CN101879332A - Polyether-ether-ketone composite material containing fluorapatite and titanium dioxide and preparation method thereof - Google Patents
Polyether-ether-ketone composite material containing fluorapatite and titanium dioxide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyether-ether-ketone composite material containing fluorapatite and titanium dioxide and a preparation method thereof, belonging to the technical field of biomedical composite materials. The composite material is a bone restoration material prepared from a polyether-ether-ketone composite material with enhanced fluorapatite and titanium dioxide and is prepared by blending fluorapatite, titanium dioxide and polyether-ether-ketone in a fusion way, wherein the fluorapatite and the titanium dioxide are respectively 10-30 percent of the total weight of the composite material, and the balance is the components of the polyether-ether-ketone. The composite material prepared from the fluorapatite, the titanium dioxide and the polyether-ether-ketone in the invention realizes good strength and toughness and consistent elastic modulus with a human bone, has bone-substitute material with bioactivity, and can overcome the defect that the traditional metal and ceramic bone-substitute material has the mechanical property which is not matched with the human bone.
Description
Technical field
The present invention relates to the compound bone reparation of polyether-ether-ketone of a kind of fluor-apatite and titanium dioxide and substitution material and preparation method thereof, specifically is a kind of fluor-apatite and titanium dioxide reinforced polyether ether ketone composite bone repairing material and preparation method thereof.This Biocomposite material is used for orthopaedics and oral medical field of surgery.
Background technology
Fluor-apatite (FA) has identical crystal structure with hydroxyapatite (HA), and just F-has replaced the OH position.Change owing to form to go up, the characteristic of respective material is also changed to some extent, the biomaterial scientist pays much attention to this both at home and abroad, and carried out comparatively deep research, because F is littler than OH group, make fluor-apatite tightr than hydroxyapatite crystal structure, therefore corresponding FA lattice paprmeter is littler than HA.Because structure is tightr, makes the dissolubility of fluor-apatite less.This characteristic is very significant in clinical practice, and fluor-apatite can be used as the substitution material of bone.
Fluor-apatite is a kind of in the numerous homotype isomers of apatite, and the FA crystal structure is close with the inorganic composition mutually of human body bone, is a kind of good biomaterial, and therefore, numerous scholars made a lot of biotic experimenies to its powder and coating.Preliminary Basic of Biology check shows that FA has good biocompatibility, has no side effect.Though have only the small amount of fluorine element to exist in people's bone, these a spot of fluorine can produce bigger influence to the performance of hydroxyl lime stone.Some scholar thinks osteogenesis when skeletonization is preponderated, and the F-ion can promote osteoblast active, forms more sclerotin, helps the growth of bone.Hydroxyapatite is during as the coating of metal implant material, owing to dissolubility dissolve too fast greatly, makes the bond strength decline of coating later stage and substrate too fast, and by comparison, fluor-apatite has than low solubility.Many scholars just are being devoted to FA is substituted the research of HA as the biological coating of embedded material, and the plasma spraying coating of FA is more stable, and can not decompose.The FA material is a kind of biomaterial likely.As the coating of metal implant material, dissolubility is little, can effectively reduce the coating and the too fast problem of embedded material bond strength decline that cause greatly owing to the coating dissolubility.And fluor-apatite also has good biological activity, increases the bond strength of embedded material and tissue, helps reducing the healing time of embedded material.
Titanium or titanium alloy becomes the most outstanding bio-medical metal material with its excellent biocompatibility and mechanics adaptability.In order further to improve its biocompatibility and biological activity, surface modification has become the focus of people's research.Studies show that, the thermal coefficient of expansion of titanium dioxide and titanium and alloy thereof is very approaching, can form firm interface with the titanio body and combine, and the biocompatibility of titanium dioxide also obtained certain confirmation, titanium dioxide also has super wettability, excellent blood compatibility, and wear resistance and corrosion resistance.Carrying out big quantity research aspect the conventional coating of titanium dioxide both at home and abroad at present, but it is still less to prepare the research report of biological activity coating of titanium dioxide about titanium and alloy surface thereof.
Shanghai Silicate Inst., Chinese Academy of Sciences's disclosed Chinese patent CN1651604 (applying date: 2005.01.07), studied a kind of method for preparing the nano-titanium oxide coating layer of biologically active, belonged to the medical bio field of ceramic coatings in 2005.It is characterized in that at first preparing nano-titanium oxide coating layer with the air plasma spraying method, nano-titanium oxide coating layer after will spraying then carries out irradiation under ultraviolet ray after cleaning, thereby make plasma spraying nano-titanium oxide coating layer surface biological activation, and can bring out osteoid apatite after body fluid contacts and form at coating surface.Described irradiation under ultraviolet ray or coating is immersed in the simulated body fluid, or in air or water, carry out, irradiation time was not less than 12 hours.This invention is that the powder of anatase is a raw material with the principal crystalline phase, and the principal crystalline phase of spraying back coating is the rutile phase.The nano-titanium oxide coating layer that is deposited on the biologically active on the medical metal matrix that is provided is a kind of novel biological activity bone substitution material.
2005, Shanghai Silicate Inst., Chinese Academy of Sciences also discloses another patent CN1739810 (applying date 2005.09.16), study a kind of hydrion and injected the method that improves bioactivity of nanometer titania coating, it is characterized in that using plasma submergence method for implanting article on plasma spraying nano-titanium oxide coating layer carries out hydrion and injects, under vacuum, gas is introduced vacuum chamber, make gas ionization form plasma by radio-frequency discharge, plasma surrounds pre-injected sample fully, under the back bias voltage traction of sample platform, the cation in the plasma is injected into the sample top layer.The result shows, handles back TiO2, and coating is soaked after 14 days in simulated body fluid, and osteoid apatite can be at the plasma spraying nano TiO 2 after hydrion injects processing, and coating surface forms, and shows that this coating has good biological activity.
Hebei University of Technology's disclosed patent CN1686643 (applying date: 2005.05.19) in 2005, studied a kind of surface TiO2 has been arranged, biomedical composite of the titanium alloy of coating and preparation method thereof, the plating that relates to metal material, TiO2 wherein, coating is a nano TiO 2, coating, nano TiO 2, the crystal grain diameter of coating are between 50～70nm, and the specific embodiment of preparation method is as follows: the pretreatment of (1) titanium alloy sample surfaces; (2) alkoxide hydrolysis prepares nanoscale anatase titanium dioxide micropowder; (3) adopt the embedding sintering process in titanium alloy substrate surface preparation Nano titanium dioxide coating.There is nano TiO 2 on this invention surface, and the biomedical composite Siberian cocklebur of the titanium alloy of coating but solved biological coating better and combine problem with the interface of matrix has also further been improved titanium alloy surface wearability, corrosion resistance and blood compatibility; The preparation method of this invention has overcome simultaneously owing to using expensive equipment, preparation condition harshness to cause the high shortcoming of cost of goods manufactured, can realize nano-TiO, the industrialization production of coating.
Taiwan National Chung Hsing University reported and utilizes katholysis to prepare nanometer titanium dioxide ferrum coated film on pure titanium in 2004, the annealing 1 hour under 300 degree of this thin film, and this thin film further is condensed into anatase tio2, gradates under 500 ℃ to be rutile TiO2.As thinking, phase specific heat growth TiO2. thin film, electrolysis TiO2, coating has better biological activity and corrosion resistance.
Foreign study mechanism such as Italian Guya Bioscience S.r1., AESCULAP AG, University of Alabama etc. are also doing certain research aspect the biological activity titania coating.
The disclosed world patent WO2006043166 (applying date: 2005.10.13) of Guya Bioscience S.r.1.2006, studied a kind of preparation that is used for the coating of titanium dioxide of endosteal implant, be specially: solvolysis Ti (1V) compound liquid state, non-gelling, stable precursor, precursor deposition is given the endosseous implant surface, in the presence of oxygen, heat treatment, obtain mechanical performance, nano-titanium dioxide film that chemical stability is good, ultraviolet radiation with lasting stability improves apparent condition, increases the decontamination of wet chemical lubricant nature and biological warfare agent.
Disclosed 248117 (the applyings date: 1986.12.05) of European patent EP of AESCULAP AG, AESCULAP-WER VORM, study employing vacuum plasma spray coating method and on the titanium alloy artificial limb, prepared TiO2, A12O3, ZrO2, or Cr2O3 coating, adopt argon or helium to produce ionizing air, the coating layer thickness that obtains is 0.1～1mm, and machine glazed finish is 0.05 μ m again.This coating and base material profit have higher bonding strength and internal diffusion.
The StanishevskY of University of Alabama, A. etc. have studied with plasma chemical depositing Ni-P-nano titanic oxide coating on titanium alloy, and the author thinks that the long-pending oxide coating of electric current can improve the biological activity and the biocompatibility thereof of planting body greatly.
Titanium dioxide has good biocompatibility, and to human body safety non-toxic not only, and anatase and rutile titanium dioxide can be induced HA.The TiO2 nanotube that Oh etc. make anodic oxidation immerses 50 ℃ NaOH solution and carries out alkali treatment, and sample soaks 5 days in simulated body fluid after, nanotube surface is induced generation nanoscale HA.Roy etc. find that in experiment the TiO2 nanotube compares with the TiO2 nano-particle, and the former can promote blood coagulation quickly, reduce amount of bleeding.Wu Zhenjun etc. studies have shown that nano material TiO2 is fairly obvious to the bacterial endotoxin degradation effect under normal temperature condition.If disposable blood taking bag inwall is added one deck TiO2 nano thin-film, not only can play antibacterial action, and can also reach the endotoxic double effects of bacterium for degrading.This can guarantee transfusion safety, reduces the blood transfusion untoward reaction that causes because of germ contamination, reduces the exothermic reaction that the patient causes because of endotoxemia.
Titanium dioxide layer can not only induce HA to generate, and improve the corrosive nature and the polishing machine of implant effectively, and the thermal linear expansion coefficient of titanium dioxide and Titanium is close, and adhesion is stronger, can satisfy the demand of clinical practice substantially.Nearest result of study shows: with respect to the HA and the TCP of conventional medical, osteoblast improves greatly at the cell attachment power and the multiplication capacity on titania nanotube surface.Titania nanotube is considerable in the application prospect of biomedical materials field.
Hydroxyapatite is very similar to the main inorganic composition of skeleton and tooth, has excellent biocompatibility and bone conductibility, and easy and osseous tissue forms firm chemical bond.If apply one deck HA layer on POROUS TITANIUM surface and hole wall, utilize the bone conduction effect of HA, in bootable new bone is grown into the hole along hole wall, to the growth of early stage area of new bone in the body be combined with clearly facilitation, can improve the biological fixation function of POROUS TITANIUM effectively.But because of HA and Titanium performance difference are bigger, cause the not enough problem of boundary strength, researcheres adopt between metallic substrates and HA coating, add TiO2 as cushion to address these problems.In fact, the TiO2 pottery has better biocompatibility equally, can induce the deposition of apatite and the formation of osseous tissue in vitro and in vivo, also is widely used in the implant surfaces coating.Therefore, adopt sol-gel process,, make the interface of coating and substrate also have higher binding strength guaranteeing the coating active while of good biological at porous Ti TiO2 biological coating.
American scholar T homas J.Webster finds that by the in vitro study to the nanometer titanium oxide ceramic function of osteoblast nanometer titanium oxide ceramic can improve the mineralising of absorption, propagation, deposition and the calcic thing of cell.
Metal and ceramic bone alternate material have the plurality of advantages of self, and, rigidity big as intensity is strong or the like, but its biocompatibility is bad, usually can cause subject discomfort.And the elastic modelling quantity of metal and ceramic bone alternate material is tens times even tens times of osseous tissue considerably beyond osseous tissue.Their combination, incompatible because of mechanical property, can not create one and be subjected to force environment preferably, produce stress shielding thus, cause bone resorption, osteanabrosis, so that complication such as bone alternate material is loosening.
Polyether-ether-ketone (PEEK) has good biological stability, has more significant advantage than medical metal alloy and ceramic material, is well suited for being used for medical implant apparatus and implants for a long time.PEEK not only has the characteristics of hard wear resistant, high rigidity, anti-creep, high impact and fabulous crooked extensibility, and coefficient of friction is low, and fatigue resistance is also very outstanding, and many chemical substances and solvent are had corrosion resistance.Most important applications of PEEK is exactly alternative metals material artificial bone, the artificial bone who makes of PEEK is except that having lightweight, nontoxic, advantage such as corrosion resistance is strong, also have and the immediate elastic modelling quantity of body bone tissue, also can organically combine with human body, so replacing the metallic body skeleton that makes children with PEEK is that it is in very important potential application aspect the medical field.Experimental results demonstrate that PEEK has excellent biological compatibility, it inherent slickness and biocompatibility up to now all polymer can't compare.
At present, PEEK is designated as " best long-term bone grafting material ", and obtains the checking of FDA, and the experiment in vivo and vitro of PEEK shows that also it and tissue have the good tissue compatibility.The U.S. develops a lot of positions such as osteoarthrosis, ligament, elbow joint, finger of long-term implant into body with PEEK, effect is fine.PEEK as timbering material as in the reparation of buttocks, this material property is near human body natural's bone, and has good plasticity and hardness, can will carry the sclerotin around passing to equably outward.
The elastic modelling quantity of PEEK Invasive lumbar fusion device and osseous tissue are very approaching, compare with the fusion device of metal material, not only can avoid stress to block and the bone amount is reduced, and at the interface of fusion device and osseous tissue stress concentration can not appear, cause fusion device depression, intervertebral height and preceding convex curvature to reduce.After osseous tissue is implanted into can with the osseous tissue good bond, can guide new bone growth, its time of fusion is generally in 3-6 month.Clinical practice shows, PEEK system Invasive lumbar fusion device has excellent biological compatibility in human body, can connect platform with neck bone tissue tight, the interface does not have bone resorption, all patients can both obtain the bone fusion in 6 months, and the cervical vertebral fusion cage X line printing opacity with PEEK makes can merge situation by clear judgement bone on X-ray sheet and CT sheet.
Because body bone tissue is a kind of natural inorganic-organic composite material.Though polymer P EEK has good toughness and near the elastic modelling quantity of people's bone, lacks biological activity.
Summary of the invention
The present invention is directed to the deficiency and the defective of reparation of above-mentioned metal and bioceramic bone and substitution material, a kind of fluor-apatite and titanium dioxide reinforced polyether ether ketone composite and preparation method thereof are provided, this composite bone repairing material is had with osseous tissue mechanical compatibility preferably, solves that bone repair that the stress shielding that now causes owing to elastic modelling quantity does not match with material at present etc. causes becomes flexible and a series of problems such as bone resorption.
The polyether-ether-ketone composite material of fluor-apatite of the present invention and titanium dioxide is a kind of bone renovating material that forms with fluor-apatite and titanium dioxide reinforced polyether ether ketone composite, be with fusion mode blend fluor-apatite, titanium dioxide and polyether-ether-ketone, wherein fluor-apatite accounts for 10～30% of composite gross weight, titanium dioxide accounts for 10～30% of composite gross weight, and all the other are the polyether-ether-ketone composition.
Described fluor-apatite is that particle diameter is the dusty material of 50～100nm.
Described titanium dioxide is that particle diameter is the dusty material of 50～100nm.
Another aspect of the present invention provides the preparation method of the polyether-ether-ketone composite bone repairing material of fluor-apatite and titanium dioxide.
Described preparation method can be divided into two kinds:
A kind of is to be the fluor-apatite of 50～100nm and titania powder with after the polyether-ether-ketone powder mixes by said proportional quantities with particle diameter, high-temperature mixing in double screw extruder, melt blending is extruded, and extrudes product cooling back pelletizing, obtains the pellet of said composite.
Wherein said with fluor-apatite, titanium dioxide and polyether-ether-ketone powder are mixed in proportion in high-speed mixer and carry out;
All raw materials all will carry out dried to remove moisture before processing, the baking temperature of raw material fluor-apatite and titania powder is 120 ℃～150 ℃, and polyether-ether-ketone is dry under 120 ℃～150 ℃ conditions;
The reuse high-temperature injection machine behind the pellet of said composite of obtaining is injection molded into the pellet of composite the composite sample (using corresponding mould) of required shape.
Can also the double screw extruder high-temperature mixing will be passed through, melt blending is extruded, extrude the pellet of the composite of product cooling back pelletizing gained and put into mould, put into press behind the matched moulds, rise to 380 ℃～420 ℃ by room temperature, pressurization 20～30MPa, heat-insulation pressure keeping 2～4 hours, the demoulding when being cooled in 100 ℃～130 ℃ scopes with the rate of temperature fall of 5～10 ℃/min obtains the polyether-ether-ketone composite material sample of fluor-apatite and titanium dioxide.
Another method for preparing composite of the present invention is compression molding.The employing compression molding is: the material (fluor-apatite that will need mold pressing, the mixed uniformly powder of titanium dioxide and polyether-ether-ketone, or the foregoing composite pellet that forms by extruding pelletization) puts into mould, put into press behind the matched moulds, pressurization is warmed up to uniform temperature, the heat-insulation pressure keeping certain hour is cooled to the demoulding in the certain temperature range then.
Preferred operating condition is: will need the pellet of the composite of mold pressing to put into mould, put into press behind the matched moulds, rise to 380 ℃～420 ℃ by room temperature, pressurization 20～30MPa, heat-insulation pressure keeping 2～4 hours, the demoulding when being cooled in 100 ℃～130 ℃ scopes with the rate of temperature fall of 5～10 ℃/min obtains the polyether-ether-ketone composite material sample of fluor-apatite and titanium dioxide.
Can also be with fluor-apatite, titanium dioxide and polyether-ether-ketone powder carry out premixing in high-speed mixer, adopt compression molding again.
Biocompatibility is one of the major issue that should at first consider in the research of titanio bio-medical material.In order to improve the biocompatibility of material, the present invention has carried out the preparation of coating of titanium dioxide and the research that surperficial alkali liquor bioactivation is handled to the titanio body, and adopts simulated body fluid culture experiment and cell culture experiments to estimate the biocompatibility and the biological activity of material after the surface modification.The biocompatibility and the biological activity of material are assessed after utilizing the simulated body fluid culture experiment to surface modification.After cultivating the identical time, find that the ability of nano TiO 2 sedimentary phosphor lime stone is the strongest.The SBF cultivation results of different surfaces method of modifying relatively is: the coating of sintering preparation under sintered titanium dioxide coating＞vacuum under nanometer titanium dioxide coating＞alkali liquor processing method＞normal pressure.Nano titanium oxide/titanium alloy biomaterial is carried out cell culture experiments, find that this material has the good cell compatibility.
Polymer P EEK has good toughness and near the elastic modelling quantity of people's bone, but lacks biological activity.Fluor-apatite and titanium dioxide biological activity are good, can combine with the firm key of bone formation, itself and PEEK is compound, not only the two premium properties can be combined fully, but also can obtain the new capability that homogenous material does not have, form intensity with good toughness, elastic modelling quantity is consistent with people's bone and the bone alternate material of biologically active.Therefore, fluor-apatite of the present invention and titanium dioxide enhancing PEEK composite can be used as the metal bone alternate material.
Because the mechanical property and the osseous tissue of fluor-apatite and titanium dioxide/PEEK composite bone substitution material are close, so both dependent variables may be consistent when loading, can produce the good mechanical compatibility, reduced stress shielding, increased interface bond strength greatly, reduce shear stress, reduced fine motion and vertical displacement, guaranteed the initial fixation of bone alternate material.And this bone alternate material may promote osseous tissue to grow into, and reaches fixing purpose biology.
The present invention adopts fluor-apatite and titanium dioxide and PEEK to form composite, has reached enhancing, benefit is tough, mechanics is compatible and has improved biocompatibility, bioactive purpose.Can overcome mechanical property and the people's bone that existing metal and ceramic bone alternate material exist with the bone alternate material of Composite Preparation and not match, cause bone resorption; Do not have activity, can not integrate with bone; Perhaps cause fracture and shortcoming such as fatigue rupture takes place in vivo because of matter is crisp.
Description of drawings
The TEM photo of Fig. 1 nanometer fluor-apatite (a) and nano titanium oxide (b);
The composite materials property specimen of Fig. 2 embodiment 2 preparations;
The fluor-apatite of Fig. 3 embodiment 2 preparations and the SEM photo of titanium dioxide/polyether-ether-ketone composite material;
(Φ 10 * 2mm) for the cell culture composite experiment sample of Fig. 4 embodiment 1 (2 disks in the left side) and embodiment 2 (2 disks in the right) preparation;
The fluor-apatite of Fig. 5 embodiment 1 and embodiment 2 preparations and the cytotoxicity experiment result of titanium dioxide/polyether-ether-ketone composite material;
Among Fig. 6 effect embodiment 3 at the CT scan figure of Canis familiaris L. tibia place composite implant material after one month;
Among Fig. 7 effect embodiment 3 at the CT scan figure of Canis familiaris L. alveolus place composite implant material after one month.
The specific embodiment
The present invention will be further described below in conjunction with accompanying drawing.It should be noted that the purpose of publicizing and implementing example is to help further to understand the present invention, but it will be appreciated by those skilled in the art that: in the spirit and scope that do not break away from the present invention and claims, various substitutions and modifications all are possible.Therefore, the present invention should not be limited to the disclosed content of embodiment, and the scope of protection of present invention is as the criterion with the scope that claims define.
Embodiment 1
The constituent of fluor-apatite and titanium dioxide/polyether-ether-ketone composite material and percentage by weight thereof are: fluor-apatite 20%, titanium dioxide 20%, polyether-ether-ketone 60%.Take by weighing the 2kg fluor-apatite, 2kg titanium dioxide and 6kg polyether-ether-ketone powder carry out premixing in high-speed mixer, then with the double screw extruder high-temperature mixing, extrude, pelletize.Particulate composite adopts the injection machine injection moulding to form needed sample.
Embodiment 2
The constituent of fluor-apatite and titanium dioxide/polyether-ether-ketone composite material and percentage by weight thereof are: fluor-apatite 30%, titanium dioxide 10%, polyether-ether-ketone 60%.Take by weighing the 3kg fluor-apatite, 1kg titanium dioxide and 6kg polyether-ether-ketone powder carry out premixing in high-speed mixer, then with the double screw extruder high-temperature mixing, extrude, pelletize.Particulate composite adopts the injection machine injection moulding to form needed sample.
Embodiment 3
The constituent of fluor-apatite and titanium dioxide/polyether-ether-ketone composite material and percentage by weight thereof are: fluor-apatite 20%, titanium dioxide 20%, polyether-ether-ketone 60%.Take by weighing the 2kg fluor-apatite, 2kg titanium dioxide and 6kg polyether-ether-ketone powder, in high-speed mixer, carry out premixing, fluor-apatite and the mixed uniformly powder of polyether-ether-ketone are put into mould, put into press behind the matched moulds, rise to 400 ℃, pressurization 30MPa by room temperature, heat-insulation pressure keeping 2～3 hours, the demoulding when being cooled in 100～120 ℃ of scopes with the rate of temperature fall of 10 ℃/min.
Embodiment 4
The constituent of fluor-apatite and titanium dioxide/polyether-ether-ketone composite material and percentage by weight thereof are: fluor-apatite 30%, titanium dioxide 10%, polyether-ether-ketone 60%.Take by weighing the 3kg fluor-apatite, 1kg titanium dioxide and 6kg polyether-ether-ketone powder, in high-speed mixer, carry out premixing, fluor-apatite and the mixed uniformly powder of polyether-ether-ketone are put into mould, put into press behind the matched moulds, rise to 400 ℃, pressurization 30MPa by room temperature, heat-insulation pressure keeping 2～3 hours, the demoulding when being cooled in 100～130 ℃ of scopes with the rate of temperature fall of 10 ℃/min.
Embodiment 5
The constituent of fluor-apatite and titanium dioxide/polyether-ether-ketone composite material and percentage by weight thereof are: fluor-apatite 30%, titanium dioxide 10%, polyether-ether-ketone 60%.Take by weighing the 3kg fluor-apatite, 1kg titanium dioxide and 6kg polyether-ether-ketone powder carry out premixing in high-speed mixer, then with the double screw extruder high-temperature mixing, extrude, pelletize.
Putting into mould through fluor-apatite and titanium dioxide/polyether-ether-ketone composite material pellet after the pelletize, put into press behind the matched moulds, rise to 400 ℃, pressurization 30MPa by room temperature, heat-insulation pressure keeping 2～3 hours, the demoulding when being cooled in 120 ℃ of scopes with the rate of temperature fall of 8 ℃/min.
Effect embodiment 1
The nanometer fluor-apatite that uses and transmission electron microscope (TEM) photo of nano titanium oxide are seen Fig. 1, and fluor-apatite average grain length is 70nm, and average diameter is 40nm.Nano titanium oxide is a spheroidal particle, and mean particle size is 50nm.
By table 1 as seen, the elastic modelling quantity of composite of the present invention and people's bone mates very much, and has good mechanical performance (Mechanics Performance Testing of composite sample is tested according to relevant national standard), is very suitable for substituting or repair materials as bone.Extrude the sample that is better than directly using powder pressing mold melt molding with the mechanical property of the goods of injection mo(u)lding.
The mechanical property of table 1 embodiment 1～5 composite
| Mechanical property | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | People's biomechanics of bone performance |
| Elastic modelling quantity (GPa) | ??3.7 | ??4.2 | ??3.1 | ??3.0 | ??4.0 | ??3～20 |
| Comprcssive strength (MPa) | ??152 | ??164 | ??132 | ??128 | ??155 | ??80～120 |
| Tensile strength (MPa) | ??98 | ??94 | ??83 | ??84 | ??102 | ??60～90 |
| Bending strength (MPa) | ??95 | ??98 | ??91 | ??92 | ??107 | ??50～80 |
The composite materials property specimen of Fig. 2 embodiment 2 preparations.Fig. 3 is the fluor-apatite of embodiment 2 preparations and scanning electron microscope (SEM) photo of titanium dioxide/polyether-ether-ketone composite material.What show is the microscopic appearance of composite material surface.As seen from the figure, fluor-apatite and titanium dioxide granule are distributed among matrix (base material) PEEK, some reunion of nano-particle, formed micron-sized particle shape, distribution of particles is even relatively, and the inorganic active granule joins in the middle of the macromolecule PEEK, can increase the mechanical property of composite.
Effect embodiment 2 cytotoxicity experiments
Embodiment 1 and 2 is made composite sample carried out cytotoxicity experiment, employed sample photo is seen Fig. 4, and wherein sample diameter is 10mm, and thickness is 2mm.
Experimental technique
Biological safety according to ISO:10993-5 cytotoxicity standard testing mesoporous material.Under 37 ℃, two kinds of composites in serum-free cell culture medium (200mg/mL) soaked 24 hours, filter lixiviating solution.With 3 * 10
3The concentration in/hole with the MC3T3-E1 cell inoculation to 96 hole tissue culturing plates, continue to hatch 1 day after, discard culture medium, PBS cleans 3 times; Add the lixiviating solution that contains 10%FBS, continue to cultivate 1 day; Do not add the material lixiviating solution that contains 10%FBS as experiment blank group.When putting in the testing time, every hole adds 30 microlitre MTT solution, continues to hatch and cultivates after 4 hours, discards culture fluid, PBS cleans 3 times, and every hole adds 100 microlitre DMSO, after room temperature leaves standstill 10 minutes, at 490nm wavelength place, survey the solution absorbency value with microplate reader, see Fig. 5.
As seen from Figure 4, (TCP of tissue culturing plate) compares with blank, and the absorbance of experimental group (embodiment 1 and 2 sample) does not have significant difference, shows that the growth of two kinds of composite pair cells does not have negative effect.As calculated as can be known, the ratio of the cell survival rate of cell in the material lixiviating solution and blank group proves that all more than 95% these two kinds of composites do not have toxicity to the MC3T3-E1 cell.
Effect embodiment 3 animals are implanted experiment
(1) composite of embodiment 2 is made the damaged place of screw implantation Canis familiaris L. tibia and carried out CT scan after 1 month.Among Fig. 6 long arrow represent bone and with the combination interface of composite, short arrow is represented the composite bone screw.As seen from Figure 6, the interface of bone and composite is fuzzy, and composite implant and osseous tissue closely in conjunction with growing together, illustrate that thus this composite has good biological activity and biocompatibility, can repair and the replacement bone tissue as body implanting material.
(2) composite of embodiment 2 is made the damaged place of tooth implant implantation Canis familiaris L. alveolar bone and carried out CT scan after 1 month.Long arrow is represented dog teeth among Fig. 7, and short arrow is represented the composite tooth implant, and the triangle arrow is represented osseous tissue and composite tooth implant at the interface.As seen from Figure 7, the interface is fuzzy, and composite dental implant and osseous tissue closely in conjunction with growing together, illustrate that this composite has good biological activity and biocompatibility, can repair and the replacement bone tissue as body implanting material.
Claims (10)
1. the polyether-ether-ketone composite material that contains fluor-apatite and titanium dioxide, it is characterized in that, with fusion mode blend fluor-apatite, titanium dioxide and polyether-ether-ketone, wherein fluor-apatite accounts for 10～30% of composite gross weight, titanium dioxide accounts for 10～30% of composite gross weight, and all the other are the polyether-ether-ketone composition.
2. the polyether-ether-ketone composite material that contains fluor-apatite and titanium dioxide as claimed in claim 1 is characterized in that, described fluor-apatite is that particle diameter is the dusty material of 50～100nm.
3. the polyether-ether-ketone composite material that contains titanium dioxide and titanium dioxide as claimed in claim 2 is characterized in that, described titanium dioxide is that particle diameter is the dusty material of 50～100nm.
4. prepare each described method that contains the polyether-ether-ketone composite material of fluor-apatite and titanium dioxide of claim 1-3, it is characterized in that, with particle diameter is the fluor-apatite of 50～100nm and titania powder with after the polyether-ether-ketone powder mixes by said proportional quantities, high-temperature mixing in double screw extruder, melt blending is extruded, extrude product cooling back pelletizing, obtain the pellet of described composite.
5. preparation method as claimed in claim 4 is characterized in that, and is described with fluor-apatite, and titanium dioxide and polyether-ether-ketone powder are mixed in proportion in high-speed mixer and carry out.
6. preparation method as claimed in claim 5, it is characterized in that described all raw materials all will carry out dried to remove moisture before processing, the baking temperature of fluor-apatite and titania powder is 120 ℃～150 ℃, and polyether-ether-ketone is dry under 120 ℃～150 ℃ conditions.
7. as each described preparation method of claim 4-6, it is characterized in that, the pellet of composite is injection molded into the composite of required shape with the high-temperature injection machine.
8. preparation method as claimed in claim 7, it is characterized in that, will be through the double screw extruder high-temperature mixing, melt blending is extruded, and extrudes the pellet of the composite of product cooling back pelletizing gained and puts into mould, put into press behind the matched moulds, rise to 380 ℃～420 ℃ by room temperature, pressurization 20～30MPa, heat-insulation pressure keeping 2～4 hours, the demoulding when being cooled in 100 ℃～130 ℃ scopes with the rate of temperature fall of 5～10 ℃/min obtains the polyether-ether-ketone composite material sample of fluor-apatite and titanium dioxide.
9. prepare each described method that contains the polyether-ether-ketone composite material of fluor-apatite and titanium dioxide of claim 1-3, it is characterized in that, adopt compression molding: the material fluor-apatite that will need mold pressing, titanium dioxide and polyether-ether-ketone powder are put into mould, put into press behind the matched moulds, rise to 380 ℃～420 ℃ by room temperature, pressurization 20～30MPa, heat-insulation pressure keeping 2～4 hours, the demoulding when being cooled in 100 ℃～130 ℃ scopes with the rate of temperature fall of 5～10 ℃/min obtains the polyether-ether-ketone composite material sample of fluor-apatite and titanium dioxide.
10. preparation method as claimed in claim 9 is characterized in that, earlier with fluor-apatite, titanium dioxide and polyether-ether-ketone powder carry out premixing in high-speed mixer, adopt compression molding again.
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