CN103242551A - Method for injecting titanium ions to modify surface of polyether-ether-ketone - Google Patents

Abstract

The invention relates to a method for modifying the surface of polyether ether ketone by implanting titanium ions. The method uses plasma immersion ion implantation technology to implant titanium ions on the surface of polyetherether ketone. The surface of the polyether ether ketone material obtained through the modification treatment of the invention can obtain different nanostructures, and the biocompatibility is significantly improved; and it has potential loading prospects of osteoinductive growth factors and antibacterial drugs.

Description

Method for modifying the surface of polyether ether ketone by implanting titanium ions

technical field

The present invention relates to a method for modifying the surface of medical polyether ether ketone, in particular to a method for modifying the surface of polyether ether ketone and its derived composite materials by using plasma immersion ion implantation technology, belonging to The technical field of surface modification of medical polymer materials. the

Background technique

In recent years, with the continuous improvement and development of the theory and technology for the preparation and use of biological materials, the application prospects of polymer implant materials will be broader. The elastic modulus of polyetheretherketone (PEEK) best matches that of human bone tissue, which can effectively reduce bone resorption and bone atrophy caused by the stress shielding effect, and has outstanding fatigue resistance, making it suitable for long-term implantation of medical implants (Biomaterials 2007, 28:4845-4869). However, the biological activity of PEEK is poor, and it is not easy to bond with human bone tissue after implantation in the human body, which limits its long-term implantation as an implant material. How to improve the biocompatibility of PEEK materials has become one of the research hotspots. the

At present, the main method for surface modification of polyetheretherketone materials is the chemical grafting method. This method has a shallow modification depth, poor effect, long reaction time and low efficiency, which is not conducive to large-scale production. the

Contents of the invention

In order to solve the problem of poor biocompatibility of the existing medical polyether ether ketone, the present invention provides a novel surface modification method of medical polyether ether ketone materials, so as to meet the requirements of medical polyether ether ketone materials. biocompatibility requirements. the

Plasma immersion ion implantation (PIII) is a new surface modification technology with all-round and high reactivity characteristics. It has the characteristics of all-round and high reactivity. In-body materials have unique advantages. When using PIII technology to modify insulator materials, the poor conductivity of insulators can easily lead to surface charge accumulation, affecting the effect of material modification, and even destroying materials (Surface & Coatings Technology, 2005, 196: 162-166.). How to apply PIII technology to achieve effective surface composition and surface structure regulation on the surface of polymer materials has become a difficult problem, especially in the preparation of material surface structures, there is still no relevant theoretical and experimental research. the

Titanium (Ti), as the traditional material of choice for hard tissue implants, has been widely proven to have good biocompatibility. Titanium and its alloy materials can be effectively combined with human tissues after implantation in the human body; at the same time, titanium oxide nanoparticles have Certain antibacterial properties can effectively inhibit bacteria from forming a biofilm on the surface of the implant. Studies have shown that nanoscale materials play an important role in evoking appropriate cell responses, regulating cell adhesion and differentiation on the surface of materials, promoting bone regeneration, and improving and prolonging the use and life of implants. Therefore, nanobiological materials and biomaterial surfaces Nanoization has become a research hotspot in the field of biomedical materials (Materials Science & Engineering R-Reports, 2010, 70:275-302.). This application proposes to use plasma immersion ion implantation technology to carry out Ti ion implantation modification on polyetheretherketone material, introduce titanium element on the surface of the material, and at the same time form an in-situ modification layer with nanostructure on the surface of the material, endowing the material with a certain Antibacterial property, while maintaining the mechanical stability of the material, it greatly improves its biocompatibility. the

Herein, the present invention provides a method for modifying the surface of polyether ether ketone by implanting titanium ions. The method uses plasma immersion ion implantation technology to perform titanium ion implantation on the surface of polyether ether ketone. the

The surface of the polyether ether ketone material obtained through the modification treatment of the invention can obtain different nanostructures, and the biocompatibility is significantly improved; and it has potential loading prospects of osteoinductive growth factors and antibacterial drugs. The cell proliferation experiment proves that the proliferation of MC3T3 osteoblasts on the surface of the modified carbon fiber reinforced PEEK material obtained by the present invention is significantly higher than that of the unmodified sample, which can meet the performance requirements required for medical carbon fiber reinforced PEEK. the

Preferably, when plasma immersion ion implantation technology is used to implant titanium ions on the surface of polyether ether ketone, pure metallic titanium is used as the cathode. Using pure metal titanium as the cathode to inject titanium ions improves the biocompatibility of polyether ether ketone while still maintaining the good mechanical properties of the material. the

Preferably, the process parameters of the titanium ion implantation include: background vacuum degree of 3×10 ^-3 to 5×10 ^-3 Pa, implantation voltage of 15 to 40 kV, implantation pulse width of 50 to 600 μs, implantation pulse frequency 5-9Hz, the trigger pulse width of the cathode source is 500-2000μs, and the injection time is 30-180 minutes.

Further preferably, the injection pulse width is 200-600 μs, and the injection time is 60-180 minutes. the

In a preferred example, the background vacuum is 3.5×10 ^-3 Pa, the injection voltage is 15kV, the injection pulse frequency is 7Hz, the injection pulse width is 450μs, and the injection time is 90 minute. In yet another preferred example, the background vacuum is 3.5×10 ^-3 Pa, the injection voltage is 30kV, the injection pulse frequency is 7Hz, the injection pulse width is 450μs, and the injection time is 120 minutes.

In the present invention, the polyether ether ketone is a pure polyether ether ketone material or a carbon fiber reinforced polyether ether ketone material. the

When the polyetheretherketone is a pure polyetheretherketone material, titanium ions are implanted on the surface of the pure polyetheretherketone to have nano particles and nano films on the surface. The introduction of titanium elements and nanostructures can improve the antibacterial properties and biocompatibility of pure PEEK. the

When the polyether ether ketone is a carbon fiber reinforced polyether ether ketone material, titanium ions are implanted into the surface of the carbon fiber reinforced polyether ether ketone so that the surface has a porous and nano-particle multi-level structure. The introduction of titanium element and nanostructure significantly improved the antibacterial and biocompatibility of carbon fiber reinforced polyetheretherketone. the

Compared with prior art, the present invention has following beneficial effect:

The polyether ether ketone material obtained through the modification method of the present invention has certain antibacterial properties, and at the same time, the biocompatibility is greatly improved. The results of the cell proliferation experiment confirmed that the polyether ether ketone material obtained by the modification method of the present invention has better cytocompatibility, and the proliferation of MC3T3 cells on the modified surface is significantly higher than that on the unmodified surface, which can meet the requirements of medical polyetherether ether. Biocompatibility requirements required for ketone materials. the

Description of drawings

Fig. 1 is a scanning electron microscope topography comparison diagram of the surface of carbon fiber reinforced polyetheretherketone and unmodified carbon fiber reinforced polyether ether ketone obtained through the modification treatment of Example 1, in the figure: (a) and (b) are unmodified Carbon fiber reinforced polyether ether ketone, (c) and (d) are carbon fiber reinforced polyether ether ketone obtained by modification treatment;

Fig. 2 is a scanning electron microscope morphology comparison diagram of the carbon fiber reinforced polyether ether ketone obtained through the modification treatment of Example 1 and the unmodified carbon fiber reinforced polyether ether ketone section, in the figure: (a) and (c) are unmodified Carbon fiber reinforced polyether ether ketone, (b) and (d) are carbon fiber reinforced polyether ether ketone obtained by modification treatment;

Fig. 3 is the XPS full spectrum spectrogram of the surface of carbon fiber reinforced polyether ether ketone obtained through the modification treatment of Example 1, in the figure: the abscissa represents the binding energy, and the ordinate represents the peak intensity;

Fig. 4 is the XPS high-resolution spectrogram of the titanium element on the surface of carbon fiber reinforced polyether ether ketone obtained through the modification treatment of Example 1, in the figure: the abscissa represents the binding energy, and the ordinate represents the peak intensity;

Fig. 5 is the carbon fiber reinforced polyetheretherketone surface element depth distribution spectrogram obtained through the modification treatment of Example 1, in the figure: the abscissa represents the depth, and the unit is nanometer; the ordinate represents the atomic percentage;

Fig. 6 is a comparison diagram of scanning electron microscope morphology of the surface of pure polyetheretherketone obtained through modification in Example 5 and the surface of unmodified pure polyether ether ketone. In the figure: (a) and (b) are unmodified pure polyetheretherketone Polyether ether ketone, (c) and (d) are pure polyether ether ketone obtained by modification treatment;

Fig. 7 is the antibacterial experiment result of carbon fiber reinforced polyetheretherketone before and after the modified treatment of the present invention, among the figure: (a) and (b) represent the sample before treatment, (c) and (d) represent Ti-120 sample, Ti -120 indicates the sample implanted with titanium ions for 120min under 30kV bias;

Fig. 8 is a scanning electron microscope image of MC3T3 osteoblasts cultured on the surface of carbon fiber reinforced polyetheretherketone before and after the modified treatment of the present invention, in the figure: (a-i) represents the sample before treatment (i=1, 4 and 7), ( b-i) indicates Ti-120 samples (i=1, 4 and 7), and Ti-120 indicates samples implanted with titanium ions for 120min under 30kV bias;

Fig. 9 is the result of the proliferation experiment of MC3T3 osteoblasts cultured on the surface of carbon fiber reinforced polyether ether ketone before and after the modified treatment of the present invention. A sample that was implanted with titanium ions for 120 minutes under pressure. the

Detailed ways

The present invention will be further described below in conjunction with the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, not to limit the present invention. the

The invention discloses a method for modifying the surface of medical polyether ether ketone and its derivative composite materials. The surface is implanted with titanium ions to solve the problems of poor biocompatibility and difficulty in bone tissue growth after the existing medical polyether ether ketone material is implanted into the human body. the

In order to solve the problems of the technologies described above, the technical scheme adopted in the present invention is as follows:

A method for surface modification of medical polyether ether ketone materials, comprising: using a titanium ion implantation method to modify the surface of pure polyetheretherketone and carbon fiber reinforced polyether ether ketone materials, and forming nanoparticles on the surface of pure polyetheretherketone structure, constructing a porous and nanoparticle coexistence structure on the surface of carbon fiber reinforced polyether ether ketone. the

As a preferred solution, plasma immersion ion implantation (PIII) technology is used to implant titanium ions on the surface of the medical polyether ether ketone material. the

Preferably, when plasma immersion ion implantation technology is used to implant titanium ions on the surface of the medical polyether ether ketone material, pure titanium is preferably used as the cathode. the

The process parameters of the titanium ion implantation include: the background vacuum degree is 3×10 ^-3 to 5×10 ^-3 Pa, the implantation voltage is 15 to 40 kV, the implantation pulse width is 50 to 600 μs (preferably 200 to 600 μs), the implantation The pulse frequency is 5-9 Hz, the trigger pulse width of the cathode source is 500-2000 μs, and the injection time is 30-180 minutes (preferably 60-180 minutes).

In a particularly preferred example, the process parameters for implanting titanium ions on the surface of medical polyetheretherketone materials by using plasma immersion ion implantation technology are preferably: the background vacuum is 3.5×10 ^-3 Pa, the implantation voltage is 15kV, and the implantation The pulse width is 450 μs, the injection pulse frequency is 7 Hz, the cathode source trigger pulse width is 500 μs, and the injection time is 90 minutes.

In yet another particularly preferred example, the process parameters for implanting titanium ions on the surface of medical polyether ether ketone materials by using plasma immersion ion implantation technology are preferably: the background vacuum degree is 3.5×10 ^-3 Pa, the implantation voltage is 30kV, The injection pulse width is 450 μs, the injection pulse frequency is 7 Hz, the cathode source trigger pulse width is 500 μs, and the injection time is 120 minutes.

The above polyetheretherketone material is a pure polyetheretherketone material or a carbon fiber reinforced polyetheretherketone material. the

The polyether ether ketone material obtained through the modification method of the invention has certain antibacterial properties, and at the same time, the biocompatibility is greatly improved. The results of the cell proliferation experiment confirmed that the polyether ether ketone material obtained by the modification method of the present invention has better cytocompatibility, and the proliferation of MC3T3 cells on the modified surface is significantly higher than that on the unmodified surface, which can meet the requirements of medical polyetherether ether. Biocompatibility requirements required for ketone materials. For example, nanoparticles and nanofilms are distributed on the surface of pure polyetheretherketone obtained through the surface modification treatment of the present invention, and the introduction of titanium elements and nanostructures can improve the antibacterial properties and biocompatibility of pure polyetheretherketone. Refer to Fig. 6, 1 which shows the comparison diagram of scanning electron microscope morphology of the surface of pure polyether ether ketone obtained by modification treatment and unmodified pure polyether ether ketone, in the figure: (a) and (b) are unmodified Pure polyether ether ketone, (c) and (d) are pure polyether ether ketone obtained by modification treatment, as can be seen from Figure 6: the surface of pure polyether ether ketone obtained by modification treatment in this example has obvious nanoparticles structure, the particle size is about 10nm, and the distribution of nanoparticles is relatively uniform. the

Also, for example, the carbon fiber reinforced polyether ether ketone obtained through the surface modification treatment of the present invention has a pore structure of about 100 nm distributed on the surface, and nanoparticles with a particle size of about 10 nm are distributed in the pore structure. The introduction of titanium element and nanostructure significantly improved the antibacterial and biocompatibility of carbon fiber reinforced polyetheretherketone. Fig. 1 and Fig. 2 respectively show the comparison diagram of scanning electron microscope morphology of the surface of carbon fiber reinforced polyether ether ketone obtained through the modification treatment of Example 1 and the surface of unmodified carbon fiber reinforced polyetheretherketone and the comparison diagram of scanning electron microscope morphology of the cross section , in Figure 1, (a) and (b) are unmodified carbon fiber reinforced polyetheretherketone, (c) and (d) are carbon fiber reinforced polyetheretherketone obtained by modification treatment, in Figure 2, (a) and (c) are unmodified carbon fiber reinforced polyether ether ketone, (b) and (d) are carbon fiber reinforced polyether ether ketone obtained by modification treatment. It can be seen from Figure 1 and Figure 2 that the surface of the carbon fiber reinforced polyether ether ketone obtained through the modification treatment of this embodiment has an obvious pore structure, the depth of the pore structure is about 700nm-800nm, and particles with a particle size of about 10nm are distributed in the pore structure. Titanium oxide nanoparticles, and the distribution of nanoparticles is relatively uniform. Fig. 3 is an XPS full-spectrum spectrum on the surface of the carbon fiber reinforced polyetheretherketone material obtained through modification treatment in this embodiment. Fig. 4 is an XPS high-resolution spectrum of titanium elements on the surface of carbon fiber reinforced polyetheretherketone obtained through the modification treatment in Example 1. Fig. 5 is a diagram showing the depth distribution of elements on the surface of carbon fiber reinforced polyetheretherketone obtained through the modification treatment in Example 1. From Figure 3, Figure 4 and Figure 5, it can be seen that the titanium element can be introduced to the surface of polyether ether ketone by using plasma immersion ion implantation technology, the surface titanium element exists in the form of titanium oxide, the titanium element is distributed in a large depth range, and the element The content decreases with increasing depth. Fig. 7 is a graph showing the morphology of carbon fiber reinforced polyether ether ketone and unmodified bacteria after modification in Example 1. It can be seen from Figure 7 that there are fewer bacteria on the surface of the modified sample, and the bacteria lose their original plump and round shape, with varying degrees of deformation and distortion, indicating that the modified material has certain antibacterial properties against Staphylococcus aureus. Fig. 8 is a scanning electron microscope image of MC3T3 osteoblasts on the surface of carbon fiber reinforced polyether ether ketone before and after the modification of the present invention, in the figure: (a-i) represents the sample before treatment (i=1, 4 and 7), (b-i ) indicates Ti-120 samples (i=1, 4 and 7). It can be seen from Figure 8 that the pseudopods of the modified samples stretched more, and the morphology was more spread out, showing that the modified samples had better cytocompatibility. Fig. 9 is the statistical result of the MC3T3 cell proliferation experiment of carbon fiber reinforced polyetheretherketone obtained through modification in Example 1 and unmodified carbon fiber reinforced polyetheretherketone. It can be seen from Figure 9 that the proliferation of MC3T3 cells on the surface of carbon fiber-reinforced polyetheretherketone modified in Example 1 is significantly better than that of unmodified carbon fiber-reinforced polyetheretherketone, showing that the modified sample has better biological compatibility. the

Examples are further given below to describe the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention, and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art according to the above contents of the present invention all belong to this invention. protection scope of the invention. The specific process parameters and the like in the following examples are only an example of the appropriate range, that is, those skilled in the art can make a selection within the appropriate range through the description herein, and are not limited to the specific values exemplified below. the

Example 1

10mm×10mm×1mm carbon fiber reinforced polyether ether ketone is polished, then ultrasonically cleaned with acetone and deionized water, each time for 30min, after cleaning, put it in an oven at 80°C to dry and store it properly. Using plasma immersion ion implantation technology, titanium ions were implanted into carbon fiber reinforced polyether ether ketone matrix. The specific process parameters are shown in Table 1, and the obtained sample number is Ti-120. the

Table 1 Titanium ion implantation parameters: Injection bias (kV) 30 Pulse width (μs) 450 Injection time (min) 120 Background vacuum (Pa) 3.5×10 ^-3 Cathode trigger pulse width (μs) 500 Frequency (Hz) 7

Figure 1 is the scanning electron microscope morphology of the surface of carbon fiber reinforced polyether ether ketone and unmodified carbon fiber reinforced polyether ether ketone obtained through the modification treatment of Example 1, in the figure: (a) and (b) are unmodified carbon fibers Reinforced polyether ether ketone, (c) and (d) are carbon fiber reinforced polyether ether ketone obtained through modification treatment. Figure 2 is the scanning electron microscope morphology of the carbon fiber reinforced polyether ether ketone and unmodified carbon fiber reinforced polyether ether ketone sections obtained through the modification treatment of Example 1, in the figure: (a) and (c) are unmodified carbon fibers Reinforced polyether ether ketone, (b) and (d) are carbon fiber reinforced polyether ether ketone obtained through modification treatment. It can be seen from Figure 1 and Figure 2 that the surface of the carbon fiber reinforced polyether ether ketone obtained through the modification treatment of this embodiment has an obvious pore structure, the depth of the pore structure is about 700nm-800nm, and particles with a particle size of about 10nm are distributed in the pore structure. Titanium oxide nanoparticles, and the distribution of nanoparticles is relatively uniform. the

Fig. 3 is an XPS full-spectrum spectrum on the surface of the carbon fiber reinforced polyetheretherketone material obtained through modification treatment in this embodiment. Fig. 4 is an XPS high-resolution spectrum of titanium elements on the surface of carbon fiber reinforced polyetheretherketone obtained through the modification treatment in Example 1. Fig. 5 is a diagram showing the depth distribution of elements on the surface of carbon fiber reinforced polyetheretherketone obtained through the modification treatment in Example 1. From Figure 3, Figure 4 and Figure 5, it can be seen that the titanium element can be introduced to the surface of polyether ether ketone by using plasma immersion ion implantation technology, the surface titanium element exists in the form of titanium oxide, the titanium element is distributed in a large depth range, and the element The content decreases with increasing depth. the

Example 2

After polishing, the 10mm×10mm×1mm carbon fiber reinforced polyetheretherketone is ultrasonically cleaned with acetone and deionized water, each time for 30min, after cleaning, it is dried in an oven at 80°C and stored properly. Using plasma immersion ion implantation technology, titanium ions were implanted into the carbon fiber reinforced polyether ether ketone matrix. The specific process parameters are shown in Table 2:

Table 2 Titanium ion implantation parameters: Injection bias (kV) 30 Pulse width (μs) 450 Injection time (min) 120 Background vacuum (Pa) 3.5×10 ^-3 Cathode trigger pulse width (μs) 500 Frequency (Hz) 5

Example 3

After polishing, the 10mm×10mm×1mm carbon fiber reinforced polyether ether ketone was cleaned ultrasonically with acetone and deionized water in sequence, each time for 30 minutes. After cleaning, it was dried in an oven at 80°C and stored properly. Using plasma immersion ion implantation technology, titanium ions were implanted into the carbon fiber reinforced polyether ether ketone matrix. The specific process parameters are shown in Table 3:

Table 3 Titanium ion implantation parameters: Injection bias (kV) 30 Pulse width (μs) 450 Injection time (min) 120 Background vacuum (Pa) 3.5×10 ^-3 Cathode trigger pulse width (μs) 500 Frequency (Hz) 9

Example 4

After polishing, the 10mm×10mm×1mm carbon fiber reinforced polyether ether ketone was cleaned ultrasonically with acetone and deionized water in sequence, each time for 30 minutes. After cleaning, it was dried in an oven at 80°C and stored properly. Using plasma immersion ion implantation technology, titanium ions were implanted into the carbon fiber reinforced polyetheretherketone matrix. The specific process parameters are shown in Table 4:

Table 4 Titanium ion implantation parameters: Injection bias (kV) 15 Pulse width (μs) 450 Injection time (min) 60 Background vacuum (Pa) 3.5×10 ^-3 Cathode trigger pulse width (μs) 500 Frequency (Hz) 7

Example 5

10mm×10mm×1mm pure polyether ether ketone is polished, then ultrasonically cleaned with acetone and deionized water in sequence, each time for 30 minutes, after cleaning, it is dried in an oven at 80°C and stored properly. Plasma immersion ion implantation technology was used to implant titanium ions into the pure polyether ether ketone matrix. The specific process parameters are shown in Table 5:

Table 5 Titanium ion implantation parameters: Injection bias (kV) 15 Pulse width (μs) 450 Injection time (min) 90 Background vacuum (Pa) 3.5×10 ^-3 Cathode trigger pulse width (μs) 500 Frequency (Hz) 7

Fig. 6 is a comparison diagram of scanning electron microscope morphology of the surface of pure polyetheretherketone obtained through modification in Example 5 and the surface of unmodified pure polyether ether ketone. In the figure: (a) and (b) are unmodified pure polyetheretherketone Polyether ether ketone, (c) and (d) are pure polyether ether ketone obtained by modification. It can be seen from FIG. 6 that the surface of the pure polyether ether ketone obtained through the modification treatment of this embodiment has an obvious nanoparticle structure, the particle size is about 10 nm, and the distribution of nanoparticles is relatively uniform. the

Example 6

Staphylococcus aureus was selected to evaluate the antibacterial property of the carbon fiber reinforced polyetheretherketone material modified in the above-mentioned Example 1 by using an antibacterial experiment, and the morphology of bacteria on the surface of the material was observed by scanning electron microscopy. The specific steps are as follows: (1) Place the sample sterilized with 75% ethanol on a culture plate, inoculate 60 μL of bacterial solution with a density of 10 ⁷ cfu/mL on the surface of the sample, keep the humidity above 90%, and place it in a 36.5°C Incubate for 24 h in an oxygen incubator. (2) The samples were taken out, fixed with 2% glutaraldehyde at room temperature for 24 hours, and washed three times with PBS. (3) Dehydrate the fixed bacteria with graded alcohol (30%, 50%, 75%, 90%, 95% and 100%). (4) Place the sample in a mixed solution of alcohol and hexamethyldisilazane (HMDS) in different proportions in turn (alcohol: HMDS=2:1, 1:1, 1:2 and 100% HMDS) Drying is carried out, and the treatment time is 10 minutes each. After the sample was sprayed with gold, the morphology of bacteria on the surface of the sample was observed by SEM.

Fig. 7 is a graph showing the morphology of carbon fiber reinforced polyether ether ketone and unmodified bacteria obtained through the modification treatment of Example 1 above. It can be seen from Figure 7 that there are fewer bacteria on the surface of the modified sample, and the bacteria lose their original plump and round shape, with varying degrees of deformation and distortion, indicating that the modified material has certain antibacterial properties against Staphylococcus aureus. the

Example 7

MC3T3 osteoblasts were selected, and the cell compatibility of the carbon fiber-reinforced polyetheretherketone material obtained through the modification in the above-mentioned Example 1 was evaluated by in vitro cell culture experiments. Use SEM to observe the cell morphology on the surface of the material. The experimental steps are as follows: (1) Put the sample sterilized with 75% ethanol into a 24-well culture plate, and add 1 mL of MC3T3 cell suspension with a density of 5×10 ⁴ cell/mL to each well. liquid. (2) Place the cell culture plate in a cell culture incubator with 5% CO ₂ saturated humidity and incubate at 36.5°C for 18h. (3) Aspirate the cell culture medium, wash the surface of the sample with PBS, transfer the sample to a new 24-well plate, and put it into an incubator to continue culturing. (4) After the cells were cultured for 1, 4 and 7 days, the samples were taken out, fixed with 2% glutaraldehyde at room temperature for 24 hours, and washed three times with PBS. (5) Dehydrate the fixed cells with graded alcohol (30%, 50%, 75%, 90%, 95% and 100%). (6) Place the sample in a mixed solution of alcohol and hexamethyldisilazane (HMDS) in different proportions in turn (alcohol: HMDS=2:1, 1:1, 1:2 and 100% HMDS) Drying is carried out, and the treatment time is 10 minutes each. After the sample was sprayed with gold, the cell morphology on the surface of the sample was observed by SEM.

Fig. 8 is a scanning electron microscope image of MC3T3 osteoblasts on the surface of carbon fiber reinforced polyether ether ketone before and after the modification of the present invention, in the figure: (a-i) represents the sample before treatment (i=1, 4 and 7), (b-i ) indicates Ti-120 samples (i=1, 4 and 7). It can be seen from Figure 8 that the pseudopods of the modified samples stretched more, and the morphology was more spread out, showing that the modified samples had better cytocompatibility. the

Example 8

The cytocompatibility of the carbon fiber reinforced polyether ether ketone material obtained through the modification treatment of the above-mentioned Example 1 was evaluated by MC3T3 cell culture experiment in vitro. AlamarBlue ^TM (AbD serotec Ltd, UK) kit was used to detect the proliferation of cells on the material surface. The method is as follows: (1) Put the sample sterilized with 75% ethanol into a 24-well culture plate, and add 1 mL of MC3T3 cell suspension with a density of 5×10 ⁴ cell/mL dropwise to each well. (2) Place the cell culture plate in a cell culture incubator with 5% CO ₂ saturated humidity and incubate at 36.5°C for 18h. (3) Aspirate the cell culture medium, wash the surface of the sample with PBS, transfer the sample to a new 24-well plate, and put it into an incubator to continue culturing. (4) After 1, 4 and 7 days of cell culture, suck off the original culture solution, add a new culture solution containing 5% AlamarBlue ^TM staining solution, place the culture plate in the incubator for 4 hours, and take out 100 μL of the culture solution from each well Place in a 96-well plate. (5) Use a microplate reader (BIO-TEK, ELX800) to measure the absorbance values of each well at wavelengths of 570 nm and 600 nm. Calculate the percentage of AlamarBlue ^TM reduced by cells according to the following formula:

Formula:

$\frac{\mathrm{<span\; class="notranslate">\; 117216</span>}<span\; class="notranslate">\; \&times;</span>{\mathrm{<span\; class="notranslate">\; A</span>}}^{\mathrm{<span\; class="notranslate">\; \&lambda;</span>}\mathrm{<span\; class="notranslate">\; 1</span>}}<span\; class="notranslate">\; -</span>\mathrm{<span\; class="notranslate">\; 80586</span>}<span\; class="notranslate">\; \&times;</span>{\mathrm{<span\; class="notranslate">\; A</span>}}^{\mathrm{<span\; class="notranslate">\; \&lambda;</span>}\mathrm{<span\; class="notranslate">\; 2</span>}}}{\mathrm{<span\; class="notranslate">\; 155677</span>}<span\; class="notranslate">\; \&times;</span>{\mathrm{<span\; class="notranslate">\; A</span>}<span\; class="notranslate">\; `</span>}^{\mathrm{<span\; class="notranslate">\; \&lambda;</span>}\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; -</span>\mathrm{<span\; class="notranslate">\; 14652</span>}<span\; class="notranslate">\; \&times;</span>{\mathrm{<span\; class="notranslate">\; A</span>}<span\; class="notranslate">\; `</span>}^{\mathrm{<span\; class="notranslate">\; \&lambda;</span>}\mathrm{<span\; class="notranslate">\; 1</span>}}}<span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; 100</span>}<span\; class="notranslate">\; \%</span>$

Among them: A is the absorbance value, A` is the absorbance value of the negative control well, λ1=570nm, λ2=600nm. the

Fig. 9 is the statistical result of the MC3T3 cell proliferation experiment of the carbon fiber reinforced polyetheretherketone obtained through the modification treatment of the above embodiment 1 and the unmodified carbon fiber reinforced polyetheretherketone. It can be seen from Figure 9 that the proliferation of MC3T3 cells on the surface of carbon fiber-reinforced polyetheretherketone modified in Example 1 is significantly better than that of unmodified carbon fiber-reinforced polyetheretherketone, showing that the modified sample has better biological compatibility. the

Industrial Applicability: The method of the present invention is simple and easy to control. The surface of the polyether ether ketone material obtained through the modification treatment of the present invention can obtain different nanostructures, and the biocompatibility is significantly improved; and it has potential osteoinductive growth Factors and antimicrobial drug loading prospects to meet the performance requirements required for medical polyetheretherketone. the

Claims (9)

1. one kind is injected the method that titanium ion carries out modification to the polyether-ether-ketone surface, it is characterized in that, described method uses the plasma immersion ion implantttion technique to carry out the titanium ion injection on the surface of polyether-ether-ketone.

2. method according to claim 1 is characterized in that, when using the plasma immersion ion implantttion technique to carry out the titanium ion injection on the surface of polyether-ether-ketone, uses pure metallic titanium as negative electrode.

3. method according to claim 1 and 2 is characterized in that, the processing parameter that described titanium ion injects comprises: the base vacuum degree is 3 * 10 ^-3～5 * 10 ^-3Pa, injecting voltage are 15～40kV, and injecting pulsewidth is 50～600 μ s, and the injected pulse frequency is 5～9Hz, and it is 500～2000 μ s that pulsewidth is triggered in the negative electrode source, and injection length is 30～180 minutes.

4. method according to claim 3 is characterized in that, described injection pulsewidth is 200～600 μ s, and described injection length is 60～180 minutes.

5. method according to claim 4 is characterized in that, described base vacuum degree is 3.5 * 10 ^-3Pa, described injecting voltage are 15kV, and described injected pulse frequency is 7Hz, and described injection pulsewidth is 450 μ s, and described injection length is 90 minutes.

6. method according to claim 4 is characterized in that, described base vacuum degree is 3.5 * 10 ^-3Pa, described injecting voltage are 30kV, and described injected pulse frequency is 7Hz, and described injection pulsewidth is 450 μ s, and described injection length is 120 minutes.

7. according to each described method in the claim 1～6, it is characterized in that described polyether-ether-ketone is pure polyetheretherketonematerials materials or carbon fiber reinforced polyether-ether-ketone material.

8. method according to claim 7 is characterized in that, described polyether-ether-ketone is pure polyetheretherketonematerials materials, and titanium ion injects pure polyether-ether-ketone surface so that its surface has nano particle and nano thin-film.

9. method according to claim 7 is characterized in that, described polyether-ether-ketone is the carbon fiber reinforced polyether-ether-ketone material, and titanium ion injects the carbon fiber reinforced polyether-ether-ketone surface so that its surface has the multilevel hierarchy of porous and nano particle.

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