CN103614699B - Inject the method for tantalum ion to surface of polyether-ether-ketone and the polyetheretherketonematerials materials of modification - Google Patents
Inject the method for tantalum ion to surface of polyether-ether-ketone and the polyetheretherketonematerials materials of modification Download PDFInfo
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Abstract
The present invention relates to and inject the method for tantalum ion to surface of polyether-ether-ketone and the polyetheretherketonematerials materials of modification, described method uses plasma immersion ion implantation technique to carry out tantalum ion injection on the surface of polyether-ether-ketone to obtain the modified layer containing tantalum element, raising polyether-ether-ketone surface elastic modulus and hardness, to make it close to Human Cortex's bone, improve polyether-ether-ketone surface biocompatible and Integrated implant character simultaneously.Through the polyetheretherketonematerials materials that method of modifying process of the present invention obtains, its biocompatibility and mechanical property have raising in various degree.In addition, bMSC cell has obvious Osteoblast Differentiation trend on the polyetheretherketonematerials materials surface obtained through method of modifying process of the present invention.
Description
Technical field
The present invention relates to a kind of to the method for surface of polyether-ether-ketone and the polyetheretherketonematerials materials of modification, specifically, relate to a kind of plasma immersion and ion implantation and deposition technique of using to the method for polyetheretherketonematerials materials modifying surface and the polyetheretherketonematerials materials of modification being filled with tantalum ion, belong to Surface Modification of Medical Polymer Materials technical field.
Background technology
In recent years, along with biomaterial preparation uses constantly improving and development of theory and technology, high performance polymer implant material is expected to substitute titanium and titanium alloys material gradually, and application prospect will be more wide.The Young's modulus of polyether-ether-ketone (PEEK) comparatively mates with body bone tissue, bone resorption and osteanabrosis that stress-shielding effect causes effectively can be reduced after implant into body, and polyetheretherketonematerials materials resistance to chemical attack, fatigue resistance is given prominence to, be suitable for medical implant apparatus to implant (Biomaterials2007,28:4845-4869) for a long time.But the biological activity of PEEK is poor, after implant into body not easily with body bone tissue bonding, limit it and implant for a long time as implant material.How to improve PEEK Biocompatibility and become one of study hotspot.
The universal method of carrying out improving for this problem of polyetheretherketonematerials materials poor biocompatibility at present uses biological active materials to carry out compound (as tricalcium phosphate and hydroxyapatite etc.), although this method can effectively improve polyether-ether-ketone biocompatibility, but significantly sacrifice its intrinsic good mechanical property, be unfavorable for its clinical medical.
Summary of the invention
The present invention solves existing medical polyether-ether-ketone to there is the not good problem of biocompatibility, provides a kind of surface modifying method of medical polyetheretherketonematerials materials of novelty, to meet the physiologically acceptable sexual demand needed for medical polyetheretherketonematerials materials.
Plasma immersion and ion implantation and deposition technique (Plasmaimmersionionimplantation & Deposition, PIII-D) be a kind of there is new surface modifications technology that is comprehensive and high reaction activity feature, for process volume is little and the implant material of abnormal shape has unique advantage.PIII-D technology is generally used for metal and semiconductor surface modification, recently along with the widespread use of macromolecular material, PIII-D modification is carried out to insulating material and also becomes study hotspot (Surface & CoatingsTechnology2010,204:2853-2863) gradually.
Tantalum (Ta) has good chemical stability, erosion resistance and biocompatibility, namely be used as hard tissue implanting material by as a kind of metal implant in 1903, and be proved there is good Biocompatibility, promote bone growth (Biomaterials2001,22:1253-1262).But the density of tantalum is up to 16.6g/cm
3, Young's modulus, especially up to 186 ~ 191GPa, far away higher than Human Cortex's bone, easily causes the problem such as osteanabrosis and bone resorption, is therefore not suitable for being directly used in load bone replacement material.Recently the research of tantalum material is focused mostly in preparing porous tantalum material with lightening material weight or carry out tantalum coating process to improve implant biocompatibility.
Therefore, based on good chemical stability, erosion resistance and the biocompatibility of plasma immersion and ion implantation and deposition technique and tantalum, the present invention proposes, by plasma immersion ion implantation technique, Ta ion implantation modification is carried out to PEEK material, in-situ modified layer is formed at material surface, raising material is biocompatible while, strongthener surface mechanical properties.
At this, the invention provides and a kind ofly inject the method for tantalum ion to surface of polyether-ether-ketone, described method uses plasma immersion ion implantation technique to carry out tantalum ion injection on the surface of polyether-ether-ketone to obtain the modified layer containing tantalum element, raising polyether-ether-ketone surface elastic modulus and hardness, to make it close to Human Cortex's bone, improve polyether-ether-ketone surface biocompatible and Integrated implant character simultaneously.
Through the polyetheretherketonematerials materials that modification of the present invention obtains, its biocompatibility and Integrated implant character are significantly improved.Cell proliferation experiment confirms, the polyetheretherketonematerials materials surface MC3T3-E1 scleroblast obtained through modification of the present invention and bMSC rat bone marrow mesenchymal stem cells propagation are several times as much as unmodified polyether-ether-ketone, promote bMSC Osteoblast Differentiation, the performance requriements needed for medical polyether-ether-ketone can be met.
Through the polyetheretherketonematerials materials that modification of the present invention obtains, its surface elastic modulus and hardness significantly improve, and elastic recovery capability also more unmodified sample increases.Nano-indenter test experiment confirms, the polyetheretherketonematerials materials surface elastic modulus obtained through modification of the present invention and hardness are all several times as much as unmodified polyether-ether-ketone, close to the bone associated energy of Human Cortex.
Through the polyetheretherketonematerials materials that modification of the present invention obtains, the Ta Element release amount of injection is few, shows that it has stronger stability and biological safety, can meet medical demand.
Preferably, when using plasma immersion ion implantation technique to carry out tantalum ion injection on the surface of polyether-ether-ketone, use pure metal tantalum as negative electrode.Adopt pure metal tantalum to inject tantalum ion as negative electrode, while improving the biocompatibility of polyether-ether-ketone, still can keep the good mechanical property of material.
Preferably, it is 3 × 10 that the processing parameter that described tantalum ion injects comprises background vacuum
-3~ 5 × 10
-3pa, injecting voltage is 15 ~ 40kV, and injecting pulsewidth is 50 ~ 600 μ s, and injected pulse frequency is 5 ~ 10Hz, and it is 500 ~ 2000 μ s that pulsewidth is triggered in negative electrode source, and injection length is 30 ~ 180 minutes.
Further preferably, described injection pulsewidth is 200 ~ 600 μ s, and described injection length is 30 ~ 120 minutes.
In a preferred example, described injecting voltage is 15 ~ 30kV, and injection length is 30 ~ 120 minutes.
In a preferred example, described injecting voltage is 30kV, and described injected pulse frequency is 7Hz, and described injection pulsewidth is 450 μ s, and described injection length is 30 ~ 120 minutes.
In the present invention, described polyether-ether-ketone can be pure polyetheretherketonematerials materials or carbon fiber reinforced polyether-ether-ketone material.
On the other hand, the present invention also provides the polyetheretherketonematerials materials of the modification prepared according to aforesaid method, and in the modified layer of the polyetheretherketonematerials materials of described modification, the content of tantalum element is 5% ~ 15%.
The shallow surface arrangement of polyetheretherketonematerials materials obtained through surface modification treatment of the present invention has tantalum element, and tantalum element content ratio is adjustable.The introducing of tantalum element significantly improves biocompatibility and the Integrated implant character of polyetheretherketonematerials materials.
In the present invention, the surface elastic modulus of the polyetheretherketonematerials materials of described modification is than the large 0 ~ 6GPa in unmodified polyether-ether-ketone surface.
In the present invention, the nano-hardness improvement of the polyetheretherketonematerials materials of described modification is than the large 0 ~ 2GPa in unmodified polyether-ether-ketone surface.
Compared with prior art, the present invention has following beneficial effect:
Through the polyetheretherketonematerials materials that method of modifying process of the present invention obtains, its biocompatibility and mechanical property have raising in various degree.Cell proliferation experiment result confirms, the polyetheretherketonematerials materials obtained through method of modifying process of the present invention has good cell compatibility, and MC3T3-E1 cell and bMSC cell are several times as much as unmodified surface in modified surface propagation.In addition, bMSC cell has obvious Osteoblast Differentiation trend on the polyetheretherketonematerials materials surface obtained through method of modifying process of the present invention.Simultaneously, nano-indentation experiment result confirms, the polyetheretherketonematerials materials surface elastic modulus obtained through method of modifying process of the present invention and nano hardness are all improved largely, and close to the bone associated energy of Human Cortex, can meet the biocompatibility requirement needed for medical polyetheretherketonematerials materials.And the Ta Element release amount of injection is few, shows that it has stronger stability and biological safety, can meet medical demand.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope shape appearance figure on the polyether-ether-ketone surface before and after modification of the present invention, in figure: PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, and Ta-3 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 120 minutes;
Fig. 2 is the polyetheretherketonematerials materials surface XPS spectrogram entirely before and after modification of the present invention, in figure: PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, and Ta-3 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 120 minutes;
Fig. 3 is the XPS depth profile of polyetheretherketonematerials materials surface Ta element before and after modification of the present invention, in figure: PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, and Ta-3 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 120 minutes;
Fig. 4 is the polyetheretherketonematerials materials surface elastic modulus test result before and after modification of the present invention, in figure: ordinate zou represents Young's modulus, X-coordinate represents the degree of depth, PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, and Ta-3 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 120 minutes;
Fig. 5 is the polyetheretherketonematerials materials nano-hardness improvement test result before and after modification of the present invention, in figure: ordinate zou represents nano hardness, X-coordinate represents the degree of depth, PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, and Ta-3 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 120 minutes;
Fig. 6 is that the polyetheretherketonematerials materials surface elasticity before and after modification of the present invention recovers test result, in figure: ordinate zou represents load force, X-coordinate represents the degree of depth, PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, and Ta-3 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 120 minutes;
Fig. 7 is the polyetheretherketonematerials materials cell proliferation experiment result before and after modification of the present invention, in figure: ordinate zou represents the AlamarBlue be reduced
tMper-cent, X-coordinate represents the cell cultures time, PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, and Ta-3 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 120 minutes;
Fig. 8 is the polyetheretherketonematerials materials bMSC cell proliferation experiment result before and after modification of the present invention, in figure: ordinate zou represents the AlamarBlue be reduced
tMper-cent, X-coordinate represents the cell cultures time, PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, and Ta-3 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 120 minutes;
Fig. 9 is that the polyetheretherketonematerials materials bMSC Cellular alkaline phosphatase before and after modification of the present invention expresses experimental result, in figure: ordinate zou represents the relative content of alkaline phosphatase, X-coordinate represents the cell cultures time, PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, and Ta-3 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 120 minutes;
Figure 10 is that the polyetheretherketonematerials materials bMSC cell collagen before and after modification of the present invention expresses experimental result, in figure: ordinate zou represents the absorbance of collagen elutriant under 492nm wavelength, X-coordinate represents the cell cultures time, PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, and Ta-3 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 120 minutes;
Figure 11 is the polyetheretherketonematerials materials bMSC cell Expression of Extracellular Matrix experimental result before and after modification of the present invention, in figure: ordinate zou represents the absorbance of extracellular matrix elutriant under 600nm wavelength, X-coordinate represents the cell cultures time, PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, and Ta-3 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 120 minutes.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
In order to solve biocompatibility and the not good problem of mechanical property of existing medical polyetheretherketonematerials materials existence, the invention discloses a kind of surface modifying method of medical polyetheretherketonematerials materials, described method comprises the Young's modulus and hardness that tantalum ion are injected medical polyetheretherketonematerials materials surface and then improve polyether-ether-ketone surface to make it close to Human Cortex's bone, improves polyether-ether-ketone surface biocompatible and Integrated implant character simultaneously.
Preferably, using plasma immersion ion injects (PIII) technology at medical polyetheretherketonematerials materials surface imp lantation tantalum ion.
Preferably, using plasma immersion ion implantttion technique is when medical polyetheretherketonematerials materials surface imp lantation tantalum ion, and preferred pure tantalum is as negative electrode.
Using plasma immersion ion implantttion technique is recommended as at the processing parameter of medical polyetheretherketonematerials materials surface imp lantation tantalum ion: background vacuum is 3 × 10
-3~ 5 × 10
-3pa, injecting voltage is 15 ~ 40kV, and injecting pulsewidth is 50 ~ 600 μ s(preferably 200 ~ 600 μ s), injected pulse frequency is 5 ~ 10Hz, it is 500 ~ 2000 μ s(preferably 500 ~ 800 μ s that pulsewidth is triggered in negative electrode source), injection length is 30 ~ 180 minutes (preferably 30 ~ 120 minutes).
In a preferred example, injecting voltage is 15 ~ 30kV, and injection length is 30 ~ 120 minutes.In an especially preferred example, using plasma immersion ion implantttion technique is preferably at the processing parameter of medical polyetheretherketonematerials materials surface imp lantation tantalum ion: background vacuum is 5 × 10
-3pa, injecting voltage is 30kV, and injecting pulsewidth is 450 μ s, and injected pulse frequency is 7Hz, and it is 500 μ s that pulsewidth is triggered in negative electrode source, and injection length is 30 ~ 120 minutes.
Above-mentioned polyetheretherketonematerials materials can be pure polyetheretherketonematerials materials or carbon fiber reinforced polyether-ether-ketone material.
The polyetheretherketonematerials materials surface obtained through surface modification treatment of the present invention has different microtextures, see Fig. 1, it illustrates the scanning electron microscope shape appearance figure on the polyether-ether-ketone surface before and after modification of the present invention, in figure: PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, Ta-3 represents the polyether-ether-ketone product of use 30kV high pressure injection tantalum after 120 minutes, show that modified material surface will occur nano particle, the size of nano particle and quantity increase along with injection length and injecting voltage strengthens and increases.Simultaneously, the shallow surface arrangement of polyetheretherketonematerials materials obtained through modification of the present invention has tantalum element, tantalum element content ratio is adjustable (5 ~ 15%), the polyetheretherketonematerials materials surface XPS spectrogram entirely obtained through modification of the present invention as shown in Figure 2, therefrom can calculate the polyetheretherketonematerials materials surface tantalum constituent content obtained through this modification of the present invention and be respectively 6.6% (Ta-1), 12.1% (Ta-2) and 10.4% (Ta-3), show that tantalum element content increases along with injection length and increases.
Injection length and injecting voltage also affect the injection degree of depth of Ta.See Fig. 3, it illustrates the XPS depth profile of polyetheretherketonematerials materials surface Ta element before and after modification of the present invention, in figure: PEEK represents the polyether-ether-ketone before modification, Ta-1 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 30 minutes, Ta-2 represents the polyether-ether-ketone of use 15kV high pressure injection tantalum after 120 minutes, Ta-3 represents the polyether-ether-ketone of use 30kV high pressure injection tantalum after 120 minutes, as seen from the figure, through the polyetheretherketonematerials materials surface Ta that method of modifying process of the present invention obtains, there is a continuous print distribution; The injection degree of depth that high-voltage injects Ta under modification is for a long time darker, and modified layer is thicker; Under same depth, the content that high-voltage injects the modification sample Ta that modification obtains for a long time is higher.
The polyetheretherketonematerials materials mechanics of surface character obtained through modification of the present invention obtains lifting in various degree, the large 0 ~ 6GPa in its modular ratio unmodified polyether-ether-ketone surface, and nano hardness is than the large 0 ~ 2GPa in unmodified polyether-ether-ketone surface.As Fig. 4 illustrates the polyetheretherketonematerials materials surface elastic modulus test result obtained through modification of the present invention, show that modified material surface Young's modulus is significantly improved.Such as, as shown in curve Ta-3 wherein, modified material surface Young's modulus is promoted to more than 12GPa, close to cortex bone correlated performance from about 7Gpa before modified.Again as shown in Figure 5, the material surface nano hardness obtained through modification of the present invention also has remarkable lifting, such as, as shown in curve Ta-3 wherein, modified material surface nano hardness is promoted to about 3GPa from about 1.4GPa before modified, shows modified material surface hardness higher.Again as shown in Figure 6, the polyetheretherketonematerials materials obtained through method of modifying process of the present invention is for unmodified polyether-ether-ketone, elastic recovery capability all increases, wherein, the sample increase rate of long-time injection modification is larger, especially adopt 30kV high pressure injection tantalum 120 minutes (Ta-3) to process the sample obtained, compression distance and the recovery degree of depth all significantly improve, and show modified sample surfaces and have stronger restorability under force.
The introducing of tantalum element effectively can improve biocompatibility and the Integrated implant character of polyetheretherketonematerials materials.By selecting different processing parameter modifications, its biocompatibility and Integrated implant character have raising in various degree, can meet the biocompatibility requirement needed for medical polyetheretherketonematerials materials.Cell proliferation experiment result confirms, the polyetheretherketonematerials materials obtained through method of modifying process of the present invention has good cell compatibility, and MC3T3-E1 cell and bMSC cell are several times as much as unmodified surface in modified surface propagation.For example, see Fig. 7, it illustrates the polyetheretherketonematerials materials cell proliferation experiment result before and after modification of the present invention, in figure: PEEK represents polyetheretherketonematerials materials before treatment, Ta-1 represents the sample using 30kV high pressure to inject 30 minutes gained, Ta-2 represents the sample using 15kV high pressure to inject 120 minutes gained, Ta-3 represents the sample using 30kV high pressure to inject 120 minutes gained, as seen from the figure, MC3T3-E1 cell in the polyetheretherketonematerials materials surface growth situation obtained through above-mentioned example embodiment modification all significantly better than unmodified sample, wherein, MC3T3-E1 cell injects the situation that polyetheretherketonematerials materials surface growth situation that 120 minutes institute's modifications obtain to inject significantly better than 30kV high pressure 30 minutes injecting 120 minutes and 30kV high pressure through 15kV high pressure, show that the polyether-ether-ketone surface that tantalum injection length is long is more conducive to cell proliferation.For example, see Fig. 8, it illustrates the polyetheretherketonematerials materials bMSC cell proliferation experiment result before and after modification of the present invention, known bMSC cell in the polyetheretherketonematerials materials surface growth situation obtained through modification of the present invention significantly better than unmodified sample.Again, the polyetheretherketonematerials materials obtained through method of modifying process of the present invention can promote bMSC Osteoblast Differentiation.For example, see Fig. 9 ~ 11, known bMSC cell has obvious Osteoblast Differentiation trend on the polyetheretherketonematerials materials surface obtained through method of modifying process of the present invention.
Embodiment of illustrating further is below to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; and limiting the scope of the invention can not be interpreted as, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The processing parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
By the pure polyether-ether-ketone of 10mm × 10mm × 1mm after polished finish, use acetone and deionized water ultrasonic cleaning successively totally, each 30min, cleaning is placed in 80 DEG C of baking ovens dries and properly preservation.Using plasma immersion ion implantttion technique, injects polyether-ether-ketone matrix (Ta-1) by tantalum ion, inject modified polyetheretherketonematerials materials and properly preserve, and its concrete processing parameter is shown in Table 1:
Table 1 tantalum ion injection parameter:
| Injecting voltage (kV) | 30 | Inject pulsewidth (μ s) | 450 |
| Injection length (min) | 30 | Base vacuum (Pa) | 5×10 -3 |
| Negative electrode triggers pulsewidth (μ s) | 700 | Frequency (Hz) | 7 |
Ta-1 in Fig. 1 is the medical polyetheretherketonematerials materials surface topography map obtained through the present embodiment modification, and showing modified material surface in figure has minimum nano particle, and size is about several nanometer; Ta-1 in Fig. 2 is the medical polyetheretherketonematerials materials surface XPS spectrogram entirely obtained through the present embodiment modification, show: use plasma immersion ion implantttion technique tantalum element can be introduced into polyetheretherketonematerials materials surface, the polyetheretherketonematerials materials surface tantalum constituent content obtained through the present embodiment modification is 6.6%.
Embodiment 2
By the pure polyether-ether-ketone of 10mm × 10mm × 1mm after polished finish, use acetone and deionized water ultrasonic cleaning successively totally, each 30min, cleaning is placed in 80 DEG C of baking ovens dries and properly preservation.Using plasma immersion ion implantttion technique, injects polyether-ether-ketone matrix (Ta-2) by tantalum ion, inject modified polyetheretherketonematerials materials and properly preserve, and its concrete processing parameter is shown in Table 2:
Table 2 tantalum ion injection parameter:
| Injecting voltage (kV) | 15 | Inject pulsewidth (μ s) | 450 |
| Injection length (min) | 120 | Base vacuum (Pa) | 5×10 -3 |
| Negative electrode triggers pulsewidth (μ s) | 700 | Frequency (Hz) | 7 |
Ta-2 in Fig. 1 is the medical polyetheretherketonematerials materials surface topography map obtained through the present embodiment modification, and showing modified material surface in figure has nano particle, and size is large compared with Ta-1, is about 10 nanometers; Ta-2 in Fig. 2 is the medical polyetheretherketonematerials materials surface XPS spectrogram entirely obtained through the present embodiment modification, show: use plasma immersion ion implantttion technique tantalum element can be introduced into polyetheretherketonematerials materials surface, the polyetheretherketonematerials materials surface tantalum constituent content obtained through the present embodiment modification is 12.1%.
Embodiment 3
By the pure polyether-ether-ketone of 10mm × 10mm × 1mm after polished finish, use acetone and deionized water ultrasonic cleaning successively totally, each 30min, cleaning is placed in 80 DEG C of baking ovens dries and properly preservation.Using plasma immersion ion implantttion technique, injects polyether-ether-ketone matrix (Ta-3) by tantalum ion, inject modified polyetheretherketonematerials materials and properly preserve, and its concrete processing parameter is shown in Table 3:
Table 3 tantalum ion injection parameter:
| Injecting voltage (kV) | 30 | Inject pulsewidth (μ s) | 450 |
| Injection length (min) | 120 | Base vacuum (Pa) | 5×10 -3 |
| Negative electrode triggers pulsewidth (μ s) | 700 | Frequency (Hz) | 7 |
Ta-3 in Fig. 1 is the medical polyetheretherketonematerials materials surface topography map obtained through the present embodiment modification, and showing modified material surface in figure has nano particle, and size is large compared with Ta-1 and Ta-2, is about 10 ~ 20 nanometers; Ta-3 in Fig. 2 is the medical polyetheretherketonematerials materials surface XPS spectrogram entirely obtained through the present embodiment modification, show: use plasma immersion ion implantttion technique tantalum element can be introduced into polyetheretherketonematerials materials surface, the polyetheretherketonematerials materials surface tantalum constituent content obtained through the present embodiment modification is 10.4%.
Embodiment 4
By the carbon fiber reinforced polyether-ether-ketone of 10mm × 10mm × 1mm after polished finish, use acetone and deionized water ultrasonic cleaning successively totally, each 30min, cleaning is placed in 80 DEG C of baking ovens dries and properly preservation.Using plasma immersion ion implantttion technique, injects carbon fiber reinforced polyether-ether-ketone matrix by tantalum ion, inject modified carbon fiber reinforced polyether-ether-ketone material and properly preserve, its concrete processing parameter is shown in Table 4:
Table 4 tantalum ion injection parameter:
| Injecting voltage (kV) | 30 | Inject pulsewidth (μ s) | 450 |
| Injection length (min) | 120 | Base vacuum (Pa) | 5×10 -3 |
| Negative electrode triggers pulsewidth (μ s) | 700 | Frequency (Hz) | 7 |
Embodiment 5
By the carbon fiber reinforced polyether-ether-ketone of 10mm × 10mm × 1mm after polished finish, use acetone and deionized water ultrasonic cleaning successively totally, each 30min, cleaning is placed in 80 DEG C of baking ovens dries and properly preservation.Using plasma immersion ion implantttion technique, injects carbon fiber reinforced polyether-ether-ketone matrix by tantalum ion, inject modified carbon fiber reinforced polyether-ether-ketone material and properly preserve, its concrete processing parameter is shown in Table 5:
Table 5 tantalum ion injection parameter:
| Injecting voltage (kV) | 15 | Inject pulsewidth (μ s) | 450 |
| Injection length (min) | 120 | Base vacuum (Pa) | 5×10 -3 |
| Negative electrode triggers pulsewidth (μ s) | 500 | Frequency (Hz) | 7 |
Embodiment 6
Adopt XPS analysis characterized by techniques through above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials surface Ta elemental distribution.Test condition is 3.96nm/min etching speed, and MTD is 100nm, corresponding with the mechanical test degree of depth;
Fig. 3 is the polyetheretherketonematerials materials surface Ta element depth distribution figure through above-described embodiment modification obtains, wherein: Ta-1 represents the sample obtained through embodiment 1 modification, Ta-2 represents the sample obtained through embodiment 2 modification, and Ta-3 represents the sample obtained through embodiment 3 modification.As seen from Figure 3: through the polyetheretherketonematerials materials surface Ta that method of modifying process of the present invention obtains, there is a continuous print distribution; The injection degree of depth that high-voltage injects Ta under modification is for a long time darker, and modified layer is thicker; Under same depth, the content that high-voltage injects the modification sample Ta that modification obtains for a long time is higher.
Embodiment 7
Adopt Nanoindentation assessment through above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials surface mechanical properties, the index of main its surface elastic modulus of test and nano hardness.Nano hardness test is carried out to the polyetheretherketonematerials materials obtained through above-described embodiment modification: utilize nano-hardness tester (Mei Tesi process system company limited of the U.S.), with continuous hardness test, nano hardness test is carried out to material, triangle Buddha's warrior attendant cone pressure head is 100nm at material surface compression distance under the promotion of load force, and computer software records corresponding data simultaneously.The Young's modulus of sample and hardness value are obtained by measure sample five different zones;
Fig. 4 and Fig. 5 is the polyetheretherketonematerials materials surface elastic modulus and depth relationship figure and nano-hardness improvement and depth relationship figure that obtain through above-described embodiment modification respectively, wherein: PEEK represents unmodified sample, Ta-1 represents the sample obtained through embodiment 1 modification, Ta-2 represents the sample obtained through embodiment 2 modification, and Ta-3 represents the sample obtained through embodiment 3 modification.From Fig. 4 and Fig. 5: the polyetheretherketonematerials materials obtained through method of modifying process of the present invention is for unmodified polyether-ether-ketone, Young's modulus and nano hardness all increase, wherein, the sample increase rate that high-voltage injects modification is larger, especially embodiment 3 is adopted to process the sample obtained, surface elastic modulus is promoted to about 12GPa, close to the bone associated energy of Human Cortex.
Embodiment 8
Adopt Nanoindentation assessment through above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials surface elasticity restorability.Concrete grammar is as follows: utilize nano-hardness tester (Mei Tesi process system company limited of the U.S.), by fixed load method, elastic recovery properties test is carried out to material, triangle Buddha's warrior attendant cone pressure head is pushed down into material surface in the promotion of load force 1.3mN, it is 200 μ N/s that load force gathers way, and the dwell time is 10s.Computer software records corresponding data simultaneously.The recovery of elasticity of sample is obtained by measure sample five different zones;
Fig. 6 is the polyetheretherketonematerials materials surface elasticity recovery figure obtained through above-described embodiment modification, wherein: PEEK represents unmodified sample, Ta-1 represents the sample obtained through embodiment 1 modification, Ta-2 represents the sample obtained through embodiment 2 modification, and Ta-3 represents the sample obtained through embodiment 3 modification.As seen from Figure 7: the polyetheretherketonematerials materials obtained through method of modifying process of the present invention is for unmodified polyether-ether-ketone, elastic recovery capability all increases, wherein, the sample increase rate of long-time injection modification is larger, especially embodiment 3 is adopted to process the sample obtained, compression distance and the recovery degree of depth all significantly improve, and show modified sample surfaces and have stronger restorability under force.
Embodiment 9
Adopt Tutofusin tris (Tris) and hydrochloric acid (HCl) solution preparation Tris-HCl buffered soln, at 36.5 DEG C, adjust ph is 7.4.Sample before and after modification of the present invention is soaked in the above-mentioned buffered soln of 5mL, solution is taken out and the buffered soln more renewed every 7 days, soak after 7,14,21 and 28 days, adopt inductive coupling plasma emission spectrograph (ICP-OES, VistaAX, Varian, USA) tantalum ion concentration in test soln.The burst size of tantalum element is as shown in table 6, and wherein: Ta-1 represents the sample obtained through embodiment 1 modification, Ta-2 represents the sample obtained through embodiment 2 modification, and Ta-3 represents the sample obtained through embodiment 3 modification;
Table 6 tantalum element burst size
Table note: fail to detect expression content lower than 0.002ppm
From table 6, Ta element is injected into after in polyetheretherketonematerials materials, and burst size is few, shows that Ta ion implantation modification polyether-ether-ketone has stronger stability and biological safety.
Embodiment 10
Adopt MC3T3-E1 cell injuring model experimental evaluation through the cell compatibility of above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials.Utilize AlamarBlue
tM(AbDserotecLtd, UK) kit detection cell is at the proliferative conditions of material surface.Method is as follows:
1) sample of use 75% ethanol sterilizing is put into 24 well culture plates, it is 5 × 10 that every hole drips 1mL density
4cell/mLMC3T3-E1 cell suspension;
2) Tissue Culture Plate is put into 5%CO
236.5 DEG C of hatching 18h in the cell culture incubator of saturated humidity;
3) suck cell culture fluid, after cleaning sample surfaces with PBS, sample is moved in 24 new orifice plates, put into incubator and continue to cultivate;
4) cell cultures is after 1,4 and 7 days, sucks original fluid, adds containing 10%AlamarBlue
tMthe new nutrient solution of dye liquor, is placed in culture plate after incubator cultivates 4h, takes out 100 μ L nutrient solutions put into 96 orifice plates from every hole;
5) microplate reader (BIO-TEK, ELX800) is utilized to measure the absorbance of each hole under 570nm and 600nm wavelength.According to following formulae discovery AlamarBlue
tMpercentage by cell reduces:
Formula:
Wherein: A is absorbance, the absorbance that A ' is negative control hole, λ
1=570nm, λ
2=600nm;
Fig. 7 is the polyether-ether-ketone and unmodified polyether-ether-ketone cell proliferation experiment statistics that obtain through above-described embodiment 1,2 and 3 modification, in figure: PEEK represents unmodified polyether-ether-ketone, Ta-1 represents Ta-1 sample, and Ta-2 represents Ta-2 sample, and Ta-3 represents Ta-3 sample.As seen from Figure 7: MC3T3-E1 cell is in the polyetheretherketonematerials materials surface growth situation obtained through above-described embodiment 1,2 and 3 modification significantly better than unmodified sample, and meanwhile, long-time high-voltage injects tantalum and is conducive to cell at polyether-ether-ketone surface growth.
Embodiment 11
Adopt rat bone marrow mesenchymal stem cells (bMSC) vitro culture experimental evaluation through the stem cells consistency of above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials.Utilize AlamarBlue
tM(AbDserotecLtd, UK) kit detection cell is at the proliferative conditions of material surface.Method is as follows:
1) sample of use 75% ethanol sterilizing is put into 24 well culture plates, it is 2.5 × 10 that every hole drips 1mL density
4cell/mLbMSC cell suspension;
2) Tissue Culture Plate is put into 5%CO
236.5 DEG C of hatching 18h in the cell culture incubator of saturated humidity;
3) suck cell culture fluid, after cleaning sample surfaces with PBS, sample is moved in 24 new orifice plates, put into incubator and continue to cultivate;
4) cell cultures is after 1,4 and 7 days, sucks original fluid, adds containing 5%AlamarBlue
tMthe new nutrient solution of dye liquor, is placed in culture plate after incubator cultivates 4h, takes out 100 μ L nutrient solutions put into 96 orifice plates from every hole;
5) microplate reader (BIO-TEK, ELX800) is utilized to measure the absorbance of each hole under 570nm and 600nm wavelength.According to following formulae discovery AlamarBlue
tMpercentage by cell reduces:
Formula:
Wherein: A is absorbance, the absorbance that A ' is negative control hole, λ
1=570nm, λ
2=600nm;
Fig. 8 is the polyether-ether-ketone and unmodified polyether-ether-ketone cell proliferation experiment statistics that obtain through above-described embodiment 1,2 and 3 modification, in figure: PEEK represents unmodified polyether-ether-ketone, Ta-1 represents Ta-1 sample, and Ta-2 represents Ta-2 sample, and Ta-3 represents Ta-3 sample.As seen from Figure 8: bMSC cell is in the polyetheretherketonematerials materials surface growth situation obtained through above-described embodiment 1,2 and 3 modification significantly better than unmodified sample, and meanwhile, high-voltage injects tantalum and is conducive to bMSC cell at polyether-ether-ketone surface growth.
Embodiment 12
Adopt the assessment of rat bone marrow mesenchymal stem cells (bMSC) experiment in vitro through stem cell alkaline phosphatase (ALP) the protein expression situation of above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials, method is as follows:
1) sample of use 75% ethanol sterilizing is put into 24 well culture plates, it is 1 × 10 that 7 days every holes of sample drip 1mL density
4cell/mLbMSC cell suspension, it is 0.5 × 10 that 14 days every holes of sample drip 1mL density
4cell/mLbMSC cell suspension;
2) Tissue Culture Plate is put into 5%CO
236.5 DEG C of cultivations in the cell culture incubator of saturated humidity; Liquid is changed every 3 days;
3) cell cultures is after 7 days and 14 days, sucks original fluid, after PBS cleans twice, uses lysate lysing cell, process lasts 40min.ALP quantitative analysis adopts the substratum containing p-nitrophenyl phosphate (p-nitrophenylphosphate, pNPP, Sigma, USA), by lysate, pNPP and damping fluid mixed solution at 36.5 DEG C and 5%CO
2cultivate 30min in atmosphere incubator, measure solution O D value under 405nm absorbing wavelength, the ALP for analytic sample superficial cell is active.Use protein determination device (Bio-Rad, USA) to calculate total protein content, under 570nm wavelength, carry out stdn;
Fig. 9 is that the polyether-ether-ketone that obtains through above-described embodiment 1,2 and 3 modification and unmodified polyether-ether-ketone ALP express experiment statistics result, in figure: PEEK represents unmodified polyether-ether-ketone, Ta-1 represents Ta-1 sample, and Ta-2 represents Ta-2 sample, and Ta-3 represents Ta-3 sample.As seen from Figure 9: when 7 days, bMSC cell is at the polyetheretherketonematerials materials surface A LP expression obtained through above-described embodiment 1,2 and 3 modification significantly better than unmodified sample, and Ta-2 is better than Ta-1 and Ta-3 simultaneously; When 14 days, bMSC cell is at the polyetheretherketonematerials materials surface A LP expression obtained through above-described embodiment 1 and 3 modification significantly better than unmodified sample, and bMSC cell is expressed substantially identical with unmodified sample at the polyetheretherketonematerials materials surface A LP obtained through embodiment 2 modification.
Embodiment 13
Adopt the assessment of rat bone marrow mesenchymal stem cells (bMSC) experiment in vitro through stem cell collagen (COI) the protein expression situation of above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials, method is as follows:
1) sample of use 75% ethanol sterilizing is put into 24 well culture plates, it is 1 × 10 that 7 days every holes of sample drip 1mL density
4cell/mLbMSC cell suspension, it is 0.5 × 10 that 14 days every holes of sample drip 1mL density
4cell/mLbMSC cell suspension;
2) Tissue Culture Plate is put into 5%CO
236.5 DEG C of cultivations in the cell culture incubator of saturated humidity; Liquid is changed every 3 days;
3) cell cultures is after 7 days and 14 days, sucks original fluid, and PBS cleans 3 times;
4) with 4% paraformaldehyde fixed sample 20min;
5), after PBS cleans 3 times, dye with the collagen of 0.1% Picro-Sirius red to emiocytosis be dissolved in saturated picric acid, dyeing course continues 18h;
6) rinsing sample is till separating out without red color repeatedly for the acetic acid of the rear 0.1M of dyeing, and use microphotograph obtains coloration result;
7) for carrying out quantitative comparison, every hole adds 0.5mL elutriant (0.2M sodium hydroxide and methyl alcohol are with 1:1 proportional arrangement), and 15min is by specimen surface dyestuff wash-out in vibration, tests its absorbance at 492nm;
Figure 10 is that the polyether-ether-ketone that obtains through above-described embodiment 1,2 and 3 modification and unmodified polyether-ether-ketone COI express experiment statistics result, in figure: PEEK represents unmodified polyether-ether-ketone, Ta-1 represents Ta-1 sample, and Ta-2 represents Ta-2 sample, and Ta-3 represents Ta-3 sample.As seen from Figure 10: when 7 days bMSC cell at the polyetheretherketonematerials materials surface C OI expression obtained through above-described embodiment 1,2 and 3 modification significantly better than unmodified sample; When 14 days, bMSC cell is at the polyetheretherketonematerials materials surface C OI expression obtained through above-described embodiment 1,2 and 3 modification significantly better than unmodified sample, and wherein Ta-1 is better than Ta-2 and Ta-3.
Embodiment 14
Adopt the assessment of rat bone marrow mesenchymal stem cells (bMSC) experiment in vitro through stem cells epimatrix (ECM) the protein expression situation of above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials, method is as follows:
1) sample of use 75% ethanol sterilizing is put into 24 well culture plates, it is 1 × 10 that 7 days every holes of sample drip 1mL density
4cell/mLbMSC cell suspension, it is 0.5 × 10 that 14 days every holes of sample drip 1mL density
4cell/mLbMSC cell suspension;
2) Tissue Culture Plate is put into 5%CO
236.5 DEG C of cultivations in the cell culture incubator of saturated humidity; Liquid is changed every 3 days;
3) cell cultures is after 7 days and 14 days, sucks original fluid, and PBS cleans 3 times;
4) with 75% alcohol fixation sample 60min;
5) dye to cell by the sodium alizarinsulfonate (pH=4.2) of 40mM, dyeing course continues 10min;
6) after dyeing, with distilled water, rinsing sample is till separating out without red color repeatedly, and use microphotograph obtains coloration result;
7) for carrying out quantitative comparison, every hole adds 0.5mL elutriant (10% cetylpyridinium chloride, solvent is the sodium phosphate of pH=7), and 15min is by specimen surface dyestuff wash-out in vibration, tests its absorbance at 600nm;
Figure 11 is that the polyether-ether-ketone that obtains through above-described embodiment 1,2 and 3 modification and unmodified polyether-ether-ketone ECM express experiment statistics result, in figure: PEEK represents unmodified polyether-ether-ketone, Ta-1 represents Ta-1 sample, and Ta-2 represents Ta-2 sample, and Ta-3 represents Ta-3 sample.As seen from Figure 11: when 7 days, bMSC cell is at the polyetheretherketonematerials materials surface ECM expression obtained through above-described embodiment 1,2 and 3 modification significantly better than unmodified sample, and Ta-2 is better than Ta-1 and Ta-3 simultaneously; When 14 days, bMSC cell is at the polyetheretherketonematerials materials surface ECM expression obtained through above-described embodiment 1,2 and 3 modification significantly better than unmodified sample, and wherein, Ta-1 is better than Ta-2 and Ta-3.
Industrial applicability: method of the present invention is simple and easy to control, through the polyetheretherketonematerials materials that modification of the present invention obtains, its biocompatibility, Integrated implant character and surface mechanical properties are significantly improved, and can meet the performance requriements needed for medical polyether-ether-ketone.
Claims (6)
1. one kind is injected the method for tantalum ion to surface of polyether-ether-ketone, it is characterized in that, described method uses plasma immersion ion implantation technique to carry out tantalum ion injection on the surface of polyether-ether-ketone to obtain the modified layer containing tantalum element, raising polyether-ether-ketone surface elastic modulus and hardness are to make it close to Human Cortex's bone, improve polyether-ether-ketone surface biocompatible and Integrated implant character simultaneously, wherein, the processing parameter that described tantalum ion injects comprises: background vacuum is 3 × 10
-3~ 5 × 10
-3pa, injecting voltage is 15 ~ 40kV, and injecting pulsewidth is 50 ~ 600 μ s, and injected pulse frequency is 5 ~ 10Hz, and it is 500 ~ 2000 μ s that pulsewidth is triggered in negative electrode source, and injection length is 30 ~ 180 minutes;
Described polyether-ether-ketone is pure polyetheretherketonematerials materials or carbon fiber reinforced polyether-ether-ketone material;
The surface elastic modulus of the polyetheretherketonematerials materials of described modification improves 0 ~ 6GPa than unmodified polyether-ether-ketone surface;
The nano-hardness improvement of the polyetheretherketonematerials materials of described modification improves 0 ~ 2GPa than unmodified polyether-ether-ketone surface.
2. method according to claim 1, is characterized in that, when using plasma immersion ion implantation technique to carry out tantalum ion injection on the surface of polyether-ether-ketone, uses pure metal tantalum as negative electrode.
3. method according to claim 1 and 2, is characterized in that, described injection pulsewidth is 200 ~ 600 μ s, and described injection length is 30 ~ 120 minutes.
4. method according to claim 3, is characterized in that, described injecting voltage is 15 ~ 30kV, and injection length is 30 ~ 120 minutes.
5. method according to claim 4, is characterized in that, described injecting voltage is 30kV, and described injected pulse frequency is 7Hz, and described injection pulsewidth is 450 μ s, and described injection length is 30 ~ 120 minutes.
6. a polyetheretherketonematerials materials for the method modification according to any one of Claims 1 to 5, is characterized in that, in the modified layer of the polyetheretherketonematerials materials of described modification, the content of tantalum element is 5% ~ 15%.
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| CN104975267B (en) * | 2014-04-09 | 2017-08-11 | 中国科学院上海硅酸盐研究所 | A kind of method that polyetheretherketonematerials materials are carried out with surface modification |
| CN105331946B (en) * | 2015-11-18 | 2018-04-03 | 中国科学院上海硅酸盐研究所 | A kind of method that zirconium-ion implantation improves medical polyetheretherketonematerials materials bioactivity |
| CN107829123B (en) * | 2017-10-09 | 2020-05-12 | 深圳市中科摩方科技有限公司 | Aluminum alloy with double-layer coating on surface and preparation method and application thereof |
| CN112321880B (en) * | 2020-11-27 | 2021-06-01 | 中国科学院兰州化学物理研究所 | Method for modifying polyether-ether-ketone surface by injecting bimetallic ions |
| CN112961565B (en) * | 2021-03-26 | 2022-05-17 | 暨南大学 | Tantalum-reinforced polyether-ether-ketone composite coating and preparation method and application thereof |
| CN113106520B (en) * | 2021-03-26 | 2022-07-01 | 暨南大学 | Tantalum carbide reinforced polyether-ether-ketone composite coating and preparation method and application thereof |
| CN113105807B (en) * | 2021-03-26 | 2022-05-20 | 暨南大学 | Tantalum nitride reinforced polyether-ether-ketone composite coating and preparation method and application thereof |
| CN115341255A (en) * | 2022-08-25 | 2022-11-15 | 暨南大学 | Ion-implanted PEEK-Cu composite coating and preparation method and application thereof |
| CN115607731A (en) * | 2022-10-17 | 2023-01-17 | 四川大学 | Polyether ketone composite material, preparation method and application |
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