CN109135175A - Polyether ketone ketone based composites, composition, dummy and preparation method, application - Google Patents

Polyether ketone ketone based composites, composition, dummy and preparation method, application Download PDF

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CN109135175A
CN109135175A CN201810904944.XA CN201810904944A CN109135175A CN 109135175 A CN109135175 A CN 109135175A CN 201810904944 A CN201810904944 A CN 201810904944A CN 109135175 A CN109135175 A CN 109135175A
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ketone
polyether
polyether ketone
based composites
silicon nitride
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CN109135175B (en
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魏杰
吴涵
汤亭亭
潘泳康
沈学宁
王德强
王雪红
杨立利
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Shanghai Hemai Medical Technology Co.,Ltd.
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/216—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

The invention discloses a kind of polyether ketone ketone based composites, composition, dummy and preparation methods, application.Polyether ketone ketone base feed composition includes following components: the mass ratio of polyether ketone ketone powder and alpha-silicon nitride powders, polyether ketone ketone powder and alpha-silicon nitride powders is (1~3): (2~4), and the D50 partial size of silicon nitride is 0.5~3.5 μm.Polyether ketone ketone based composites of the invention have good rush osteogenic and biocompatibility, can promote adherency, proliferation and the differentiation of osteoblast.It can inhibit infection after in bone repair implantation organism of the invention, promote new osteanagenesis, guarantee the steady in a long-term of implant.Preparation method is simple for polyether ketone ketone based composites of the invention, can accordingly adjust the preparation process of polyether ketone ketone based composites according to clinical demand to prepare different shape, specification and the bone repair of mechanical property.

Description

Polyether ketone ketone based composites, composition, dummy and preparation method, application
Technical field
The present invention relates to medical biotechnology Material Field more particularly to a kind of polyether ketone ketone based composites, composition, reparation Body and preparation method, application.
Background technique
With aging of population, the increase of young and middle-aged wound, bone renovating material becomes the maximum biology doctor of clinical demand amount With one of material.Annual bone tissue defect patient has millions of people, but clinically widely applied orthopaedics fixes material at present And bone impairment renovation material has that bioactivity is poor.Better bone tissue regeneration repair materials are found, are biologies The forward position of medical material research and hot spot.
Common bone renovating material is broadly divided into three categories currently on the market: metal material, bioceramic/bio-vitric and High molecular material.Metal material, such as titanium alloy have been widely used for clinic, but its price with excellent mechanical property Expensive and elasticity modulus is significantly larger than bone tissue, and stress shielding can be generated after implanting, causes bone resorption, osteanabrosis, in turn Implant loosening is caused to cause a series of complication；Bioceramic material, such as hydroxyapatite have biological living well Property, but it is a kind of fragile material, is unfit to do load-bearing Bone Defect Repari；High molecular material, such as polyether ketone ketone, elasticity modulus and bone It is close, it not will cause bone resorption and interface loosen, good mechanical performance, and its good biocompatibility, corrosion resistance and good.But it is poly- Ether ketone ketone is a kind of bio-inert material, cannot form synostosis；After polyether ketone ketone implantation, in polyether ketone ketone material and tissue Between easily form fiber limitans, and then cause polyether ketone ketone implant loosening even fall off.It is implanted into surface meeting and the people of material Cell, the tissue of body carry out reciprocal influence, and the surface texture and characteristic of material will affect cell adherence, proliferation and differentiation, most Eventually determine tissue production quantity, 1 this be also to directly affect the whether successful fundamental cause of implant surgery.
Chinese patent application CN104870564A discloses a kind of polymer composition, is used as artificial body portion for manufacturing The prosthetic appliance divided, the polymer composition include at least one poly aryl ether ketone polymer [(PAEK) polymer and at least one The nitride of the element of from 1.3 to 2.5 electronegativity (ε), but its mechanical performance for only stressing material, it is not living to biology The index of property is tested, and does not refer to the anti-microbial property of material.Moreover, common bone renovating material often only has biology living Property, the regeneration of new bone can be promoted, but tend not to solve the problems, such as that postoperative infection, bioactivity are also not high enough.
Summary of the invention
Technical problem solved by the invention is to overcome bone renovating material bioactivity in the prior art low, antibiotic property Can difference defect, provide a kind of polyether ketone ketone based composites, composition, dummy and preparation method, application.Of the invention Polyether ketone ketone based composites, composition, dummy and preparation method, using the life that can be improved polyether ketone ketone based composites Object activity, has good biocompatibility, osteogenic and antibiotic property, has more matched mechanical property with bone tissue, can promote Adherency, proliferation and the differentiation of osteoblast inhibit bacterium infection.Mediated cell oriented growth.The polyether ketone ketone based composites Preparation method is simple, and adjustable preparation process comes to prepare the bone renovating material of different shape, specification and mechanical property Clinical use demand is adapted to, provides important materials basis for bioactive bone reparation or the preparation of alternative materials.
The present invention solves above-mentioned technical problem by the following technical programs.
The present invention provides a kind of polyether ketone ketone base feed composition comprising following components: polyether ketone ketone powder and nitridation Si powder；The mass ratio of the polyether ketone ketone powder and the alpha-silicon nitride powders is (1~3): (2~4), the silicon nitride D50 partial size is 0.5~3.5 μm.
In the present invention, the D50 partial size of the silicon nitride can be 0.5 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm. Preferably, the D50 partial size of the silicon nitride is 1.5~3 μm.It is further preferred that the D50 partial size of the silicon nitride is 2.5 μm.
Preferably, in the polyether ketone ketone base feed composition, the polyether ketone ketone powder and the alpha-silicon nitride powders Mass ratio be (20wt%~60wt%): (40wt%~80wt%), for example, 54wt%:46wt%, 44wt%:56wt%, 34wt%:66wt%, 28wt%:72wt%.
It is further preferred that in the polyether ketone ketone base feed composition, the polyether ketone ketone and the silicon nitride Ratio is (28wt%~54wt%): (46wt%~72wt%).
It is further preferred that in the polyether ketone ketone base feed composition, the polyether ketone ketone and the silicon nitride Ratio is 28wt%:72wt%.
The present invention has found that silicon nitride content is higher, and the bioactivity and anti-microbial property of material are better by repetition test, but When being that the mass ratio of silicon nitride is more than 72%, the mechanical properties decrease of material, it is advantageous to the powder of polyether ketone ketone and silicon nitride Mass ratio be 28wt%:72wt%.
Polyether ketone ketone of the invention is conventional medical grade, it is preferable that the degree of polymerization of the polyether ketone ketone is 103-105, Further preferably 104, it is preferable that the density of the polyether ketone ketone is 1.2g/cm3~1.4g/cm3, further preferably 1.3g/cm3。
Preferably, alpha-silicon nitride powders density of the invention is 3.1g/cm3~3.3g/cm3, further preferably 3.2g/ cm3。
Preferably, the D50 partial size of the polyether ketone ketone is 15~25 μm, such as 15 μm, 20 μm, 25 μm.
Polyether ketone ketone of the invention is purchased from Enfield Oxford performance materials, and D50 partial size is 15 μm, 20 μm and 25 μm, type Number be OXPEKK-C.Silicon nitride of the invention is purchased from Shanghai Aladdin biochemical technology limited liability company, model β phase, purity It is 1.5 μm, 2 μm, 2.5 μm and 3 μm for 99.9%, D50 particle size range.
In the present invention, the preparation method of the polyether ketone ketone base feed composition can be made by conventional method in that art, Generally after mixing by each component, it first cleans, dries in ethanol, after then cleaning in deionized water, drying.
Preferably, the material after mixing is taken up in order of priority and is poured into dehydrated alcohol and deionized water, ultrasound is clear It washes dispersion and is placed on 70~80 DEG C of drying in oven to get the polyether ketone ketone base feed composition.
The present invention also provides a kind of polyether ketone ketone based composites, the polyether ketone ketone based composites include polyether-ketone Ketone group body and alpha-silicon nitride powders, the partial size of the silicon nitride are 0.5~3.5 μm, the wherein at least particle of the part silicon nitride The exposed surface in the polyether ketone ketone based composites, and the silicon nitride is on the surface of the polyether ketone ketone based composites Average area accounting be 20%-62%.
In the present invention, average area accounting of the silicon nitride on the surface of the polyether ketone ketone based composites can be with It is 20%, 26%, 34%, 43%, 44%, 51%, 60%, 62%.Preferably, the silicon nitride is multiple in the polyether-ketone ketone group The average area accounting on the surface of condensation material is 34%-62%, is further preferably 51%-60%.
Preferably, the polyether ketone ketone based composites are made of the polyether ketone ketone base feed composition.
Preferably, the surface roughness Ra value of the polyether ketone ketone based composites is 2.09~2.92 μm.
Preferably, the surface of the polyether ketone ketone based composites is porous pattern or groove pattern.
Wherein, when the surface of the polyether ketone ketone based composites has porous structure, it is further preferred that aperture is big Small is 3~5 μm, and the alpha-silicon nitride powders are embedded in porous.
Wherein, when the surface of the polyether ketone ketone based composites has groove structure, it is further preferred that ditch groove width Degree is 20~60 μm, and trench spacing is 20~60 μm, and trench depth is 5~10 μm.
The present invention also provides a kind of preparation methods of polyether ketone ketone based composites comprising following step: will be described Polyether ketone ketone base feed composition machine-shaping, wherein the machine-shaping is cold press and sintering, Thermocompressed sintering and forming Or squeeze out injection molding.
In the present invention, the shape of the polyether ketone ketone based composites obtained after the machine-shaping is unlimited.If the processing Mold used in molding is the mold of bone repair product, then the polyether ketone ketone based composites can be directly used as bone and repair Complex.If mold used in the machine-shaping is not the mold of bone repair product, subsequent working process can be passed through The processes such as operation, such as grinding, machining, to prepare the bone repair of required shape.
When the machine-shaping is cold press and sintering, it is preferable that by the polyether ketone ketone base feed composition in mould Compression moulding in tool, then the sinter molding in sintering furnace.During the sinter molding, the heating rate of sintering furnace is preferably For 2~3 DEG C/min.The temperature of the sinter molding is preferably 358~378 DEG C.The soaking time of the sinter molding is preferred Ground is 2~3 hours.
When the machine-shaping is Thermocompressed sintering and forming, it is preferable that adding the polyether ketone ketone base feed composition Thermocompressed sintering and forming is carried out in mold heat.Wherein, during the Thermocompressed sintering and forming, hot pressing temperature is preferably 350~365 ℃.Hot pressing pressure is preferably 2~5MPa.Hot pressing soaking time is preferably 0.5~1 hour.
When the machine-shaping is to squeeze out injection molding, it is preferable that carry out the polyether ketone ketone base feed composition Melt blending, extrusion molding form the master batch that size is 2~4mm, and by the master batch, injection molding in injection molding machine to obtain the final product.Institute Stating extrusion molding preferably uses double screw extruder to carry out.The temperature of the extrusion molding is preferably 380~400 DEG C.Institute The pressure for stating extrusion molding is preferably 80~100MPa.The temperature of the injection molding is preferably 380~400 DEG C.It is described The pressure of injection molding is preferably 100~120MPa.
Preferably, in the preparation method of the polyether ketone ketone based composites, after machine-shaping, femtosecond laser is utilized Instrument performs etching on the surface of the polyether ketone ketone based composites, and the surface of the polyether ketone ketone based composites is made to form ditch Slot structure.
In the present invention, the operation of etching is this field routine operation.Preferably, under the operation of the etching includes It states step: femtosecond laser hot spot is focused on into polyether ketone ketone based composites surface, and scanning etching at same direction.It is described to fly During second laser ablation, design parameter is preferably as follows: the output wavelength of femtosecond laser is preferably 800nm, pulse width Preferably 300fs, frequency are preferably 1000Hz, and optical power is preferably 0~50mW, and scanning speed is preferably 400~ 800μm/s。
In the present invention, groove structure is the groove structure of this field routine.The size of the groove structure is preferred As follows: groove width is preferably 20~60 μm, and trench spacing is preferably 20~60 μm, and trench depth is preferably 5~10 μ m。
The present invention also provides a kind of preparation methods of polyether ketone ketone based composites, wherein right in concentrated sulfuric acid suspension Sintered polyether ketone ketone material surface is corroded, after cleaning to obtain the final product.Wherein, in the concentrated sulfuric acid suspension, silicon nitride powder The content at end is 5wt%~10wt%.Average area of the silicon nitride on the surface of the polyether ketone ketone based composites accounts for Than being 20%~62%.
In the present invention, the preparation method of the concentrated sulfuric acid suspension is conventional method in that art.Preferably, described The preparation method of concentrated sulfuric acid suspension preferably includes following step: the alpha-silicon nitride powders are added to 96%~98% concentrated sulfuric acid In solution, 20~30min of ultrasonic disperse.
Preferably, in the concentrated sulfuric acid suspension, nitridation silicon concentration is 10wt%.When silicon nitride suspending liquid concentration reaches When 10wt%, polyether ketone ketone material surface has almost filled silicon nitride.
In the present invention, the preparation method of the polyether ketone ketone material is the powder sintering method of this field routine.It is described Sintered polyether ketone ketone material is preferably made by following step: polyether ketone ketone powder is sequentially placed into ethyl alcohol and deionized water In, after ultrasonic cleaning, cold press and sintering to obtain the final product.Wherein, the D50 partial size of the polyether ketone ketone powder is 15~25 μm.It is described During cold-rolled sintered, heating rate is preferably 2~3 DEG C/min, and temperature is preferably 350~365 DEG C, and soaking time is preferred Ground is 2~3 hours.
In the present invention, the method for the corrosion is conventional method in that art.Preferably, the operation of the corrosion is excellent Choosing includes the following steps: for sintered polyether ketone ketone material to be put into 10~20min of stirring in the concentrated sulfuric acid suspension.
In the present invention, the method for the cleaning is conventional method in that art.The step of cleaning, preferably includes Following step: after being impregnated 12~16 hours in 100 DEG C of water-baths, then respectively in ethyl alcohol and deionized water sonic oscillation 20~ 30min.
In the present invention, the porous aperture that polyether ketone ketone based composites surface is formed is this field conventional aperture ?.Preferably, the porous aperture that polyether ketone ketone based composites surface is formed is 3~5 μm.
The present invention also provides a kind of polyether ketone ketone based composites, and above-mentioned preparation method is used to be made.
The present invention also provides a kind of application of above-mentioned polyether ketone ketone based composites in bone repair.
The present invention also provides a kind of preparation methods of bone repair, and above-mentioned polyether ketone ketone based composites is used to process Molding, wherein the machine-shaping is cold press and sintering, Thermocompressed sintering and forming or extrusion injection molding.
The present invention also provides a kind of bone repairs, and the preparation method of above-mentioned bone repair is used to prepare.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention Example.
In the present invention, the mechanical performance indexs of the polyether ketone ketone based composites approximately as:
Elasticity modulus is 4.4~5.5GPa, and compression strength is 144~158MPa, and tensile strength is 86~91MPa, bending resistance Intensity is 85~87MPa.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
(1) polyether ketone ketone based composites of the invention have good rush osteogenic and biocompatibility, can promote Adherency, proliferation and the differentiation of osteoblast.The release of surface silicon ion can stimulating cellular growth, stimulation osteoblast is to osteocyte Differentiation.
(2) polyether ketone ketone based composites of the invention have good anti-microbial property, can be effectively prevented postoperative infection, Avoid the risk of second operation.It can inhibit infection after in implantation organism, promote new osteanagenesis, guarantee the long-term steady of implant It is fixed.
(3) preparation method is simple for polyether ketone ketone based composites of the invention, can accordingly be adjusted according to clinical demand The preparation process of whole polyether ketone ketone based composites prepares bone repair (such as orthopaedics of different shape, specification and mechanical property Fixed instrument, bone defect packing material etc.).
(4) bone repair of the invention had not only remained the original property of polyether-ketone ketone group bone repair, but also made bone repair Surface exposes more silicon nitrides, improves the bioactivity of bone repair, and surface groove structures energy mediated cell orients Growth promotes Integrated implant, the stability after improving implantation.
(5) polyether ketone ketone based composites good mechanical performance of the invention, simultaneously significantly improve into bone bioactivity and Antibiotic property provides important experiment basis for the preparation of bioactive bone dummy or alternative materials.
Detailed description of the invention
Fig. 1 is the SEM of pure polyether ketone ketone material and the polyether ketone ketone based composites of embodiment 1-2 preparation in embodiment 7 Photo, wherein a, d are pure polyether ketone ketone materials；B, e are polyether ketone ketone based composites prepared by embodiment 1；C, f are embodiments The polyether ketone ketone based composites of 2 preparations.
Fig. 2 is the polyether ketone ketone based composites water contact of pure polyether ketone ketone material and embodiment 1-2 preparation in embodiment 7 Corner post shape figure.
Fig. 3 be rat bone marrow mesenchymal stem cells in embodiment 7 pure polyether ketone ketone material and embodiment 1-2 preparation it is poly- The 3D laser confocal microscope photo of cell adherence after ether ketone ketone group composite material surface culture for 24 hours.A is pure polyether ketone ketone Material；B is polyether ketone ketone based composites prepared by embodiment 1；C is polyether ketone ketone based composites prepared by embodiment 2.
Fig. 4 be rat bone marrow mesenchymal stem cells in embodiment 7 pure polyether ketone ketone material and embodiment 1-2 preparation it is poly- The OD value histogram of ether ketone ketone group composite material surface culture different time cell.
Fig. 5 be rat bone marrow mesenchymal stem cells in embodiment 7 pure polyether ketone ketone material and embodiment 1-2 preparation it is poly- The ALP activity histogram of ether ketone ketone group composite material surface culture different time cell.
Fig. 6 be in embodiment 7 pure polyether ketone ketone material and embodiment 1-2 preparation polyether ketone ketone based composites to golden yellow The staphylococcic inhibition zone photo of color.A is pure polyether ketone ketone material；B is polyether ketone ketone based composites prepared by embodiment 1；c It is polyether ketone ketone based composites prepared by embodiment 2.
Fig. 7 is the polyether ketone ketone material of the pure polyether ketone ketone material of modification prepared by comparative example 1 and embodiment 7-8 preparation SEM photograph.Wherein a, d are the pure polyether ketone ketone materials of modification prepared by comparative example 1；B, e are polyether-ketone ketone groups prepared by embodiment 7 Composite material；C, f are polyether ketone ketone based composites prepared by embodiment 8.
Fig. 8 is the surface modified polyether ketone ketone of the pure polyether ketone ketone material of modification prepared by comparative example 1 and embodiment 7-8 preparation The water contact angle histogram of material.
Fig. 9 is that rat bone marrow mesenchymal stem cells change on surface prepared by the pure polyether ketone ketone material of modification and embodiment 7-8 Property polyether ketone ketone surface culture for 24 hours after cell adherence 3D laser confocal microscope photo.A is modified pure polyether ketone ketone material Material；B is polyether ketone ketone based composites prepared by embodiment 7；C is polyether ketone ketone based composites prepared by embodiment 8.
Figure 10 is the pure polyether ketone ketone material of modification and embodiment 7- that rat bone marrow mesenchymal stem cells are prepared in comparative example 1 The histogram of the OD value of the surface modified polyether ketone ketone surface covering silicon nitride material surface culture different time cell of 8 preparations.
Figure 11 is the pure polyether ketone ketone material of modification and embodiment 7- that rat bone marrow mesenchymal stem cells are prepared in comparative example 1 The ALP activity histogram of the surface modified polyether ketone ketone surface covering silicon nitride material surface culture different time cell of 8 preparations.
Figure 12 is the SEM photograph of the polyether ketone ketone based composites of embodiment 9-11 preparation.A is the poly- of the preparation of embodiment 9 Ether ketone ketone group composite material；B is polyether ketone ketone based composites prepared by embodiment 10；C is polyether-ketone prepared by embodiment 11 Ketone group composite material.
Figure 13 is the polyether ketone ketone based composites and embodiment 9- that rat bone marrow mesenchymal stem cells are prepared in embodiment 2 Cell adherence photo after the polyether ketone ketone based composites surface culture for 24 hours of 11 preparations.A is polyether-ketone prepared by embodiment 2 Ketone group composite material；B is polyether ketone ketone based composites prepared by embodiment 9；C is that polyether-ketone ketone group prepared by embodiment 10 is multiple Condensation material；D is polyether ketone ketone based composites prepared by embodiment 11.
Figure 14 is the surface modified polyether ketone ketone group composite wood that rat bone marrow mesenchymal stem cells are prepared in embodiment 9-11 Expect the OD value histogram of surface culture different time cell.
Figure 15 is the surface modified polyether ketone ketone group composite wood that rat bone marrow mesenchymal stem cells are prepared in embodiment 9-11 Expect the ALP activity histogram of surface culture different time cell.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient The selection of product specification.
Polyether ketone ketone of the invention is purchased from Enfield Oxford performance materials, and D50 partial size is 15 μm, 20 μm and 25 μm, type Number be OXPEKK-C.Silicon nitride of the invention is purchased from Shanghai Aladdin biochemical technology limited liability company, model β phase, purity It is 1.5 μm, 2 μm, 2.5 μm and 3 μm for 99.9%, D50 particle size range.
Embodiment 1
By 4.6kg D50 partial size be 2.5 μm alpha-silicon nitride powders and 5.4kg D50 partial size be that 20 μm of polyether ketone ketone powder are equal Even mixing, obtains mixed-powder；Then mixed-powder is poured into dehydrated alcohol, ultrasonic cleaning dispersion is subsequently placed in 80 DEG C of baking ovens Interior drying, then pour into deionized water, ultrasonic cleaning dispersion, 80 DEG C of drying in oven are subsequently placed in get polyether-ketone ketone group is arrived Feedstock composition；By polyether ketone ketone base feed composition, Thermocompressed sintering and forming is compound to get polyether-ketone ketone group in heating mould Material；Hot pressing temperature is 356 DEG C；Pressure is 3MPa；Hot pressing soaking time is 40min.
Embodiment 2
By 7.2kg D50 partial size be 2 μm alpha-silicon nitride powders and 2.8kg D50 partial size be 15 μm polyether ketone ketone powder it is equal Even mixing, obtains mixed-powder；Then extruding pelletization after mixed-powder being blended with double screw extruder high-temperature fusion, obtains polyethers Ketone ketone group composite material master batch, the temperature of melting extrusion are 390 DEG C；The pressure of double screw extruder is 90MPa.By polyether ketone ketone Based composites master batch carries out injection molding in injection molding machine to get polyether ketone ketone based composites；Injection temperature is 390 DEG C； Injection molding pressure is 110MPa.
Embodiment 3
By 4.6g D50 partial size be 3 μm alpha-silicon nitride powders and 5.4g D50 partial size be 25 μm polyether ketone ketone powder it is uniform Mixing；Then mixed-powder is poured into dehydrated alcohol, ultrasonic cleaning dispersion is subsequently placed in 80 DEG C of drying in oven, then pour into In deionized water, ultrasonic cleaning dispersion is subsequently placed in 80 DEG C of drying in oven to get polyether ketone ketone base feed composition is arrived；It will Polyether ketone ketone base feed composition is by cold press and sintering to get polyether ketone ketone based composites；Wherein, the heating of sintering furnace Speed is 2 DEG C/min；Sintering temperature is 360 DEG C；The sintered heat insulating time is 2 hours.
Embodiment 4
By 5.6g D50 partial size be 3 μm alpha-silicon nitride powders and 4.4g D50 partial size be 25 μm polyether ketone ketone powder it is uniform Mixing；Then mixed-powder is poured into dehydrated alcohol, ultrasonic cleaning dispersion is subsequently placed in 80 DEG C of drying in oven, then pour into In deionized water, ultrasonic cleaning dispersion is subsequently placed in 80 DEG C of drying in oven to get polyether ketone ketone base feed composition is arrived；It will Polyether ketone ketone base feed composition is by cold press and sintering to get polyether ketone ketone based composites；The heating rate of sintering furnace For 2 DEG C/min；Sintering temperature is 362 DEG C；The sintered heat insulating time is 2 hours.
Embodiment 5
By 6.6g D50 partial size be 1.5 μm alpha-silicon nitride powders and 3.4g D50 partial size be 15 μm polyether ketone ketone powder it is equal Even mixing；Then mixed-powder is poured into dehydrated alcohol, ultrasonic cleaning dispersion is subsequently placed in 80 DEG C of drying in oven, then fall Enter in deionized water, ultrasonic cleaning dispersion, is subsequently placed in 80 DEG C of drying in oven to get polyether ketone ketone base feed composition is arrived； By polyether ketone ketone base feed composition by cold press and sintering to get polyether ketone ketone based composites；The heating speed of sintering furnace Degree is 2 DEG C/min；Sintering temperature is 368 DEG C；The sintered heat insulating time is 2.5 hours.
Embodiment 6
By 7.2g D50 partial size be 1.5 μm alpha-silicon nitride powders and 2.8g D50 partial size be 15 μm polyether ketone ketone powder it is equal Even mixing；Then mixed-powder is poured into dehydrated alcohol, ultrasonic cleaning dispersion is subsequently placed in 80 DEG C of drying in oven, then fall Enter in deionized water, ultrasonic cleaning dispersion, is subsequently placed in 80 DEG C of drying in oven to get polyether ketone ketone base feed composition is arrived； By polyether ketone ketone base feed composition by cold press and sintering to get polyether ketone ketone based composites；The heating speed of sintering furnace Degree is 2 DEG C/min；Sintering temperature is 368 DEG C；The sintered heat insulating time is 2.5 hours.
Embodiment 7
Prepare pure polyether ketone ketone material: by D50 partial size be 20 μm of pure polyether ketone ketone powder be first placed on dehydrated alcohol and In deionized water, ultrasonic cleaning, remove impurity, then by cold press and sintering to get；The heating rate of sintering be 2 DEG C/ min；Sintering temperature is 355 DEG C；The sintered heat insulating time is 2 hours.
Then 2g alpha-silicon nitride powders are weighed to be added in the concentrated sulfuric acid solution of 20mL98%, are placed in sonic oscillation instrument ultrasonic Disperse 20min, the concentrated sulfuric acid suspension of finely dispersed 5wt% silicon nitride is made；Sintered polyether ketone ketone material is added 10min is stirred into suspension, is taken out, is placed in 100 DEG C of water-baths and impregnates 12 hours, then cleaned respectively with ethyl alcohol, deionized water To remove acid substance, then place the material in be cleaned by ultrasonic 30min removal in sonic oscillation instrument to be embedded in unstable silicon nitride powder End is to get polyether ketone ketone based composites.
Embodiment 8
Prepare pure polyether ketone ketone material: by D50 partial size be 20 μm of pure polyether ketone ketone powder be first placed on dehydrated alcohol and In deionized water, ultrasonic cleaning, remove impurity, then by cold press and sintering to get；The heating rate of sintering be 2 DEG C/ min；Sintering temperature is 355 DEG C；The sintered heat insulating time is 2 hours.
Then 4g alpha-silicon nitride powders are weighed to be added in the concentrated sulfuric acid solution of 20mL98%, are placed in sonic oscillation instrument ultrasonic Disperse 20min, the concentrated sulfuric acid suspension of finely dispersed 10wt% silicon nitride is made；It will be sintered that polyether ketone ketone material is added 10min is stirred into suspension, is taken out, is placed in 100 DEG C of water-baths and impregnates 12 hours, then cleaned respectively with ethyl alcohol, deionized water To remove acid substance, then place the material in ultrasound 30min removals in sonic oscillation instrument to be embedded in unstable alpha-silicon nitride powders, i.e., Obtain polyether ketone ketone based composites.
Embodiment 9
Photoetching is carried out in the same direction using surface of the femtosecond laser to polyether ketone ketone based composites made from embodiment 2 Erosion.The parameter of femtosecond laser are as follows: output wavelength 800nm, pulse width 300fs, frequency 1000Hz, optical power 25mW, scanning speed Spend 400 μm/s.Scanning times are adjusted, so that the groove etched, in arranged in parallel, the width of groove is 20 μm, depth is 10 μ M, trench spacing are 20 μm.
Embodiment 10
Photoetching is carried out in the same direction using surface of the femtosecond laser to polyether ketone ketone based composites made from example 4 Erosion.The parameter of femtosecond laser are as follows: output wavelength 800nm, pulse width 300fs, frequency 1000Hz, optical power 20mW, scanning speed Spend 600 μm/s.Scanning times are adjusted, so that the groove etched, in arranged in parallel, the width of groove is 40 μm, depth is 10 μ M, trench spacing are 40 μm.
Embodiment 11
Photoetching is carried out in the same direction using surface of the femtosecond laser to polyether ketone ketone based composites made from example 4 Erosion.The parameter of the femtosecond laser are as follows: output wavelength 800nm, pulse width 300fs, frequency 1000Hz, optical power 15mW are swept Retouch 800 μm/s of speed.Scanning times are adjusted, so that the groove etched, in arranged in parallel, the width of groove is 60 μm, and depth is 10 μm, trench spacing is 60 μm.
Comparative example 1
The modified pure polyether ketone ketone material of preparation: sintered pure polyether ketone ketone material is immersed in 98% concentrated sulfuric acid solution In, 10min is stirred, is taken out, is placed in 100 DEG C of water-baths and impregnates 12 hours, then cleaned respectively with ethyl alcohol, deionized water to go to deacidify Substance, then place the material in be cleaned by ultrasonic 30min in sonic oscillation instrument to get the pure polyether ketone ketone material of modification.
Effect example 1
Mechanical property test:
Elasticity modulus testing standard: ISO 527
Intensity test standard: ISO 527
Tensile strength test standard: GB/T228.1-2010
Bending strength test standard: GB/T 6569-86
Mechanics Performance Testing is carried out to the polyether ketone ketone based composites of above-described embodiment 1-6 preparation, test result is shown in Table 1.
The mechanical property of the polyether ketone ketone based composites of each embodiment of table 1
In following effect examples, SEM photograph, water contact angle experiment, cell adherence and proliferation experiment, cell differentiation are real Test, antibiotic property test used by sample shape be diameter be 10mm, with a thickness of the disk of 2mm.
Seen from table 1, the pure PEKK of modular ratio of polyether ketone ketone based composites of the invention is slightly excellent, also, nitrogenizes Silicone content is higher, and elasticity modulus is higher.Elasticity modulus range compared to people's bone 3-8, polyether-ketone ketone group composite wood of the invention The elasticity modulus of material is closer to the median with people's bone.The compression strength of polyether ketone ketone based composites of the invention is apparently higher than Pure PEKK, and silicon nitride content is higher, and compression strength is higher.The tensile strength of polyether ketone ketone based composites of the invention with People's bone is close, hence it is evident that is lower than pure PEKK, and same silicon nitride content is higher, tensile strength is higher.Polyether ketone ketone of the invention The bending strength of based composites is slightly more excellent than pure PEKK, also, silicon nitride content is higher, and bending strength is higher.It can be seen that In the present invention, silicon nitride, which is added, has promotion for every mechanical property of polyether ketone ketone matrix.
Polyether ketone ketone based composites of the present invention are close with the elasticity modulus of people's bone, and the parameters in mechanical property In terms of index, polyether ketone ketone based composites of the present invention have more excellent mechanical property compared to pure PEKK, are very suitable for Alternative materials as human body hard tissue.
Effect example 2
SEM photograph and water contact angle experiment
As shown in fig. 1, Fig. 1 a and Fig. 1 d is the SEM photograph of the pure polyether ketone ketone material in embodiment 7, it can be seen that The surface of pure polyether ketone ketone material is more smooth.Fig. 1 d and Fig. 1 e are polyether ketone ketone based composites prepared by embodiment 1, due to It joined and account for the alpha-silicon nitride powders that polyether ketone ketone based composites mass fraction is 46%, therefore surface roughness is increased. Fig. 1 c and Fig. 1 f are polyether ketone ketone based composites prepared by embodiment 2, account for polyether ketone ketone based composites matter due to joined The alpha-silicon nitride powders that score is 72% are measured, therefore surface roughness is significantly increased relative to the sample of embodiment 1.
As shown in Fig. 2, the polyether-ketone ketone group composite wood prepared to polyether ketone ketone material pure in embodiment 7 and embodiment 1-2 Material does water contact angle experiment display, and the water contact angle of pure polyether ketone ketone material is 81.87 ° in embodiment 7, prepared by embodiment 1 The water contact angle of polyether ketone ketone based composites is 70.74 °, the water contact of polyether ketone ketone based composites prepared by embodiment 2 Angle is 63.65 °.It is therefore seen that the hydrophily of polyether ketone ketone based composites is significantly improved relative to pure polyether ketone ketone material, And surface topography is more coarse, and water contact angle is smaller, and hydrophily is better.
Effect example 3
Cell adherence and proliferation experiment
Cell adherence and proliferation experiment is carried out to polyether ketone ketone based composites made from embodiment 1-6, wherein cell adherence The specific method is as follows for proliferation experiment:
Rat bone marrow mesenchymal stem cells are seeded in specimen surface with the density in every hole 1 × 104, culture is distinguished afterwards for 24 hours Nucleus and cytoplasm are contaminated using DAPI (4', 6- diamidino -2-phenylindone) and FITC (fluorescein isothiocynate) Color observes cell adherence situation, such as Fig. 3 under 3D laser confocal microscope.A is that pure polyether ketone ketone material group is thin for 24 hours in Fig. 3 Born of the same parents adhere to situation, and b is the cell adherence situation for 24 hours of polyether ketone ketone based composites made from embodiment 1, and c is made from embodiment 2 Polyether ketone ketone based composites cell adherence situation for 24 hours.The result shows that two kinds of polyether ketone ketone based composites surfaces have it is more Cell adherence, and cell sprawl it is in good condition；The cell quantity of the polyether ketone ketone based composites group adherency of embodiment 2 is more, And there is preferably adherency form, show it with better cell compatibility.
Cell proliferation experiment is carried out using CCK8 method.CCK8 is the abbreviation of Cell Counting Kit, (CCK-8/WST- 8) kit is a kind of based on WST-8 (chemical name: 2- (2- methoxyl group -4- nitre phenyl) -3- (4- nitre phenyl) -5- (2,4- bis- Sulphophenyl) -2H- tetrazolium monosodium salt) the fast high-sensitive degree detection kit for being widely used in cell Proliferation and cytotoxicity. Before cell inoculation starts, material sample is sterilized by oxirane disinfection first, puts into 24 orifice plates, is then connect on sample 1 × 104 cell/mL rat bone marrow mesenchymal stem cells of kind.The cell culture fluid of replacement in every two days in incubation, Cell culture at corresponding time point, was taken out material and is put into 24 new orifice plates after 1,3 and 7 day, 500 μ L's of addition CCK8 reagent is put back in incubator and is cultivated 4 hours, then therefrom inhaled in 100 μ L culture solutions to 96 orifice plates, existed using microplate reader The position 490nm measures corresponding OD value (OD).Fig. 4 is rat bone marrow mesenchymal stem cells pure polyether-ketone in embodiment 7 Cultivate the OD value column of 1 day, 3 days and 5 days cell in the polyether ketone ketone based composites surface of ketone material and embodiment 1-2 preparation Figure, it is seen that the ability of cell proliferation highest of the polyether ketone ketone based composites of embodiment 2, embodiment 1 are taken second place.Pure polyether ketone ketone material The ability of cell proliferation of material is minimum.In cell adherence and proliferation experiment embodiment 3-6,6 material surface cell adherence and proliferation of embodiment Situation is best, i.e., as silicon nitride content increases, the cell adherence and proliferation ability of composite material is significantly improved.
Effect example 4
Cell differentiation experimentation
Cell differentiation experimentation is carried out to polyether ketone ketone based composites made from embodiment 1-6, wherein cell differentiation experimentation The specific method is as follows:
Using alkaline phosphatase (ALP) testing cassete, differentiation situation of the cell on material is studied.First with ethylene oxide by sample Product carry out disinfection sterilizing, are then placed in 24 orifice plates, are inoculated between 2.5 × 104 cell/mL rat marrows and fill on the surface of the material Matter stem cell.Differentiation situation after observation cell is cultivated 7,10 and 14 days on the surface of the material, the mistake of cell culture are dyed using ALP Cheng Zhong rechanges a cell culture fluid every three days.In the corresponding time, the culture medium in orifice plate is sucked, it is then slow with PBS Fliud flushing cleans hole three times.
The Nonidet P40 solution that 500 μ L concentration are 1% is added in the hole for being placed with material, is split with obtaining cell Solve liquid.After cracking is completed, 50 μ L are added in every hole in the P- Nitrophenyl phosphate salting liquid of 1mg/mL, pass through 15min at room temperature Afterwards, reaction is terminated by adding the NaOH solution of the 0.1M of 100 μ L.Finally with microplate reader at the wavelength of 405nm in measured hole OD value, and according to OD value calculate cell ALP activity.Not add the pure polyether ketone ketone material of silicon nitride as control group.Knot Fruit sees Fig. 5.Fig. 5 be rat bone marrow mesenchymal stem cells in embodiment 7 pure polyether ketone ketone material and
The polyether ketone ketone based composites surface of embodiment 1-2 preparation is cultivated 7 days, 10 days and the ALP of 14 days cells (alkalinity Phosphatase) activity histogram.
As seen from Figure 5, with the extension of cell culture time, the cell ALP activity on three kinds of samples is all gradually increased. In general, the cell differentiation activity highest of polyether ketone ketone based composites made from embodiment 2, embodiment 1 are taken second place.Pure polyethers The cell differentiation activity of ketone ketone material is minimum.So polyether ketone ketone based composites divide cell with the addition of silicon nitride Change has good facilitation.In cell differentiation experimentation embodiment 3-6,6 material surface cell Osteoblast Differentiation situation of embodiment is most Good, i.e., as silicon nitride content increases, the cell differentiation of composite material is significantly improved.
Effect example 5
Antibacterial experiment
Antibacterial experiment is carried out to polyether ketone ketone based composites made from embodiment 1-6, wherein testing using inhibition zone method Antibacterial effect of the polyether ketone ketone based composites to S. aureus L-forms.Inhibition zone test method: with each test tube slant of oese picking For strain in the sterile water with bead, being vibrated several minutes with hand disperses spore, and mixing spore suspension is made after filtering；With nothing Bacterium suction pipe (or syringe) injects certain density mixing spore suspension 0.5mL into each culture dish；It is injected into each culture dish The fusing shape agar medium (about 45 DEG C) of 15~20mL, bacterium solution is uniformly mixed with culture medium, to its cooling.With tweezers by sample Product are placed in the center for the culture medium flat plate that carries disease germs, and close the lid and are placed under preference temperature, cultivate 2~3 days, observation filter paper disk week Enclose the presence or absence of inhibition zone and size.Test result is shown in Fig. 6.Fig. 6 is pure polyether ketone ketone material and embodiment 1-2 system in embodiment 7 Inhibition zone photo of the standby polyether ketone ketone based composites to staphylococcus aureus.A is pure polyether ketone ketone material；B is to implement Polyether ketone ketone based composites prepared by example 1；C is polyether ketone ketone based composites prepared by embodiment 2.
As can be seen from Figure 6 there is not inhibition zone in the culture dish of bacterium in pure polyether ketone ketone material group, illustrates pure Polyether ketone ketone material does not have inhibiting effect to S. aureus L-forms.Example 1 group and 2 groups of embodiment all occur obvious in culture dish Inhibition zone, wherein 2 groups of embodiment of inhibition zone is bigger than example 1 group, illustrates the increase with silicon nitride content, polyether ketone ketone The anti-microbial property of based composites is gradually increased.In antibacterial experiment embodiment 3-6,6 material anti-microbial property of embodiment is best, i.e., with Silicon nitride content increase, the antibacterial ability of composite material significantly improves.
Effect example 6
SEM photograph and water contact angle experiment
As shown in Figure 7, Fig. 7 a and Fig. 7 d is the SEM photograph of the pure polyether ketone ketone material of modification in comparative example 1, can be seen Out, the surface of modified pure polyether ketone ketone material has micropore that is very thin and being evenly distributed.Fig. 7 d and Fig. 7 e are prepared by embodiment 7 Polyether ketone ketone based composites, due to the concentrated sulfuric acid suspension using 5wt% silicon nitride pure polyether ketone ketone material is carried out it is rotten Erosion, therefore surface is embedded in a certain amount of alpha-silicon nitride powders.Fig. 7 c and Fig. 7 f are polyether-ketone ketone group composite woods prepared by embodiment 8 Material, due to being corroded using the concentrated sulfuric acid suspension of 5wt% silicon nitride to pure polyether ketone ketone material, surface is embedded in more More alpha-silicon nitride powders.As shown in figure 8, to the table of the comparative example 1 pure polyether ketone ketone material of modification prepared and embodiment 7-8 preparation Face modified polyether ketone ketone material does water contact angle experiment display, and the water contact angle of modified pure polyether ketone ketone material is in comparative example 1 90 °, the water contact angle of surface modified polyether ketone ketone group composite material prepared by embodiment 7 is 57 °, surface prepared by embodiment 8 The water contact angle of modified polyether ketone ketone group composite material is 54 °.It is therefore seen that using the concentrated sulfuric acid suspension corrosion mistake of silicon nitride The hydrophilies of polyether ketone ketone based composites be significantly improved relative to the pure polyether ketone ketone material corroded with the concentrated sulfuric acid, and And silicon nitride content is higher, water contact angle is smaller, and hydrophily is better.
Effect example 7
Cell adherence and proliferation experiment
Cell adherence and proliferation experiment is carried out to polyether-ketone ketone group bone renovating material prepared by embodiment 7 and 8, wherein cell is viscous The specific method is as follows for attached proliferation experiment:
By rat bone marrow mesenchymal stem cells with every hole 1 × 104Density be seeded in composite sample surface, after culture for 24 hours Nucleus and cytoplasm are dyed using DAPI and FITC respectively, observe cell adherence under 3D laser confocal microscope Situation, such as Fig. 9.Fig. 9 a is pure concentrated sulfuric acid modified PE KK group cell adherence situation for 24 hours, and Fig. 9 b is 7 groups of embodiment cell adherence for 24 hours Situation, Fig. 9 c are 8 groups of embodiment cell adherence situation for 24 hours.The result shows that crossed using the concentrated sulfuric acid suspension corrosion of silicon nitride There is a more cell adherence on polyether ketone ketone based composites surface, and cell sprawl it is in good condition；The cell of 8 groups of adherency of embodiment It is more, and there is preferably adherency form, there is better cell compatibility, show polyether ketone ketone based composites surface Silicon nitride content it is higher, cell adherence effect is better.
Cell proliferation experiment is carried out using CCK8 method.Before cell inoculation starts, material sample is first passed through ethylene oxide Sterilization is put into 24 orifice plates, and 1 × 10 is then inoculated on material4The rat bone marrow mesenchymal stem cells of a cell/mL are thin Born of the same parents.The cell culture fluid of replacement in every two days in incubation, after cell culture 1,3 and 7 day, in the corresponding time Point takes out material and puts into 24 new orifice plates, add the CCK8 reagent of 500 μ L, puts back to and cultivate 4 hours in incubator, then from In 100 μ L culture solutions to 96 orifice plates of middle suction, using microplate reader in the position 490nm, corresponding OD value (OD) is measured.As a result see Figure 10, it is seen that the ability of cell proliferation highest of polyether ketone ketone based composites prepared by embodiment 8, polyethers prepared by embodiment 7 The ability of cell proliferation of ketone ketone group composite material takes second place, the cell Proliferation energy of the pure polyether ketone ketone material of modification prepared by comparative example 1 Power is minimum.
Effect example 8
Cell differentiation experimentation
Cell differentiation experimentation is carried out to polyether ketone ketone based composites prepared by embodiment 7 and 8, wherein cell differentiation experimentation The specific method is as follows:
Using alkaline phosphatase (ALP) testing cassete, differentiation situation of the cell on material is studied.First with ethylene oxide by sample Product carry out disinfection sterilizing, are then placed in 24 orifice plates, are inoculated between 2.5 × 104 cell/mL rat marrows and fill on the surface of the material Matter stem cell.Differentiation situation after observation cell is cultivated 7,10 and 14 days on the surface of the material, the mistake of cell culture are dyed using ALP Cheng Zhong rechanges a cell culture fluid every three days.In the corresponding time, the culture medium in orifice plate is sucked, it is then slow with PBS Fliud flushing cleans hole three times.
The Nonidet P40 solution that 500 μ L concentration are 1% is added in the hole for being placed with material, is split with obtaining cell Solve liquid.After cracking is completed, 50 μ L are added in every hole in the P- Nitrophenyl phosphate salting liquid of 1mg/mL, pass through 15min at room temperature Afterwards, reaction is terminated by adding the NaOH solution of the 0.1M of 100 μ L.Finally with microplate reader at the wavelength of 405nm in measured hole OD value, and according to OD value calculate cell ALP activity.It is pair with the pure polyether ketone ketone material sample of modification prepared by comparative example 1 According to group.The result is shown in Figure 11.
As seen from Figure 11, with the extension of cell culture time, the cell ALP activity on three kinds of samples all gradually increases By force.In general, the cell differentiation activity highest of polyether ketone ketone based composites made from embodiment 8 is gathered made from embodiment 7 The cell differentiation activity of ether ketone ketone group composite material takes second place.The cell differentiation of the pure polyether ketone ketone material of modification prepared by comparative example 1 Activity is minimum.So polyether ketone ketone based composites are used with the concentrated sulfuric acid suspension corrosion of silicon nitride, have to the differentiation of cell Good facilitation.
Effect example 9
It carries out SEM to the polyether ketone ketone based composites that embodiment 9,10 and 11 femtosecond lasers etch to take pictures, such as Figure 12 institute Show, wherein Figure 12 a is polyether ketone ketone based composites prepared by embodiment 9；Figure 12 b is polyether-ketone ketone group prepared by embodiment 10 Composite material；Figure 12 c is polyether ketone ketone based composites prepared by embodiment 11.It can be seen from the figure that prepared by embodiment 9 Polyether ketone ketone based composites trench spacing is minimum, and polyether ketone ketone based composites trench spacing prepared by embodiment 11 is maximum, Polyether ketone ketone based composites trench spacing prepared by embodiment 10 is placed in the middle.
Effect example 10
Cell adherence and proliferation experiment
The polyether ketone ketone based composites etched to embodiment 9,10 and 11 femtosecond lasers carry out cell adherence and proliferation experiment, Wherein the specific method is as follows for cell adherence and proliferation experiment:
By rat bone marrow mesenchymal stem cells with every hole 1 × 104Density be seeded in composite sample surface, after culture for 24 hours Nucleus and cytoplasm are dyed using DAPI and FITC respectively, observe cell adherence under 3D laser confocal microscope Situation, as shown in figure 13, wherein Figure 13 a is the cell adherence situation of polyether ketone ketone based composites made from embodiment 2, figure 13b, Figure 13 c and Figure 13 d are respectively
The cell adherence situation on polyether ketone ketone based composites surface made from embodiment 9,10 and 11.The result shows that real The superficial cell for applying polyether ketone ketone based composites made from example 2 has more cell adherence, and cell is sprawled more unordered；Embodiment 9 groups of superficial cells are elongated, and it is poor to sprawl situation；The cell on embodiment 10 and 11 group surface along groove sprawl by direction, cell shape Looks are preferable, and wherein the cell in embodiment 11 in groove is more.The result shows that the groove that spacing is 60 μm can be mediated preferably carefully Born of the same parents' oriented growth.
Cell proliferation experiment is carried out using CCK8 method.Before cell inoculation starts, material sample is first passed through ethylene oxide Sterilization is put into 24 orifice plates, and 1 × 10 is then inoculated on material4The rat bone marrow mesenchymal stem cells of a cell/mL are thin Born of the same parents.The cell culture fluid of replacement in every two days in incubation, after cell culture 1,3 and 7 day, in the corresponding time Point takes out material and puts into 24 new orifice plates, add the CCK8 reagent of 500 μ L, puts back to and cultivate 4 hours in incubator, then from In 100 μ L culture solutions to 96 orifice plates of middle suction, using microplate reader in the position 490nm, corresponding OD value (OD) is measured.As a result see Figure 14, it is seen that the ability of cell proliferation highest of polyether ketone ketone based composites made from embodiment 11 is gathered made from embodiment 10 The ability of cell proliferation of ether ketone ketone group composite material takes second place.The cell on polyether ketone ketone based composites surface made from embodiment 9 Proliferative capacity is minimum.
Effect example 11
Cell differentiation experimentation
The polyether ketone ketone based composites etched to embodiment 9,10 and 11 femtosecond lasers carry out cell differentiation experimentation, wherein The specific method is as follows for cell differentiation experimentation:
Using alkaline phosphatase (ALP) testing cassete, differentiation situation of the cell on material is studied.First with ethylene oxide by sample Product carry out disinfection sterilizing, are then placed in 24 orifice plates, are inoculated with 2.5 × 10 on the surface of the material4It is filled between the rat marrow of a cell/mL Matter stem cell.Differentiation situation after observation cell is cultivated 7,10 and 14 days on the surface of the material, the mistake of cell culture are dyed using ALP Cheng Zhong rechanges a cell culture fluid every three days.In the corresponding time, the culture medium in orifice plate is sucked, it is then slow with PBS Fliud flushing cleans hole three times.
The Nonidet P40 solution that 500 μ L concentration are 1% is added in the hole for being placed with material, is split with obtaining cell Solve liquid.After cracking is completed, 50 μ L are added in every hole in the P- Nitrophenyl phosphate salting liquid of 1mg/mL, pass through 15min at room temperature Afterwards, reaction is terminated by adding the NaOH solution of the 0.1M of 100 μ L.Finally with microplate reader at the wavelength of 405nm in measured hole OD value, and according to OD value calculate cell ALP activity.Using polyether ketone ketone based composites made from embodiment 2 as control group. The result is shown in Figure 15.
As seen from Figure 15, the cell differentiation activity highest of polyether ketone ketone based composites made from embodiment 11 is implemented The cell differentiation activity of polyether ketone ketone based composites made from example 10 takes second place.Polyether-ketone ketone group composite wood made from embodiment 9 The cell differentiation activity of material is minimum.The result shows that having better facilitation to the differentiation of cell when groove is 60 μm.
The biocompatibility of the polyether ketone ketone based composites of each embodiment of table 2
In the present invention, the state of water contact angle is measured marked as GB/T 30693-2014.
From table 2 it can be seen that the content of silicon nitride is higher for embodiment 1-6, composite material surface silicon nitride area ratio It is bigger.Since silicon nitride is evenly distributed in the entirety of material in embodiment 1-6, composite material surface silicon nitride area ratio Equal to volume ratio shared by silicon nitride in entire material.And for embodiment 7 and 8, since the matrix of composite material is pure PEKK Therefore volume ratio can not be converted into mass ratio to indicate composite material surface silicon nitride area ratio, and can only be by observing Know.By being observed to the obtained composite material of embodiment 7 and 8, it can be deduced that its surfaces nitrided silicon area ratio is respectively 34% and 60%.The surfaces nitrided silicon area of embodiment 9 is than same as Example 2, the surfaces nitrided silicon area of embodiment 10,11 Than same as Example 4.
Composite material surface silicon nitride area ratio is bigger, and the water contact angle of material surface is smaller, and hydrophily is better.Embodiment 8 hydrophily is best, and embodiment 6 is taken second place, and embodiment 2 is third.Embodiment 9-11 has groove structure, water droplet due to surface It scatter at once up, observable droplet can not be formed.
And preferably for cell adherence and proliferation, cell differentiation and antibacterial effect and embodiment 8, embodiment 6 is taken second place, real Apply example 2 third.
It can be seen that the exposed silicon nitride in composite material surface has significantly the biocompatibility for improving material Facilitation, and composite material surface silicon nitride area ratio is bigger, and biocompatibility is better.And for the surface grooves of material The spacing of pattern, groove is bigger, and biocompatibility is better.
In cell adherence and proliferation effect, " excellent " is meant that material has good facilitation to the adherency proliferation of cell, " good " is meant that material has certain facilitation to the adherency proliferation of cell, " in " it is meant that adherency of the material to cell The facilitation of proliferation is unobvious, and " poor " is meant that material is proliferated no facilitation to the adherency of cell.
In cell differentiation effect, " excellent " is meant that material has good facilitation to the differentiation of cell, and " good " contains Justice is that material has certain facilitation to the differentiation of cell, " in " it is meant that the facilitation of differentiation of the material to cell not Obviously, " poor " is meant that material to the no facilitation of the differentiation of cell.
In antibacterial effect, " excellent " is meant that material has good antibacterial action, and it is certain that " good " is meant that material has Antibacterial action, " in " it is meant that the antibacterial action of material is unobvious, " poor " is meant that material does not have antibacterial action.
Although specific embodiments of the present invention have been described above, it will be appreciated by those of skill in the art that this is only For example, protection scope of the present invention is to be defined by the appended claims.Those skilled in the art without departing substantially from Under the premise of the principle and substance of the present invention, many changes and modifications may be made, but these change and Modification each falls within protection scope of the present invention.

Claims (10)

1. a kind of polyether ketone ketone base feed composition, which is characterized in that it includes following components: polyether ketone ketone powder and silicon nitride The mass ratio of powder, the polyether ketone ketone powder and the alpha-silicon nitride powders is (1~3): (2~4), the D50 of the silicon nitride Partial size is 0.5~3.5 μm.
2. polyether ketone ketone base feed composition as described in claim 1, which is characterized in that the D50 partial size of the silicon nitride is 1.5~3 μm, preferably 2.5 μm；
And/or in the polyether ketone ketone base feed composition, the quality of the polyether ketone ketone powder and the alpha-silicon nitride powders Than for (20wt%~60wt%): (40wt%~80wt%), further preferably (28wt%~54wt%): (46wt%~ 72wt%)；
And/or the degree of polymerization of the polyether ketone ketone is 103~105, further preferably 104；
And/or the density of the polyether ketone ketone is 1.2g/cm3~1.4g/cm3, further preferably 1.3g/cm3；
And/or the density of the alpha-silicon nitride powders is 3.1g/cm3~3.3g/cm3, further preferably 3.2g/cm3；
And/or the D50 partial size of the polyether ketone ketone is 15~25 μm.
3. a kind of polyether ketone ketone based composites, which is characterized in that the polyether ketone ketone based composites include polyether-ketone ketone group Body and alpha-silicon nitride powders, the D50 partial size of the silicon nitride are 0.5~3.5 μm, and the wherein at least part silicon nitride is exposed in institute The surface of polyether ketone ketone based composites is stated, and the silicon nitride is in the centre plane on the surface of the polyether ketone ketone based composites Product accounting is 20%~62%；
Average area accounting of the silicon nitride on the surface of the polyether ketone ketone based composites is preferably 34%-62%；
Average area accounting of the silicon nitride on the surface of the polyether ketone ketone based composites is preferably 51%-60%；
The polyether ketone ketone based composites are preferably made of polyether ketone ketone base feed composition as claimed in claim 1 or 2；
The surface roughness Ra value of the polyether ketone ketone based composites is preferably 2.09~2.92 μm；
The surface of the polyether ketone ketone based composites is preferably porous pattern or groove pattern；
Wherein, when the surface of the polyether ketone ketone based composites has porous structure, pore size is preferably 3~5 μm, and The alpha-silicon nitride powders are embedded in porous；
Wherein, when the surface of the polyether ketone ketone based composites has groove structure, groove width is preferably 20~60 μm, Trench spacing is 20~60 μm, and trench depth is 5~10 μm.
4. a kind of preparation method of polyether ketone ketone based composites, which is characterized in that it includes the following steps: such as claim Polyether ketone ketone base feed composition machine-shaping described in 1 or 2, wherein the machine-shaping is cold press and sintering, heat It presses sinter molding or squeezes out injection molding.
5. the preparation method of polyether ketone ketone based composites as claimed in claim 4, which is characterized in that when the machine-shaping When for cold press and sintering, it is sintered by the polyether ketone ketone base feed composition compression moulding in a mold, then in sintering furnace Molding；
Wherein, during the sinter molding, the heating rate of sintering furnace is preferably 2~3 DEG C/min；The sinter molding Temperature be preferably 358~378 DEG C；The soaking time of the sinter molding is preferably 2~3 hours；
Preferably, when the machine-shaping is Thermocompressed sintering and forming, by the polyether ketone ketone base feed composition in heated mould Thermocompressed sintering and forming is carried out in tool；
Wherein, during the Thermocompressed sintering and forming, hot pressing temperature is preferably 350~365 DEG C；Hot pressing pressure is preferably 2 ~5MPa；Hot pressing soaking time is preferably 0.5~1 hour；
Preferably, when the machine-shaping is to squeeze out injection molding, the polyether ketone ketone base feed composition is melted It is blended, extrusion molding, forms size as the master batch of 2~4mm, injection molding in injection molding machine by the master batch to obtain the final product；
Wherein, the extrusion molding preferably uses double screw extruder to carry out；The temperature of the extrusion molding is preferably 380 ~400 DEG C；The pressure of the extrusion molding is preferably 80~100MPa；The temperature of the injection molding is preferably 380~ 400℃；The pressure of the injection molding is preferably 100~120Mpa；
After the machine-shaping, carved preferably by femtosecond laser instrument on the surface of the polyether ketone ketone based composites Erosion makes the surface of the polyether ketone ketone based composites form groove structure；
Wherein, the operation of the etching preferably includes following step: femtosecond laser hot spot is focused on polyether-ketone ketone group composite wood Expect surface, and scanning etching at same direction；
During the femtosecond laser etching, design parameter is preferably as follows: the output wavelength of femtosecond laser is 800nm, pulse Width is 300fs, and frequency 1000Hz, optical power is 0~50mW, and scanning speed is 400~800 μm/s；
Wherein, the size of the groove structure is preferably as follows: groove width is 20~60 μm, and trench spacing is 20~60 μm, ditch Groove depth is 5~10 μm.
6. a kind of preparation method of polyether ketone ketone based composites, which is characterized in that sintered in concentrated sulfuric acid suspension Polyether ketone ketone material surface is corroded, after cleaning to obtain the final product；Wherein, in the concentrated sulfuric acid suspension, the content of alpha-silicon nitride powders For 5wt%~10wt%；Average area accounting of the silicon nitride on the surface of the polyether ketone ketone based composites is 20% ~62%；
Wherein, the preparation method of the concentrated sulfuric acid suspension preferably includes following step: the alpha-silicon nitride powders are added to 96% In~98% concentrated sulfuric acid solution, 20~30min of ultrasonic disperse；
Wherein, the sintered polyether ketone ketone material is preferably made by following step: polyether ketone ketone powder is sequentially placed into In ethyl alcohol and deionized water, after ultrasonic cleaning, cold press and sintering to obtain the final product；Wherein, the D50 partial size of the polyether ketone ketone powder is 15~25 μm；
In the preparation process of the sintered polyether ketone ketone material, it is described it is cold-rolled sintered during, heating rate is preferably 2 ~3 DEG C/min, temperature is preferably 350~365 DEG C, and soaking time is preferably 2~3 hours；
Wherein, the operation of the corrosion preferably includes following step: the sintered polyether ketone ketone material being put into described dense 10~20min is stirred in Potassium salts；
Wherein, the step of cleaning preferably includes following step: after impregnating 12~16 hours in 100 DEG C of water-baths, then distinguishing 20~30min of sonic oscillation in ethyl alcohol and deionized water；
Wherein, the surface apertures of the polyether ketone ketone based composites are having a size of 3~5 μm.
7. a kind of polyether ketone ketone based composites as made from claim 4~6 described in any item preparation methods.
8. a kind of application of the polyether ketone ketone based composites in bone repair as described in claim 3 or 7.
9. a kind of preparation method of bone repair, which is characterized in that it uses the polyether-ketone ketone group as described in claim 3 or 7 Composite processing molding, wherein the machine-shaping is that cold press and sintering, Thermocompressed sintering and forming or extrusion are molded into Type, wherein the cold press and sintering, Thermocompressed sintering and forming or the design parameter for squeezing out injection molding and condition are preferably such as right It is required that 5 is identical.
10. bone repair made from a kind of preparation method as claimed in claim 9.
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