CN104725771A - Nano calcium silicate-polyetheretherketone (PEEK) composite material and preparation method thereof - Google Patents
Nano calcium silicate-polyetheretherketone (PEEK) composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a nano calcium silicate-polyetheretherketone (PEEK) composite material which is composed of nano calcium silicate and PEEK in a volume ratio of (10-30):(70-90). The nano calcium silicate-PEEK composite material maintains the excellent biomechanical characteristics of the PEEK, and greatly enhances the biological activity of the PEEK. After being implanted into the body, the nano calcium silicate-PEEK composite material can be matched with peripheral normal bones in the mechanical aspect, can be well integrated with the host bone, promotes the adhesion, proliferation and osteogenesis differentiation of the bone source cells, can keep long-term stability, can be used in clinic as a spine interbody fusion device material and a joint prosthesis material, has active practical meanings, and can generate huge social and economic benefits.
Description
Technical field
The present invention relates to a kind of polymer composite, particularly relate to a kind of nanometer Calucium Silicate powder-Peek Composite Material and Preparation Method.
Background technology
In fields such as orthopaedics, plastic surgery, Oral and Maxillofacial Surgerys, implant is the Main Means of reconstruction both injured bones and articulation structure and function.Implant material conventional on Present clinical comprises: metal species, inorganic non-metallic class, high score subclass and matrix material.Metal species (as stainless steel, titanium or titanium alloy, vitallium), has the advantages such as intensity is high, rub resistance, nontoxicity, is used widely clinically.But the intensity of metal group material and Young's modulus, far away higher than normal human's osseous tissue, can make bone absorption around by stress occlusion effect after implanting, affect the integration of implant/bone interface; Can electrolytic reaction be there is in longer-term persistence body and cause local bone dissolving; Metal material shielding ray can cause the disappearance in the image check visual field.Inorganic non-metallic class material, as hydroxyapatite (HA), tricalcium phosphate (TCP), bio-vitric, glass-ceramic A-W etc., there is good biocompatibility, the advantage such as corrosion-resistant, but because their toughness is poor, intensity is lower, fragility is comparatively large, Young's modulus is higher, can not meet the reparation requirement at human bearing position.Have now a large amount of high score subclass material because its wide material sources, workability are strong, good biocompatibility and be applied to clinical, as ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE), polymethylmethacrylate (PMMA), poly(lactic acid) etc.But also there is obvious weak point in high score subclass material: great majority mechanical strength when being used alone is not ideal enough; Can not absorbed themselves when some polymer (as PMMA) uses as bone filler; Sterilizing process also may affect the characteristic of some polymer.These shortcomings greatly limit the application clinically of high score subclass material.
Polyether-ether-ketone (PEEK) is the fragrant thermoplastic macromolecule material of the linear many cyclophanes of a kind of hypocrystalline.PEEK advantage is numerous: have stable physics and chemistry character, as high temperature resistant, wear-resisting, resistance to burning, hydrolysis, chemical-resistant resistance etc.; Good in vitro and in vivo biocompatibility, nontoxicity, without teratogenesis, mutagenic effect; Radioactive rays can be through, and magnetic resonance imaging also can not produce artifact; The most important thing is, biomechanical strength and Human Cortex's bone of PEEK are comparatively close.At present, existing Invasive lumbar fusion device, the artificial joint prosthesis made as raw material using PEEK and matrix material thereof is applied to clinical and achieves good recent follow-up effect.But PEEK has a fatal shortcoming---biologically inert, that is PEEK can not integrate with host bone after implanting well, significantly limit its widespread use clinically.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency, modification is carried out to improve its biological activity and Integrated implant to PEEK.Nanometer calcium silicate particle and PEEK compound are prepared nanometer Calucium Silicate powder-PEEK matrix material (nm-CS/PEEK), many-sided problem can be solved: first, Calucium Silicate powder mix the biological activity that can increase substantially PEEK, can integrate well with host bone after making it implant; The second, nanometer Calucium Silicate powder-PEEK matrix material can retain the excellent biomechanics characteristic of PEEK to a great extent, can match after implanting with surrounding normal sclerotin in terms of mechanics; Three, PEEK matrix can prevent Calucium Silicate powder from degrading too quickly, the Calucium Silicate powder making to retain in body play the longer time bone conduction and bone inductive effect; 4th, nano particle not only can play the biological effect of nano material, promotes the adhesion of bone-derived cell, propagation and Osteoblast Differentiation; 5th, nano particle is owing to having larger specific surface area, more firm than micron particle with the combination of PEEK matrix, therefore nano particle mix the fatigue resistance that can improve PEEK matrix material, long-term stability can be obtained after implanting.
First aspect of the present invention is to provide a kind of nanometer Calucium Silicate powder-polyether-ether-ketone composite material, the moiety of described nanometer Calucium Silicate powder-polyether-ether-ketone composite material comprises nanometer Calucium Silicate powder and polyether-ether-ketone, and the volume ratio of nanometer Calucium Silicate powder and polyether-ether-ketone is (10-30): (70-90).
Preferably, in described nanometer Calucium Silicate powder-polyether-ether-ketone composite material, the volume ratio of nanometer Calucium Silicate powder and polyether-ether-ketone is (15-25): (75-85).
Further preferably, in described nanometer Calucium Silicate powder-polyether-ether-ketone composite material, the volume ratio of nanometer Calucium Silicate powder and polyether-ether-ketone is 20:80.
Second aspect of the present invention is to provide the preparation method of nanometer Calucium Silicate powder-polyether-ether-ketone composite material that a kind of the present invention first aspect provides.
Described preparation method comprises the following steps:
Step 1, by nanometer Calucium Silicate powder and polyether-ether-ketone powder according to (10-30): the volume ratio mixing of (70-90);
Step 2, the nanometer Calucium Silicate powder adopting injection molding technology step 1 to be obtained and polyether-ether-ketone mixture compound, obtained nanometer Calucium Silicate powder-polyether-ether-ketone composite material.
Preferably, in step 1, the volume ratio of nanometer Calucium Silicate powder and polyether-ether-ketone powder is (15-25): (75-85).
Further preferably, in step 1, the volume ratio of nanometer Calucium Silicate powder and polyether-ether-ketone powder is 20:80.
Preferably, in step 1, nanometer Calucium Silicate powder and being blended in high speed ball mill of polyether-ether-ketone powder are carried out, and mixing 0.5-2 hour, rotating speed is 300-800 rev/min.
Preferably, in step 2, when adopting injection molding technology to prepare nanometer Calucium Silicate powder-polyether-ether-ketone composite material, injection temperature is 350-420 DEG C.
Described nanometer Calucium Silicate powder can be obtained by purchase, also can prepare voluntarily.Preferably, described nanometer Calucium Silicate powder is by Ca (NO
3)
24H
2o and Na
2siO
39H
2o reaction and follow-up hydro-thermal reaction, dry obtained.
Further preferably, the concrete preparation method of described nanometer Calucium Silicate powder is as follows:
By the Ca (NO of mol ratio 1:1
3)
24H
2o and Na
2siO
39H
2o is dissolved in water respectively, and the polyoxyethylene glycol of 0.05-0.5% is joined Ca (NO
3)
2in solution, then by Na
2siO
3solution is added drop-wise to Ca (NO
3)
2in solution, generate CaSiO
3precipitation; CaSiO
3after precipitate with deionized water cleaning, add dimethyl formamide, stir lower temperature and rise to 100-150 DEG C of transpiring moisture gradually, then extraction removes DMF, and the product obtained drying at 50-70 DEG C obtains nanometer silicic acid calcium powder.
Novel nm-CS/PEEK matrix material provided by the invention, a large amount of early-stage Study invention: this composite material surface has a large amount of nanometer CS particles, is evenly distributed, and wherein has sub-fraction nanometer CS particle to define micron order aggregate; Test through water contact angle finds, nanometer CS mixes the wetting ability that can improve PEEK to a certain extent, and the raising of material hydrophilic is conducive to cell adhesion in material surface; Nm-CS/PEEK matrix material can a large amount of calcium ion of sustained release and silicon ion be for 21 days in vitro, and the calcium ion of these releases and silicon ion are promoting to be proved in osteoblastic propagation and differentiation and will play positive effect; Soak through simulated body fluid, the surface of nm-CS/PEEK matrix material can form great amount of hydroxy group phosphatic rock island and increase gradually and become very thick apatite layer within 7 days, being formed of these apatite layers is beneficial to osteoblastic propagation and differentiation, is conducive to the integration of implant and osseous tissue after implanting; In vitro cell experiment confirms, compare with pure PEEK material with UHMWPE material, there is more cell adhesion in nm-CS/PEEK composite material surface, and these cells are sprawled better, state is better, rate of propagation is faster, can secrete more alkaline phosphatase (ALP) and calcium tubercle, can also promote the expression of Osteoblast Differentiation genes involved (ALP, Bone Gla protein, osteopontin and NTx).
While nanometer Calucium Silicate powder-polyether-ether-ketone composite material provided by the invention remains the excellent biomechanics characteristic of PEEK, increase substantially the biological activity of PEEK, after implanting, energy and surrounding normal sclerotin match in terms of mechanics, integrate well with host bone, promote the adhesion of bone-derived cell, propagation and Osteoblast Differentiation, can stable for extended periods of time, can as backbone Invasive lumbar fusion device material and artificial joint prosthesis materials application in clinical, there is positive realistic meaning, huge Social and economic benef@will be produced.
Accompanying drawing explanation
Fig. 1 is the sign of nanometer provided by the invention Calucium Silicate powder-polyether-ether-ketone composite material (nm-CS/PEEK matrix material) and wetting ability detected result: A is scanning electron microscope detected result; B is energy dispersion spectrum analysis result; C is water contact angle detected result; From scanning electron microscopic observation result, nm-CS/PEEK composite material surface has a large amount of nanometer CS particle, distribution uniform, but some nanometer CS particle define aggregate (Figure 1A, 3000 ×, arrow indication), diameter hundreds of nanometer to several microns not etc.The high electron density particle that energy dispersion spectrum analysis determines the existence of nm-CS/PEEK composite material surface is calcium silicate particle really.Water contact angle is measured and is found, the water contact angle of UHMWPE material, PEEK material and nm-CS/PEEK matrix material is respectively 78 ± 8 °, 76 ± 2 ° and 62 ± 9 °, the water contact angle of nm-CS/PEEK matrix material, well below the above two (P<0.05), illustrates that the wetting ability of nm-CS/PEEK matrix material is higher than UHMWPE material and PEEK material.
Fig. 2 is the degradation property detected result of nm-CS/PEEK matrix material: A is the release profiles of calcium ion; B is the release profiles of silicon ion; C is nm-CS/PEEK surface scan electron microscopic observation result after 28 days.Within 3 days, nm-CS/PEEK matrix material can discharge a large amount of calcium ions and silicon ion fast; 3 days to 21 days, the burst size of calcium ion and silicon ion reduced gradually; 21 days to 28 days, release profiles entered plateau, illustrated and did not have more calcium ion and silicon ion to discharge.After 28 days, nm-CS/PEEK matrix material can discharge the calcium ion of 0.6492 mM/l and the silicon ion of 0.6774 mM/l, the small rut (Fig. 2 C) that its remained on surface is many, not of uniform size, and out-of-shape stays after calcium silicate particle dissociates.
Fig. 3 is the simulated body fluid immersion test result of nm-CS/PEEK matrix material: A is the scanning electron microscope detected result of PEEK material surface; B is the scanning electron microscope detected result of nm-CS/PEEK composite material surface; C is the energy dispersion spectrum analysis result that nm-CS/PEEK composite material surface newly forms phosphatic rock.Through the immersion of 28 days, PEEK material surface is without any change, but, soak the 7th day, nm-CS/PEEK composite material surface has a large amount of phosphatic rock island and is formed, when 14 days, phosphatic rock island increasing number, substantially being covered by nm-CS/PEEK composite material surface, during to 28 days, what existing one deck was very thick is that the apatite layer of tile is by the surface coverage of nm-CS/PEEK matrix material.
Fig. 4 is the cell adhesion experiments result of nm-CS/PEEK composite material surface: A is CCK-8 quantitative analysis results; B be 12 and 24 hours laser confocal microscope (CLSM) observe situation of the sprawling result of material surface cytoskeleton; C is the form of 24 hours scanning electron microscopic observation material surface cells and sprawls situation.From the quantitative analysis results of cell adhesion, within 6,12 and 24 hours, the quantity at the cell of nm-CS/PEEK surface adhesion is all higher than UHMWPE material and PEEK material; From CLSM observations, the cytoskeleton of nm-CS/PEEK composite material surface is sprawled better, has more actinmicrofilament interconnection; From scanning electron microscopic observation result, the cell drawout completely of nm-CS/PEEK composite material surface, have a lot of pseudopodium to be anchored on material surface, and the cell of UHMWPE material and PEEK material surface is shrunk, pseudopodium is little.
Fig. 5 is the cell proliferation experiment result of nm-CS/PEEK composite material surface: A is cell proliferation curve; B is the relative appreciation rate of cell; C is 4', 6-diamidino-2-phenylindone (DAPI) coloration result; D is nm-CS/PEEK composite material surface cellscan Electronic Speculum detected result.The cell of nm-CS/PEEK composite material surface from 1 day to 3 days, within 3 days, be in obvious vegetative state by 7 days always; And the cell of PEEK material surface from 1 day to 3 days, the cell of UHMWPE material surface bred trend from 3 days to 7 days all not obvious.Relative proliferation rate aspect, when 7 days, nm-CS/PEEK matrix material is higher than the polyethylene of UHMWPE(molecular weight more than 1,500,000) material and PEEK material.From DAPI coloration result, 1 day, 3 days and 7 days time, the nucleus amount of nm-CS/PEEK composite material surface is all more than both other.Scanning electron microscopic observation found that, when 3 days, nm-CS/PEEK composite material surface is occupied by a large amount of cell, when 7 days surface almost completely cover by cell; 3 days and 7 days time, the cell of UHMWPE material surface not only in quantity will lower than nm-CS/PEEK matrix material, and when 7 days, state is also poor; Although PEEK material surface was covered by a large amount of cell 7 days time, the cell quantity of 2 time points is all less than nm-CS/PEEK matrix material.
Fig. 6 is the Osteoblast Differentiation experimental result of nm-CS/PEEK composite material surface cell: A is ALP coloration result; B is ALP active level detected result; C is Alizarin red staining result; D is sodium alizarinsulfonate detection by quantitative result; E is real-time quantitative polymerase chain reaction (PCR) result of Osteoblast Differentiation genes involved.No matter from qualitative or quantitative result, the ALP of the cell expressing of nm-CS/PEEK composite material surface is apparently higher than UHMWPE material and PEEK material.From the result of Alizarin red staining, 21 days and 28 time, the dye levels of nm-CS/PEEK composite material surface is all higher than the above two, consistent with qualitative results, illustrate that nm-CS/PEEK matrix material can promote that superficial cell produces calcium tubercle, from the result of real-time quantitative PCR, compare with PEEK material with UHMWPE material, nm-CS/PEEK matrix material can promote the expression of alkaline phosphatase, Bone Gla protein, osteopontin and NTx to a certain extent.
Embodiment
With reference to the accompanying drawings, in conjunction with concrete embodiment, the invention will be further described, to understand the present invention better.
Embodiment 1
(1) material needed for experiment and instrument
Material: (mean particle size is 20 μm to PEEK powder, purchased from Britain
company); Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) plate (molecular weight is 2000000, purchased from German Roechling Engineered Plastics); Tissue Culture Plate (Costar, Corning company, the U.S.); MC3T3-E1 cell (for the cell that this laboratory liquid nitrogen tank storage is deposited); Other reagent are commercially available analytical reagent.
Instrument: Bechtop (BIO-HAZARD, VCM-420, TaiWan, China), electronic analytical balance (METTLERTOLEDO, AB204-E, Switzerland), magnetic stirrer (STUART, SM24, Britain), high speed ball mill (QM-3B, NanjingT-BotaScietechInstruments & EquipmentLtd., China), injection forming instrument (BA-300/050CD, Battenfeld, Belgium), scanning electron microscope (S-4800, Hitachi, Japan), energy dispersive spectrometry (X-Max, Horiba, Japan), Shape Analyzer (JC-2000D3, ShanghaiZhongchengDigitalTechnologyCo., China), inductively coupled plasma atomic emission spectrometer (Varian, PaloAlto, the U.S.), fluorescent microscope (LeicaMicrosystems, Heidelberg, Germany), laser confocal scanning microscope (TCSSP2, Leica, Germany).
(2) preparation of material
Ca (NO
3)
24H
2o and Na
2siO
39H
2o(mol ratio is 1:1) be dissolved in respectively and fill in the beaker of deionized water, concentration is adjusted to 0.5 mol/L.The polyoxyethylene glycol of 0.2% is added 300 milliliters of Ca (NO prepared under room temperature
3)
2in solution, the Na while stirring 300 milliliters prepared
2siO
3dropwise adds Ca (NO
3)
2solution, generates CaSiO
3precipitation.CaSiO
3precipitation is placed in there-necked flask by washed with de-ionized water again, and adds the dimethyl formamide (DMF) of 300 milliliters, and under magnetic bar stirs, temperature rises to 120 DEG C gradually and keeps 5 hours with transpiring moisture, then extracts DMF.The product obtained drying at 60 DEG C obtains nanometer silicic acid calcium powder.Nanometer silicic acid calcium powder and PEEK powder mix 1 hour according to the ratio of volume ratio 20:80 in high speed ball mill, and rotating speed is 500 revs/min, the mixture obtained at 150 DEG C dry 24 hours.Then make nm-CS/PEEK mixture with injection molding instrument, injection temperature is 380 DEG C.The UHMWPE material that control group is used and PEEK material also use the same method preparation.
(3) material characterizes and observes and wetting ability test
Material surface does scanning electron microscope, observes the surface topography of material and the distribution situation of calcium silicate particle; Material surface does the chemical constitution of energy dispersion spectrum analysis material surface; Measured the water contact angle of material surface with Shape Analyzer by sessile drop method, with the hydrophilicity on this assessment material surface, detected result as shown in Figure 1.Nm-CS/PEEK composite material surface has a large amount of nanometer CS particles, distribution uniform, and some nanometer CS particle defines aggregate, diameter hundreds of nanometer to several microns not etc.Water contact angle measure find, nanometer CS particle mix the wetting ability that greatly can improve PEEK, be conducive to cell adhesion in material surface.
(4) the outer degradation property research of material bodies
Nm-CS/PEEK matrix material and PEEK material are dipped in Tris-HCl damping fluid, keep temperature 37 DEG C, rotating speed 120 revs/min concussion, 1, after 3,7,14,21,28 days, take out material, dry, with the metamorphosis of scanning electron microscopic observation material surface, damping fluid after immersion inductively coupled plasma atomic emission spectrometer measures calcium ion and silicon ion concentration, and detected result as shown in Figure 2.
Nm-CS/PEEK matrix material is a large amount of calcium ion of sustained release and silicon ion in 21 days, wherein quick release period in 3 days, after 3 days, burst size reduces gradually, and the calcium ion of release and silicon ion are promoting to be proved in osteoblastic propagation and differentiation and will play positive effect.Through the immersion of 28 days, nm-CS/PEEK composite material surface remained the small rut stayed after many CS particles dissociate, not of uniform size, out-of-shape.
(5) material simulation body fluid immersion test
Nm-CS/PEEK and PEEK material is dipped in simulated body fluid, keeps temperature 37 DEG C, rotating speed 120 revs/min concussion, 7, material is taken out after 14,21,28 days, cleaning, drying, do the formational situation of scanning electron microscope and energy spectrum analysis observation material surface phosphatic rock, result as shown in Figure 3.
Simulated body fluid soaks the 7th day, nm-CS/PEEK composite material surface has a large amount of phosphatic rock and is formed, extend with soak time, phosphatic rock quantity increases gradually, to having one deck very thick apatite layer in tile when 28 days by the surface coverage of mixture, being formed of these apatite layers is beneficial to osteoblastic propagation and differentiation, is conducive to the integration of implant and osseous tissue after implanting.
(6) material and cell interaction are studied
Mouse preosteoblast system (MC3T3-E1) is selected to carry out following cell experiment:
1, cell adhesion experiments: by cell and material Dual culture after 6,12,24 hours, sticked to the cell number of material surface by CCK-8 method counting, with the impact of assessment material on cell adhesion, result as shown in Figure 4.12 and 24 hours, the quantity of the cell that nm-CS/PEEK composite material surface adheres to was all higher than UHMWPE material and PEEK material.
2, cell proliferation experiment: by cell and material Dual culture after 1,3,7 days, by the cell number of CCK-8 method counting in material surface growth, and after carrying out DAPI staining cell core, with fluorescence microscope, with the impact of assessment material on cell proliferation, result as shown in Figure 5.
The cell of nm-CS/PEEK composite material surface is in obvious vegetative state from 1 day by 7 days always; And the cell of PEEK material surface from 1 day to 3 days, propagation trend was not clearly from 3 days to 7 days for the cell of UHMWPE material surface.When 7 days, the relative proliferation rate of nm-CS/PEEK composite material surface cell is higher than UHMWPE material and PEEK material.DAPI coloration result finds, the nucleus amount of three time point nm-CS/PEEK composite material surfaces is all more than both other.Scanning electron microscopic observation found that, when 3 days, nm-CS/PEEK composite material surface is occupied by the cell of breeding in a large number, and quantity is more than UHMWPE material and PEEK material; When 7 days, nm-CS/PEEK composite material surface almost completely cover by cell; And the cell of UHMWPE material surface not only in quantity will lower than nm-CS/PEEK matrix material, state is also poor, although PEEK material surface is covered by a large amount of cell, quantity is less than nm-CS/PEEK matrix material.
3, cell sprawls experiment: cell and material Dual culture, after 12,24 hours, are used phalloidin actinmicrofilament, and that observes material surface cytoskeleton with laser confocal scanning microscope sprawls situation; By cell and material Dual culture after 1,3,7 days, glutaraldehyde is fixed, the displacement of alcohol serial dehydration, hexamethyldisilazane alcohol, metal spraying, by the form of surface sweeping electron microscopic observation material surface cell with sprawl situation.
12 and 24 hours, the cytoskeleton that CLSM observes nm-CS/PEEK composite material surface was sprawled better than UHMWPE material and PEEK material, has more interconnection actinmicrofilament.24 hours, scanning electron microscopic observation was to the cell drawout completely on nm-CS/PEEK surface, and have a lot of pseudopodium to be anchored on material surface, and the cell on UHMWPE and PEEK surface is shrunk, pseudopodium is little.
4, cell Osteoblast Differentiation experiment: cell Osteoinductive differentiation, after 7,10,14 days, is dyeed by ALP and the experiment of ALP active level, detects the expression of ALP at material surface; Cell osteogenic induction is after 21,28 days, and by Alizarin red staining and quantitative experiment thereof, test material surface cells differentiate produces the situation of calcium tubercle; Cell osteogenic induction is after 7,14,21,28 days, by the expression of real-time quantitative PCR test material superficial cell Osteoblast Differentiation genes involved (as ALP, Bone Gla protein, osteopontin, type i collagen), with the impact of assessment material on cell Osteoblast Differentiation function, result as shown in Figure 6.
Compare with PEEK material with UHMWPE material, no matter from qualitative or quantitative result, nm-CS/PEEK matrix material can both promote the expression of ALP and the generation of calcium tubercle.From gene level, nm-CS/PEEK matrix material can promote the expression of alkaline phosphatase, Bone Gla protein, osteopontin and NTx to a certain extent.
Embodiment 2
The difference of the present embodiment and embodiment 1 is, the nm-CS/PEEK matrix material that the present embodiment provides is in preparation process, and the volume ratio of nanometer silicic acid calcium powder and PEEK powder is 15:85.
Embodiment 3
The difference of the present embodiment and embodiment 1 is, the nm-CS/PEEK matrix material that the present embodiment provides is in preparation process, and the volume ratio of nanometer silicic acid calcium powder and PEEK powder is 25:75.
Embodiment 4
The difference of the present embodiment and embodiment 1 is, the nm-CS/PEEK matrix material that the present embodiment provides is in preparation process, and the volume ratio of nanometer silicic acid calcium powder and PEEK powder is 18:82.
Embodiment 5
The difference of the present embodiment and embodiment 1 is, the nm-CS/PEEK matrix material that the present embodiment provides is in preparation process, and the volume ratio of nanometer silicic acid calcium powder and PEEK powder is 22:78.
Embodiment 6
The difference of the present embodiment and embodiment 1 is, the nm-CS/PEEK matrix material that the present embodiment provides is in preparation process, and the volume ratio of nanometer silicic acid calcium powder and PEEK powder is 12:88.
Embodiment 7
The difference of the present embodiment and embodiment 1 is, the nm-CS/PEEK matrix material that the present embodiment provides is in preparation process, and the volume ratio of nanometer silicic acid calcium powder and PEEK powder is 26:74.
The method identical according to embodiment 1 carries out material sign, degradation property test, In vitro cell experiment etc. to nm-CS/PEEK matrix material prepared by embodiment 2-7.
There is a large amount of nanometer CS particles on the surface of the nm-CS/PEEK matrix material that embodiment 2-7 provides, is evenly distributed, and wherein has sub-fraction nanometer CS particle to define micron order aggregate; The wetting ability of the nm-CS/PEEK matrix material that embodiment 2-7 provides, all than the height of PEEK material, is conducive to cell adhesion in material surface; The nm-CS/PEEK matrix material that embodiment 2-7 provides all can a large amount of calcium ion of sustained release and silicon ion be for 21 days in vitro, and the calcium ion of these releases and silicon ion are promoting to be proved in osteoblastic propagation and differentiation and will play positive effect; Simulated body fluid soaks, the surface of the nm-CS/PEEK matrix material that embodiment 2-7 provides can form great amount of hydroxy group phosphatic rock island and increase gradually and become very thick apatite layer within 7 days, being formed of these apatite layers is beneficial to osteoblastic propagation and differentiation, is conducive to the integration of implant and osseous tissue after implanting; In vitro cell experiment confirms, compare with pure PEEK material with UHMWPE material, there is the nm-CS/PEEK surface that more cell adhesion provides in embodiment 2-7, and these cells are sprawled better, state is better, rate of propagation is faster, can secrete more alkaline phosphatase (ALP) and calcium tubercle, can also promote the expression of Osteoblast Differentiation genes involved (ALP, Bone Gla protein, osteopontin and NTx).
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (10)
1. nanometer Calucium Silicate powder-polyether-ether-ketone composite material, it is characterized in that, the moiety of described nanometer Calucium Silicate powder-polyether-ether-ketone composite material comprises nanometer Calucium Silicate powder and polyether-ether-ketone, and the volume ratio of nanometer Calucium Silicate powder and polyether-ether-ketone is (10-30): (70-90).
2. nanometer Calucium Silicate powder-polyether-ether-ketone composite material according to claim 1, is characterized in that, in described nanometer Calucium Silicate powder-polyether-ether-ketone composite material, the volume ratio of nanometer Calucium Silicate powder and polyether-ether-ketone is (15-25): (75-85).
3. nanometer Calucium Silicate powder-polyether-ether-ketone composite material according to claim 2, is characterized in that, in described nanometer Calucium Silicate powder-polyether-ether-ketone composite material, the volume ratio of nanometer Calucium Silicate powder and polyether-ether-ketone is 20:80.
4. a preparation method for nanometer Calucium Silicate powder-polyether-ether-ketone composite material as claimed in claim 1, is characterized in that, comprise the following steps:
Step 1, by nanometer Calucium Silicate powder and polyether-ether-ketone powder according to (10-30): the volume ratio mixing of (70-90); Step 2, the nanometer Calucium Silicate powder adopting injection molding technology step 1 to be obtained and polyether-ether-ketone mixture compound, obtained nanometer Calucium Silicate powder-polyether-ether-ketone composite material.
5. preparation method according to claim 4, is characterized in that, in step 1, the volume ratio of nanometer Calucium Silicate powder and polyether-ether-ketone powder is (15-25): (75-85).
6. preparation method according to claim 5, is characterized in that, in step 1, the volume ratio of nanometer Calucium Silicate powder and polyether-ether-ketone powder is 20:80.
7. preparation method according to claim 4, is characterized in that, in step 1, nanometer Calucium Silicate powder and being blended in high speed ball mill of polyether-ether-ketone powder are carried out, and mixing 0.5-2 hour, rotating speed is 300-800 rev/min.
8. preparation method according to claim 4, is characterized in that, in step 2, when adopting injection molding technology to prepare nanometer Calucium Silicate powder-polyether-ether-ketone composite material, injection temperature is 350-420 DEG C.
9. preparation method according to claim 4, is characterized in that, described nanometer Calucium Silicate powder is by Ca (NO
3)
24H
2o and Na
2siO
39H
2o reaction and follow-up hydro-thermal reaction, dry obtained.
10. preparation method according to claim 9, is characterized in that, concrete preparation method is as follows for described nanometer Calucium Silicate powder:
By the Ca (NO of mol ratio 1:1
3)
24H
2o and Na
2siO
39H
2o is dissolved in water respectively, and the polyoxyethylene glycol of 0.05-0.5% is joined Ca (NO
3)
2in solution, then by Na
2siO
3solution is added drop-wise to Ca (NO
3)
2in solution, generate CaSiO
3precipitation; CaSiO
3after precipitate with deionized water cleaning, add dimethyl formamide, stir lower temperature and rise to 100-150 DEG C of transpiring moisture gradually, then extraction removes DMF, and the product obtained drying at 50-70 DEG C obtains nanometer silicic acid calcium powder.
Priority Applications (1)
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| CN106729977A (en) * | 2017-01-12 | 2017-05-31 | 上海锐植医疗器械有限公司 | A kind of bioactivity Invasive lumbar fusion device |
| CN108186102A (en) * | 2018-02-05 | 2018-06-22 | 上海锐植医疗器械有限公司 | Non metal implant screw locking structure |
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| CN105233335B (en) * | 2015-11-06 | 2018-07-13 | 四川大学 | Biologically active porous poly(aryl ether ketone) material of one kind and the preparation method and application thereof |
| CN105233335A (en) * | 2015-11-06 | 2016-01-13 | 四川大学 | Porous polyaryletherketone material with bioactivity, and preparation method and application thereof |
| CN106620858A (en) * | 2016-11-18 | 2017-05-10 | 汤亭亭 | CS (calcium silicate)/PEEK (poly(ether-ether-ketone)) composite bone repair material, bone repair body as well as preparation method and application of material |
| CN106729977A (en) * | 2017-01-12 | 2017-05-31 | 上海锐植医疗器械有限公司 | A kind of bioactivity Invasive lumbar fusion device |
| US11510716B2 (en) | 2018-02-05 | 2022-11-29 | Shanghai Reach Medical Instrument Co., Ltd. | Nonmetallic implant screw locking structure |
| CN108186102A (en) * | 2018-02-05 | 2018-06-22 | 上海锐植医疗器械有限公司 | Non metal implant screw locking structure |
| WO2019148773A1 (en) * | 2018-02-05 | 2019-08-08 | 上海锐植医疗器械有限公司 | Nonmetal implant screw locking structure |
| CN108186102B (en) * | 2018-02-05 | 2023-12-05 | 上海锐植医疗器械有限公司 | Non-metallic implant screw locking structure |
| CN110559488A (en) * | 2019-10-25 | 2019-12-13 | 中国科学院长春应用化学研究所 | calcium sulfate-containing polyetheretherketone particulate bone filling material and preparation method thereof |
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| CN112972768A (en) * | 2020-03-26 | 2021-06-18 | 上海交通大学医学院附属第九人民医院 | Polyether-ether-ketone composite material and preparation method and application thereof |
| CN113201163A (en) * | 2021-04-20 | 2021-08-03 | 上海交通大学医学院附属仁济医院 | Modified polyether-ether-ketone and preparation method and application thereof |
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