CN104975267B - A kind of method that polyetheretherketonematerials materials are carried out with surface modification - Google Patents
A kind of method that polyetheretherketonematerials materials are carried out with surface modification Download PDFInfo
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Abstract
The present invention relates to a kind of method that polyetheretherketonematerials materials are carried out with surface modification, methods described includes：By plasma immersion ion implantation technique, zinc ion injection or zinc/oxygen binary ion implanting are carried out on the surface of polyetheretherketonematerials materials, modified polyetheretherketonematerials materials are obtained.
Description
Technical field
The present invention relates to a kind of method that polyetheretherketonematerials materials are carried out with surface modification, and in particular to one kind passes through plasma
The method that body immersion ion injection technique carries out surface modification to polyetheretherketonematerials materials.
Background technology
In recent years, as biomaterial prepares constantly improve and the development using theory and technology, macromolecule implant material
The application prospect of material will be more wide.The modulus of elasticity of medical polyetheretherketonematerials materials (PEEK) is matched the most with body bone tissue,
Bone information and osteanabrosis that stress-shielding effect is caused are effectively reduced, and fatigue resistance is protruded, and is suitable for medical treatment implantation dress
Put and be chronically implanted (Biomaterials2007,28:4845-4869.).However, PEEK bioactivity is poor, after implantation human body not
Easily it is bonded with body bone tissue, while PEEK is without obvious antibiotic property, easy breed bacteria, limits it as implant material after implantation
Material is chronically implanted.How to improve PEEK Integrated implants and antibiotic property has become study hotspot.Polyetheretherketonematerials materials are entered at present
The main method that row surface is modified is chemical graft process, and this method is modified depth as shallow, and effect is poor, and the reaction time is long, effect
Rate is low, is unfavorable for large-scale production.
Therefore, how by easy-to-use mode, surface modification is carried out to polyetheretherketonematerials materials, polyether-ether-ketone material is improved
The biocompatibility and antibiotic property of material, have become one of study hotspot.
The content of the invention
It is contemplated that overcoming the defect of the existing method that polyetheretherketonematerials materials are carried out with surface modification, polyether-ether-ketone is improved
The biocompatibility and antibiotic property of material, the present invention provide one kind by plasma immersion ion implantation technique to polyether-ether-ketone
The method that material carries out surface modification.
The present invention provides a kind of method that polyetheretherketonematerials materials are carried out with surface modification, and methods described includes：By wait from
Daughter immersion ion injection technique, zinc ion injection or zinc/oxygen binary ion implanting are carried out on the surface of polyetheretherketonematerials materials,
Obtain modified polyetheretherketonematerials materials.
Surface texture is the key factor for determining material surface biological property.In human body, bone, tooth, DNA and albumen
Deng all containing the micrometer/nanometer structure for possessing specific function.There are some researches show nanometer sized materials are to arousing appropriate cell effect,
Adhesion and differentiation of the cell in material surface are adjusted, promotes osteanagenesis, improving and extending implant using effect and life-span has
Important function, so, the research as biomedical materials field is hot for nano meter biomaterial and biomaterial surface nanosizing
Point (Materials Science＆Engineering R-Reports, 2010,70:275-302.).Nanostructured can be stimulated
The adhesion of (promotion) skeletonization relevant cell, propagation and bone are to differentiation, in sclerous tissues's implant material field by wide coverage.This
Outside, the nanostructured of special size is also inhibited to the formation of bacterial migration, propagation and bacterial biof iotalm.Therefore, build
Micrometer/nanometer structure is based on selection surface-functionalized to polyetheretherketonematerials materials in practical application.
However, realizing that having concurrently for Integrated implant and antibiotic property is more difficult by structure merely.Research shows that Zn-ef ficiency is
The important trace element of bone composition, appropriate zinc supply has very positive effect for the regulation of bone stable state, not only can
Enough accelerate maturation and the differentiation of Gegenbaur's cell, promote the formation and reconstruction of new bone, additionally it is possible to while suppressing the shape in osteoclast hole
Into the bone resorption activity of reduction osteoclast.In addition, Zn-ef ficiency has broad spectrum antibacterial, drug resistance is not likely to produce, and in right amount
Zinc to maintaining human normal immunologic function that there is important effect, advantageously reduce inflammatory reaction, promote wound healing (Acta
biomaterialia,2012,8:904-915.).Therefore, in polyetheretherketonematerials materials surface construction nanostructured, and introduce simultaneously
Zn-ef ficiency is advantageously implemented having concurrently for Integrated implant and antibiotic property.
It is preferred that the technological parameter for carrying out zinc ion injection by plasma immersion ion implantation technique includes：
Background vacuum is 3 × 10-3~5 × 10-3Pa, zinc injecting voltage is 15~40kV, and zinc injection pulsewidth is 50~600 microseconds, zinc
Injected pulse frequency is 5~10Hz, and negative electrode source triggering pulsewidth is 500~2000 microseconds, and injection length is 30~180 minutes.
A preferred embodiment of the present invention is that the plasma immersion ion implantation technique carries out zinc ion injection
Technological parameter is：Zinc injection pulsewidth is 200~600 microseconds, and injection length is 60~180 minutes.
The present invention a particularly preferred embodiment be, the technological parameter of the plasma immersion ion implantation technique：
Background vacuum is 3.5 × 10-3Pa, the zinc injecting voltage is 30kV, and the zinc injected pulse frequency is 8Hz, the zinc note
Enter pulsewidth for 450 microseconds, negative electrode source triggering pulsewidth is 500 microseconds, the zinc injection length is 180 minutes.
It is preferred that the polyetheretherketonematerials materials can be pure polyetheretherketonematerials materials, the modified pure polyetheretherketonematerials materials
Surface has nanoparticle structure.
It is preferred that the polyetheretherketonematerials materials can be carbon fiber reinforced polyether-ether-ketone material, modified fibre reinforced
Polyether-ether-ketone surface has nanoparticle structure or nano-porous structure.
It is preferred that the technique for carrying out zinc/oxygen binary ion implanting by plasma immersion ion implantation technique is joined
Number includes：Zinc injection background vacuum is 3 × 10-3~5 × 10-3Pa, zinc injecting voltage is 15~40kV, and zinc injection pulsewidth is
50~600 microseconds, zinc injected pulse frequency is 5~10Hz, and negative electrode source triggering pulsewidth is 500~2000 microseconds, zinc injection length
For 30~180 minutes, oxygen injection background vacuum was 3 × 10-3~5 × 10-3Pa, oxygen injecting voltage is 15~40kV, oxygen injection
Pulsewidth is 50~600 microseconds, and oxygen injected pulse frequency is 20~200Hz, and oxygen flow is 5~200sccm (standard state milliliters
It is per minute), oxygen injection length is 30~120 minutes.
A preferred embodiment of the present invention is that the technological parameter of the plasma immersion ion implantation technique is：Zinc
Injection pulsewidth is 200~600 microseconds, and zinc injection length is 60~180 minutes, and oxygen injected pulse frequency is 50~150Hz, oxygen note
The angle of incidence is 30~60 minutes.
The present invention a particularly preferred embodiment be, the technological parameter of the plasma immersion ion implantation technique：
Zinc injection background vacuum is 3.5 × 10-3Pa, the zinc injecting voltage is 30kV, and the zinc injected pulse frequency is 8Hz, institute
It is 450 microseconds to state zinc injection pulsewidth, and negative electrode source triggering pulsewidth is 500 microseconds, and the zinc injection length is 180 minutes, oxygen injection
Background vacuum is 3.5 × 10-3Pa, the oxygen injecting voltage is 15kV, and the oxygen injected pulse frequency is 50Hz, the oxygen note
Enter pulsewidth for 200 microseconds, oxygen flow is 120sccm, the oxygen injection length is 60 minutes.
Noted altogether it is preferred that the order of the injection zinc/oxygen binary ion can be zinc after oxygen, first oxygen after first zinc or zinc oxygen, its
In, the injection order of oxygen after preferably first zinc.
It is preferred that the polyetheretherketonematerials materials can be carbon fiber reinforced polyether-ether-ketone material, modified fibre reinforced
Polyether-ether-ketone surface has the multi-level nano-structure of nano particle and nanometer sawtooth.
It is preferred that described polyetheretherketonematerials materials can be pure polyetheretherketonematerials materials or carbon fiber reinforced polyether-ether-ketone material.
It is preferred that simple metal zinc can be used to be used as negative electrode.
Beneficial effects of the present invention：
Obtained polyetheretherketonematerials materials are handled by method of modifying of the present invention, biocompatibility is greatly increased,
There is certain antibiotic property simultaneously.MC3T3-E1 osteoblastic proliferations experimental result is confirmed, is handled by method of modifying of the present invention
Obtained polyetheretherketonematerials materials have a preferable cell compatibility, and MC3T3-E1 cells are bred apparently higher than not changing in modified surface
Property surface.Antibacterial experiment confirms that the polyetheretherketonematerials materials surface obtained by modification of the present invention is to staphylococcus aureus
There is different degrees of antibacterial (antibacterial) property with Escherichia coli.Material after modification can meet clinical practice demand.
Brief description of the drawings
Fig. 1 is the carbon fiber reinforced polyether-ether-ketone and unmodified carbon fiber obtained through embodiment 1 and the modification of embodiment 2
In the ESEM pattern compares figure on reinforced polyether ether ketone surface, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone,
Zn-180 is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, and Zn-O is to be obtained through the modification of embodiment 2
Carbon fiber reinforced polyether-ether-ketone；
Fig. 2 is carbon fiber reinforced polyether-ether-ketone surface that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2
XPS spectrogram and the carbon fiber reinforced polyether-ether-ketone surface Zn-ef ficiency obtained through embodiment 1 and the modification of embodiment 2 entirely
XPS high-resolution spectrograms, in figure：(A), (B) and (C) is respectively unmodified, is obtained through embodiment 1 and the modification of embodiment 2
Carbon fiber reinforced polyether-ether-ketone surface XPS spectrograms entirely, (D) and (E) is respectively through embodiment 1 and the modification of embodiment 2
The XPS high-resolution spectrograms of obtained carbon fiber reinforced polyether-ether-ketone surface Zn-ef ficiency；Abscissa represents that, with reference to energy, ordinate is represented
Peak intensity；
Fig. 3 is carbon fiber reinforced polyether-ether-ketone surface that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2
In water contact angle, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is to be obtained through the modification of embodiment 1
Carbon fiber reinforced polyether-ether-ketone, Zn-O is the carbon fiber reinforced polyether-ether-ketone that is obtained through the modification of embodiment 2；
Fig. 4 is carbon fiber reinforced polyether-ether-ketone material sample that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2
The zeta current potentials on product surface are with pH change curves, in figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is
The carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, Zn-O is the carbon fiber obtained through the modification of embodiment 2
Reinforced polyether ether ketone；
Fig. 5 is the carbon fiber reinforced polyether-ether-ketone material surface Zn-ef ficiency obtained through embodiment 1 and the modification of embodiment 2
Burst size, in figure：Zn-180 is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, and Zn-O is through implementing
The carbon fiber reinforced polyether-ether-ketone that the modification of example 2 is obtained；
Fig. 6 is carbon fiber reinforced polyether-ether-ketone surface gold that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2
In staphylococcus aureus clump count result, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is through implementing
The carbon fiber reinforced polyether-ether-ketone that the modification of example 1 is obtained, Zn-O is that the fibre reinforced obtained through the modification of embodiment 2 gathers
Ether ether ketone；
Fig. 7 is carbon fiber reinforced polyether-ether-ketone surface gold that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2
In staphylococcus aureus clump count statistical result, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is warp
The carbon fiber reinforced polyether-ether-ketone that the modification of embodiment 1 is obtained, Zn-O is that the carbon fiber obtained through the modification of embodiment 2 increases
Strong polyether-ether-ketone, ordinate is antibiotic rate；
The carbon fiber reinforced polyether-ether-ketone surface that Fig. 8 is unmodified, obtained through embodiment 1 and the modification of embodiment 2 is big
In enterobacteria clump count result, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is to be modified through embodiment 1
Obtained carbon fiber reinforced polyether-ether-ketone is handled, Zn-O is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 2；
The carbon fiber reinforced polyether-ether-ketone surface that Fig. 9 is unmodified, obtained through embodiment 1 and the modification of embodiment 2 is big
In enterobacteria clump count statistical result, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is through embodiment 1
The carbon fiber reinforced polyether-ether-ketone that modification is obtained, Zn-O is the fibre reinforced polyethers obtained through the modification of embodiment 2
Ether ketone, ordinate is antibiotic rate；
Figure 10 is that carbon fiber reinforced polyether-ether-ketone surface that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2 is trained
Support in 1,3,6 and 24 hour adhesion topography scan electron microscope of MC3T3-E1 Gegenbaur's cells, figure：CFRPEEK is unmodified carbon fiber
Reinforced polyether ether ketone, Zn-180 is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, and Zn-O is through embodiment
The carbon fiber reinforced polyether-ether-ketone that 2 modifications are obtained；
Figure 11 is that carbon fiber reinforced polyether-ether-ketone surface that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2 is trained
Support in MC3T3-E1 Gegenbaur's cells Isosorbide-5-Nitrae and the proliferation results of 7 days, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone,
Zn-180 is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, and Zn-O is to be obtained through the modification of embodiment 2
Carbon fiber reinforced polyether-ether-ketone, ordinate is is reduced AlamarBlueTMPercentage.
Embodiment
By detailed description below and the present invention is described in further detail referring to the drawings, it is thus understood that, below
Embodiment is only the description of the invention, is not the limitation to present invention, any not make substance to present invention
The technical scheme of change still falls within protection scope of the present invention.
The present invention is in order to which the Integrated implant for solving existing medical polyetheretherketonematerials materials presence is poor and without antibacterial sex chromosome mosaicism, discloses
A kind of surface modifying method of medical polyetheretherketonematerials materials, methods described is included zinc ion or zinc/oxygen binary ion implanting
Medical polyetheretherketonematerials materials surface.The present invention can be in polyetheretherketonematerials materials surface construction nanoparticle structure, nano-porous structure
With the multi-level nano-structure of nano particle/nanometer sawtooth.The polyetheretherketonematerials materials obtained by modification of the present invention, its surface
Biocompatibility, Integrated implant and antibiotic property performance are significantly improved, and with potential bone inductive factor and antibacterial
Medicine loads prospect.Cell proliferation experiment confirmation, the polyetheretherketonematerials materials surface MC3T3- obtained by modification of the present invention
E1 osteoblastic proliferations are significantly better than unmodified polyether-ether-ketone, and antibacterial experiment shows, by gathering that modification of the present invention is obtained
Ether ether ketone material surface has preferable antibiotic property to staphylococcus aureus, has certain biocidal property to Escherichia coli, can meet
Performance requirement needed for medical polyether-ether-ketone, while improving medical polyetheretherketonematerials materials Integrated implant and antibiotic property, meets it
Clinical practice demand.
The present invention provides a kind of surface modifying method of medical polyetheretherketonematerials materials, and the present invention provides a kind of injection zinc ion
Or the method that zinc/oxygen binary ion pair polyetheretherketonematerials materials surface is modified, methods described using plasma immersion from
Sub- injection technique carries out zinc ion injection or zinc/oxygen binary ion implanting on the surface of medical polyetheretherketonematerials materials.
Using plasma immersion ion implantation technique carried out on the surface of medical polyether-ether-ketone zinc ion injection or zinc/
During oxygen binary ion implanting, negative electrode is used as using simple metal zinc.
It is 3 × 10 that the technological parameter of the zinc ion injection or zinc/oxygen binary ion implanting, which includes background vacuum,-3~
5×10-3Pa (handkerchief), zinc injecting voltage be 15~40kV (kilovolt), zinc injection pulsewidth be 50~600 μ s (microsecond) (preferably 200~
600 μ s), zinc injected pulse frequency is 5~10Hz (hertz), and negative electrode source triggering pulsewidth is 500~2000 μ s, and zinc injection length is
30~180min (minute) (preferably 60~180min).The technological parameter of the O +ion implanted includes：Local vacuum is 3 ×
10-3~5 × 10-3Pa, oxygen injecting voltage is 15~40kV, and oxygen injection pulsewidth is 50~600 μ s, and oxygen injected pulse frequency is 20
~200Hz (preferably 50~150Hz), oxygen flow is 5~200sccm (standard state milliliter is per minute), and injection length is 30
~120min (preferably 30~60min).
In the especially preferred example of the present invention, the background vacuum is 3.5 × 10-3Pa, the zinc injection electricity
Press as 30kV, the zinc injected pulse frequency is 8Hz, the zinc injection pulsewidth is 450 μ s, and negative electrode source triggering pulsewidth is 500 μ s,
The zinc injection length is 180 minutes.In another especially preferred example, the technique of the zinc/oxygen binary ion implanting
It is 3.5 × 10 that parameter, which includes background vacuum,-3Pa, the zinc injecting voltage is 30kV, and the zinc injecting voltage is 30kV, described
Zinc injected pulse frequency is 8Hz, and the zinc injection pulsewidth is 450 μ s, and the injection length is 180min；The oxygen injected pulse
Frequency is 50Hz, and the injection pulsewidth is 200 μ s, and the oxygen flow is 120sccm, and the injection length is 60min.
Using plasma immersion ion injection technique medical polyetheretherketonematerials materials material surface injection zinc/oxygen binary from
The order of son is that zinc after oxygen, first oxygen after first zinc or zinc oxygen note mode altogether, is preferably sequentially injected into oxygen after first zinc.Above method for implanting
Zn-ef ficiency can be introduced while medical polyetheretherketonematerials materials surface construction nanostructured.
Described polyether-ether-ketone is pure polyetheretherketonematerials materials or carbon fiber reinforced polyether-ether-ketone material.
When described polyether-ether-ketone is pure polyetheretherketonematerials materials, using zinc ion injection method, zinc ion injects pure polyethers ether
Ketone
Surface is so that its surface has nanoparticle structure.The introducing of Zn-ef ficiency and nanostructured can improve pure polyethers ether
The biocompatibility and antibiotic property of ketone.
When described polyether-ether-ketone is carbon fiber reinforced polyether-ether-ketone material, zinc ion injection method, zinc ion injection are used
Carbon
Fiber reinforcement polyether-ether-ketone surface is so that its surface has nano-porous structure.The introducing of Zn-ef ficiency and nanostructured
The biocompatibility and antibiotic property of carbon fiber reinforced polyether-ether-ketone can be improved.
When described polyether-ether-ketone is carbon fiber reinforced polyether-ether-ketone material, using zinc/oxygen binary ion implantation, zinc/
Oxygen binary ion implanting fibre reinforced polyether-ether-ketone surface is so that there is nano particle and the multistage of nanometer sawtooth to receive on its surface
Rice structure.The introducing of Zn-ef ficiency and multi-level nano-structure significantly improve carbon fiber reinforced polyether-ether-ketone biocompatibility and
Antibiotic property.
Surface texture is the key factor for determining material surface biological property.In human body, bone, tooth, DNA and albumen
Deng all containing the micrometer/nanometer structure for possessing specific function.There are some researches show nanometer sized materials are to arousing appropriate cell effect,
Adhesion and differentiation of the cell in material surface are adjusted, promotes osteanagenesis, improving and extending implant using effect and life-span has
Important function, so, the research as biomedical materials field is hot for nano meter biomaterial and biomaterial surface nanosizing
Point (Materials Science＆Engineering R-Reports, 2010,70:275-302.).Nanostructured can be stimulated
The adhesion of (promotion) skeletonization relevant cell, propagation and bone are to differentiation, in sclerous tissues's implant material field by wide coverage.This
Outside, the nanostructured of special size is also inhibited to the formation of bacterial migration, propagation and bacterial biof iotalm.Therefore, build
Micrometer/nanometer structure is based on selection surface-functionalized to polyetheretherketonematerials materials in practical application.
However, realizing that having concurrently for Integrated implant and antibiotic property is more difficult by structure merely.Research shows that Zn-ef ficiency is
The important trace element of bone composition, appropriate zinc supply has very positive effect for the regulation of bone stable state, not only can
Enough accelerate maturation and the differentiation of Gegenbaur's cell, promote the formation and reconstruction of new bone, additionally it is possible to while suppressing the shape in osteoclast hole
Into the bone resorption activity of reduction osteoclast.In addition, Zn-ef ficiency has broad spectrum antibacterial, drug resistance is not likely to produce, and in right amount
Zinc to maintaining human normal immunologic function that there is important effect, advantageously reduce inflammatory reaction, promote wound healing (Acta
biomaterialia,2012,8:904-915.).Therefore, in polyetheretherketonematerials materials surface construction nanostructured, and introduce simultaneously
Zn-ef ficiency is advantageously implemented having concurrently for Integrated implant and antibiotic property.
Plasma immersion ion implantation technique (Plasma immersion ion implantation, PIII) is one
Kind there is comprehensive and high reaction activity feature new surface modifications technology, the characteristics of with comprehensive and high reaction activity,
There is unique advantage for the implant material of processing small volume and abnormal shape.Insulating material is changed using PIII technologies
Property when, be easily caused due to insulator poorly conductive surface charge accumulation, influence material modification effect, or even damage material
(Surface&Coatings Technology,2005,196:162-166.).How PIII technology is applied to high polymer material
Surface realizes that effective surface composition and surface texture regulation and control turn into a problem, is especially prepared to material surface structure
Aspect, does not there is correlation theory and experimental study yet.
Fig. 1 is the carbon fiber reinforced polyether-ether-ketone and unmodified carbon fiber obtained through embodiment 1 and the modification of embodiment 2
In the ESEM pattern compares figure on reinforced polyether ether ketone surface, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone,
Zn-180 is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, and Zn-O is to be obtained through the modification of embodiment 2
Carbon fiber reinforced polyether-ether-ketone；
Fig. 2 is carbon fiber reinforced polyether-ether-ketone surface that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2
XPS spectrogram and the carbon fiber reinforced polyether-ether-ketone surface Zn-ef ficiency obtained through embodiment 1 and the modification of embodiment 2 entirely
XPS high-resolution spectrograms, in figure：(A), (B) and (C) is respectively unmodified, is obtained through embodiment 1 and the modification of embodiment 2
Carbon fiber reinforced polyether-ether-ketone surface XPS spectrograms entirely, (D) and (E) is respectively through embodiment 1 and the modification of embodiment 2
The XPS high-resolution spectrograms of obtained carbon fiber reinforced polyether-ether-ketone surface Zn-ef ficiency；Abscissa represents that, with reference to energy, ordinate is represented
Peak intensity；
Fig. 3 is carbon fiber reinforced polyether-ether-ketone surface that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2
In water contact angle, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is to be obtained through the modification of embodiment 1
Carbon fiber reinforced polyether-ether-ketone, Zn-O is the carbon fiber reinforced polyether-ether-ketone that is obtained through the modification of embodiment 2；
Fig. 4 is carbon fiber reinforced polyether-ether-ketone material sample that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2
The zeta current potentials on product surface are with pH change curves, in figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is
The carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, Zn-O is the carbon fiber obtained through the modification of embodiment 2
Reinforced polyether ether ketone；
Fig. 5 is the carbon fiber reinforced polyether-ether-ketone material surface Zn-ef ficiency obtained through embodiment 1 and the modification of embodiment 2
Burst size, in figure：Zn-180 is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, and Zn-O is through implementing
The carbon fiber reinforced polyether-ether-ketone that the modification of example 2 is obtained；
Fig. 6 is carbon fiber reinforced polyether-ether-ketone surface gold that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2
In staphylococcus aureus clump count result, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is through implementing
The carbon fiber reinforced polyether-ether-ketone that the modification of example 1 is obtained, Zn-O is that the fibre reinforced obtained through the modification of embodiment 2 gathers
Ether ether ketone；
Fig. 7 is carbon fiber reinforced polyether-ether-ketone surface gold that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2
In staphylococcus aureus clump count statistical result, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is warp
The carbon fiber reinforced polyether-ether-ketone that the modification of embodiment 1 is obtained, Zn-O is that the carbon fiber obtained through the modification of embodiment 2 increases
Strong polyether-ether-ketone, ordinate is antibiotic rate；
The carbon fiber reinforced polyether-ether-ketone surface that Fig. 8 is unmodified, obtained through embodiment 1 and the modification of embodiment 2 is big
In enterobacteria clump count result, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is to be modified through embodiment 1
Obtained carbon fiber reinforced polyether-ether-ketone is handled, Zn-O is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 2；
The carbon fiber reinforced polyether-ether-ketone surface that Fig. 9 is unmodified, obtained through embodiment 1 and the modification of embodiment 2 is big
In enterobacteria clump count statistical result, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is through embodiment 1
The carbon fiber reinforced polyether-ether-ketone that modification is obtained, Zn-O is the fibre reinforced polyethers obtained through the modification of embodiment 2
Ether ketone, ordinate is antibiotic rate；
Figure 10 is that carbon fiber reinforced polyether-ether-ketone surface that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2 is trained
Support in 1,3,6 and 24 hour adhesion topography scan electron microscope of MC3T3-E1 Gegenbaur's cells, figure：CFRPEEK is unmodified carbon fiber
Reinforced polyether ether ketone, Zn-180 is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, and Zn-O is through embodiment
The carbon fiber reinforced polyether-ether-ketone that 2 modifications are obtained；
Figure 11 is that carbon fiber reinforced polyether-ether-ketone surface that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2 is trained
Support in MC3T3-E1 Gegenbaur's cells Isosorbide-5-Nitrae and the proliferation results of 7 days, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone,
Zn-180 is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, and Zn-O is to be obtained through the modification of embodiment 2
Carbon fiber reinforced polyether-ether-ketone, ordinate is is reduced AlamarBlueTMPercentage.
For example, handling obtained carbon fiber reinforced polyether-ether-ketone surface distributed by zinc injection surface modification of the present invention has
100nm or so pore structures.In another example, the fibre reinforced obtained by zinc of the present invention/oxygen binary injection surface modification processing gathers
Ether ether ketone surface distributed has 300nm or so broached-tooth designs, and broached-tooth design surface distributed has 10nm or so nano particle.Zn-ef ficiency
Introducing with nanostructured significantly improves the biocompatibility and antibiotic property of carbon fiber reinforced polyether-ether-ketone.Fig. 1 show through
The carbon fiber reinforced polyether-ether-ketone that embodiment 1 and the modification of embodiment 2 are obtained and unmodified carbon fiber reinforced polyether-ether-ketone table
In the ESEM pattern compares figure in face, Fig. 1, CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is through implementing
The carbon fiber reinforced polyether-ether-ketone that the modification of example 1 is obtained, Zn-O is that the fibre reinforced obtained through the modification of embodiment 2 gathers
Ether ether ketone.As seen from Figure 1：The carbon fiber reinforced polyether-ether-ketone surface obtained through the modification of embodiment 1 has obvious nanometer
Loose structure, the diameter of nano-pore is about 100nm or so, and is distributed than more uniform；The carbon obtained through the modification of embodiment 2 is fine
Dimension reinforced polyether ether ketone surface has the multi-level nano-structure that obvious nano particle and nanometer sawtooth coexist, broached-tooth design size
About 300nm or so, nanoparticle size 10nm or so, two kinds of structures are distributed all more uniform in material surface.Fig. 2 is not change
Property, XPS spectrogram, the Yi Jijing entirely on the carbon fiber reinforced polyether-ether-ketone surface obtained through embodiment 1 and the modification of embodiment 2
The XPS high-resolution spectrograms for the carbon fiber reinforced polyether-ether-ketone surface Zn-ef ficiency that embodiment 1 and the modification of embodiment 2 are obtained, by
Fig. 2 is understood：Zn-ef ficiency can be introduced to polyether-ether-ketone surface, surface Zn-ef ficiency using zinc plasma immersion and ion implantation method
Coexisted with simple substance zinc and zinc oxide form；Can also can be by Zn-ef ficiency using zinc/oxygen Binary plasma body immersion ion injection method
Polyether-ether-ketone surface is introduced to, surface Zn-ef ficiency exists in zinc oxide form.Fig. 6 and Fig. 7 are that staphylococcus aureus exists respectively
Unmodified sample, the carbon fiber reinforced polyether-ether-ketone culture obtained through embodiment 1 and the modification of embodiment 2 clump count experiment and
Corresponding statistical result.From Fig. 6 and Fig. 7：Modified sample surface colony number is less, and antibiotic rate respectively reaches 90% He
100%, show that the material through embodiment 1 and the modification of embodiment 2 is respectively provided with certain antibiotic property to staphylococcus aureus.Fig. 8 and
Fig. 9 is Escherichia coli respectively in unmodified sample, the fibre reinforced polyethers ether obtained through embodiment 1 and the modification of embodiment 2
The clump count experiment of ketone culture and corresponding statistical result.From Fig. 8 and Fig. 9：Modified sample antibacterial surface is totally different, through reality
Apply the material surface bacterial population of the modification of example 1 increases on the contrary, and the material being modified through embodiment 2 then has about 25% or so antibacterial
Rate, it is seen that modified material is not so good as staphylococcus aureus to Escherichia coli antibacterial effect.Figure 10 is unmodified, through embodiment 1
The carbon fiber reinforced polyether-ether-ketone surface culture MC3T3-E1 Gegenbaur's cells 1,3,6 and 24 obtained with the modification of embodiment 2 are small
When adhere to topography scan electron microscope.As can be seen from Figure 10：MC3T3-E1 faster, during 1h has greatly in modified sample surface adhesion speed
Cell adherence is measured in sample surfaces.And modified sample cell pseudopodium stretches more, and form is more sprawled, and shows modified sample
With more preferable cell compatibility.Figure 11 is the carbon fiber reinforced polyether-ether-ketone obtained through embodiment 1 and the modification of embodiment 2
With unmodified carbon fiber reinforced polyether-ether-ketone surface MC3T3-E1 cells Isosorbide-5-Nitrae and 7 days proliferation experiment statistical results.Can by Figure 11
See：MC3T3-E1 cells the carbon fiber reinforced polyether-ether-ketone surface growth situation that is obtained through the modification of above-described embodiment 1 with
Unmodified sample is without significant difference, and MC3T3-E1 cells are in the fibre reinforced polyethers obtained through the modification of above-described embodiment 2
Ether ketone surface growth situation is then substantially better than unmodified sample, shows modified sample without obvious cytotoxicity, and can promote into
Bone cell proliferation.
Some exemplary embodiments are included further below the present invention is better described.It should be understood that the present invention is in detail
The above-mentioned embodiment stated, and following examples are only illustrative of the invention and is not intended to limit the scope of the invention, this area
Technical staff the protection of the present invention is belonged to according to some nonessential modifications and adaptations for making of the above of the present invention
Scope.In addition, specific proportioning, time, temperature in following technological parameters etc. is also only exemplary, those skilled in the art can be with
Suitable value is selected in the range of above-mentioned restriction.
Embodiment 1
10mm × 10mm × 1mm carbon fiber reinforced polyether-ether-ketone is after polishing, successively with acetone and deionization
Water is cleaned by ultrasonic clean, each 30min, is placed in after cleaning and dries and properly preserve in 80 DEG C of baking ovens.Using plasma is submerged
Ion implantation technique, carbon fiber reinforced polyether-ether-ketone matrix is injected by zinc ion, and its specific technological parameter is shown in Table 1, institute
Obtain sample number into spectrum Zn-180.
The zinc ion injection parameter of table 1：
| Injection bias (kV) | 30 | Pulsewidth (μ s) | 450 |
| Injection length (min) | 180 | Base vacuum (Pa) | 3.5×10-3 |
| Negative electrode triggering pulsewidth (μ s) | 500 | Frequency (Hz) | 8 |
Embodiment 2
After the 10mm × 10mm × 1mm polished processing of carbon fiber reinforced polyether-ether-ketone, successively with acetone and deionized water
It is cleaned by ultrasonic clean, each 30min, is placed in after cleaning and dries and properly preserve in 80 DEG C of baking ovens.Using plasma submerge from
Sub- injection technique, by zinc/oxygen binary ion implanting fibre reinforced polyether-ether-ketone matrix, its specific technological parameter is shown in Table 2 institutes
Show, obtain sample number into spectrum Zn-O.
2 zinc of table/oxygen binary ion implanting parameter：
Fig. 1 is the carbon fiber reinforced polyether-ether-ketone and unmodified carbon fiber obtained through embodiment 1 and the modification of embodiment 2
In the ESEM pattern on reinforced polyether ether ketone surface, figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, Zn-180
For the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, Zn-O is the carbon fibre obtained through the modification of embodiment 2
Tie up reinforced polyether ether ketone.As seen from Figure 1：The carbon fiber reinforced polyether-ether-ketone surface obtained through the modification of embodiment 1 has bright
Aobvious nano-porous structure, the diameter of nano-pore is about 100nm or so, and is distributed than more uniform；Obtained through the modification of embodiment 2
To carbon fiber reinforced polyether-ether-ketone surface there is the multi-level nano-structure that obvious nano particle and nanometer sawtooth coexist, sawtooth
Physical dimension is about 300nm or so, nanoparticle size 10nm or so, and two kinds of structures are distributed all more uniform in material surface.
Fig. 2 is that the XPS on carbon fiber reinforced polyether-ether-ketone surface that is unmodified, being obtained through embodiment 1 and the modification of embodiment 2 is composed entirely
The XPS high scores of figure and the carbon fiber reinforced polyether-ether-ketone surface Zn-ef ficiency obtained through embodiment 1 and the modification of embodiment 2
Spectrogram is distinguished, as shown in Figure 2：Zn-ef ficiency can be introduced to polyether-ether-ketone surface using zinc plasma immersion and ion implantation method,
Surface Zn-ef ficiency is coexisted with simple substance zinc and zinc oxide form；Can be also using zinc/oxygen Binary plasma body immersion ion injection method
Zn-ef ficiency can be introduced to polyether-ether-ketone surface, surface Zn-ef ficiency exists in zinc oxide form.
Embodiment 3
10mm × 10mm × 1mm carbon fiber reinforced polyether-ether-ketone is after polishing, successively with acetone and deionization
Water is cleaned by ultrasonic clean, each 30min, is placed in after cleaning and dries and properly preserve in 80 DEG C of baking ovens.Using plasma is submerged
Ion implantation technique, carbon fiber reinforced polyether-ether-ketone matrix is injected by zinc ion, and its specific technological parameter is shown in Table 3.
The zinc ion injection parameter of table 3：
| Injection bias (kV) | 30 | Pulsewidth (μ s) | 450 |
| Injection length (min) | 60 | Base vacuum (Pa) | 3.5×10-3 |
| Negative electrode triggering pulsewidth (μ s) | 500 | Frequency (Hz) | 8 |
The carbon fiber reinforced polyether-ether-ketone surface that modification is obtained has obvious nanoparticle structure, using zinc etc. from
Zn-ef ficiency can be introduced to polyether-ether-ketone surface by daughter immersion ion injection method, and surface Zn-ef ficiency is with simple substance zinc and zinc oxide shape
Formula coexists.
Embodiment 4
10mm × 10mm × 1mm pure polyether-ether-ketone is clear with acetone and deionized water ultrasound successively after polishing
Wash clean, each 30min is placed in after cleaning and dries and properly preserve in 80 DEG C of baking ovens.Using plasma immersion ion injects
Technology, pure polyether-ether-ketone matrix is injected by zinc ion, and its specific technological parameter is shown in Table 4.
The zinc ion injection parameter of table 4：
| Injection bias (kV) | 15 | Pulsewidth (μ s) | 450 |
| Injection length (min) | 180 | Base vacuum (Pa) | 3.5×10-3 |
| Negative electrode triggering pulsewidth (μ s) | 500 | Frequency (Hz) | 5 |
The pure polyether-ether-ketone surface that modification is obtained has obvious nano particle, uses zinc plasma immersion ion
Zn-ef ficiency can be introduced to polyether-ether-ketone surface by injection method, and surface Zn-ef ficiency is coexisted with simple substance zinc and zinc oxide form.
Embodiment 5
10mm × 10mm × 1mm carbon fiber reinforced polyether-ether-ketone is after polishing, successively with acetone and deionization
Water is cleaned by ultrasonic clean, each 30min, is placed in after cleaning and dries and properly preserve in 80 DEG C of baking ovens.Using plasma is submerged
Ion implantation technique, by zinc/oxygen binary ion implanting fibre reinforced polyether-ether-ketone matrix, its specific technological parameter is shown in Table 5
It is shown.
5 zinc of table/oxygen binary ion implanting parameter：
Embodiment 6
10mm × 10mm × 1mm carbon fiber reinforced polyether-ether-ketone is after polishing, successively with acetone and deionization
Water is cleaned by ultrasonic clean, each 30min, is placed in after cleaning and dries and properly preserve in 80 DEG C of baking ovens.Using plasma is submerged
Ion implantation technique, by zinc/oxygen binary ion implanting fibre reinforced polyether-ether-ketone matrix, its specific technological parameter is shown in Table 6
It is shown.
6 zinc of table/oxygen binary ion implanting parameter：
Embodiment 7
Using Static water contact angle tester (Automatic Contact Angle Meter Model SL200B,
Solon information technology Co., Ltd, China) test material surface wettability, by syringe by 2 μ L
The vertical hanging drop of ultra-pure water carries imaging system shooting drop photo using machine and analyzes contact angle size to sample surfaces.
3 measurement data are taken to average on sample.
The surface water contact angle of carbon fiber reinforced polyether-ether-ketone material after Fig. 3 is shown before modified.In figure：CFRPEEK is not
Modified carbon fiber reinforced polyether ether ketone, Zn-180 is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, Zn-O
For the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 2.It can be seen that CFRPEEK sample surfaces connect
Feeler is about 68 °, and Zn-180 sample surfaces contact angles are about 120 °, and Zn-O sample surfaces contact angles reach 145 °, close super
Hydrophobic state.Zinc ion injection or zinc/oxygen binary ion implanting are shown after material surface introduces Zn-ef ficiency and structure simultaneously,
Material surface gradually switchs to hydrophobic by hydrophilic, and micrometer/nanometer composite construction can assign material high hydrophobic state.
Embodiment 8
Using zeta potential tests instrument (Anton Parr, Austria) to rear carbon fiber reinforced polyether-ether-ketone material before modified
The surface zeta potential current potential of material is characterized.Specific method is as follows：Use 0.01M hydrochloric acid (HCl) and 0.01M sodium hydroxides (NaOH)
Potassium chloride (KCl) solution ph is adjusted, during test, KCl solution flows along sample surfaces under stress, according to Helmholtz-
Smoluchowski formula, calculate relative motion of the ion in diffusion layer to obtain zeta potential values：
ζ represents zeta current potentials in formula, and dU/dP represents the slope of streaming potential/pressure, η, ε0, ε and K represent electricity respectively
Solve fluid viscosity, permittivity of vacuum, dielectric Constant and electrical conductivity.Zeta potential (ζ) is calculated automatically by instrument.By taking
4 measurement data try to achieve the average value of zeta current potentials.
The surface zeta potential current potential of carbon fiber reinforced polyether-ether-ketone material sample is with pH change curves after Fig. 4 is shown before modified.
In figure：CFRPEEK is unmodified carbon fiber reinforced polyether-ether-ketone, and Zn-180 is the carbon fiber obtained through the modification of embodiment 1
Reinforced polyether ether ketone, Zn-O is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 2.It can be seen that
During pH=7.4, CFRPEEK, the surface zeta potential potential value of Zn-180 and Zn-O samples respectively may be about -69mV, -62mV and -40mV,
Show after zinc ion injection or zinc/oxygen binary ion implanting, rising is presented in pH=7.4 and becomes for sample surfaces zeta current potentials
Gesture.
Embodiment 9
Tris-HCl cushioning liquid is prepared using trishydroxymethylaminomethane (Tris) and hydrochloric acid (HCl) solution, 36.5
It is 7.4 that pH value is adjusted at DEG C.Sample before and after the processing modified by this invention is soaked in the above-mentioned cushioning liquid of 5mL, every 7 days
Solution and the cushioning liquid that more renews are taken out, 7 are soaked, after 14,21 and 28 days, using inductive coupling plasma emission spectrograph
Zinc ion concentration in (ICP-OES, Vista AX, Varian, USA) test solution.
Fig. 5 is shown through carbon fiber reinforced polyether-ether-ketone material surface Zn-ef ficiency obtained by embodiment 1 and the modification of embodiment 2
Burst size.In figure：Zn-180 is the carbon fiber reinforced polyether-ether-ketone obtained through the modification of embodiment 1, and Zn-O is through implementing
The carbon fiber reinforced polyether-ether-ketone that the modification of example 2 is obtained.It can be seen that Zn-O surfaces zinc burst size is higher than Zn-
180。
Embodiment 10
From staphylococcus aureus (Staphylococcus aureus, S.aureus, ATCC25923) and large intestine bar
Bacterium (Escherichia coli, E.coli, ATCC25922), is assessed through above-described embodiment 1 and embodiment 2 using antibacterial experiment
The antibiotic property of modified gained carbon fiber reinforced polyether-ether-ketone material.Comprise the following steps that：1) sample that will be sterilized using 75% ethanol
Product are placed in culture plate, and it is 10 to draw 60 μ L density7Cfu/mL bacterium solution is inoculated in sample surfaces, keeps humidity to be more than 90%,
It is placed in 36.5 DEG C of anaerobism insulating boxs and cultivates 24h；2) specimen surface bacterium solution is washed down with 4.5ml physiological saline, and is diluted to one
Determine concentration.Taking the μ L of bacterium solution 100 after dilution to be inoculated in nutrient agar culture dish, (TSB agar plates are used to cultivate S.aureus, LB fine jades
Fat plate is used to cultivate E.coli)；3) 36.5 DEG C of anaerobism insulating box culture 18h~24h are placed in after coated plate again, surviving colonies are recorded
Number, antibiotic rate is calculated according to below equation：
In formula：A is the clump count on Zn-180 or Zn-O surfaces, and B is the clump count on CFRPEEK surfaces.
Fig. 6 and Fig. 7 are that staphylococcus aureus obtains in unmodified sample, through embodiment 1 and the modification of embodiment 2 respectively
Carbon fiber reinforced polyether-ether-ketone culture clump count experiment and corresponding statistical result.From Fig. 6 and Fig. 7：Modified sample
Surface colony number is less, and antibiotic rate respectively reaches 90% and 100%, shows the material through embodiment 1 and the modification of embodiment 2 to gold
Staphylococcus aureus are respectively provided with certain antibiotic property.Fig. 8 and Fig. 9 are Escherichia coli respectively in unmodified sample, through embodiment 1 and implementation
The clump count experiment for the carbon fiber reinforced polyether-ether-ketone culture that the modification of example 2 is obtained and corresponding statistical result.By Fig. 8 and figure
9 understand：Modified sample antibacterial surface is totally different, and the material surface bacterial population being modified through embodiment 1 increases on the contrary, and through embodiment
2 materials being modified then have about 25% or so antibiotic rate, it is seen that modified material is to Escherichia coli antibacterial effect not as golden yellow
Color staphylococcus.
Embodiment 11
From MC3T3-E1 Gegenbaur's cells, assessed and changed through above-described embodiment 1 and embodiment 2 using cell culture experiments in vitro
Property processing gained carbon fiber reinforced polyether-ether-ketone material cell compatibility.Material surface cell morphology, experiment are observed using SEM
Step is as follows：1) sample sterilized using 75% ethanol is put into 24 well culture plates, be added dropwise per hole 1mL density be 5 ×
104Cell/mL MC3T3-E1 cell suspensions；2) Tissue Culture Plate is put into 5%CO236.5 in the cell culture incubator of saturated humidity
DEG C hatching 18h；3) cell culture fluid is sucked, after PBS sample surfaces, sample is moved in 24 new orifice plates, is put into training
Support and continue to cultivate in case；4) cell culture 1, after 4 and 7 days, take out sample, fix 24 hours at room temperature with 2% glutaraldehyde, use
PBS three times；5) fixed cell is taken off with graded ethanol (30%, 50%, 75%, 90%, 95% and 100%)
Water process；6) sample is sequentially placed into the alcohol of different ratio and the mixed solution (alcohol of HMDS (HMDS)：
HMDS=2:1、1:1、1:2 and 100%HMDS) in be dried, processing time each 10min.After sample metal spraying sample is observed with SEM
The cellular morphology on product surface.
Figure 10 is carbon fiber reinforced polyether-ether-ketone surface MC3T3-E1 Gegenbaur's cell 1h before and after the processing modified by this invention,
3h, 6h and 24h adhere to topography scan electron microscope.As can be seen from the figure：MC3T3-E1 in modified sample surface adhesion speed more
It hurry up, have a large amount of cell adherences during 1h in sample surfaces.And modified sample cell pseudopodium stretches more, and form is more sprawled,
Show that modified sample has more preferable cell compatibility.
Embodiment 12
Using MC3T3-E1 cell injuring models experimental evaluation through carbon obtained by above-described embodiment 1 and the modification of embodiment 2
The cell compatibility of fiber reinforcement polyetheretherketonematerials materials.Utilize AlamarBlueTM(AbD serotec Ltd, UK) kit is examined
Survey proliferative conditions of the cell in material surface.Method is as follows：1) sample sterilized using 75% ethanol is put into 24 well culture plates
In, it is 5 × 10 that 1mL density is added dropwise per hole4Cell/mL MC3T3-E1 cell suspensions；2) Tissue Culture Plate is put into 5%CO2It is full
With 36.5 DEG C of hatching 18h in the cell culture incubator of humidity；3) cell culture fluid is sucked, after PBS sample surfaces, by sample
Move in 24 new orifice plates, be put into incubator and continue to cultivate；4) cell culture 1, after 4 and 7 days, suck original fluid, add
Contain 5%AlamarBlueTMThe new nutrient solution of dye liquor, culture plate is placed in incubator and cultivated after 4h, and 100 μ L are taken out from every hole
Nutrient solution is put into 96 orifice plates；5) each hole is measured under 570nm and 600nm wavelength using ELIASA (BIO-TEK, ELX800)
Absorbance.AlamarBlue is calculated according to below equationTMThe percentage reduced by cell：
Formula：
Wherein：A is absorbance, and A' is the absorbance of negative control hole, λ1=570nm, λ2=600nm.
Figure 11 is that the carbon fiber reinforced polyether-ether-ketone and unmodified carbon obtained through embodiment 1 and the modification of embodiment 2 is fine
Tie up the MC3T3-E1 cell proliferation experiment statistical results of reinforced polyether ether ketone.As can be seen from Figure：MC3T3-E1 cells are in warp
Carbon fiber reinforced polyether-ether-ketone surface growth situation that the modification of above-described embodiment 1 is obtained with unmodified sample without significant difference,
And MC3T3-E1 cells are then bright in the carbon fiber reinforced polyether-ether-ketone surface growth situation obtained through the modification of above-described embodiment 2
It is aobvious to be better than unmodified sample, modified sample is shown without obvious cytotoxicity, and can promote osteoblastic proliferation.
Industrial applicability
The method of the present invention is simple and easy to control, and the polyetheretherketonematerials materials obtained by modification of the present invention, its surface can be obtained
Different nanostructureds are obtained, biocompatibility is significantly improved；And with potential bone inductive factor and antibacterials
Loading prospect, can meet the performance requirement needed for medical polyether-ether-ketone.
Claims (7)
1. a kind of method that polyetheretherketonematerials materials are carried out with surface modification, it is characterised in that methods described includes：Pass through plasma
Body immersion ion injection technique, carries out zinc/oxygen binary ion implanting on the surface of polyetheretherketonematerials materials, obtains modified polyethers
Ether ketone material, the technological parameter for carrying out zinc/oxygen binary ion implanting by plasma immersion ion implantation technique includes：
Zinc injection background vacuum is 3 × 10-3~5 × 10-3Pa, zinc injecting voltage is 15~40kV, and zinc injection pulsewidth is 50~600
Microsecond, zinc injected pulse frequency be 5~10Hz, negative electrode source triggering pulsewidth be 500~2000 microseconds, zinc injection length be 30~
180 minutes, oxygen injection background vacuum was 3 × 10-3~5 × 10-3Pa, oxygen injecting voltage is 15~40kV, and oxygen injection pulsewidth is
50~600 microseconds, oxygen injected pulse frequency be 20~200Hz, oxygen flow be 5~200sccm, oxygen injection length be 30~
120 minutes.
2. according to the method described in claim 1, it is characterised in that the technique ginseng of the plasma immersion ion implantation technique
Number is：Zinc injection pulsewidth be 200~600 microseconds, zinc injection length be 60~180 minutes, oxygen injected pulse frequency be 50~
150Hz, oxygen injection length is 30~60 minutes.
3. according to the method described in claim 1, it is characterised in that the technique ginseng of the plasma immersion ion implantation technique
Number is：Zinc injection background vacuum is 3.5 × 10-3Pa, the zinc injecting voltage is 30kV, and the zinc injected pulse frequency is
8Hz, the zinc injection pulsewidth is 450 microseconds, and negative electrode source triggering pulsewidth is 500 microseconds, and the zinc injection length is 180 minutes,
Oxygen injection background vacuum is 3.5 × 10-3Pa, the oxygen injecting voltage is 15kV, and the oxygen injected pulse frequency is 50Hz, institute
It is 200 microseconds to state oxygen injection pulsewidth, and oxygen flow is 120sccm, and the oxygen injection length is 60 minutes.
4. according to the method described in claim 1, it is characterised in that after the order of the injection zinc/oxygen binary ion is first zinc
Zinc or zinc oxygen are noted altogether after oxygen, first oxygen.
5. according to the method described in claim 1, it is characterised in that the polyetheretherketonematerials materials are carbon fiber reinforced polyether-ether-ketone
Material, modified carbon fiber reinforced polyether-ether-ketone surface has the multi-level nano-structure of nano particle and nanometer sawtooth.
6. according to the method described in claim 1, it is characterised in that described polyetheretherketonematerials materials be pure polyetheretherketonematerials materials or
Carbon fiber reinforced polyether-ether-ketone material.
7. according to the method described in claim 1, it is characterised in that use simple metal zinc as negative electrode.
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| CN103225067A (en) * | 2013-05-20 | 2013-07-31 | 中国科学院上海硅酸盐研究所 | Method for modifying polyetheretherketone surface by implanting calcium ions |
| CN103242551A (en) * | 2013-05-20 | 2013-08-14 | 中国科学院上海硅酸盐研究所 | Method for injecting titanium ions to modify surface of polyether-ether-ketone |
| CN103614699A (en) * | 2013-12-16 | 2014-03-05 | 中国科学院上海硅酸盐研究所 | Method for modifying surface of polyetheretherketone by injecting tantalum ion and modified polyetheretherketone material |
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| CN103225067A (en) * | 2013-05-20 | 2013-07-31 | 中国科学院上海硅酸盐研究所 | Method for modifying polyetheretherketone surface by implanting calcium ions |
| CN103242551A (en) * | 2013-05-20 | 2013-08-14 | 中国科学院上海硅酸盐研究所 | Method for injecting titanium ions to modify surface of polyether-ether-ketone |
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