublimed sulfur powder as a raw material, and grows a layer of film on the surface of the medical titanium metal in situ, so the method has the advantages of simple operation, good repeatability and low cost, and can be used for batch production;

2. the invention dopes sulfur powder to the surface of a pure titanium substrate through the processes of high-temperature sublimation and low-temperature deposition, and simultaneously, TiO on the surface of the substrate₂The crystal form is transformed to be rawForming a crystal structure with oxygen defects, thereby enhancing the acoustic catalysis photo-thermal property of the medical titanium metal;

3. s-doped S-TiO prepared by the invention_2-xThe film has excellent photo-thermal performance under near-infrared irradiation, can generate active oxygen (hydroxyl free radical and singlet oxygen) under the action of ultrasonic waves, has excellent bactericidal performance (the bactericidal rate is as high as 99.99%), and biological experiments show that the film has good cell compatibility and osteogenic performance, and is beneficial to the proliferation and differentiation of osteoblasts.

Drawings

FIG. 1 is a graph showing the comparison of the appearance of untreated titanium nails and treated titanium nails in example 1;

FIG. 2 shows S-TiO in example 1_2-xSurface topography of the film (5 microns on the high power scale and 1 micron on the low power scale);

FIG. 3 shows S-TiO in example 1_2-xA cross-sectional profile of the film;

FIG. 4 shows S-TiO in example 1_2-xAn X-ray photoelectron spectrum of the film;

FIG. 5 shows S-TiO in example 1_2-xUV-vis-NIR diffuse reflectance spectra of the films;

FIG. 6 shows S-TiO in example 1_2-xElectron paramagnetic resonance (ESR) map of the film;

FIG. 7 shows S-TiO in example 1_2-xCoating pattern and antibacterial rate of the antibacterial flat plate of the film;

FIG. 8 shows S-TiO in example 1_2-xAnd (3) detecting the cytocompatibility of the osteoblasts of the film.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments.

Example 1

And sequentially placing the micro-arc oxidized medical titanium nail into acetone, ethanol and deionized water for ultrasonic cleaning for 15min, performing vacuum drying at room temperature for later use, uniformly spreading 1.5g of sublimed sulfur powder into one porcelain boat, and simultaneously placing the prepared medical titanium nail on another porcelain boat. Will be divided intoPlacing the porcelain boat containing sublimed sulfur powder and titanium nails into a double-temperature-zone tube furnace, vacuumizing to 10Pa, introducing high-purity argon gas for gas washing, and repeating for 3 times with argon gas flow of 20cm³Min, heating the sulfur powder to 230 ℃ at the speed of 6 ℃/min, heating the medical titanium nail to 750 ℃ at the speed of 20 ℃/min, preserving the heat for 1h, naturally cooling to room temperature in a high-temperature tubular atmosphere furnace, taking out a sample, ultrasonically cleaning by using deionized water, and drying at room temperature to obtain S-TiO_2-xA film.

Example 2

And sequentially placing the micro-arc oxidized medical titanium nail into acetone, ethanol and deionized water for ultrasonic cleaning for 15min, performing vacuum drying at room temperature for later use, uniformly spreading 1.5g of sublimed sulfur powder into one porcelain boat, and simultaneously placing the prepared medical titanium nail on another porcelain boat. Placing the porcelain boat respectively filled with sublimed sulfur powder and titanium nails into a two-temperature-zone tube furnace, vacuumizing to 10Pa, introducing high-purity argon gas for gas washing treatment, repeating for 3 times, wherein the argon gas flow is 30cm³Min, heating the sulfur powder to 220 ℃ at the speed of 6 ℃/min, heating the medical titanium nail to 750 ℃ at the speed of 20 ℃/min, preserving the heat for 1h, naturally cooling to room temperature in a high-temperature tubular atmosphere furnace, taking out a sample, ultrasonically cleaning by using deionized water, and drying at room temperature to obtain S-TiO_2-xA film.

Example 3

And sequentially placing the micro-arc oxidized medical titanium nail into acetone, ethanol and deionized water for ultrasonic cleaning for 15min, performing vacuum drying at room temperature for later use, uniformly spreading 1.0g of sublimed sulfur powder into one porcelain boat, and simultaneously placing the prepared medical titanium nail on another porcelain boat. Placing the porcelain boat respectively filled with sublimed sulfur powder and titanium nails into a two-temperature-zone tube furnace, vacuumizing to 10Pa, introducing high-purity argon gas for gas washing treatment, repeating for 3 times, wherein the argon gas flow is 20cm³Min, heating the sulfur powder to 230 ℃ at the speed of 6 ℃/min, heating the medical titanium nail to 740 ℃ at the speed of 20 ℃/min, preserving the heat for 1h, naturally cooling to room temperature in a high-temperature tubular atmosphere furnace, taking out a sample, ultrasonically cleaning by using deionized water, and drying at room temperature to obtain S-TiO_2-xA film.

Example 4

And sequentially placing the micro-arc oxidized medical titanium nail into acetone, ethanol and deionized water for ultrasonic cleaning for 15min, performing vacuum drying at room temperature for later use, uniformly spreading 2.0g of sublimed sulfur powder into one porcelain boat, and simultaneously placing the prepared medical titanium nail on another porcelain boat. Placing the porcelain boat respectively filled with sublimed sulfur powder and titanium nails into a two-temperature-zone tube furnace, vacuumizing to 10Pa, introducing high-purity argon gas for gas washing treatment, repeating for 3 times, wherein the argon gas flow is 40cm³Min, heating the sulfur powder to 230 ℃ at the speed of 6 ℃/min, heating the medical titanium nail to 750 ℃ at the speed of 20 ℃/min, preserving the heat for 1h, naturally cooling to room temperature in a high-temperature tubular atmosphere furnace, taking out a sample, ultrasonically cleaning by using deionized water, and drying at room temperature to obtain S-TiO_2-xA film.

Under the process conditions, S-doped S-TiO with excellent antibacterial performance and osseointegration performance can be prepared on the surface of medical titanium metal_2-xA film. Fig. 1 shows the change before and after the titanium nail treatment, and the surface of the titanium nail is obviously changed into black after the titanium nail treatment. FIG. 2 shows, S-TiO_2-xThe film has a micro-nano morphology with a laminated structure. FIG. 3 shows, S-TiO_2-xThe thickness of the film is about 1.1 μm. Fig. 4 shows that the surface of the sample contains Ti and O elements, and since S is doped in a small amount, no sign of S element is detected in the vicinity of 160 eV. FIG. 5 shows, S-TiO_2-xThe absorbance of the film at 400 to 1400nm is significantly enhanced. FIG. 6 shows the increased signal intensity of the treated titanium nails, indicating TiO₂S doping in (b) results in the creation of oxygen vacancies. FIG. 7 shows, S-TiO_2-xThe film has excellent bactericidal performance and excellent photoacoustic response capability. FIG. 8 shows, S-TiO_2-xThe film has excellent biocompatibility.

Although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims

1. Medical S-TiO on titanium metal surface_2-xThe preparation method of the film is characterized by comprising the following steps:

step one, pretreating a medical titanium metal substrate

step two, preparing the film

2. The medical titanium metal surface S-TiO according to claim 1_2-xThe preparation method of the film is characterized in that in the first step, the surface of the medical titanium metal substrate is subjected to micro-arc oxidation treatment.

3. The medical titanium metal surface S-TiO according to claim 1_2-xThe preparation method of the film is characterized in that the porcelain boat is made of corundum.

4. The medical titanium metal surface S-TiO according to claim 1_2-xThe preparation method of the film is characterized in that in the second step, the reaction furnace is a dual-temperature-zone atmosphere furnace.

5. The medical titanium metal surface S-TiO according to claim 1_2-xThe preparation method of the film is characterized in that in the second step, the flow of argon is 20-40 cm³Min, the charging direction is from the low temperature region toA high temperature zone.

6. The medical titanium metal surface S-TiO according to claim 1_2-xThe preparation method of the film is characterized in that in the second step, the heating rate is 1-20 ℃/min during heating.