CN103614699A - Method for modifying surface of polyetheretherketone by injecting tantalum ion and modified polyetheretherketone material - Google Patents
Method for modifying surface of polyetheretherketone by injecting tantalum ion and modified polyetheretherketone material Download PDFInfo
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Abstract
The invention relates to a method for modifying the surface of polyetheretherketone by injecting tantalum ions and a modified polyetheretherketone material. According to the method, the tantalum element containing modified layer is obtained by injecting the tantalum ions to the surface of the polyetheretherketone by adopting a plasma immersion ion injection technology, the polyetheretherketone approaches the cortical bone of a human body by enhancing the elastic modulus and rigidity of the surface of the polyetheretherketone and the biocompatibility and osseointegration property of the surface of the polyetheretherketone are improved. The polyetheretherketone material obtained through the treatment of the modifying method is enhanced in biocompatibility and mechanical property at different degrees. Besides, a bMSC (Bone Marrow Stromal Cells) cell has an obvious osteogenic differentiation trend on the surface of the polyetheretherketone material obtained through the treatment of the modifying method.
Description
Technical field
The present invention relates to a kind of polyetheretherketonematerials materials to the method for polyether-ether-ketone modifying surface and modification, specifically, relate to a kind of use plasma immersion ion to inject and deposition technique to the method for polyetheretherketonematerials materials modifying surface and the polyetheretherketonematerials materials of having injected the modification of tantalum ion, belong to Surface Modification of Medical Polymer Materials technical field.
Background technology
In recent years, along with constantly improving and development of theory and technology used in biomaterial preparation, high performance polymer implant material is expected to instead of titanium and alloy material thereof gradually, and application prospect will be more wide.The Young's modulus of polyether-ether-ketone (PEEK) comparatively mates with body bone tissue, after implant into body, can effectively reduce bone resorption and the osteanabrosis that stress-shielding effect causes, and polyetheretherketonematerials materials resistance to chemical attack, fatigue resistance is outstanding, be suitable for medical implant apparatus and implant for a long time that (Biomaterials 2007,28:4845-4869).Yet the biological activity of PEEK is poor, after implant into body, be difficult for and body bone tissue bonding, limited it and implanted for a long time as implant material.How to improve PEEK Biocompatibility and become one of study hotspot.
For poor this problem of polyetheretherketonematerials materials biocompatibility, carrying out improved universal method is at present to use 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 sacrificed its intrinsic good mechanical property, be unfavorable for its clinical medical.
Summary of the invention
There is the not good problem of biocompatibility for solving existing medical polyether-ether-ketone in the present invention, provides a kind of surface modifying method of medical polyetheretherketonematerials materials of novelty, to meet the required physiologically acceptable sexual demand of medical polyetheretherketonematerials materials.
Plasma immersion ion injects and deposition technique (Plasma immersion ion implantation & Deposition, PIII-D) be a kind of novel surface modification technology with comprehensive and high reaction activity feature, for processing the little and special-shaped implant material of volume, there is unique advantage.PIII-D technology is generally used for metal and semiconductor surface modification, the recent widespread use along with macromolecular material, to insulating material carry out PIII-D modification also become gradually study hotspot (Surface & Coatings Technology 2010,204:2853-2863).
Tantalum (Ta) has good chemical stability, erosion resistance and biocompatibility, in 1903, be used as a kind of metal implant as hard tissue implanting material, and be proved and there is good Biocompatibility, (Biomaterials 2001,22:1253-1262) to promote bone growth.Yet the density of tantalum is up to 16.6g/cm
3, Young's modulus, especially up to 186～191GPa, far away higher than human body cortex bone, easily causes the problems 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 carrying out tantalum coating process and improve implant biocompatibility.
Therefore, good chemical stability, erosion resistance and biocompatibility based on plasma immersion ion injection and deposition technique and tantalum, the present invention proposes by plasma immersion ion implantation technique PEEK material is carried out to Ta ion implantation modification, at material surface, form in-situ modified layer, improving biocompatible while of material, strongthener surface mechanical properties.
At this, the invention provides a kind of method of tantalum ion to polyether-ether-ketone modifying surface of injecting, described method is used plasma immersion ion implantation technique on the surface of polyether-ether-ketone, to carry out tantalum ion injection to obtain the modified layer that contains tantalum element, improve polyether-ether-ketone surface elastic modulus and hardness so that it approaches human body cortex bone, improve polyether-ether-ketone surface biological consistency and bone simultaneously and integrate character.
The polyetheretherketonematerials materials obtaining through modification of the present invention, its biocompatibility and bone are integrated character and are significantly improved.Cell proliferation experiment confirms, the polyetheretherketonematerials materials surface MC3T3-E1 scleroblast and the bMSC rat bone marrow mesenchymal stem cells propagation that through modification of the present invention, obtain are several times as much as unmodified polyether-ether-ketone, promote bMSC Osteoblast Differentiation, can meet the required performance requriements of medical polyether-ether-ketone.
The polyetheretherketonematerials materials obtaining through modification of the present invention, its surface elastic modulus and hardness significantly improve, and elastic recovery capability also more unmodified sample increases.Nano-indenter test experiment confirmation, the polyetheretherketonematerials materials surface elastic modulus and the hardness that through modification of the present invention, obtain are all several times as much as unmodified polyether-ether-ketone, approach human body cortex bone correlated performance.
The polyetheretherketonematerials materials obtaining through modification of the present invention, the Ta Element release amount of injection is few, shows that it has stronger stability and biological safety, can meet medical demand.
Preferably, while 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, when improving the biocompatibility of polyether-ether-ketone, still can keep the good mechanical property of material.
Preferably, the processing parameter that described tantalum ion injects comprises that base vacuum degree 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, 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 of preparing 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 obtaining through surface modification treatment of the present invention has tantalum element, and tantalum element content ratio is adjustable.The introducing of tantalum element has improved significantly biocompatibility and the bone of polyetheretherketonematerials materials and has integrated character.
In the present invention, the surface elastic modulus of the polyetheretherketonematerials materials of described modification is than the unmodified polyether-ether-ketone large 0～6GPa in surface.
In the present invention, the nano-hardness improvement of the polyetheretherketonematerials materials of described modification is than the unmodified polyether-ether-ketone large 0～2GPa in surface.
Compared with prior art, the present invention has following beneficial effect:
Through method of modifying of the present invention, process the polyetheretherketonematerials materials obtaining, its biocompatibility and mechanical property have raising in various degree.Cell proliferation experiment result confirms, processes the polyetheretherketonematerials materials obtaining have good cell compatibility through method of modifying of the present invention, 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 obtaining through method of modifying processing of the present invention.Simultaneously, nano-indentation experiment result confirms, through method of modifying of the present invention, process the polyetheretherketonematerials materials surface elastic modulus and the nano hardness that obtain and be all improved largely, approach human body cortex bone correlated performance, can meet the required biocompatibility requirement of medical polyetheretherketonematerials materials.And the Ta Element release amount of injection is few, show 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 to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, and Ta-3 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 120 minutes;
Fig. 2 is the surperficial XPS of the polyetheretherketonematerials materials before and after modification of the present invention spectrogram entirely, in figure: PEEK represents the polyether-ether-ketone before modification, Ta-1 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, and Ta-3 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV 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 to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, and Ta-3 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV 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 to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, and Ta-3 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV 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 to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, and Ta-3 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV 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 to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, and Ta-3 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV 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 being reduced
tMper-cent, X-coordinate represents the cell cultures time, PEEK represents the polyether-ether-ketone before modification, Ta-1 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, and Ta-3 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV 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 being reduced
tMper-cent, X-coordinate represents the cell cultures time, PEEK represents the polyether-ether-ketone before modification, Ta-1 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, and Ta-3 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 120 minutes;
Fig. 9 is the polyetheretherketonematerials materials bMSC cell alkaline phosphatase expression of enzymes experimental result before and after modification of the present invention, 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 to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, and Ta-3 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 120 minutes;
Figure 10 is that the polyetheretherketonematerials materials bMSC cell collagen before and after modification of the present invention is expressed 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 to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, and Ta-3 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV 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 to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, and Ta-3 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 120 minutes.
Embodiment
Below in conjunction with accompanying drawing and following embodiment, further illustrate the present invention, should be understood that accompanying drawing and following embodiment are only for the present invention is described, and unrestricted the present invention.
The biocompatibility and the not good problem of mechanical property that in order to solve existing medical polyetheretherketonematerials materials, exist, the invention discloses a kind of surface modifying method of medical polyetheretherketonematerials materials, described method comprise tantalum ion is injected to medical polyetheretherketonematerials materials surface so that improve the Young's modulus on polyether-ether-ketone surface and hardness so that it approaches human body cortex bone, improve polyether-ether-ketone surface biological consistency and bone simultaneously and integrate character.
As preferred version, using plasma immersion ion injects (PIII) technology and injects tantalum ion on medical polyetheretherketonematerials materials surface.
Preferably, when using plasma immersion ion implantttion technique is injected tantalum ion on medical polyetheretherketonematerials materials surface, preferred pure tantalum is as negative electrode.
The processing parameter that using plasma immersion ion implantttion technique is injected tantalum ion on medical polyetheretherketonematerials materials surface is recommended as: base vacuum degree is 3 * 10
-3～5 * 10
-3pa, injecting voltage is 15～40kV, and injecting pulsewidth is preferably 200～600 μ s of 50～600 μ s(), injected pulse frequency is 5～10Hz, it is preferably 500～800 μ s of 500～2000 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, the optimal process parameter that using plasma immersion ion implantttion technique is injected tantalum ion on medical polyetheretherketonematerials materials surface is: base vacuum degree 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, 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 obtaining through surface modification treatment of the present invention has different microtextures, referring to 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 to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, Ta-3 represents to use the polyether-ether-ketone product of the high pressure injection tantalum of 30kV after 120 minutes, after showing modification will there is nano particle in material surface, the size of nano particle and quantity are along with injection length increase and injecting voltage strengthen and increase.Simultaneously, the shallow surface arrangement of polyetheretherketonematerials materials obtaining through modification of the present invention has tantalum element, tantalum element content ratio is adjustable (5～15%), the polyetheretherketonematerials materials surface XPS obtaining through modification of the present invention is as shown in Figure 2 spectrogram entirely, therefrom can calculate the polyetheretherketonematerials materials surface tantalum element content obtaining 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 is along with injection length increases and increases.
Injection length and injecting voltage also affect the injection degree of depth of Ta.Referring to 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 to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 30 minutes, Ta-2 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 15kV after 120 minutes, Ta-3 represents to use the polyether-ether-ketone of the high pressure injection tantalum of 30kV after 120 minutes, as seen from the figure, through method of modifying of the present invention, process the polyetheretherketonematerials materials surface Ta obtaining and there is a continuous distribution; It is darker that high-voltage injects the injection degree of depth of Ta under modification for a long time, and modified layer is thicker; Under same depth, the content that high-voltage injects the modification sample Ta that modification obtains is for a long time higher.
The polyetheretherketonematerials materials mechanics of surface character obtaining through modification of the present invention obtains lifting in various degree, the unmodified polyether-ether-ketone of its modular ratio large 0～6GPa in surface, and nano hardness is than the unmodified polyether-ether-ketone large 0～2GPa in surface.As Fig. 4 illustrates the polyetheretherketonematerials materials surface elastic modulus test result obtaining through modification of the present invention, show modification after material surface Young's modulus be significantly improved.For example, as shown in curve Ta-3 wherein, the material surface Young's modulus after modification from modification more than approximately 7Gpa is promoted to 12GPa, approach cortex bone correlated performance.Again as shown in Figure 5, the material surface nano hardness obtaining through modification of the present invention also has remarkable lifting, for example, and as shown in curve Ta-3 wherein, the approximately 1.4GPa of material surface nano hardness after modification from modification is promoted to about 3GPa, shows that the material surface hardness after modification is higher.Again as shown in Figure 6, the polyetheretherketonematerials materials obtaining through method of modifying processing 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 the high pressure injection tantalum of 30kV 120 minutes (Ta-3) to process the sample obtaining, compression distance and the recovery degree of depth all significantly improve, and show that the sample surfaces after modification has stronger restorability under the effect of power.
The introducing of tantalum element can effectively improve biocompatibility and the bone of polyetheretherketonematerials materials and integrate character.By selecting different processing parameter modifications, its biocompatibility and bone are integrated character raising in various degree, can meet the required biocompatibility requirement of medical polyetheretherketonematerials materials.Cell proliferation experiment result confirms, processes the polyetheretherketonematerials materials obtaining have good cell compatibility through method of modifying of the present invention, and MC3T3-E1 cell and bMSC cell are several times as much as unmodified surface in modified surface propagation.For example, referring to Fig. 7, it illustrates the polyetheretherketonematerials materials cell proliferation experiment result before and after modification of the present invention, in figure: PEEK represents the polyetheretherketonematerials materials before processing, Ta-1 represents to use 30kV high pressure to inject the sample of 30 minutes gained, Ta-2 represents to use 15kV high pressure to inject the sample of 120 minutes gained, Ta-3 represents to use 30kV high pressure to inject the sample of 120 minutes gained, as seen from the figure, MC3T3-E1 cell in the polyetheretherketonematerials materials surface growth situation obtaining through above-mentioned example embodiment modification all significantly better than unmodified sample, wherein, MC3T3-E1 cell is injecting 120 minutes through 15kV high pressure and 30kV high pressure injects the polyetheretherketonematerials materials surface growth situation that 120 minutes institute's modifications obtain and significantly better than 30kV high pressure, injects the situation of 30 minutes, show that the polyether-ether-ketone surface that tantalum injection length is long is more conducive to cell proliferation.For example, referring to 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 obtaining through modification of the present invention significantly better than unmodified sample.Through method of modifying of the present invention, process the polyetheretherketonematerials materials obtaining and can promote bMSC Osteoblast Differentiation again.For example, referring to Fig. 9～11, known bMSC cell has obvious Osteoblast Differentiation trend on the polyetheretherketonematerials materials surface obtaining through method of modifying processing of the present invention.
Below further for example embodiment to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; and can not be interpreted as limiting the scope of the invention, 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 that following example is concrete etc. is only also an example in OK range, and those skilled in the art can be done in suitable scope and be selected by explanation herein, and do not really want to be defined in the below concrete numerical value of example.
After polished finish, use successively acetone and deionized water ultrasonic cleaning clean the pure polyether-ether-ketone of 10mm * 10mm * 1mm, each 30min, cleans to be placed in 80 ℃ of baking ovens and dries and properly preserve.Using plasma immersion ion implantttion technique, injects polyether-ether-ketone matrix (Ta-1) by tantalum ion, and the polyetheretherketonematerials materials of injecting after modification is properly preserved, 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 |
The medical polyetheretherketonematerials materials surface topography map of Ta-1 in Fig. 1 for obtaining through the present embodiment modification, shows in figure that the material surface after modification has minimum nano particle, and size is about several nanometers; Ta-1 in Fig. 2 is the medical polyetheretherketonematerials materials surface XPS that obtains through the present embodiment modification spectrogram entirely, show: use plasma immersion ion implantation technique tantalum element can be introduced into polyetheretherketonematerials materials surface, the polyetheretherketonematerials materials obtaining through the present embodiment modification surface tantalum element content is 6.6%.
After polished finish, use successively acetone and deionized water ultrasonic cleaning clean the pure polyether-ether-ketone of 10mm * 10mm * 1mm, each 30min, cleans to be placed in 80 ℃ of baking ovens and dries and properly preserve.Using plasma immersion ion implantttion technique, injects polyether-ether-ketone matrix (Ta-2) by tantalum ion, and the polyetheretherketonematerials materials of injecting after modification is properly preserved, 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 |
The medical polyetheretherketonematerials materials surface topography map of Ta-2 in Fig. 1 for obtaining through the present embodiment modification, shows in figure that the material surface after modification 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 that obtains through the present embodiment modification spectrogram entirely, show: use plasma immersion ion implantation technique tantalum element can be introduced into polyetheretherketonematerials materials surface, the polyetheretherketonematerials materials obtaining through the present embodiment modification surface tantalum element content is 12.1%.
After polished finish, use successively acetone and deionized water ultrasonic cleaning clean the pure polyether-ether-ketone of 10mm * 10mm * 1mm, each 30min, cleans to be placed in 80 ℃ of baking ovens and dries and properly preserve.Using plasma immersion ion implantttion technique, injects polyether-ether-ketone matrix (Ta-3) by tantalum ion, and the polyetheretherketonematerials materials of injecting after modification is properly preserved, 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 |
The medical polyetheretherketonematerials materials surface topography map of Ta-3 in Fig. 1 for obtaining through the present embodiment modification, shows in figure that the material surface after modification 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 that obtains through the present embodiment modification spectrogram entirely, show: use plasma immersion ion implantation technique tantalum element can be introduced into polyetheretherketonematerials materials surface, the polyetheretherketonematerials materials obtaining through the present embodiment modification surface tantalum element content is 10.4%.
Embodiment 4
After polished finish, use successively acetone and deionized water ultrasonic cleaning clean the carbon fiber reinforced polyether-ether-ketone of 10mm * 10mm * 1mm, each 30min, cleans to be placed in 80 ℃ of baking ovens and dries and properly preserve.Using plasma immersion ion implantttion technique, injects carbon fiber reinforced polyether-ether-ketone matrix by tantalum ion, and the carbon fiber reinforced polyether-ether-ketone material injecting after modification is properly preserved, and 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 |
After polished finish, use successively acetone and deionized water ultrasonic cleaning clean the carbon fiber reinforced polyether-ether-ketone of 10mm * 10mm * 1mm, each 30min, cleans to be placed in 80 ℃ of baking ovens and dries and properly preserve.Using plasma immersion ion implantttion technique, injects carbon fiber reinforced polyether-ether-ketone matrix by tantalum ion, and the carbon fiber reinforced polyether-ether-ketone material injecting after modification is properly preserved, and 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 |
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 obtaining through above-described embodiment modification, wherein: Ta-1 represents the sample obtaining through embodiment 1 modification, Ta-2 represents the sample obtaining through embodiment 2 modifications, and Ta-3 represents the sample obtaining through embodiment 3 modifications.As seen from Figure 3: through method of modifying of the present invention, process the polyetheretherketonematerials materials surface Ta obtaining and there is a continuous distribution; It is darker that high-voltage injects the injection degree of depth of Ta under modification for a long time, and modified layer is thicker; Under same depth, the content that high-voltage injects the modification sample Ta that modification obtains is for a long time higher.
Adopt Nanoindentation assessment through above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials surface mechanical properties, the index of mainly testing its surface elastic modulus and nano hardness.The polyetheretherketonematerials materials obtaining through above-described embodiment modification is carried out to nano hardness test: utilize nano-hardness tester (U.S. Mei Tesi process system company limited), by continuous hardness test method, material is carried out to nano hardness test, 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 obtain by five different zones of measure sample;
Fig. 4 and Fig. 5 are respectively polyetheretherketonematerials materials surface elastic modulus and depth relationship figure and nano-hardness improvement and the depth relationship figure obtaining through above-described embodiment modification, wherein: PEEK represents unmodified sample, Ta-1 represents the sample obtaining through embodiment 1 modification, Ta-2 represents the sample obtaining through embodiment 2 modifications, and Ta-3 represents the sample obtaining through embodiment 3 modifications.From Fig. 4 and Fig. 5: process the polyetheretherketonematerials materials that obtains for unmodified polyether-ether-ketone through method of modifying of the present invention, Young's modulus and nano hardness all increase, wherein, the sample increase rate that high-voltage injects modification is larger, especially adopt embodiment 3 to process the sample obtaining, surface elastic modulus is promoted to about 12GPa, approaches human body cortex bone correlated performance.
Adopt Nanoindentation assessment through above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials surface elasticity restorabilities.Concrete grammar is as follows: utilize nano-hardness tester (U.S. Mei Tesi process system company limited), by fixed load method, material is carried out to elastic recovery properties test, 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 obtains by five different zones of measure sample;
Fig. 6 is the polyetheretherketonematerials materials surface elasticity recovery figure obtaining through above-described embodiment modification, wherein: PEEK represents unmodified sample, Ta-1 represents the sample obtaining through embodiment 1 modification, Ta-2 represents the sample obtaining through embodiment 2 modifications, and Ta-3 represents the sample obtaining through embodiment 3 modifications.As seen from Figure 7: the polyetheretherketonematerials materials obtaining through method of modifying processing 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 embodiment 3 to process the sample obtaining, compression distance and the recovery degree of depth all significantly improve, and show that the sample surfaces after modification has stronger restorability under the effect of power.
Adopt Tutofusin tris (Tris) and hydrochloric acid (HCl) solution preparation Tris-HCl buffered soln, at 36.5 ℃, regulating pH value is 7.4.Sample before and after modification of the present invention is soaked in the above-mentioned buffered soln of 5mL, the buffered soln that took out solution and more renewed every 7 days, soak after 7,14,21 and 28 days, adopt inductive coupling plasma emission spectrograph (ICP-OES, Vista AX, 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 obtaining through embodiment 1 modification, Ta-2 represents the sample obtaining through embodiment 2 modifications, and Ta-3 represents the sample obtaining through embodiment 3 modifications;
Table 6 tantalum element burst size
Table is noted: fail to detect expression content lower than 0.002ppm
From table 6, after Ta element is injected in polyetheretherketonematerials materials, burst size is few, shows that Ta ion implantation modification polyether-ether-ketone has stronger stability and biological safety.
Adopt the assessment of MC3T3-E1 cells in vitro culture experiment through the cell compatibility of above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials.Utilize AlamarBlue
tM(AbD serotec Ltd, UK) kit detection cell is in the propagation situation of material surface.Method is as follows:
1) will use the sample of 75% ethanol sterilizing to put into 24 well culture plates, it be 5 * 10 that every hole drips 1mL density
4cell/mL MC3T3-E1 cell suspension;
2) Tissue Culture Plate is put into 5%CO
236.5 ℃ of hatching 18h in the cell culture incubator of saturated humidity;
3) suck cell culture fluid, with PBS, clean after sample surfaces, sample is moved in 24 new orifice plates, put into incubator and continue to cultivate;
4) cell cultures, after 1,4 and 7 days, sucks original fluid, adds and contains 10%AlamarBlue
tMthe new nutrient solution of dye liquor, is placed in incubator by culture plate and cultivates after 4h, takes out 100 μ L nutrient solutions put into 96 orifice plates from every hole;
5) utilize microplate reader (BIO-TEK, ELX800) to measure the absorbance of each hole under 570nm and 600nm wavelength.According to following formula, calculate AlamarBlue
tMthe percentage being reduced by cell:
Formula:
Wherein: A is absorbance, the absorbance of the negative control wells of A ', λ
1=570nm, λ
2=600nm;
Fig. 7 is polyether-ether-ketone and the unmodified polyether-ether-ketone cell proliferation experiment statistics obtaining through above-described embodiment 1,2 and 3 modifications, 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 obtaining through above-described embodiment 1,2 and 3 modifications significantly better than unmodified sample, and meanwhile, long-time high-voltage injects tantalum and is conducive to cell at polyether-ether-ketone surface growth.
Adopt rat bone marrow mesenchymal stem cells (bMSC) vitro culture experimental evaluation through the stem cell cell compatibility of above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials.Utilize AlamarBlue
tM(AbD serotec Ltd, UK) kit detection cell is in the propagation situation of material surface.Method is as follows:
1) will use the sample of 75% ethanol sterilizing to put into 24 well culture plates, it be 2.5 * 10 that every hole drips 1mL density
4cell/mL bMSC cell suspension;
2) Tissue Culture Plate is put into 5%CO
236.5 ℃ of hatching 18h in the cell culture incubator of saturated humidity;
3) suck cell culture fluid, with PBS, clean after sample surfaces, sample is moved in 24 new orifice plates, put into incubator and continue to cultivate;
4) cell cultures, after 1,4 and 7 days, sucks original fluid, adds and contains 5%AlamarBlue
tMthe new nutrient solution of dye liquor, is placed in incubator by culture plate and cultivates after 4h, takes out 100 μ L nutrient solutions put into 96 orifice plates from every hole;
5) utilize microplate reader (BIO-TEK, ELX800) to measure the absorbance of each hole under 570nm and 600nm wavelength.According to following formula, calculate AlamarBlue
tMthe percentage being reduced by cell:
Formula:
Wherein: A is absorbance, the absorbance of the negative control wells of A ', λ
1=570nm, λ
2=600nm;
Fig. 8 is polyether-ether-ketone and the unmodified polyether-ether-ketone cell proliferation experiment statistics obtaining through above-described embodiment 1,2 and 3 modifications, 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 obtaining through above-described embodiment 1,2 and 3 modifications significantly better than unmodified sample, and meanwhile, high-voltage injects tantalum and is conducive to bMSC cell at polyether-ether-ketone surface growth.
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) will use the sample of 75% ethanol sterilizing to put into 24 well culture plates, it be 1 * 10 that 7 days every holes of sample drip 1mL density
4cell/mL bMSC cell suspension, it is 0.5 * 10 that 14 days every holes of sample drip 1mL density
4cell/mL bMSC cell suspension;
2) Tissue Culture Plate is put into 5%CO
236.5 ℃ of cultivations in the cell culture incubator of saturated humidity; Every 3 days, change liquid;
3) cell cultures, after 7 days and 14 days, sucks original fluid, and PBS cleans after twice, uses lysate lysing cell, and process continues 40min.ALP quantitative analysis adopts the substratum contain p-nitrophenyl phosphate (p-nitrophenyl phosphate, pNPP, Sigma, USA), by lysate, pNPP and damping fluid mixed solution at 36.5 ℃ and 5%CO
2in atmosphere incubator, cultivate 30min, under 405nm absorbing wavelength, measure solution O D value, active for the ALP of analytic sample superficial cell.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 and the unmodified polyether-ether-ketone ALP that through above-described embodiment 1,2 and 3 modifications, obtain 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: in the time of 7 days, bMSC cell is at the polyetheretherketonematerials materials surface A LP expression obtaining through above-described embodiment 1,2 and 3 modifications significantly better than unmodified sample, and Ta-2 is better than Ta-1 and Ta-3 simultaneously; In the time of 14 days, bMSC cell is at the polyetheretherketonematerials materials surface A LP expression obtaining through above-described embodiment 1 and 3 modifications significantly better than unmodified sample, and bMSC cell is expressed with unmodified sample basic identical at the polyetheretherketonematerials materials surface A LP obtaining through embodiment 2 modifications.
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) will use the sample of 75% ethanol sterilizing to put into 24 well culture plates, it be 1 * 10 that 7 days every holes of sample drip 1mL density
4cell/mL bMSC cell suspension, it is 0.5 * 10 that 14 days every holes of sample drip 1mL density
4cell/mL bMSC cell suspension;
2) Tissue Culture Plate is put into 5%CO
236.5 ℃ of cultivations in the cell culture incubator of saturated humidity; Every 3 days, change liquid;
3) cell cultures, after 7 days and 14 days, sucks original fluid, and PBS cleans 3 times;
4) with 4% paraformaldehyde fixed sample 20min;
5) PBS cleans after 3 times, with 0.1% Picro-Sirius red being dissolved in saturated picric acid, the collagen of emiocytosis is dyeed, and dyeing course continues 18h;
6) after dyeing, with the acetic acid of 0.1M, rinsing sample is until separate out without red color repeatedly, 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, at 492nm, tests its absorbance;
Figure 10 is that the polyether-ether-ketone and the unmodified polyether-ether-ketone COI that through above-described embodiment 1,2 and 3 modifications, obtain 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: in the time of 7 days bMSC cell at the polyetheretherketonematerials materials surface C OI expression obtaining through above-described embodiment 1,2 and 3 modifications significantly better than unmodified sample; In the time of 14 days, bMSC cell is at the polyetheretherketonematerials materials surface C OI expression obtaining through above-described embodiment 1,2 and 3 modifications significantly better than unmodified sample, and wherein Ta-1 is better than Ta-2 and Ta-3.
Adopt the assessment of rat bone marrow mesenchymal stem cells (bMSC) experiment in vitro through stem cell extracellular matrix (ECM) the protein expression situation of above-described embodiment 1,2 and 3 modification gained polyetheretherketonematerials materials, method is as follows:
1) will use the sample of 75% ethanol sterilizing to put into 24 well culture plates, it be 1 * 10 that 7 days every holes of sample drip 1mL density
4cell/mL bMSC cell suspension, it is 0.5 * 10 that 14 days every holes of sample drip 1mL density
4cell/mL bMSC cell suspension;
2) Tissue Culture Plate is put into 5%CO
236.5 ℃ of cultivations in the cell culture incubator of saturated humidity; Every 3 days, change liquid;
3) cell cultures, after 7 days and 14 days, sucks original fluid, and PBS cleans 3 times;
4) with 75% alcohol fixation sample 60min;
5) by the sodium alizarinsulfonate (pH=4.2) of 40mM, cell is dyeed, dyeing course continues 10min;
6) after dyeing with distilled water repeatedly rinsing sample until separate out without red color, use microphotograph to obtain coloration result;
7) for carrying out quantitative comparison, every hole adds 0.5mL elutriant (10% cetylpyridinium chloride, the sodium phosphate that solvent is pH=7), and 15min is by specimen surface dyestuff wash-out in vibration, at 600nm, tests its absorbance;
Figure 11 is that the polyether-ether-ketone and the unmodified polyether-ether-ketone ECM that through above-described embodiment 1,2 and 3 modifications, obtain 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: in the time of 7 days, bMSC cell is at the polyetheretherketonematerials materials surface ECM expression obtaining through above-described embodiment 1,2 and 3 modifications significantly better than unmodified sample, and Ta-2 is better than Ta-1 and Ta-3 simultaneously; In the time of 14 days, bMSC cell is at the polyetheretherketonematerials materials surface ECM expression obtaining through above-described embodiment 1,2 and 3 modifications 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, the polyetheretherketonematerials materials obtaining through modification of the present invention, its biocompatibility, bone integrate character and surface mechanical properties is significantly improved, and can meet the required performance requriements of medical polyether-ether-ketone.
Claims (10)
1. one kind is injected the method for tantalum ion to polyether-ether-ketone modifying surface, it is characterized in that, described method is used plasma immersion ion implantation technique on the surface of polyether-ether-ketone, to carry out tantalum ion injection to obtain the modified layer that contains tantalum element, improve polyether-ether-ketone surface elastic modulus and hardness so that it approaches human body cortex bone, improve polyether-ether-ketone surface biological consistency and bone simultaneously and integrate character.
2. method according to claim 1, is characterized in that, while 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, the processing parameter that described tantalum ion injects comprises: base vacuum degree 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, 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 30～120 minutes.
5. according to the method described in claim 3 or 4, it is characterized in that, described injecting voltage is 15～30kV, and injection length is 30～120 minutes.
6. method according to claim 5, 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.
7. according to the method described in any one in 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. according to a polyetheretherketonematerials materials for the modification described in any one in claim 1～7, it is characterized in that, in the modified layer of the polyetheretherketonematerials materials of described modification, the content of tantalum element is 5%～15%.
9. the polyetheretherketonematerials materials of modification according to claim 8, is characterized in that, the surface elastic modulus of the polyetheretherketonematerials materials of described modification improves 0～6GPa than unmodified polyether-ether-ketone surface.
10. the polyetheretherketonematerials materials of modification according to claim 8, is characterized in that, the nano-hardness improvement of the polyetheretherketonematerials materials of described modification improves 0～2GPa than unmodified polyether-ether-ketone surface.
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