Biological coating and preparation method thereof
By preparing a multilayer coating of nano-Ag and nano-Ta on the surface of bone implants, the problem of insufficient antibacterial and osteogenic properties in existing technologies is solved, achieving highly efficient antibacterial and osteocyte regeneration-promoting effects.
Patent Information
- Application Number
- CN202411761184.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-03
- Publication Date
- 2025-01-10
AI Technical Summary
While existing antibacterial coatings on bone implants improve antibacterial properties, they also have poor osteogenic properties, which affects wound healing efficiency.
A bio-coating consisting of sequentially stacked nano-Ag and nano-Ta layers was prepared on the surface of a bone implant. A multilayer structure was formed using magnetron sputtering technology. Combining the superior properties of nano-silver and nano-tantalum, this coating promotes bone cell regeneration and has antibacterial effects.
It achieves excellent antibacterial and osteogenic properties, promotes osteoblast growth, shortens wound recovery time, and has good coating stability and durability, providing long-term antibacterial effects.
Smart Images
Figure CN119280480A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of coatings, and in particular to a biological coating and a preparation method thereof. Background Art
[0002] With the update and iteration of medical materials, people are more stringent on the performance of orthopedic implants. Postoperative infection often causes redness and swelling of surrounding tissues, which is not conducive to the recovery of wound surface. Therefore, improving the antibacterial properties of bone implants is an effective way to accelerate wound healing and reduce postoperative infection.
[0003] At present, there are several ways to improve the antibacterial properties of bone implants: using antibacterial synthetic materials, implant injection and surface nano-coating. However, the production process of antibacterial synthetic materials is relatively complex and costly, and implant injection is usually only suitable for small fractures or injuries, and larger fractures require more complicated surgery. Therefore, preparing a nano-antibacterial coating on the surface of bone implants can effectively reduce bacterial infection.
[0004] Patent CN118241203A uses magnetron sputtering and electrochemical methods to plate a silver coating on the surface of titanium alloy, which can reduce bacterial infection in the fields of orthopedics and dentistry. However, the osteogenic performance of this antibacterial coating is relatively poor. Therefore, it is very important to improve the osteogenic performance of the coating and improve the efficiency of wound healing while effectively preventing infection. Summary of the invention
[0005] The object of the present invention is to provide a biological coating and a preparation method thereof. The biological coating of the present invention has excellent antibacterial properties and osteogenic properties.
[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions: The invention provides a biological coating, which is: a nano Ag layer and a nano Ta layer which are repeatedly stacked in sequence.
[0007] Preferably, the particle size of Ta in the nano-Ta layer is 5-15 nm, and the particle size of Ag in the nano-Ag layer is 10-30 nm.
[0008] Preferably, the repetition cycle is ≥5 times.
[0009] Preferably, the thickness of each nano-Ag layer is independently 2-4.5 nm; the thickness of each nano-Ta layer is independently 11-12.5 nm.
[0010] The present invention also provides a method for preparing the biological coating described in the above technical solution, comprising the following steps: The biological coating is obtained by sequentially and periodically performing magnetron sputtering on the Ag target and the Ta target on the substrate.
[0011] Preferably, before the magnetron sputtering, the method further comprises: cleaning the substrate; The cleaning comprises: immersing in acetone and ethanol successively and performing ultrasonication.
[0012] Preferably, the magnetron sputtering is performed under a flowing protective atmosphere; the flow rate of the protective atmosphere is 28-32 sccm; and the working gas pressure of the magnetron sputtering is 0.5-0.75 Pa.
[0013] Preferably, the magnetron sputtering performed on the Ag target is radio frequency magnetron sputtering, the radio frequency magnetron sputtering power is independently 26-34W, and the radio frequency magnetron sputtering time of the single-layer nano-Ag layer is independently 1-5s; The magnetron sputtering performed on the Ta target is DC magnetron sputtering, the DC magnetron sputtering power is independently 95-105W, and the DC magnetron sputtering time of a single-layer nano-Ta layer is 10s.
[0014] Preferably, the distance between the Ag target and the ion source and the distance between the Ta target and the ion source are independently 5 to 6 cm.
[0015] Preferably, the Ag target and the Ta target are on the same substrate fixing table, and the rotation speed of the substrate fixing table is 3.8-5.2 r / s.
[0016] The invention provides a biological coating, which is: a nano Ag layer and a nano Ta layer which are repeatedly stacked in sequence.
[0017] Compared with the traditional silver layer, the nanosilver in the nanosilver layer has a larger specific surface area, can achieve excellent antibacterial effects at low doses, and helps kill a variety of bacteria; the nanotantalum layer can effectively enhance the osteogenic properties of the matrix, promote the regeneration of bone cells, and shorten the time for patients to recover from wounds; the nanotantalum in the nanotantalum layer is combined with the nanosilver layer to prepare a nano-multilayer structure biological coating, which can give full play to the advantages of both materials and make it more suitable for bone implants; in addition, the nano-multilayer structure formed by repeated stacking helps to enhance the durability and stability of the biological coating. The results of the embodiment show that the biological coating of the present invention does not show cytotoxicity to rat bone marrow mesenchymal stem cells (rBMSCs) and can promote the growth of bone marrow mesenchymal stem cells. Ag in the coating + and Ta 5+ It can be released layer by layer, and can inhibit the growth of Staphylococcus aureus for a long time, thus achieving a long-term antibacterial effect.
[0018] The preparation method of the present invention has the advantages of high deposition rate, high purity, good uniformity, etc., and can meet different needs. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1is the relative cell viability when the bio-coating obtained in Examples 1 to 5 is co-cultured with rBMSCs cells for 1, 3, and 5 days; Figure 2 is a graph showing the results of bacterial colony culture counting on the surface of the biological coating obtained in Examples 1 to 5; Figure 3 It is the antibacterial rate of the biological coating obtained in Examples 1 to 5 against Staphylococcus aureus. DETAILED DESCRIPTION
[0020] The invention provides a biological coating, which is: a nano Ag layer and a nano Ta layer which are repeatedly stacked in sequence.
[0021] In the present invention, the repeated cycle is preferably ≥5 times.
[0022] In the present invention, the thickness of each nano-Ag layer is preferably independently 2-4.5 nm; the thickness of each nano-Ta layer is preferably independently 11-12.5 nm.
[0023] The present invention also provides a method for preparing the biological coating described in the above technical solution, comprising the following steps: The biological coating is obtained by sequentially and repeatedly performing magnetron sputtering on the Ag target and the Ta target on the substrate.
[0024] In the present invention, before the magnetron sputtering, it is preferred that the substrate is also cleaned and dried; the cleaning preferably includes: immersing in acetone and ethanol successively for ultrasound; the frequency of the ultrasound is preferably independently 15~30kHz, more preferably 20~25kHz; the time is preferably independently 25~30min, more preferably 26~30min.
[0025] In the present invention, the substrate preferably comprises TC4 titanium alloy.
[0026] In the present invention, the magnetron sputtering is preferably carried out under a flowing protective atmosphere; the flow rate of the protective atmosphere is preferably 28-32 sccm; and the working gas pressure of the magnetron sputtering is preferably 0.5-0.75 Pa.
[0027] In the present invention, the magnetron sputtering performed on the Ag target is preferably RF magnetron sputtering, and the RF magnetron sputtering power is preferably independently 26~34W, more preferably 28~30W; the RF magnetron sputtering time of a single-layer nano-Ag layer is independently 1~5s, more preferably 2~4s; the magnetron sputtering performed on the Ta target is preferably DC magnetron sputtering, and the DC magnetron sputtering power is preferably independently 95~105W, more preferably 98~100W; the DC magnetron sputtering time of a single-layer nano-Ta layer is preferably 10s.
[0028] In the present invention, the distance between the Ag target and the ion source and the distance between the Ta target and the ion source are preferably independently 5 to 6 cm.
[0029] In the present invention, the Ag target and the Ta target are preferably on the same substrate fixing table, and the rotation speed of the substrate fixing table is preferably 3.8-5.2 r / s. In the present invention, the Ag target and the Ta target are preferably repeatedly magnetron sputtered by rotating the substrate fixing table.
[0030] In the present invention, unless otherwise specified, the raw materials used in the present invention are preferably commercially available products.
[0031] The biological coating and the preparation method thereof provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0032] Preparation, characterization and measurement instruments used in the embodiments of the present invention: JGP-450 magnetron sputtering system, Shenyang Scientific Instrument Research and Development Center Co., Ltd., Chinese Academy of Sciences; D8 Advance X-ray diffractometer, Bruker, Germany; Gemini 300 scanning electron microscope, ZEISS, Germany; Dimension Icon atomic force microscope, Bruker, Germany; Tecnai G2 20 high-resolution transmission electron microscope, FEI Company, USA; JC2000C1 interfacial tension measuring instrument, Shanghai Zhongchen Digital Technology Equipment Co., Ltd.; Agilent 7800 Inductively Coupled Plasma Mass Spectrometer, Agilent Technologies, USA.
[0033] Example 1
[0034] The TC4 titanium alloy substrate was immersed in acetone and ethanol successively for ultrasonication and drying; the ultrasonication frequency was 30 kHz; and the drying time was 25 min.
[0035] Pure Ta target and pure Ag target were used, with a diameter of 75mm and a thickness of 3mm; Ar gas flow rate: 30sccm; Ta target DC sputtering power 100W; Ag target RF sputtering power 30W; single layer deposition time of Ta target and Ag target were 10s and 1s respectively; deposition cycle T = 5 layers; working gas pressure was 0.5Pa; target-substrate distance was 5cm, and the rotation speed of the substrate fixing plate was controlled to be 3.8r / s. The coating was recorded as Ta / Ag-1 group. Among them, the thickness of the single-layer nano-Ta layer was 11.8nm, the particle size of Ta in the Ta layer was 5~15nm, the thickness of the single-layer nano-Ag layer was 2.0nm, and the particle size of Ag in the Ag layer was 10~30nm.
[0036] Example 2
[0037] The deposition time of a single layer is 10s for Ta target and 2s for Ag target, respectively, and the coating is recorded as Ta / Ag-2 group. Among them, the thickness of the single layer of nano-Ta layer is 11.8nm, the particle size of Ta in the Ta layer is 5~15nm, the thickness of the single layer of nano-Ag layer is 2.4nm, and the particle size of Ag in the Ag layer is 10~30nm.
[0038] The rest is the same as in Example 1.
[0039] Example 3
[0040] The deposition time of a single layer is 10s for Ta target and 3s for Ag target, respectively, and the coating is recorded as Ta / Ag-3 group. Among them, the thickness of the single layer of nano-Ta layer is 11.8nm, the particle size of Ta in the Ta layer is 5~15nm, the thickness of the single layer of nano-Ag layer is 2.9nm, and the particle size of Ag in the Ag layer is 10~30nm.
[0041] The rest is the same as in Example 1.
[0042] Example 4
[0043] The deposition time of a single layer is 10s for Ta target and 4s for Ag target, and the coating is recorded as Ta / Ag-4 group. The thickness of a single layer of nano-Ta layer is 11.8nm, the particle size of Ta in the Ta layer is 5-15nm, the thickness of a single layer of nano-Ag layer is 3.6nm, and the particle size of Ag in the Ag layer is 10-30nm.
[0044] The rest is the same as in Example 1.
[0045] Example 5
[0046] The deposition time of a single layer is 10s for Ta target and 5s for Ag target, respectively, and the coating is recorded as Ta / Ag-5 group. Among them, the thickness of a single layer of nano-Ta layer is 11.8m, the particle size of Ta in the Ta layer is 5~15nm, the thickness of a single layer of nano-Ag layer is 4.2nm, and the particle size of Ag in the Ag layer is 10~30nm.
[0047] The rest is the same as in Example 1.
[0048] The cytotoxicity of the corresponding Ta / Ag-1, Ta / Ag-2, Ta / Ag-3, Ta / Ag-4, and Ta / Ag-5 coatings obtained in Examples 1 to 5 and the TC4 alloy substrate after cleaning in Example 1 were measured. Figure 1 Table 1 shows the relative cell viability (RGR) and cytotoxicity level of each coating group when co-cultured with rBMSCs cells for different time periods.
[0049] Table 1 RGR and cytotoxicity levels of each group of samples after co-culture with rBMSCs
[0050] As shown in Table 1, the relative cell viability of each group of samples after co-culture with rBMSCs cells was greater than 75%, and the toxicity level was level I, which met the biosafety requirements. With the increase of co-culture time, the relative cell viability basically showed a trend of first increasing and then decreasing. Among them, the relative cell viability of the Ta / Ag-2 group was stable and greater than 100%, without showing cytotoxicity, and the cell growth rate was fast, which met the biosafety requirements.
[0051] The antibacterial properties of the corresponding Ta / Ag-1, Ta / Ag-2, Ta / Ag-3, Ta / Ag-4, and Ta / Ag-5 coatings obtained in Examples 1 to 5 were measured, and the samples were co-cultured with Staphylococcus aureus and subjected to a plate coating test. The results are as follows: Figure 2~3 As shown. Among them, Figure 2 The results of colony culture counting on the surface of each coating group ( Figure 2 (a) is the result of colony culture counting on the surface of Ta / Ag-1 coating group; Figure 2 Middle (b) is the result of colony culture counting on the surface of Ta / Ag-2 coating group; Figure 2 Middle (c) is the result of colony culture counting on the surface of Ta / Ag-3 coating group; Figure 2 Middle (d) is the result of colony culture counting on the surface of Ta / Ag-4 coating group; Figure 2 (e) is the result of colony culture counting on the surface of Ta / Ag-5 coating group). Figure 3 is the antibacterial rate of the coating against Staphylococcus aureus. Figure 3 It can be seen that the antibacterial rate of the biological coating under different deposition cycles is different. This is because the different deposition cycles cause changes in the internal structure of the multilayer coating, which affects the antibacterial properties of the coating from a macroscopic point of view. Among them, the Ta / Ag-2 group has the highest antibacterial rate, which can reach 99.43%, and has strong antibacterial properties.
[0052] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A biological coating, characterized in that: For: sequentially repeatedly stacked nano-Ag layer and nano-Ta layer; The method for preparing the biological coating comprises the following steps: Repeating magnetron sputtering of Ag target and Ta target on the substrate to obtain the biological coating; The magnetron sputtering performed on the Ag target is radio frequency magnetron sputtering, the radio frequency magnetron sputtering power is independently 26-34W, and the radio frequency magnetron sputtering time of the single-layer nano-Ag layer is independently 1-5s; The magnetron sputtering performed on the Ta target is DC magnetron sputtering, the DC magnetron sputtering power is independently 95-105W, and the DC magnetron sputtering time of a single-layer nano-Ta layer is 10s.
2. The bio-coating according to claim 1, characterized in that The particle size of Ta in the nano-Ta layer is 5-15 nm, and the particle size of Ag in the nano-Ag layer is 10-30 nm.
3. The bio-coating according to claim 1, characterized in that The repeated cycle is ≥5 times.
4. The biological coating according to claim 1 or 3, characterized in that The thickness of each nano-Ag layer is independently 2-4.5 nm; the thickness of each nano-Ta layer is independently 11-12.5 nm.
5. The method for preparing the biological coating according to any one of claims 1 to 4, characterized in that: The following steps are involved: Repeating magnetron sputtering of Ag target and Ta target on the substrate to obtain the biological coating; The magnetron sputtering performed on the Ag target is radio frequency magnetron sputtering, the radio frequency magnetron sputtering power is independently 26-34W, and the radio frequency magnetron sputtering time of the single-layer nano-Ag layer is independently 1-5s; The magnetron sputtering performed on the Ta target is DC magnetron sputtering, the DC magnetron sputtering power is independently 95-105W, and the DC magnetron sputtering time of a single-layer nano-Ta layer is 10s.
6. The preparation method according to claim 5, characterized in that: Before the magnetron sputtering, the method further includes: cleaning the substrate; The cleaning comprises: immersing in acetone and ethanol successively and performing ultrasonication.
7. The preparation method according to claim 5, characterized in that: The magnetron sputtering is performed under a flowing protective atmosphere; the flow rate of the protective atmosphere is 28-32 sccm; and the working gas pressure of the magnetron sputtering is 0.5-0.75 Pa.
8. The preparation method according to claim 5, characterized in that: The distance between the Ag target and the ion source and the distance between the Ta target and the ion source are independently 5 to 6 cm.
9. The preparation method according to claim 5, characterized in that: The Ag target and the Ta target are on the same substrate fixing table, and the rotation speed of the substrate fixing table is 3.8-5.2 r / s.