CN103585672A - Preparation method of bioglass fiber reinforced hydroxyapatite porous composite material - Google Patents
Preparation method of bioglass fiber reinforced hydroxyapatite porous composite material Download PDFInfo
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- CN103585672A CN103585672A CN201310575200.5A CN201310575200A CN103585672A CN 103585672 A CN103585672 A CN 103585672A CN 201310575200 A CN201310575200 A CN 201310575200A CN 103585672 A CN103585672 A CN 103585672A
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Abstract
The invention discloses a preparation method of a bioglass fiber reinforced hydroxyapatite porous composite material. The preparation method is characterized by comprising the following steps: silicon dioxide, calcium oxide, sodium carbonate, phosphorus pentoxide and the like are used as raw materials for preparing bioglass fibers; calcium nitrate, diammonium hydrogen phosphate, ammonium hydroxide and the like are used as raw materials for preparing hydroxyapatite; the bioglass fibers and the hydroxyapatite are mixed with each other, are reacted with an ethylene glycol solution, a methyl cellulose solution and a hydrogen peroxide solution, and are subjected to the microwave-assisted pore forming and the drying to prepare a porous composite material blank; the normal-pressure sintering is implemented to prepare the bioglass fiber reinforced hydroxyapatite porous composite material. The porous composite material prepared by the invention has the characteristic of adopting a penetrating pore structure for providing an excellent microenvironment for growth of bone tissues, supply of oxygen and nutritive substances and loading and release of genes and medicines, has an excellent biological activity and a mechanical property, and can be used as an excellent human body bone repairing material and a bone tissue engineering bracket material.
Description
Technical field
The invention belongs to the preparation of biomedical material, relate to a kind of biological glass fiber and strengthen the composite porous preparation method of hydroxyapatite.Adopt biological glass fiber prepared by the present invention to strengthen hydroxyapatite composite porous applicable do good human bone repair materials and bone tissue engineering stent material.
Background technology
Along with social population's aging, popularization of Sports and vehicle accident increase, the number of patients of suffering from all kinds of clinical orthopaedics diseases and wound is increasing, and people increase day by day to the demand of human body hard tissue repair materials (as artificial bone).Hydroxyapatite (chemical formula: Ca
10(PO
4)
6(OH)
2) similar with crystal structure to the inanimate matter composition of skeleton, there is good biological activity and biocompatibility, be considered to one of the most representative current, the most active bioactive ceramics of research, can be used as human bone repair materials and bone tissue engineering stent material, be widely used in the clinical fields such as orthopaedics, dentistry and the reparation of cranium face.
Porous Hydroxyapatite Ceramic, except having general bioactive ceramics advantage, because self has loose structure, is therefore more suitable in defect of human body bone reparation.The connectivity pore structure of the inner both macro and micro existing of Porous Hydroxyapatite Ceramic can promote cross coupled between growing into of osseous tissue and osseous tissue, thereby forms more firm implant-bone interface.Secondly, Porous Hydroxyapatite Ceramic pore structure not only can be body fluid microcirculation, oxygen and nutrient substance supply and metabolite discharge provides good microenvironment, also can be used as the excellent carrier of loading, release gene and medicine.In addition, Porous Hydroxyapatite Ceramic can also serve as bone tissue engineering stent material in osseous tissue reconstruction and regenerative process.Therefore, Porous Hydroxyapatite Ceramic is repaired and bone tissue engineering stent material as a kind of function admirable bone, in field of biomedical materials, has caused countries in the world researcher extensive concern.
Yet bending strength and the fracture toughness of Porous Hydroxyapatite Ceramic are lower, cause its anti-fatigue ability under physiological environment poor, thereby limit its sclerous tissues at human body bearing position, replace and repair.Therefore, how to improve Porous Hydroxyapatite Ceramic mechanical strength is one of biomedical ceramic field study hotspot and difficult point always.In prior art, researcher mainly adopts zirconium dioxide, aluminium oxide, carbon fiber, silver, titanium, titanium-ferrum granule and polymethyl methacrylate etc. to strengthen hydroxylapatite ceramic both at home and abroad.Yet above-mentioned reinforcement is bio-inert material, do not there is biological activity, after implanting, can not form firm chemical key and be combined between osseous tissue, thereby reduce the steadiness of implant-bone interface.
Summary of the invention
Object of the present invention is intended to overcome deficiency of the prior art, provides a kind of biological glass fiber to strengthen the composite porous preparation method of hydroxyapatite; The inventive method adopts biological glass fiber as reinforcing material, hydroxyapatite is as matrix material, hydrogen peroxide is as pore creating material, Polyethylene Glycol and methylcellulose are as binding agent, by recipe design and microwave-assisted boring technique, adopt normal pressure-sintered legal system to strengthen hydroxyapatite for a kind of high-quality biological glass fiber composite porous; Prepared by the inventive method composite porously not only has and can load and discharge the connectivity pore structure that a good microenvironment is provided for osteogenesis, gene and medicine, also there is good biological activity and mechanical property, can be used as a kind of good human bone repair materials and bone tissue engineering stent material.
Content of the present invention is: a kind of biological glass fiber strengthens the composite porous preparation method of hydroxyapatite, it is characterized in that being completed by following steps:
A, prepare biological glass fiber:
According to silicon dioxide: calcium oxide: sodium carbonate: phosphorus pentoxide is (35～65): (15～55): (5～50): the molar ratio weighing of (1～10) is got each component raw material, even mixed compound is added to platinum crucible, with the firing rate of 2.5～20 ℃/min, be warming up to 1100～1600 ℃ compound is carried out to high-temperature process 2～6 hours, compound after high-temperature process is poured into fast and in deionized water, carried out shrend, the solids that shrend is formed leaches, the temperature that is placed at 50～70 ℃ is dried 12～24 hours, make bio-vitric, standby; The bio-vitric making is put into band small opening platinum crucible, with the firing rate of 2.5～20 ℃/min, be warming up to 1200～1500 ℃ bio-vitric is carried out to melt process 2～4 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk and to the bobbins of rotation, carry out wire drawing processing, on bobbins, obtain biological glass fiber;
B, prepare hydroxyapatite:
By calcium: the mol ratio that phosphorus is 1.67:1 is got lime nitrate and diammonium phosphate, lime nitrate is mixed with to calcium nitrate aqueous solution that molar concentration is 0.3～2.8mol/L, diammonium phosphate is mixed with to the ammonium dibasic phosphate aqueous solution that molar concentration is 0.3～3.2mol/L, under (constantly) stirs, ammonium dibasic phosphate aqueous solution is added drop-wise in calcium nitrate aqueous solution and is reacted with the speed of 3～20ml/min, obtain reactant liquor, and then the ammonia that is 5%～25% by mass percent concentration is added drop-wise in reactant liquor, controlling reacting liquid pH value is 8～11, keep reaction temperature at 40～95 ℃, after dripping (and after complete reaction), standing 3～20 minutes, ageing (placing) is processed 12～36 hours, make hydroxyapatite slurry, by this slurry after washed with de-ionized water to pH value is 7～7.2, be placed in again at the temperature of 50～70 ℃ and dry 12～24 hours, must dry rear material, by drying rear material: mill ball is 1: 1.5～3.5 mass ratio, after adopting planetary ball mill to dry, material grinds 12～24 hours, make hydroxyapatite,
C, prepare biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite:
Biological glass fiber is mixed, obtains mixture with hydroxyapatite, wherein: the interpolation weight of biological glass fiber accounts for 5%～45% of biological glass fiber and hydroxyapatite gross weight, the methylated cellulose aqueous solution that the Aqueous Solutions of Polyethylene Glycol that the mass percent concentration that adds again 20～60 weight portions in the biological glass fiber of 100 weight portions and the mixture of hydroxyapatite is 5%～30% and the mass percent concentration of 10～40 weight portions are 1%～20%, (fully) stirs 10～30 minutes, the aqueous hydrogen peroxide solution that the mass percent concentration that adds again 5～35 weight portions is 5%～30%, (fully) stirs 3～5 minutes again, obtain compound, compound is packed in the container that is applicable to microwave oven, the microwave oven that this container is placed in to 500～2000 watts carries out microwave-assisted pore-creating 0.5～5 minute, again the compound after microwave-assisted pore-creating is added in the mould with permeability and breathability, the temperature of 30～80 ℃, dries 12～24 hours, make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite,
D, normal pressure-sinteredly prepare biological glass fiber to strengthen hydroxyapatite composite porous:
Biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, firing rate with 2.5～20 ℃/min is warming up to 1000～1200 ℃ of sintering 0.5～4 hour, obtains (high-quality) biological glass fiber enhancing hydroxyapatite composite porous.
In content of the present invention: the diameter of the biological glass fiber obtaining on bobbins described in step a is 5～25 microns preferably.
In content of the present invention: carry out wire drawing described in step a and process to be preferably according to the drawing speed of 50～500m/min and carry out wire drawing processing.
In content of the present invention: ammonia described in step b is added drop-wise to and is preferably ammonia in reactant liquor and is added drop-wise in reactant liquor with the speed of 15～25ml/min.
In content of the present invention: making the composite porous porosity of biological glass fiber enhancing hydroxyapatite described in steps d is 20%～70%, and pore-size is 50～450 microns, connects mutually between both macro and micro hole.
In content of the present invention: in described Aqueous Solutions of Polyethylene Glycol, the molecular weight of Polyethylene Glycol is 4000～10000 preferably; Production enterprise has: Chemical Reagent Co., Ltd., Sinopharm Group, Tianjin Kermel Chemical Reagent Co., Ltd., Aladdin reagent (Shanghai) Co., Ltd. etc.
In content of the present invention: in described methylated cellulose aqueous solution, the viscosity of methylcellulose is 200～1000mPas preferably; Production enterprise has: Sigma-Aldrich group, Chemical Reagent Co., Ltd., Sinopharm Group, Aladdin reagent (Shanghai) Co., Ltd. etc.
Compared with prior art, the present invention has following feature and beneficial effect:
(1) the present invention adopts biological glass fiber as reinforcing material, hydroxyapatite is as matrix material, hydrogen peroxide is as pore creating material, Polyethylene Glycol and methylcellulose are as binding agent, by recipe design and microwave-assisted boring technique, adopt normal pressure-sintered legal system to strengthen hydroxyapatite for a kind of high-quality biological glass fiber composite porous; The biological glass fiber reinforcing material that the present invention adopts not only has good biological activity, also has good mechanical property, its specific modulus is high, specific strength large, corrosion resistance and endurance quality good; The present invention utilizes mechanical property and the physicochemical property that biological glass fiber is good, using biological glass fiber as reinforcing material, hydroxyapatite is as matrix material, is conducive to like this prepare have good mechanical property and bioactive biological glass fiber concurrently to strengthen hydroxyapatite composite porous;
(2) the present invention adopts biological glass fiber as reinforcing material, the mechanical properties such as its specific strength and specific modulus are all very high, the introducing of biological glass fiber can guarantee that biological glass fiber strengthens composite porous good mechanical property and the good connectivity pore structure of having concurrently of hydroxyapatite, thereby obtains biocompatibility and biological activity excellent in human body environment; Biological glass fiber and hydroxyapatite that the present invention adopts all belong to the Inorganic Non-metallic Materials that contains phosphate groups, and when biological glass fiber and hydroxyapatite are in contact with one another, its interface has good interface compatibility; Simultaneously, the thermal coefficient of expansion of biological glass fiber is close with the thermal coefficient of expansion of hydroxyapatite, this makes the contact interface of biological glass fiber and hydroxyapatite have less residual thermal stress, be conducive to like this increase the adhesion strength between biological glass fiber and hydroxyapatite interface, thereby improve the mechanical property that biological glass fiber strengthens the composite porous integral body of hydroxyapatite;
(3) the present invention adopts the hydrogen peroxide of the easy decomposition gasification of heating as pore creating material, by the heat producing in microwave-assisted pore-creating process, hydrogen peroxide is decomposed and produce water and oxygen, utilize hydrogen peroxide to decompose the oxygen producing and carry out pore-creating processing, thereby build the both macro and micro connectivity pore structure that biological glass fiber strengthens the composite porous inside of hydroxyapatite; The heat simply, producing in practical microwave-assisted pore-creating process only decomposes hydrogen peroxide and generates water and oxygen, can not strengthen the remaining objectionable impurities of the composite porous middle generation of hydroxyapatite at biological glass fiber, thereby can not reduce biological glass fiber, not strengthen the composite porous biocompatibility of hydroxyapatite;
(4) adopting the composite porous porosity of biological glass fiber enhancing hydroxyapatite prepared by the present invention is 20%～70%, and pore-size is 50～450 microns, between both macro and micro hole, connects mutually; Biological glass fiber strengthens that the composite porous inner this connectivity pore structure existing of hydroxyapatite is extremely conducive to the growing into of osteoblastic propagation and differentiation, osseous tissue, oxygen and nutrient substance is supplied with and the discharge of metabolite; Biological glass fiber strengthens that hydroxyapatite is composite porous has various biological performances such as better biological activity, bone conductibility and osteoinductive;
(5) preparation technology of the present invention simply, easily operation, preparation composite porous not only have can grow into for osseous tissue, oxygen and nutrient substance supply, gene and medicine load and discharge the connectivity pore structure that good microenvironment is provided, also there is good biological activity and mechanical property, can be used as a kind of good human bone repair materials and bone tissue engineering stent material, practical.
The specific embodiment
Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1:
According to silicon dioxide: calcium oxide: sodium carbonate: the mol ratio of phosphorus pentoxide is that 45:45:8:2 weighs, after evenly mixing, be added to platinum crucible, with 2.5 ℃/min firing rate, be warming up to 1100 ℃ raw material is carried out to high-temperature process 2 hours, raw material after high-temperature process is poured into fast and in deionized water, carried out shrend, the bio-vitric that shrend is formed leaches, be placed at 50 ℃ and dry 12 hours, can make bio-vitric standby, the bio-vitric making is put into band small opening platinum crucible, with 2.5 ℃/min firing rate, be warming up to 1200 ℃ bio-vitric is carried out to melt process 2 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk to the bobbins of rotation, according to the drawing speed of 500m/min, carry out wire drawing processing, can on bobbins, obtain diameter and be the biological glass fiber of 5 microns, press calcium phosphorus mol ratio 1.67, the ammonium dibasic phosphate aqueous solution that the calcium nitrate aqueous solution that configuration molar concentration is 0.3mol/L and molar concentration are 0.3mol/L, under constantly stirring, the ammonium dibasic phosphate aqueous solution of configuration is added drop-wise in calcium nitrate aqueous solution and is reacted with 3ml/min speed, and then the ammonia of percent concentration 5% is added drop-wise in reactant liquor with 15ml/min speed, controlling reacting liquid pH value is 8, keep reaction temperature at 40 ℃, after complete reaction, standing 3 minutes, ripening 12 hours, can make hydroxyapatite slurry, by this slurry, through washed with de-ionized water to pH value, be 7, at 50 ℃, dry 12 hours, according to material to be ground: the mass ratio of mill ball is 1: 1.5, adopt planetary ball mill to grind 12 hours, make hydroxyapatite, biological glass fiber is mixed with hydroxyapatite, and wherein the interpolation weight of biological glass fiber accounts for 5% of biological glass fiber and hydroxyapatite gross weight, in the biological glass fiber of 100 weight portions and hydroxyapatite mixture, add mass percent concentration 5% polyglycol solution of 20 weight portions and mass percent concentration 1% methocel solution of 10 weight portions, fully stir 10 minutes, mass percent concentration 5% hydrogenperoxide steam generator that adds again 5 weight portions, again fully stir and pack in the container that is applicable to microwave oven afterwards for 3 minutes, the microwave oven that this container is placed in to 500 watts carries out microwave-assisted pore-creating 0.5 minute, mixed material after microwave-assisted pore-creating is added in the mould with permeability and breathability, at 30 ℃, dries 12 hours, can make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite, biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, with 2.5 ℃/min firing rate, be warming up to 1000 ℃ of sintering 0.5 hour, obtain high-quality biological glass fiber enhancing hydroxyapatite composite porous.
Embodiment 2:
According to silicon dioxide: calcium oxide: sodium carbonate: the mol ratio of phosphorus pentoxide is that 50:35:10:5 weighs, after evenly mixing, be added to platinum crucible, with 5 ℃/min firing rate, be warming up to 1200 ℃ raw material is carried out to high-temperature process 3 hours, raw material after high-temperature process is poured into fast and in deionized water, carried out shrend, the bio-vitric that shrend is formed leaches, be placed at 55 ℃ and dry 16 hours, can make bio-vitric standby, the bio-vitric making is put into band small opening platinum crucible, with 5 ℃/min firing rate, be warming up to 1300 ℃ bio-vitric is carried out to melt process 3 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk to the bobbins of rotation, according to the drawing speed of 450m/min, carry out wire drawing processing, can on bobbins, obtain diameter and be the biological glass fiber of 8 microns, press calcium phosphorus mol ratio 1.67, the ammonium dibasic phosphate aqueous solution that the calcium nitrate aqueous solution that configuration molar concentration is 0.8mol/L and molar concentration are 0.8mol/L, under constantly stirring, the ammonium dibasic phosphate aqueous solution of configuration is added drop-wise in calcium nitrate aqueous solution and is reacted with 5ml/min speed, and then the ammonia of percent concentration 10% is added drop-wise in reactant liquor with 18ml/min speed, controlling reacting liquid pH value is 9, keep reaction temperature at 50 ℃, after complete reaction, standing 5 minutes, ripening 16 hours, can make hydroxyapatite slurry, by this slurry, through washed with de-ionized water to pH value, be 7, at 55 ℃, dry 16 hours, according to material to be ground: the mass ratio of mill ball is 1: 2, adopt planetary ball mill to grind 16 hours, make hydroxyapatite, biological glass fiber is mixed with hydroxyapatite, and wherein the interpolation weight of biological glass fiber accounts for 10% of biological glass fiber and hydroxyapatite gross weight, in the biological glass fiber of 100 weight portions and hydroxyapatite mixture, add mass percent concentration 10% polyglycol solution of 25 weight portions and mass percent concentration 5% methocel solution of 15 weight portions, fully stir 15 minutes, mass percent concentration 10% hydrogenperoxide steam generator that adds again 10 weight portions, again fully stir and pack in the container that is applicable to microwave oven afterwards for 3 minutes, the microwave oven that this container is placed in to 800 watts carries out microwave-assisted pore-creating 1 minute, mixed material after microwave-assisted pore-creating is added in the mould with permeability and breathability, at 35 ℃, dries 12 hours, can make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite, biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, with 5 ℃/min firing rate, be warming up to 1050 ℃ of sintering 1 hour, obtain high-quality biological glass fiber enhancing hydroxyapatite composite porous.
Embodiment 3:
According to silicon dioxide: calcium oxide: sodium carbonate: the mol ratio of phosphorus pentoxide is that 50:40:9:1 weighs, after evenly mixing, be added to platinum crucible, with 8 ℃/min firing rate, be warming up to 1250 ℃ raw material is carried out to high-temperature process 4 hours, raw material after high-temperature process is poured into fast and in deionized water, carried out shrend, the bio-vitric that shrend is formed leaches, be placed at 60 ℃ and dry 12 hours, can make bio-vitric standby, the bio-vitric making is put into band small opening platinum crucible, with 8 ℃/min firing rate, be warming up to 1300 ℃ bio-vitric is carried out to melt process 2 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk to the bobbins of rotation, according to the drawing speed of 400m/min, carry out wire drawing processing, can on bobbins, obtain diameter and be the biological glass fiber of 10 microns, press calcium phosphorus mol ratio 1.67, the ammonium dibasic phosphate aqueous solution that the calcium nitrate aqueous solution that configuration molar concentration is 1.2mol/L and molar concentration are 1.2mol/L, under constantly stirring, the ammonium dibasic phosphate aqueous solution of configuration is added drop-wise in calcium nitrate aqueous solution and is reacted with 8ml/min speed, and then the ammonia of percent concentration 8% is added drop-wise in reactant liquor with 18ml/min speed, controlling reacting liquid pH value is 9, keep reaction temperature at 55 ℃, after complete reaction, standing 6 minutes, ripening 24 hours, can make hydroxyapatite slurry, by this slurry, through washed with de-ionized water to pH value, be 7, at 65 ℃, dry 12 hours, according to material to be ground: the mass ratio of mill ball is 1: 2.5, adopt planetary ball mill to grind 12 hours, make hydroxyapatite, biological glass fiber is mixed with hydroxyapatite, and wherein the interpolation weight of biological glass fiber accounts for 20% of biological glass fiber and hydroxyapatite gross weight, in the biological glass fiber of 100 weight portions and hydroxyapatite mixture, add mass percent concentration 35% polyglycol solution of 40 weight portions and mass percent concentration 8% methocel solution of 35 weight portions, fully stir 15 minutes, mass percent concentration 8% hydrogenperoxide steam generator that adds again 15 weight portions, again fully stir and pack in the container that is applicable to microwave oven afterwards for 3 minutes, the microwave oven that this container is placed in to 900 watts carries out microwave-assisted pore-creating 2 minutes, mixed material after microwave-assisted pore-creating is added in the mould with permeability and breathability, at 65 ℃, dries 12 hours, can make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite, biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, with 8 ℃/min firing rate, be warming up to 1150 ℃ of sintering 2.5 hours, obtain high-quality biological glass fiber enhancing hydroxyapatite composite porous.
Embodiment 4:
According to silicon dioxide: calcium oxide: sodium carbonate: the mol ratio of phosphorus pentoxide is that 55:25:15:5 weighs, after evenly mixing, be added to platinum crucible, with 10 ℃/min firing rate, be warming up to 1350 ℃ raw material is carried out to high-temperature process 4.5 hours, raw material after high-temperature process is poured into fast and in deionized water, carried out shrend, the bio-vitric that shrend is formed leaches, be placed at 60 ℃ and dry 24 hours, can make bio-vitric standby, the bio-vitric making is put into band small opening platinum crucible, with 15 ℃/min firing rate, be warming up to 1300 ℃ bio-vitric is carried out to melt process 2 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk to the bobbins of rotation, according to the drawing speed of 350m/min, carry out wire drawing processing, can on bobbins, obtain diameter and be the biological glass fiber of 12 microns, press calcium phosphorus mol ratio 1.67, the ammonium dibasic phosphate aqueous solution that the calcium nitrate aqueous solution that configuration molar concentration is 1.6mol/L and molar concentration are 1.6mol/L, under constantly stirring, the ammonium dibasic phosphate aqueous solution of configuration is added drop-wise in calcium nitrate aqueous solution and is reacted with 16ml/min speed, and then the ammonia of percent concentration 18% is added drop-wise in reactant liquor with 18ml/min speed, controlling reacting liquid pH value is 10, keep reaction temperature at 80 ℃, after complete reaction, standing 10 minutes, ripening 24 hours, can make hydroxyapatite slurry, by this slurry, through washed with de-ionized water to pH value, be 7, at 55 ℃, dry 24 hours, according to material to be ground: the mass ratio of mill ball is 1: 3, adopt planetary ball mill to grind 24 hours, make hydroxyapatite, biological glass fiber is mixed with hydroxyapatite, and wherein the interpolation weight of biological glass fiber accounts for 20% of biological glass fiber and hydroxyapatite gross weight, in the biological glass fiber of 100 weight portions and hydroxyapatite mixture, add mass percent concentration 20% polyglycol solution of 55 weight portions and mass percent concentration 15% methocel solution of 30 weight portions, fully stir 15 minutes, mass percent concentration 20% hydrogenperoxide steam generator that adds again 15 weight portions, again fully stir and pack in the container that is applicable to microwave oven afterwards for 4 minutes, the microwave oven that this container is placed in to 1000 watts carries out microwave-assisted pore-creating 2.5 minutes, mixed material after microwave-assisted pore-creating is added in the mould with permeability and breathability, at 70 ℃, dries 24 hours, can make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite, biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, with 10 ℃/min firing rate, be warming up to 1200 ℃ of sintering 3 hours, obtain high-quality biological glass fiber enhancing hydroxyapatite composite porous.
Embodiment 5:
According to silicon dioxide: calcium oxide: sodium carbonate: the mol ratio of phosphorus pentoxide is that 50:25:15:10 weighs, after evenly mixing, be added to platinum crucible, with 20 ℃/min firing rate, be warming up to 1400 ℃ raw material is carried out to high-temperature process 5 hours, raw material after high-temperature process is poured into fast and in deionized water, carried out shrend, the bio-vitric that shrend is formed leaches, be placed at 65 ℃ and dry 12 hours, can make bio-vitric standby, the bio-vitric making is put into band small opening platinum crucible, with 15 ℃/min firing rate, be warming up to 1350 ℃ bio-vitric is carried out to melt process 3 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk to the bobbins of rotation, according to the drawing speed of 300m/min, carry out wire drawing processing, can on bobbins, obtain diameter and be the biological glass fiber of 15 microns, press calcium phosphorus mol ratio 1.67, the ammonium dibasic phosphate aqueous solution that the calcium nitrate aqueous solution that configuration molar concentration is 2mol/L and molar concentration are 2mol/L, under constantly stirring, the ammonium dibasic phosphate aqueous solution of configuration is added drop-wise in calcium nitrate aqueous solution and is reacted with 16ml/min speed, and then the ammonia of percent concentration 25% is added drop-wise in reactant liquor with 18ml/min speed, controlling reacting liquid pH value is 10, keep reaction temperature at 90 ℃, after complete reaction, standing 20 minutes, ripening 24 hours, can make hydroxyapatite slurry, by this slurry, through washed with de-ionized water to pH value, be 7, at 65 ℃, dry 12 hours, according to material to be ground: the mass ratio of mill ball is 1: 3.5, adopt planetary ball mill to grind 24 hours, make hydroxyapatite, biological glass fiber is mixed with hydroxyapatite, and wherein the interpolation weight of biological glass fiber accounts for 35% of biological glass fiber and hydroxyapatite gross weight, in the biological glass fiber of 100 weight portions and hydroxyapatite mixture, add mass percent concentration 25% polyglycol solution of 55 weight portions and mass percent concentration 15% methocel solution of 40 weight portions, fully stir 25 minutes, mass percent concentration 25% hydrogenperoxide steam generator that adds again 25 weight portions, again fully stir and pack in the container that is applicable to microwave oven afterwards for 5 minutes, the microwave oven that this container is placed in to 1200 watts carries out microwave-assisted pore-creating 4 minutes, mixed material after microwave-assisted pore-creating is added in the mould with permeability and breathability, at 55 ℃, dries 24 hours, can make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite, biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, with 15 ℃/min firing rate, be warming up to 1150 ℃ of sintering 2 hours, obtain high-quality biological glass fiber enhancing hydroxyapatite composite porous.
Embodiment 6:
According to silicon dioxide: calcium oxide: sodium carbonate: the mol ratio of phosphorus pentoxide is that 60:15:20:5 weighs, after evenly mixing, be added to platinum crucible, with 16 ℃/min firing rate, be warming up to 1500 ℃ raw material is carried out to high-temperature process 2 hours, raw material after high-temperature process is poured into fast and in deionized water, carried out shrend, the bio-vitric that shrend is formed leaches, be placed at 70 ℃ and dry 12 hours, can make bio-vitric standby, the bio-vitric making is put into band small opening platinum crucible, with 10 ℃/min firing rate, be warming up to 1400 ℃ bio-vitric is carried out to melt process 2 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk to the bobbins of rotation, according to the drawing speed of 200m/min, carry out wire drawing processing, can on bobbins, obtain diameter and be the biological glass fiber of 18 microns, press calcium phosphorus mol ratio 1.67, the ammonium dibasic phosphate aqueous solution that the calcium nitrate aqueous solution that configuration molar concentration is 2.2mol/L and molar concentration are 2.2mol/L, under constantly stirring, the ammonium dibasic phosphate aqueous solution of configuration is added drop-wise in calcium nitrate aqueous solution and is reacted with 18ml/min speed, and then the ammonia of percent concentration 20% is added drop-wise in reactant liquor with 25ml/min speed, controlling reacting liquid pH value is 11, keep reaction temperature at 95 ℃, after complete reaction, standing 20 minutes, ripening 12 hours, can make hydroxyapatite slurry, by this slurry, through washed with de-ionized water to pH value, be 7, at 55 ℃, dry 24 hours, according to material to be ground: the mass ratio of mill ball is 1: 1.5, adopt planetary ball mill to grind 12 hours, make hydroxyapatite, biological glass fiber is mixed with hydroxyapatite, and wherein the interpolation weight of biological glass fiber accounts for 25% of biological glass fiber and hydroxyapatite gross weight, in the biological glass fiber of 100 weight portions and hydroxyapatite mixture, add mass percent concentration 25% polyglycol solution of 55 weight portions and mass percent concentration 15% methocel solution of 35 weight portions, fully stir 15 minutes, mass percent concentration 15% hydrogenperoxide steam generator that adds again 25 weight portions, again fully stir and pack in the container that is applicable to microwave oven afterwards for 4 minutes, the microwave oven that this container is placed in to 1500 watts carries out microwave-assisted pore-creating 1 minute, mixed material after microwave-assisted pore-creating is added in the mould with permeability and breathability, at 70 ℃, dries 12 hours, can make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite, biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, with 10 ℃/min firing rate, be warming up to 1200 ℃ of sintering 3 hours, obtain high-quality biological glass fiber enhancing hydroxyapatite composite porous.
Embodiment 7:
According to silicon dioxide: calcium oxide: sodium carbonate: the mol ratio of phosphorus pentoxide is that 60:20:10:10 weighs, after evenly mixing, be added to platinum crucible, with 15 ℃/min firing rate, be warming up to 1550 ℃ raw material is carried out to high-temperature process 3 hours, raw material after high-temperature process is poured into fast and in deionized water, carried out shrend, the bio-vitric that shrend is formed leaches, be placed at 70 ℃ and dry 24 hours, can make bio-vitric standby, the bio-vitric making is put into band small opening platinum crucible, with 20 ℃/min firing rate, be warming up to 1450 ℃ bio-vitric is carried out to melt process 4 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk to the bobbins of rotation, according to the drawing speed of 100m/min, carry out wire drawing processing, can on bobbins, obtain diameter and be the biological glass fiber of 20 microns, press calcium phosphorus mol ratio 1.67, the ammonium dibasic phosphate aqueous solution that the calcium nitrate aqueous solution that configuration molar concentration is 2.8mol/L and molar concentration are 2.8mol/L, under constantly stirring, the ammonium dibasic phosphate aqueous solution of configuration is added drop-wise in calcium nitrate aqueous solution and is reacted with 20ml/min speed, and then the ammonia of percent concentration 25% is added drop-wise in reactant liquor with 25ml/min speed, controlling reacting liquid pH value is 9, keep reaction temperature at 90 ℃, after complete reaction, standing 20 minutes, ripening 12 hours, can make hydroxyapatite slurry, by this slurry, through washed with de-ionized water to pH value, be 7, at 55 ℃, dry 24 hours, according to material to be ground: the mass ratio of mill ball is 1: 3, adopt planetary ball mill to grind 24 hours, make hydroxyapatite, biological glass fiber is mixed with hydroxyapatite, and wherein the interpolation weight of biological glass fiber accounts for 40% of biological glass fiber and hydroxyapatite gross weight, in the biological glass fiber of 100 weight portions and hydroxyapatite mixture, add mass percent concentration 25% polyglycol solution of 55 weight portions and mass percent concentration 15% methocel solution of 35 weight portions, fully stir 25 minutes, mass percent concentration 25% hydrogenperoxide steam generator that adds again 30 weight portions, again fully stir and pack in the container that is applicable to microwave oven afterwards for 4 minutes, the microwave oven that this container is placed in to 1800 watts carries out microwave-assisted pore-creating 4.5 minutes, mixed material after microwave-assisted pore-creating is added in the mould with permeability and breathability, at 75 ℃, dries 24 hours, can make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite, biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, with 15 ℃/min firing rate, be warming up to 1200 ℃ of sintering 3.5 hours, obtain high-quality biological glass fiber enhancing hydroxyapatite composite porous.
Embodiment 8:
According to silicon dioxide: calcium oxide: sodium carbonate: the mol ratio of phosphorus pentoxide is that 65:20:10:5 weighs, after evenly mixing, be added to platinum crucible, with 20 ℃/min firing rate, be warming up to 1600 ℃ raw material is carried out to high-temperature process 6 hours, raw material after high-temperature process is poured into fast and in deionized water, carried out shrend, the bio-vitric that shrend is formed leaches, be placed at 70 ℃ and dry 24 hours, can make bio-vitric standby, the bio-vitric making is put into band small opening platinum crucible, with 20 ℃/min firing rate, be warming up to 1500 ℃ bio-vitric is carried out to melt process 4 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk to the bobbins of rotation, according to the drawing speed of 50m/min, carry out wire drawing processing, can on bobbins, obtain diameter and be the biological glass fiber of 25 microns, press calcium phosphorus mol ratio 1.67, the ammonium dibasic phosphate aqueous solution that the calcium nitrate aqueous solution that configuration molar concentration is 2.8mol/L and molar concentration are 3.2mol/L, under constantly stirring, the ammonium dibasic phosphate aqueous solution of configuration is added drop-wise in calcium nitrate aqueous solution and is reacted with 20ml/min speed, and then the ammonia of percent concentration 25% is added drop-wise in reactant liquor with 25ml/min speed, controlling reacting liquid pH value is 11, keep reaction temperature at 95 ℃, after complete reaction, standing 20 minutes, ripening 36 hours, can make hydroxyapatite slurry, by this slurry, through washed with de-ionized water to pH value, be 7, at 70 ℃, dry 24 hours, according to material to be ground: the mass ratio of mill ball is 1: 3.5, adopt planetary ball mill to grind 24 hours, make hydroxyapatite, biological glass fiber is mixed with hydroxyapatite, and wherein the interpolation weight of biological glass fiber accounts for 45% of biological glass fiber and hydroxyapatite gross weight, in the biological glass fiber of 100 weight portions and hydroxyapatite mixture, add mass percent concentration 30% polyglycol solution of 60 weight portions and mass percent concentration 20% methocel solution of 40 weight portions, fully stir 30 minutes, mass percent concentration 30% hydrogenperoxide steam generator that adds again 35 weight portions, again fully stir and pack in the container that is applicable to microwave oven afterwards for 5 minutes, the microwave oven that this container is placed in to 2000 watts carries out microwave-assisted pore-creating 5 minutes, mixed material after microwave-assisted pore-creating is added in the mould with permeability and breathability, at 80 ℃, dries 24 hours, can make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite, biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, with 20 ℃/min firing rate, be warming up to 1200 ℃ of sintering 4 hours, obtain high-quality biological glass fiber enhancing hydroxyapatite composite porous.
Embodiment 9:
Biological glass fiber strengthens the composite porous preparation method of hydroxyapatite, by following steps, is completed:
A, prepare biological glass fiber:
According to silicon dioxide: calcium oxide: sodium carbonate: the molar ratio weighing that phosphorus pentoxide is 35:15:5:1 is got each component raw material, even mixed compound is added to platinum crucible, with the firing rate of 2.5 ℃/min, be warming up to 1100 ℃ compound is carried out to high-temperature process 6 hours, compound after high-temperature process is poured into fast and in deionized water, carried out shrend, the solids that shrend is formed leaches, the temperature that is placed at 50 ℃ is dried 24 hours, makes bio-vitric, standby; The bio-vitric making is put into band small opening platinum crucible, with the firing rate of 2.5 ℃/min, be warming up to 1200 ℃ bio-vitric is carried out to melt process 4 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk to the bobbins of rotation, according to the drawing speed of 50m/min, carry out wire drawing processing, on bobbins, obtain biological glass fiber;
B, prepare hydroxyapatite:
By calcium: the mol ratio that phosphorus is 1.67:1 is got lime nitrate and diammonium phosphate, lime nitrate is mixed with to calcium nitrate aqueous solution that molar concentration is 0.3mol/L, diammonium phosphate is mixed with to the ammonium dibasic phosphate aqueous solution that molar concentration is 0.3mol/L, under (constantly) stirs, ammonium dibasic phosphate aqueous solution is added drop-wise in calcium nitrate aqueous solution and is reacted with the speed of 3ml/min, obtain reactant liquor, and then the ammonia that is 5% by mass percent concentration is added drop-wise in reactant liquor, controlling reacting liquid pH value is 8, keep reaction temperature at 40 ℃, after dripping (and after complete reaction), standing 3 minutes, ageing (placing) is processed 12 hours, make hydroxyapatite slurry, by this slurry after washed with de-ionized water to pH value is 7, be placed in again at the temperature of 50 ℃ and dry 24 hours, must dry rear material, by drying rear material: the mass ratio that mill ball is 1: 1.5, after adopting planetary ball mill to dry, material grinds 12 hours, make hydroxyapatite,
C, prepare biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite:
Biological glass fiber is mixed, obtains mixture with hydroxyapatite, wherein: the interpolation weight of biological glass fiber accounts for 5% of biological glass fiber and hydroxyapatite gross weight; The methylated cellulose aqueous solution that the Aqueous Solutions of Polyethylene Glycol that the mass percent concentration that adds again 20 weight portions in the biological glass fiber of 100 weight portions and the mixture of hydroxyapatite is 5% and the mass percent concentration of 10 weight portions are 1%, (fully) stirs 10 minutes, the aqueous hydrogen peroxide solution that the mass percent concentration that adds again 5 weight portions is 5%, again (fully) stir 3 minutes, compound, compound is packed in the container that is applicable to microwave oven, the microwave oven that this container is placed in to 500 watts carries out microwave-assisted pore-creating 5 minutes; Again the compound after microwave-assisted pore-creating is added in the mould with permeability and breathability, the temperature of 30 ℃, dries 24 hours, make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite;
D, normal pressure-sinteredly prepare biological glass fiber to strengthen hydroxyapatite composite porous:
Biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, firing rate with 2.5 ℃/min is warming up to 1000 ℃ of sintering 4 hours, obtains (high-quality) biological glass fiber enhancing hydroxyapatite composite porous.
Embodiment 10:
Biological glass fiber strengthens the composite porous preparation method of hydroxyapatite, by following steps, is completed:
A, prepare biological glass fiber:
According to silicon dioxide: calcium oxide: sodium carbonate: the molar ratio weighing that phosphorus pentoxide is 65:55:50:10 is got each component raw material, even mixed compound is added to platinum crucible, with the firing rate of 20 ℃/min, be warming up to 1600 ℃ compound is carried out to high-temperature process 2 hours, compound after high-temperature process is poured into fast and in deionized water, carried out shrend, the solids that shrend is formed leaches, the temperature that is placed at 70 ℃ is dried 12 hours, makes bio-vitric, standby; The bio-vitric making is put into band small opening platinum crucible, with the firing rate of 20 ℃/min, be warming up to 1500 ℃ bio-vitric is carried out to melt process 2 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk to the bobbins of rotation, according to the drawing speed of 500m/min, carry out wire drawing processing, on bobbins, obtain biological glass fiber;
B, prepare hydroxyapatite:
By calcium: the mol ratio that phosphorus is 1.67:1 is got lime nitrate and diammonium phosphate, lime nitrate is mixed with to calcium nitrate aqueous solution that molar concentration is 2.8mol/L, diammonium phosphate is mixed with to the ammonium dibasic phosphate aqueous solution that molar concentration is 3.2mol/L, under (constantly) stirs, ammonium dibasic phosphate aqueous solution is added drop-wise in calcium nitrate aqueous solution and is reacted with the speed of 20ml/min, obtain reactant liquor, and then the ammonia that is 25% by mass percent concentration is added drop-wise in reactant liquor, controlling reacting liquid pH value is 11, keep reaction temperature at 95 ℃, after dripping (and after complete reaction), standing 3 minutes, ageing (placing) is processed 12 hours, make hydroxyapatite slurry, by this slurry after washed with de-ionized water to pH value is 7.2, be placed in again at the temperature of 70 ℃ and dry 12 hours, must dry rear material, by drying rear material: the mass ratio that mill ball is 1: 3.5, after adopting planetary ball mill to dry, material grinds 24 hours, make hydroxyapatite,
C, prepare biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite:
Biological glass fiber is mixed, obtains mixture with hydroxyapatite, wherein: the interpolation weight of biological glass fiber accounts for 5% of biological glass fiber and hydroxyapatite gross weight; The methylated cellulose aqueous solution that the Aqueous Solutions of Polyethylene Glycol that the mass percent concentration that adds again 20 weight portions in the biological glass fiber of 100 weight portions and the mixture of hydroxyapatite is 30% and the mass percent concentration of 40 weight portions are 20%, (fully) stirs 30 minutes, the aqueous hydrogen peroxide solution that the mass percent concentration that adds again 35 weight portions is 30%, again (fully) stir 5 minutes, compound, compound is packed in the container that is applicable to microwave oven, the microwave oven that this container is placed in to 2000 watts carries out microwave-assisted pore-creating 0.5 minute; Again the compound after microwave-assisted pore-creating is added in the mould with permeability and breathability, the temperature of 80 ℃, dries 12 hours, make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite;
D, normal pressure-sinteredly prepare biological glass fiber to strengthen hydroxyapatite composite porous:
Biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, firing rate with 20 ℃/min is warming up to 1200 ℃ of sintering 0.5 hour, obtains (high-quality) biological glass fiber enhancing hydroxyapatite composite porous.
Embodiment 11:
Biological glass fiber strengthens the composite porous preparation method of hydroxyapatite, by following steps, is completed:
A, prepare biological glass fiber:
According to silicon dioxide: calcium oxide: sodium carbonate: the molar ratio weighing that phosphorus pentoxide is 50:35:27:5.5 is got each component raw material, even mixed compound is added to platinum crucible, with the firing rate of 11 ℃/min, be warming up to 1350 ℃ compound is carried out to high-temperature process 4 hours, compound after high-temperature process is poured into fast and in deionized water, carried out shrend, the solids that shrend is formed leaches, the temperature that is placed at 60 ℃ is dried 18 hours, makes bio-vitric, standby; The bio-vitric making is put into band small opening platinum crucible, with the firing rate of 11 ℃/min, be warming up to 1350 ℃ bio-vitric is carried out to melt process 3 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk to the bobbins of rotation, according to, the drawing speed of 270m/min carries out wire drawing processing, obtains biological glass fiber on bobbins;
B, prepare hydroxyapatite:
By calcium: the mol ratio that phosphorus is 1.67:1 is got lime nitrate and diammonium phosphate, lime nitrate is mixed with to calcium nitrate aqueous solution that molar concentration is 1.5mol/L, diammonium phosphate is mixed with to the ammonium dibasic phosphate aqueous solution that molar concentration is 1.5mol/L, under (constantly) stirs, ammonium dibasic phosphate aqueous solution is added drop-wise in calcium nitrate aqueous solution and is reacted with the speed of 11ml/min, obtain reactant liquor, and then the ammonia that is 15% by mass percent concentration is added drop-wise in reactant liquor, controlling reacting liquid pH value is 9, keep reaction temperature at 70 ℃, after dripping (and after complete reaction), standing 11 minutes, ageing (placing) is processed 24 hours, make hydroxyapatite slurry, by this slurry after washed with de-ionized water to pH value is 7.1, be placed in again at the temperature of 60 ℃ and dry 18 hours, must dry rear material, by drying rear material: the mass ratio that mill ball is 1: 2.5, after adopting planetary ball mill to dry, material grinds 18 hours, make hydroxyapatite,
C, prepare biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite:
Biological glass fiber is mixed, obtains mixture with hydroxyapatite, wherein: the interpolation weight of biological glass fiber accounts for 25% of biological glass fiber and hydroxyapatite gross weight; The methylated cellulose aqueous solution that the Aqueous Solutions of Polyethylene Glycol that the mass percent concentration that adds again 40 weight portions in the biological glass fiber of 100 weight portions and the mixture of hydroxyapatite is 17% and the mass percent concentration of 25 weight portions are 10%, (fully) stirs 20 minutes, the aqueous hydrogen peroxide solution that the mass percent concentration that adds again 20 weight portions is 17%, again (fully) stir 4 minutes, compound, compound is packed in the container that is applicable to microwave oven, the microwave oven that this container is placed in to 1200 watts carries out microwave-assisted pore-creating 2.7 minutes; Again the compound after microwave-assisted pore-creating is added in the mould with permeability and breathability, the temperature of 55 ℃, dries 18 hours, make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite;
D, normal pressure-sinteredly prepare biological glass fiber to strengthen hydroxyapatite composite porous:
Biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, firing rate with 11 ℃/min is warming up to 1100 ℃ of sintering 2.2 hours, obtains (high-quality) biological glass fiber enhancing hydroxyapatite composite porous.
Embodiment 12:
Biological glass fiber strengthens the composite porous preparation method of hydroxyapatite, by following steps, is completed:
A, prepare biological glass fiber:
According to silicon dioxide: calcium oxide: sodium carbonate: phosphorus pentoxide is (35～65): (15～55): (5～50): the molar ratio weighing of (1～10) is got each component raw material, even mixed compound is added to platinum crucible, with the firing rate of 2.5～20 ℃/min, be warming up to 1100～1600 ℃ compound is carried out to high-temperature process 2～6 hours, compound after high-temperature process is poured into fast and in deionized water, carried out shrend, the solids that shrend is formed leaches, the temperature that is placed at 50～70 ℃ is dried 12～24 hours, make bio-vitric, standby; The bio-vitric making is put into band small opening platinum crucible, with the firing rate of 2.5～20 ℃/min, be warming up to 1200～1500 ℃ bio-vitric is carried out to melt process 2～4 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk and to the bobbins of rotation, carry out wire drawing processing, on bobbins, obtain biological glass fiber;
B, prepare hydroxyapatite:
By calcium: the mol ratio that phosphorus is 1.67:1 is got lime nitrate and diammonium phosphate, lime nitrate is mixed with to calcium nitrate aqueous solution that molar concentration is 0.3～2.8mol/L, diammonium phosphate is mixed with to the ammonium dibasic phosphate aqueous solution that molar concentration is 0.3～3.2mol/L, under (constantly) stirs, ammonium dibasic phosphate aqueous solution is added drop-wise in calcium nitrate aqueous solution and is reacted with the speed of 3～20ml/min, obtain reactant liquor, and then the ammonia that is 5%～25% by mass percent concentration is added drop-wise in reactant liquor, controlling reacting liquid pH value is 8～11, keep reaction temperature at 40～95 ℃, after dripping (and after complete reaction), standing 3～20 minutes, ageing (placing) is processed 12～36 hours, make hydroxyapatite slurry, by this slurry after washed with de-ionized water to pH value is 7～7.2, be placed in again at the temperature of 50～70 ℃ and dry 12～24 hours, must dry rear material, by drying rear material: mill ball is 1: 1.5～3.5 mass ratio, after adopting planetary ball mill to dry, material grinds 12～24 hours, make hydroxyapatite,
C, prepare biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite:
Biological glass fiber is mixed, obtains mixture with hydroxyapatite, wherein: the interpolation weight of biological glass fiber accounts for 5%～45% of biological glass fiber and hydroxyapatite gross weight, the methylated cellulose aqueous solution that the Aqueous Solutions of Polyethylene Glycol that the mass percent concentration that adds again 20～60 weight portions in the biological glass fiber of 100 weight portions and the mixture of hydroxyapatite is 5%～30% and the mass percent concentration of 10～40 weight portions are 1%～20%, (fully) stirs 10～30 minutes, the aqueous hydrogen peroxide solution that the mass percent concentration that adds again 5～35 weight portions is 5%～30%, (fully) stirs 3～5 minutes again, obtain compound, compound is packed in the container that is applicable to microwave oven, the microwave oven that this container is placed in to 500～2000 watts carries out microwave-assisted pore-creating 0.5～5 minute, again the compound after microwave-assisted pore-creating is added in the mould with permeability and breathability, the temperature of 30～80 ℃, dries 12～24 hours, make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite,
D, normal pressure-sinteredly prepare biological glass fiber to strengthen hydroxyapatite composite porous:
Biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, firing rate with 2.5～20 ℃/min is warming up to 1000～1200 ℃ of sintering 0.5～4 hour, obtains (high-quality) biological glass fiber enhancing hydroxyapatite composite porous.
Embodiment 13～19:
Biological glass fiber strengthens the composite porous preparation method of hydroxyapatite, by following steps, is completed:
A, prepare biological glass fiber:
According to silicon dioxide: calcium oxide: sodium carbonate: phosphorus pentoxide is (35～65): (15～55): (5～50): the molar ratio weighing of (1～10) is got each component raw material, even mixed compound is added to platinum crucible, with the firing rate of 2.5～20 ℃/min, be warming up to 1100～1600 ℃ compound is carried out to high-temperature process 2～6 hours, compound after high-temperature process is poured into fast and in deionized water, carried out shrend, the solids that shrend is formed leaches, the temperature that is placed at 50～70 ℃ is dried 12～24 hours, make bio-vitric, standby; The bio-vitric making is put into band small opening platinum crucible, with the firing rate of 2.5～20 ℃/min, be warming up to 1200～1500 ℃ bio-vitric is carried out to melt process 2～4 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk to the bobbins of rotation, according to the drawing speed of 50～500m/min, carry out wire drawing processing, on bobbins, obtain biological glass fiber;
In each embodiment, the concrete mol ratio consumption of each component raw material sees the following form:
B, prepare hydroxyapatite:
By calcium: the mol ratio that phosphorus is 1.67:1 is got lime nitrate and diammonium phosphate, lime nitrate is mixed with to calcium nitrate aqueous solution that molar concentration is 0.3～2.8mol/L, diammonium phosphate is mixed with to the ammonium dibasic phosphate aqueous solution that molar concentration is 0.3～3.2mol/L, under (constantly) stirs, ammonium dibasic phosphate aqueous solution is added drop-wise in calcium nitrate aqueous solution and is reacted with the speed of 3～20ml/min, obtain reactant liquor, and then the ammonia that is 5%～25% by mass percent concentration is added drop-wise in reactant liquor, controlling reacting liquid pH value is 8～11, keep reaction temperature at 40～95 ℃, after dripping (and after complete reaction), standing 3～20 minutes, ageing (placing) is processed 12～36 hours, make hydroxyapatite slurry, by this slurry after washed with de-ionized water to pH value is 7～7.2, be placed in again at the temperature of 50～70 ℃ and dry 12～24 hours, must dry rear material, by material after drying: mill ball is that (mass ratio of embodiment 13～19 can be respectively: 1: 1.7 for 1: 1.5～3.5 mass ratio, 1: 2, 1: 2.3, 1: 2.6, 1: 2.8, 1: 3.1, 1: 3.3), after adopting planetary ball mill to dry, material grinds 12～24 hours, make hydroxyapatite,
C, prepare biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite:
Biological glass fiber is mixed, obtains mixture with hydroxyapatite, wherein: the percentage ratio that the interpolation weight that the interpolation weight of biological glass fiber accounts for biological glass fiber in 5%～45%(embodiment 13～19 of biological glass fiber and hydroxyapatite gross weight accounts for biological glass fiber and hydroxyapatite gross weight can be respectively: 10%, 15%, 20%, 25%, 30%, 35%, 40%), the methylated cellulose aqueous solution that the Aqueous Solutions of Polyethylene Glycol that the mass percent concentration that adds again 20～60 weight portions in the biological glass fiber of 100 weight portions and the mixture of hydroxyapatite is 17% and the mass percent concentration of 10～40 weight portions are 10%, (fully) stirs 10～30 minutes, the aqueous hydrogen peroxide solution that the mass percent concentration that adds again 5～35 weight portions is 17%, (fully) stirs 3～5 minutes again, obtain compound, compound is packed in the container that is applicable to microwave oven, the microwave oven that this container is placed in to 500～2000 watts carries out microwave-assisted pore-creating 0.5～5 minute, again the compound after microwave-assisted pore-creating is added in the mould with permeability and breathability, the temperature of 30～80 ℃, dries 12～24 hours, make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite,
In each embodiment, the concrete weight portion consumption of each component raw material sees the following form:
D, normal pressure-sinteredly prepare biological glass fiber to strengthen hydroxyapatite composite porous:
Biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, firing rate with 2.5～20 ℃/min is warming up to 1000～1200 ℃ of sintering 0.5～4 hour, obtains (high-quality) biological glass fiber enhancing hydroxyapatite composite porous.
In above-described embodiment 9～19: it is 5～25 microns that the diameter of the biological glass fiber obtaining on bobbins described in step a is controlled preferably.
In above-described embodiment 9～19: ammonia described in step b is added drop-wise to and is preferably ammonia in reactant liquor and is added drop-wise in reactant liquor with the speed of 15～25ml/min.
In above-described embodiment 9～19: making the composite porous porosity of biological glass fiber enhancing hydroxyapatite described in steps d is 20%～70%, and pore-size is 50～450 microns, connects mutually between both macro and micro hole.
In above-described embodiment 1～8 and present specification: described polyglycol solution, methocel solution, hydrogenperoxide steam generator are Aqueous Solutions of Polyethylene Glycol, methylated cellulose aqueous solution, aqueous hydrogen peroxide solution.
In above-described embodiment: each raw material adopting is commercially available prod.
In above-described embodiment: in the percentage adopting, do not indicate especially, be quality (weight) percentage or well known to a person skilled in the art percentage; Described weight (quality) part can be all gram or kilogram.
In above-described embodiment: the technological parameter in each step (temperature, time, concentration etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of technology contents of narrating in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, all can implement and have described good result described in content of the present invention.
Claims (7)
1. biological glass fiber strengthens the composite porous preparation method of hydroxyapatite, it is characterized in that being completed by following steps:
A, prepare biological glass fiber:
According to silicon dioxide: calcium oxide: sodium carbonate: the molar ratio weighing that phosphorus pentoxide is 35～65:15～55:5～50:1～10 is got each component raw material, even mixed compound is added to platinum crucible, with the firing rate of 2.5～20 ℃/min, be warming up to 1100～1600 ℃ compound is carried out to high-temperature process 2～6 hours, compound after high-temperature process is poured into fast and in deionized water, carried out shrend, the solids that shrend is formed leaches, the temperature that is placed at 50～70 ℃ is dried 12～24 hours, make bio-vitric, standby; The bio-vitric making is put into band small opening platinum crucible, with the firing rate of 2.5～20 ℃/min, be warming up to 1200～1500 ℃ bio-vitric is carried out to melt process 2～4 hours, the molten state bio-vitric at the small opening place of platinum crucible is drawn to silk and to the bobbins of rotation, carry out wire drawing processing, on bobbins, obtain biological glass fiber;
B, prepare hydroxyapatite:
By calcium: the mol ratio that phosphorus is 1.67:1 is got lime nitrate and diammonium phosphate, lime nitrate is mixed with to calcium nitrate aqueous solution that molar concentration is 0.3～2.8mol/L, diammonium phosphate is mixed with to the ammonium dibasic phosphate aqueous solution that molar concentration is 0.3～3.2mol/L, under agitation, ammonium dibasic phosphate aqueous solution is added drop-wise in calcium nitrate aqueous solution and is reacted with the speed of 3～20ml/min, obtain reactant liquor, and then the ammonia that is 5%～25% by mass percent concentration is added drop-wise in reactant liquor, controlling reacting liquid pH value is 8～11, keep reaction temperature at 40～95 ℃, after dripping, standing 3～20 minutes, ripening 12～36 hours, make hydroxyapatite slurry, by this slurry after washed with de-ionized water to pH value is 7～7.2, be placed in again at the temperature of 50～70 ℃ and dry 12～24 hours, must dry rear material, by drying rear material: mill ball is 1: 1.5～3.5 mass ratio, after adopting planetary ball mill to dry, material grinds 12～24 hours, make hydroxyapatite,
C, prepare biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite:
Biological glass fiber is mixed, obtains mixture with hydroxyapatite, wherein: the interpolation weight of biological glass fiber accounts for 5%～45% of biological glass fiber and hydroxyapatite gross weight, the methylated cellulose aqueous solution that the Aqueous Solutions of Polyethylene Glycol that the mass percent concentration that adds again 20～60 weight portions in the biological glass fiber of 100 weight portions and the mixture of hydroxyapatite is 5%～30% and the mass percent concentration of 10～40 weight portions are 1%～20%, stir 10～30 minutes, the aqueous hydrogen peroxide solution that the mass percent concentration that adds again 5～35 weight portions is 5%～30%, again stir 3～5 minutes, obtain compound, compound is packed in the container that is applicable to microwave oven, the microwave oven that this container is placed in to 500～2000 watts carries out microwave-assisted pore-creating 0.5～5 minute, again the compound after microwave-assisted pore-creating is added in the mould with permeability and breathability, the temperature of 30～80 ℃, dries 12～24 hours, make biological glass fiber and strengthen the composite porous base substrate of hydroxyapatite,
D, normal pressure-sinteredly prepare biological glass fiber to strengthen hydroxyapatite composite porous:
Biological glass fiber is strengthened to the composite porous base substrate of hydroxyapatite and be placed in constant-pressure and high-temperature sintering furnace, firing rate with 2.5～20 ℃/min is warming up to 1000～1200 ℃ of sintering 0.5～4 hour, obtains biological glass fiber enhancing hydroxyapatite composite porous.
2. by biological glass fiber described in claim 1, strengthen the composite porous preparation method of hydroxyapatite, it is characterized in that: the diameter of the biological glass fiber obtaining on bobbins described in step a is 5～25 microns.
3. by biological glass fiber described in claim 1 or 2, strengthen the composite porous preparation method of hydroxyapatite, it is characterized in that: described in step a, carrying out wire drawing processing is to carry out wire drawing processing according to the drawing speed of 50～500m/min.
4. profit requires described in 1 or 2 biological glass fiber to strengthen the composite porous preparation method of hydroxyapatite, it is characterized in that: ammonia described in step b is added drop-wise in reactant liquor, and to be ammonia be added drop-wise in reactant liquor with the speed of 15～25ml/min.
5. by biological glass fiber described in claim 3, strengthen the composite porous preparation method of hydroxyapatite, it is characterized in that: ammonia described in step b is added drop-wise in reactant liquor, and to be ammonia be added drop-wise in reactant liquor with the speed of 15～25ml/min.
6. by biological glass fiber described in claim 1,2 or 5, strengthen the composite porous preparation method of hydroxyapatite, it is characterized in that: described in steps d, making the composite porous porosity of biological glass fiber enhancing hydroxyapatite is 20%～70%, pore-size is 50～450 microns, between both macro and micro hole, connects mutually.
7. by biological glass fiber described in claim 3, strengthen the composite porous preparation method of hydroxyapatite, it is characterized in that: described in steps d, making the composite porous porosity of biological glass fiber enhancing hydroxyapatite is 20%～70%, pore-size is 50～450 microns, between both macro and micro hole, connects mutually.
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