Ion implanted PEEK-Cu composite coating and its preparation method and application

Abstract

The present invention belongs to the technical field of biological implant materials, and particularly relates to an ion-implanted PEEK-Cu composite coating and its preparation method and application. The method disperses the mixed particles of TaB2 and PEEK evenly in a chitosan suspension to obtain an electrophoretic deposition solution; the sample obtained after cathode deposition is heat-treated and then copper ions are implanted to obtain the final composite coating. In the present invention, different doses of Cu (1×10 17 ions / cm 2 , 3×10 17 ions / cm 2 , 6×10 17 ions / cm 2 ) are introduced onto the surface of the TaB2 / PEEK composite material to obtain a material with a continuous antibacterial effect and osteogenesis.

Description

Technical Field

[0001] The present invention belongs to the technical field of biological implant materials, and particularly relates to an ion implanted PEEK-Cu composite coating and a preparation method and application thereof. Background Art

[0002] The most serious complication after artificial joint replacement is infection around the artificial joint prosthesis. There is a gap between the implanted prosthetic material and the bone. If the bacterial adhesion rate is faster than the host tissue regeneration rate, it will lead to the occurrence of bone joint prosthesis-related infection. Preventing bacterial adhesion is crucial to preventing implant-related infection. Existing technology has proved that TaB2 / PEEK (tantalum boride / polyetheretherketone) materials have good tribology and biocompatibility, and have a tendency to promote macrophage differentiation to M2, but TaB2 and PEEK materials themselves do not have antibacterial properties. Therefore, it is of great significance to develop TaB2 / PEEK composite materials with antibacterial properties to promote cell adhesion and proliferation while inhibiting bacterial adhesion and growth.

[0003] Copper is an essential trace element for the human body. Copper antibacterial elements have good antibacterial effects and are effective antibacterial agents in vivo and in vitro. However, excessive intake of copper may cause cellular oxidative damage and cell death. It is challenging to deposit a copper film on a polymer matrix using traditional deposition methods (such as magnetron sputtering and wire arc deposition), which involve very high working temperatures. In addition, PEEK does not combine well with copper and cannot achieve a sustained release effect on copper. Summary of the invention

[0004] In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a method for preparing an ion-implanted PEEK-Cu composite coating.

[0005] Another object of the present invention is to provide an ion-implanted PEEK-Cu composite coating.

[0006] Another object of the present invention is to provide application of the ion-implanted PEEK-Cu composite coating in the preparation of bionic materials.

[0007] The purpose of the present invention is achieved through the following solutions:

[0008] A method for preparing an ion-implanted PEEK-Cu composite coating comprises the following steps:

[0009] (1) uniformly dispersing the mixed particles of TaB2 and PEEK in a chitosan suspension to obtain an electrophoretic deposition solution;

[0010] (2) performing electrophoretic deposition in an electrophoretic deposition solution to deposit a TaB2 / PEEK composite coating on a cathode;

[0011] (3) heat treating the deposited TaB2 / PEEK sample and cooling it in the furnace;

[0012] (4) placing the Cu target into a cathode arc source, placing the sample obtained in step (3) on a sample stage and evacuating the sample, then introducing argon gas into the cathode arc source, injecting copper ions by applying a pulsed negative high voltage, and obtaining an ion-implanted PEEK-Cu composite coating.

[0013] The concentration of the chitosan suspension in step (1) is 0.5-3 g / L.

[0014] The concentration of TaB2 in the electrophoretic deposition solution of step (1) is 1-5wt%, preferably 3wt%; the concentration of PEEK is 1-5wt%, preferably 2.5wt%.

[0015] The applied voltage of the electrophoretic deposition in step (2) is 10-20V, and the applied voltage time is 10-240s, preferably 60-120s.

[0016] The heat treatment temperature in step (3) is 350-450° C., and the heat treatment time is 40-90 min.

[0017] The copper ion implantation dose in step (4) is 1.0 to 6.0×10 17 ions·cm -2 .

[0018] An ion-implanted PEEK-Cu composite coating is prepared by the method.

[0019] Application of the ion-implanted PEEK-Cu composite coating in the preparation of bionic materials.

[0020] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0021] The present invention uses PIII technology (plasma immersion ion implantation) to implant different doses of Cu (1×10 17 ions / cm 2 , 3×10 17 ions / cm 2 , 6×10 17 ions / cm 2 ) was introduced into the surface of TaB2 / PEEK composite material to obtain an osteogenic material with sustained antibacterial effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 (a)-(d) are SEM images of PTB3 / 390 and antibacterial composite materials; (a`)-(d`) are local enlarged images of (a)-(d); (a``)-(d``) are element distribution diagrams of Cu. DETAILED DESCRIPTION

[0023] The present invention is further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

[0024] Unless otherwise specified, the reagents used in the examples can be purchased from the market.

[0025] The antibacterial effect characterization operation in the embodiment is as follows:

[0026] In this experiment, Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) were used to evaluate the antibacterial ability of PTB3 / 390 and copper antibacterial composites with different injection doses according to the plate count method of Chinese national standards JISZ 2801-2000, ISO 22196, and GB / T31402-2015.

[0027] Different materials (15 mm × 10 mm × 2 mm) were sterilized by high pressure at 121 °C for 30 min. Before bacterial inoculation, the samples were soaked in PBS for 10 min and then discarded. 5 cfu / mL bacterial solution (co-cultured for 6 h), 1×10 6 cfu / mL (co-cultured for 24 h) bacterial solution was added to the sample wells and co-cultured in a shaker. Three parallel test samples were set for each group.

[0028] The bacterial solution was aspirated according to the time point and diluted with PBS to a concentration of 1×10 4 cfu / mL, take 30μL and evenly spread it on the agar surface, then put it in a 37℃ constant temperature incubator for 18h, take it out and take pictures according to the time node. Set up 3 parallel test groups for each sample. Calculate the antibacterial rate.

[0029] Example 1

[0030] A method for preparing an ion-implanted PEEK-Cu composite coating comprises the following steps:

[0031] (1) A pure titanium sheet (TA2) was sandblasted and then ultrasonically cleaned in ethanol for three times for later use.

[0032] (2) Chitosan powder was dissolved in 1 vol% glacial acetic acid aqueous solution and magnetically stirred at 500 rpm for 24 h at room temperature to obtain a 1 g / L chitosan suspension. 3 wt% TaB2 and 2.5 wt% PEEK particle electrophoretic deposition solution was ultrasonically treated for 30 min and magnetically stirred for 24 h until TaB2 and PEEK particles were fully dispersed in the deposition solution.

[0033] (3) The distance between the cathode (TA2) and the anode counter electrode (platinum, 3×3 cm) was kept constant at 10 mm. The applied voltage and time during the EPD process were adjusted by repeated experiments, and the material deposition was performed using 15 V and a deposition time of 100 s. In order to avoid particle sedimentation, the EPD solution was continuously magnetically stirred during the EPD process.

[0034] (4) The TaB2 / PEEK samples were heated to a target temperature of 390°C at a rate of 4.5°C / min in a tube furnace under air atmosphere, kept at that temperature for 60 min, and then cooled in the furnace.

[0035] (5) Before plasma injection, the sample was ultrasonically cleaned in ethanol. The pure Cu target was placed in the cathode arc source, and the sample was placed on the sample stage and vacuumed to 5×10 -4 Pa, argon (Ar) was introduced into the cathode arc source at a flow rate of 6 sccm (standard cubic centimeters per minute). Copper ions were injected by applying pulsed negative high voltage. The injection dosage was 1.0×10 17 , 3.0×10 17 , 6.0×10 17 ions·cm -2 , and obtained Cu / TaB2 / PEEK materials, which were respectively recorded as PTB3 / 390 / 1Cu, PTB3 / 390 / 3Cu, and PTB3 / 390 / 6Cu.

[0036] Comparative Example 1

[0037] The difference between this comparative example and Example 1 is that step (5) is not included. The obtained sample is recorded as PTB3 / 390 comparative example 2

[0038] The difference between this comparative example and Example 1 is that TaB2 particles are not added in step (2). The obtained sample is recorded as PEEK / 390 / 1Cu

[0039] Depend on Figure 1 It can be seen that the Cu element on the surface exists in the form of Cu2O and CuO after Cu ion implantation. And the Cu element mainly exists inside the coating, so it will have a positive effect on the slow release of copper ions.

[0040] Table 1 Antibacterial rate of different samples and bacteria after 6h and 24h of culture

[0041]

[0042] It can be seen from Table 1 that the copper composite antibacterial material obtained in the present invention has a good antibacterial effect. The antibacterial effect of the copper composite antibacterial material may be related to the Cu released from the material. + and Cu 2+Ions. When the copper composite antibacterial material is co-cultured with Staphylococcus aureus and Escherichia coli, the copper ions released in the sample quickly destroy the cell membrane and combine with the sulfhydryl groups in the protein, making it impossible to synthesize the ATPase required for bacterial respiration, leading to bacterial death. When TaB2 is not added to the material, the antibacterial effect of PEEK / 390 / 1Cu is weakened, and it is unable to continuously release Cu ions. When Cu is not injected, the antibacterial effect of PTB3 / 390 is less than 40%.

[0043] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing an ion-implanted PEEK-Cu composite coating, characterized in that The following steps are involved: (1) uniformly dispersing the mixed particles of TaB2 and PEEK in a chitosan suspension to obtain an electrophoretic deposition solution; (2) performing electrophoretic deposition in an electrophoretic deposition solution to deposit a TaB2 / PEEK composite coating on a cathode; (3) heat treating the deposited TaB2 / PEEK sample and cooling it in the furnace; (4) placing the Cu target into a cathode arc source, placing the sample obtained in step (3) on a sample stage and evacuating the sample, then introducing argon gas into the cathode arc source, injecting copper ions by applying a pulsed negative high voltage, and obtaining an ion-implanted PEEK-Cu composite coating; The copper ion implantation dose in step (4) is 1.0 to 6.0×10 17 ions·cm -2 .

2. The method according to claim 1, characterized in that: The concentration of the chitosan suspension in step (1) is 0.5-3 g / L.

3. The method according to claim 1, characterized in that: The concentration of TaB2 in the electrophoretic deposition solution of step (1) is 1 to 5 wt%.

4. The method according to claim 1, characterized in that: The concentration of PEEK in the electrophoretic deposition solution of step (1) is 1 to 5 wt%.

5. The method according to claim 1, characterized in that: In step (1), the concentration of TaB2 in the electrophoretic deposition solution is 3 wt %, and the concentration of PEEK is 2.5 wt %.

6. The method according to claim 1, characterized in that: The applied voltage of the electrophoretic deposition in step (2) is 10-20V, and the applied voltage time is 10-240s.

7. The method according to claim 1, characterized in that: The heat treatment temperature in step (3) is 350-450° C., and the heat treatment time is 40-90 min.

8. An ion-implanted PEEK-Cu composite coating prepared by the method according to any one of claims 1 to 7.

9. Use of the ion-implanted PEEK-Cu composite coating according to claim 8 in the preparation of bionic materials.

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