CN105477681A - Preparation method of titanium polymer fiber-reinforced porous magnesium-based medical material - Google Patents
Preparation method of titanium polymer fiber-reinforced porous magnesium-based medical material Download PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
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- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention relates to a preparation method of a titanium polymer fiber-reinforced porous magnesium-based medical material, and belongs to the field of preparation of medical materials. The material is formed by preparing a reinforced porous material through ball-milling, pressing, sintering and alkaline leaching of a titanium polymer fiber, magnesium and potassium carbonate, and coating the material surface with hydroxyapatite through an electrophoretic deposition device, so that the defect of poor biocompatibility due to the fact that magnesium is corroded by a body fluid and a toxic substance is dissociated is avoided; the problem that the hydroxyapatite is brittle when individually used is solved; and the titanium polymer fiber-reinforced porous magnesium-based medical material is a good biological bone replacement material.
Description
Technical field
The present invention relates to a kind of preparation method of being polymerized titanium fiber reinforcement porous magnesio medical material, belong to medical material preparation field.
Background technology
Biomedical metallic material shows good mechanical property in biological bone tissue is replaced.But because it is serious by corrosion in body fluid in vivo, some metal ion that dissociates is toxic to organism, and biocompatibility is not good, still can not become desirable bone substitution material.
The elastic modelling quantity of magnesium metal and biological bone are comparatively close, and magnesium ion is organism desired ion, but the activity of magnesium metal is high, even more serious by corrosion in body fluid in vivo.Hydroxyapatite is the excellent Bone Defect Repari of a kind of biocompatibility and alternate material, can be combined as a whole after implantable bioartificial body with biological bone, but the fragility of pottery limits its application in osseous tissue is replaced.
Tradition unitary type bio-medical material, as metal material, ceramic material, macromolecular material have application in organism, but as bone alternate material, has its limitation.Biomedical metallic material easily corrodes in vivo, and many metal ions are harmful, and metal fillings can cause surrounding biological tissue to change, in addition, metallic element to various organ metastasis, the problem such as cause that tissue metamorphosis reacts.The fragility of biomedical ceramics material determines its scope of application, and the intensity of macromolecular material is not high, also limit it and substitutes use in especially load-bearing bone substitution material at bone.
High compact solid often pursued by man-made structures material, but nature often selects born of the same parents' shape material as the structure body of macro-organism or plant.Nature bone is made up of the hone lamella of concentric arrays and havers' system, and skin is fine and close cortical bone, and internal layer is loose porous spongy bone.The major part of ripe bone is closely embedded in collagen matrices by hydroxyapatite crystal and forms, and therefore bone may be regarded as a double-phase composite in the base containing crystal.Therefore natural bone is also a kind of composite, but its each phase constituent has meticulousr organizational structure in crystal habit, orderly orientation, spatial distribution etc.According to the feature of nature bone, Cranial defect material should have heterogeneous body porous and be communicated with gradient-structure.
Summary of the invention
The technical problem that the present invention mainly solves: for the high activity of current conventional porous magnesio medical material due to magnesium, easily be subject to the corrosion of biological fluid, the magnesium ion that of dissociating is toxic to organism, poor biocompatibility, and hydroxyapatite is the good material of a kind of biocompatibility, but its fragility again limit the present situation of its application, provide a kind of utilization and be polymerized titanium fiber reinforcement porous magnesio, and the medical material on its surface is modified with hydroxyapatite deposition, this material is by polymerization titanium fiber, the ball milling of magnesium and potassium carbonate, compacting, sintering and the standby porous material that is enhanced of alkali infuse, again hydroxyapatite is coated on material surface by electrophoretic deposition set, both solved magnesium metal easily to dissociate noxious substance by corrosion in body fluid, with the defect of poor biocompatibility, solve again hydroxyapatite and be used alone the crisp deficiency of matter, it is a kind of well biological bone tissue alternate material.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
(1) 10 ~ 15g butyl titanate is got and 6 ~ 8g zinc acetate is dissolved in 50 ~ 60mL dimethyl formamide and 20 ~ 30mL dehydrated alcohol mixed liquor, stir with Glass rod, add 3 ~ 5g polyvinylpyrrolidone again and regulate viscosity of mixed liquid, be placed on magnetic stirrer, stir with the rotating speed of 300 ~ 400r/min and spend the night;
(2) high-voltage electrostatic spinning device hopper put into by the mixed liquor after above-mentioned stirring being spent the night, start HV generator, spinning liquid infusion pump extruded and sprayed by spinning nozzle, the mixed liquor jet of ejection is cured and forms polymerization titanium fiber, is arranged on collecting board with unordered shape;
(3) sieve gets the potassium carbonate powder that 500 ~ 600g crosses the magnesium powder after 100 ~ 130 mesh standard sieves and 100 ~ 200g one-size, planetary ball mill is put into by after both mix homogeneously, continue to add the above-mentioned polymerization titanium fiber prepared of 50 ~ 100g, add 10 ~ 20g tungsten carbide ball milling pearl, ball milling 1 ~ 2h under the protection of argon;
(4) under ball milling product being placed on press pressing plate, suppress with the pressure of 0.5 ~ 1MPa, after reaching predetermined pressure, pressurize 5 ~ 10min, obtain pressboard sample, plate sample is moved in high temperature sintering furnace, is filled with nitrogen, 650 ~ 700 DEG C are warming up to, heat preservation sintering 50 ~ 60min with the rate program of 5 ~ 8 DEG C/min;
(5) model after heat preservation sintering being immersed mass concentration is the sodium hydroxide solution of 40%, shaking table oscillating reactions 3 ~ 6h, until specimen surface bubble-free produces, put into baking oven after taking-up at 105 ~ 110 DEG C, be dried to constant weight obtained polymerization titanium fiber reinforced magnesium based porous materials;
(6) with emery paper, above-mentioned obtained polymerization titanium fiber reinforced magnesium base porous material surface is polished 1 ~ 3 time, put it in the dislodger of electrophoretic deposition equipment, add the calcium nitrate solution that mass concentration is 60% inwards, until the submergence of titanium fiber reinforced magnesium based porous materials will be polymerized, the concentration adding lime nitrate cumulative volume 2/3 is again the ammonium phosphate solution of 0.5mol/L, stirs with Glass rod;
(7) after stirring, be heated to 75 ~ 85 DEG C, add a graphite rod as anode, mg-based material is negative electrode, connect DC source, electric deep pulse amasss 1 ~ 2h, makes calcium hydroxy phosphate be deposited on material surface, use deionized water rinsing 3 ~ 5 times after taking out, after drying, namely obtain a kind of polymerization titanium fiber reinforcement porous magnesio medical material.
Described spinning jet curing be the aqueous solution that is made into for 5:1 in mass ratio using sulphuric acid and sodium sulfate as coagulating bath, spinning jet is solidified.
Embody rule method of the present invention: polymerization titanium fiber reinforcement porous magnesio medical material the present invention obtained makes emulation aggregate, first by its high-temperature disinfection treatment 3 ~ 5h at 600 DEG C, after being cooled to room temperature afterwards, by osteoblast (2 × 10
4) direct inoculation in emulation aggregate surface, in 37 DEG C of constant temperature and 5%CO
2humid air atmosphere under cultivate, detected cell number every 3 ~ 5 days, find that cell rate of increase reaches 30 ~ 40%, prove that this material can be used for viable transplantation.
The invention has the beneficial effects as follows: the present invention had both solved magnesium metal and easily to have dissociated noxious substance by corrosion in body fluid, with the defect of poor biocompatibility, solved again hydroxyapatite and was used alone the crisp deficiency of matter, is a kind of well biological bone tissue alternate material.
Detailed description of the invention
Get 10 ~ 15g butyl titanate and 6 ~ 8g zinc acetate is dissolved in 50 ~ 60mL dimethyl formamide and 20 ~ 30mL dehydrated alcohol mixed liquor, stir with Glass rod, add 3 ~ 5g polyvinylpyrrolidone again and regulate viscosity of mixed liquid, be placed on magnetic stirrer, stir with the rotating speed of 300 ~ 400r/min and spend the night; High-voltage electrostatic spinning device hopper put into by mixed liquor after above-mentioned stirring being spent the night, start HV generator, spinning liquid infusion pump extruded and sprayed by spinning nozzle, the mixed liquor jet of ejection is cured and forms polymerization titanium fiber, is arranged on collecting board with unordered shape; Sieve gets the potassium carbonate powder that 500 ~ 600g crosses the magnesium powder after 100 ~ 130 mesh standard sieves and 100 ~ 200g one-size, planetary ball mill is put into by after both mix homogeneously, continue to add the above-mentioned polymerization titanium fiber prepared of 50 ~ 100g, add 10 ~ 20g tungsten carbide ball milling pearl, ball milling 1 ~ 2h under the protection of argon; Under ball milling product is placed on press pressing plate, suppress with the pressure of 0.5 ~ 1MPa, after reaching predetermined pressure, pressurize 5 ~ 10min, obtain pressboard sample, plate sample is moved in high temperature sintering furnace, is filled with nitrogen, 650 ~ 700 DEG C are warming up to, heat preservation sintering 50 ~ 60min with the rate program of 5 ~ 8 DEG C/min; It is the sodium hydroxide solution of 40% that model after heat preservation sintering is immersed mass concentration, shaking table oscillating reactions 3 ~ 6h, until specimen surface bubble-free produces, put into baking oven after taking-up at 105 ~ 110 DEG C, be dried to constant weight obtained polymerization titanium fiber reinforced magnesium based porous materials; With emery paper by above-mentioned obtained polymerization titanium fiber reinforced magnesium base porous material surface polishing 1 ~ 3 time, put it in the dislodger of electrophoretic deposition equipment, add the calcium nitrate solution that mass concentration is 60% inwards, until the submergence of titanium fiber reinforced magnesium based porous materials will be polymerized, the concentration adding lime nitrate cumulative volume 2/3 is again the ammonium phosphate solution of 0.5mol/L, stirs with Glass rod; After stirring, be heated to 75 ~ 85 DEG C, add a graphite rod as anode, mg-based material is negative electrode, connect DC source, electric deep pulse amasss 1 ~ 2h, makes calcium hydroxy phosphate be deposited on material surface, use deionized water rinsing 3 ~ 5 times after taking out, after drying, namely obtain a kind of polymerization titanium fiber reinforcement porous magnesio medical material.
Described spinning jet curing be the aqueous solution that is made into for 5:1 in mass ratio using sulphuric acid and sodium sulfate as coagulating bath, spinning jet is solidified.
Example 1
Get 10g butyl titanate and 6 ~ 8g zinc acetate is dissolved in 50mL dimethyl formamide and 20mL dehydrated alcohol mixed liquor, stir with Glass rod, add 3g polyvinylpyrrolidone again and regulate viscosity of mixed liquid, be placed on magnetic stirrer, stir with the rotating speed of 300r/min and spend the night; High-voltage electrostatic spinning device hopper put into by mixed liquor after above-mentioned stirring being spent the night, start HV generator, spinning liquid infusion pump extruded and sprayed by spinning nozzle, the mixed liquor jet of ejection is cured and forms polymerization titanium fiber, is arranged on collecting board with unordered shape; Sieve gets the potassium carbonate powder that 500g crosses the magnesium powder after 100 mesh standard sieves and 100g one-size, planetary ball mill is put into by after both mix homogeneously, continue to add the above-mentioned polymerization titanium fiber prepared of 50g, add 10g tungsten carbide ball milling pearl, ball milling 1h under the protection of argon; Under ball milling product is placed on press pressing plate, suppress, after reaching predetermined pressure with the pressure of 0.5MPa, pressurize 5min, obtains pressboard sample, is moved into by plate sample in high temperature sintering furnace, be filled with nitrogen, be warming up to 650 DEG C with the rate program of 5 DEG C/min, heat preservation sintering 50min; It is the sodium hydroxide solution of 40% that model after heat preservation sintering is immersed mass concentration, shaking table oscillating reactions 3h, until specimen surface bubble-free produces, puts into baking oven at 105 DEG C, be dried to constant weight obtained polymerization titanium fiber reinforced magnesium based porous materials after taking-up; With emery paper, above-mentioned obtained polymerization titanium fiber reinforced magnesium base porous material surface is polished 1 time, put it in the dislodger of electrophoretic deposition equipment, add the calcium nitrate solution that mass concentration is 60% inwards, until the submergence of titanium fiber reinforced magnesium based porous materials will be polymerized, the concentration adding lime nitrate cumulative volume 2/3 is again the ammonium phosphate solution of 0.5mol/L, stirs with Glass rod; After stirring, be heated to 75 DEG C, add a graphite rod as anode, mg-based material is negative electrode, connect DC source, electric deep pulse amasss 1h, makes calcium hydroxy phosphate be deposited on material surface, use deionized water rinsing 3 times after taking out, after drying, namely obtain a kind of polymerization titanium fiber reinforcement porous magnesio medical material.
Described spinning jet curing be the aqueous solution that is made into for 5:1 in mass ratio using sulphuric acid and sodium sulfate as coagulating bath, spinning jet is solidified.
Embody rule method of the present invention: polymerization titanium fiber reinforcement porous magnesio medical material the present invention obtained makes emulation aggregate, first by its high-temperature disinfection treatment 3h at 600 DEG C, after being cooled to room temperature afterwards, by osteoblast (2 × 10
4) direct inoculation in emulation aggregate surface, in 37 DEG C of constant temperature and 5%CO
2humid air atmosphere under cultivate, detected cell number every 3 days, find that cell rate of increase reaches 30%, prove that this material can be used for viable transplantation.
Example 2
Get 13g butyl titanate and 7g zinc acetate is dissolved in 55mL dimethyl formamide and 25mL dehydrated alcohol mixed liquor, stir with Glass rod, add 4g polyvinylpyrrolidone again and regulate viscosity of mixed liquid, be placed on magnetic stirrer, stir with the rotating speed of 350r/min and spend the night; High-voltage electrostatic spinning device hopper put into by mixed liquor after above-mentioned stirring being spent the night, start HV generator, spinning liquid infusion pump extruded and sprayed by spinning nozzle, the mixed liquor jet of ejection is cured and forms polymerization titanium fiber, is arranged on collecting board with unordered shape; Sieve gets the potassium carbonate powder that 550g crosses the magnesium powder after 120 mesh standard sieves and 150g one-size, planetary ball mill is put into by after both mix homogeneously, continue to add the above-mentioned polymerization titanium fiber prepared of 80g, add 15g tungsten carbide ball milling pearl, ball milling 1h under the protection of argon; Under ball milling product is placed on press pressing plate, suppress, after reaching predetermined pressure with the pressure of 0.8MPa, pressurize 8min, obtains pressboard sample, is moved into by plate sample in high temperature sintering furnace, be filled with nitrogen, be warming up to 680 DEG C with the rate program of 7 DEG C/min, heat preservation sintering 55min; It is the sodium hydroxide solution of 40% that model after heat preservation sintering is immersed mass concentration, shaking table oscillating reactions 4h, until specimen surface bubble-free produces, puts into baking oven at 108 DEG C, be dried to constant weight obtained polymerization titanium fiber reinforced magnesium based porous materials after taking-up; With emery paper, above-mentioned obtained polymerization titanium fiber reinforced magnesium base porous material surface is polished 2 times, put it in the dislodger of electrophoretic deposition equipment, add the calcium nitrate solution that mass concentration is 60% inwards, until the submergence of titanium fiber reinforced magnesium based porous materials will be polymerized, the concentration adding lime nitrate cumulative volume 2/3 is again the ammonium phosphate solution of 0.5mol/L, stirs with Glass rod; After stirring, be heated to 80 DEG C, add a graphite rod as anode, mg-based material is negative electrode, connect DC source, electric deep pulse amasss 1 ~ 2h, makes calcium hydroxy phosphate be deposited on material surface, use deionized water rinsing 4 times after taking out, after drying, namely obtain a kind of polymerization titanium fiber reinforcement porous magnesio medical material.
Described spinning jet curing be the aqueous solution that is made into for 5:1 in mass ratio using sulphuric acid and sodium sulfate as coagulating bath, spinning jet is solidified.
Embody rule method of the present invention: polymerization titanium fiber reinforcement porous magnesio medical material the present invention obtained makes emulation aggregate, first by its high-temperature disinfection treatment 4h at 600 DEG C, after being cooled to room temperature afterwards, by osteoblast (2 × 10
4) direct inoculation in emulation aggregate surface, in 37 DEG C of constant temperature and 5%CO
2humid air atmosphere under cultivate, detected cell number every 4 days, find that cell rate of increase reaches 35%, prove that this material can be used for viable transplantation.
Example 3
Get 15g butyl titanate and 8g zinc acetate is dissolved in 60mL dimethyl formamide and 30mL dehydrated alcohol mixed liquor, stir with Glass rod, add 5g polyvinylpyrrolidone again and regulate viscosity of mixed liquid, be placed on magnetic stirrer, stir with the rotating speed of 400r/min and spend the night; High-voltage electrostatic spinning device hopper put into by mixed liquor after above-mentioned stirring being spent the night, start HV generator, spinning liquid infusion pump extruded and sprayed by spinning nozzle, the mixed liquor jet of ejection is cured and forms polymerization titanium fiber, is arranged on collecting board with unordered shape; Sieve gets the potassium carbonate powder that 600g crosses the magnesium powder after 130 mesh standard sieves and 200g one-size, planetary ball mill is put into by after both mix homogeneously, continue to add the above-mentioned polymerization titanium fiber prepared of 100g, add 20g tungsten carbide ball milling pearl, ball milling 2h under the protection of argon; Under ball milling product is placed on press pressing plate, suppress, after reaching predetermined pressure with the pressure of 1MPa, pressurize 10min, obtains pressboard sample, is moved into by plate sample in high temperature sintering furnace, be filled with nitrogen, be warming up to 700 DEG C with the rate program of 8 DEG C/min, heat preservation sintering 60min; It is the sodium hydroxide solution of 40% that model after heat preservation sintering is immersed mass concentration, shaking table oscillating reactions 6h, until specimen surface bubble-free produces, puts into baking oven at 110 DEG C, be dried to constant weight obtained polymerization titanium fiber reinforced magnesium based porous materials after taking-up; With emery paper, above-mentioned obtained polymerization titanium fiber reinforced magnesium base porous material surface is polished 3 times, put it in the dislodger of electrophoretic deposition equipment, add the calcium nitrate solution that mass concentration is 60% inwards, until the submergence of titanium fiber reinforced magnesium based porous materials will be polymerized, the concentration adding lime nitrate cumulative volume 2/3 is again the ammonium phosphate solution of 0.5mol/L, stirs with Glass rod; After stirring, be heated to 85 DEG C, add a graphite rod as anode, mg-based material is negative electrode, connect DC source, electric deep pulse amasss 2h, makes calcium hydroxy phosphate be deposited on material surface, use deionized water rinsing 5 times after taking out, after drying, namely obtain a kind of polymerization titanium fiber reinforcement porous magnesio medical material.
Described spinning jet curing be the aqueous solution that is made into for 5:1 in mass ratio using sulphuric acid and sodium sulfate as coagulating bath, spinning jet is solidified.
Embody rule method of the present invention: polymerization titanium fiber reinforcement porous magnesio medical material the present invention obtained makes emulation aggregate, first by its high-temperature disinfection treatment 5h at 600 DEG C, after being cooled to room temperature afterwards, by osteoblast (2 × 10
4) direct inoculation in emulation aggregate surface, in 37 DEG C of constant temperature and 5%CO
2humid air atmosphere under cultivate, detected cell number every 5 days, find that cell rate of increase reaches 40%, prove that this material can be used for viable transplantation.
Claims (2)
1. be polymerized a preparation method for titanium fiber reinforcement porous magnesio medical material, it is characterized in that concrete preparation process is:
(1) 10 ~ 15g butyl titanate is got and 6 ~ 8g zinc acetate is dissolved in 50 ~ 60mL dimethyl formamide and 20 ~ 30mL dehydrated alcohol mixed liquor, stir with Glass rod, add 3 ~ 5g polyvinylpyrrolidone again and regulate viscosity of mixed liquid, be placed on magnetic stirrer, stir with the rotating speed of 300 ~ 400r/min and spend the night;
(2) high-voltage electrostatic spinning device hopper put into by the mixed liquor after above-mentioned stirring being spent the night, start HV generator, spinning liquid infusion pump extruded and sprayed by spinning nozzle, the mixed liquor jet of ejection is cured and forms polymerization titanium fiber, is arranged on collecting board with unordered shape;
(3) sieve gets the potassium carbonate powder that 500 ~ 600g crosses the magnesium powder after 100 ~ 130 mesh standard sieves and 100 ~ 200g one-size, planetary ball mill is put into by after both mix homogeneously, continue to add the above-mentioned polymerization titanium fiber prepared of 50 ~ 100g, add 10 ~ 20 tungsten carbide ball milling pearls, ball milling 1 ~ 2h under the protection of argon;
(4) under ball milling product being placed on press pressing plate, suppress with the pressure of 0.5 ~ 1MPa, after reaching predetermined pressure, pressurize 5 ~ 10min, obtain pressboard sample, plate sample is moved in high temperature sintering furnace, is filled with nitrogen, 650 ~ 700 DEG C are warming up to, heat preservation sintering 50 ~ 60min with the rate program of 5 ~ 8 DEG C/min;
(5) model after heat preservation sintering being immersed mass concentration is the sodium hydroxide solution of 40%, shaking table oscillating reactions 3 ~ 6h, until specimen surface bubble-free produces, put into baking oven after taking-up at 105 ~ 110 DEG C, be dried to constant weight obtained polymerization titanium fiber reinforced magnesium based porous materials;
(6) with emery paper, above-mentioned obtained polymerization titanium fiber reinforced magnesium base porous material surface is polished 1 ~ 3 time, put it in the dislodger of electrophoretic deposition equipment, add the calcium nitrate solution that mass concentration is 60% inwards, until the submergence of titanium fiber reinforced magnesium based porous materials will be polymerized, the concentration adding lime nitrate cumulative volume 2/3 is again the ammonium phosphate solution of 0.5mol/L, stirs with Glass rod;
(7) after stirring, be heated to 75 ~ 85 DEG C, add a graphite rod as anode, mg-based material is negative electrode, connect DC source, electric deep pulse amasss 1 ~ 2h, makes calcium hydroxy phosphate be deposited on material surface, use deionized water rinsing 3 ~ 5 times after taking out, after drying, namely obtain a kind of polymerization titanium fiber reinforcement porous magnesio medical material.
2. a kind of preparation method of being polymerized titanium fiber reinforcement porous magnesio medical material according to claim 1, it is characterized in that: described spinning jet curing be the aqueous solution that is made into for 5:1 in mass ratio using sulphuric acid and sodium sulfate as coagulating bath, spinning jet is solidified.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107137773A (en) * | 2017-05-19 | 2017-09-08 | 广州迈普再生医学科技有限公司 | Three-dimensional porous composite of fiber base for Bone Defect Repari and preparation method thereof and products formed |
| CN110616388A (en) * | 2019-10-16 | 2019-12-27 | 上海晶维材料科技有限公司 | Preparation method of anti-pulverization block getter |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101879332A (en) * | 2010-07-13 | 2010-11-10 | 北京大学 | Polyether-ether-ketone composite material containing fluorapatite and titanium dioxide and preparation method thereof |
| CN104947008A (en) * | 2015-05-21 | 2015-09-30 | 太原理工大学 | Preparation method of carbon fiber reinforced magnesium matrix composite |
| CN105040146A (en) * | 2015-09-11 | 2015-11-11 | 江苏锦宇环境工程有限公司 | Preparing method for electrostatic spinning lignin/cellulose acetate nanometer composite material |
-
2015
- 2015-12-31 CN CN201511015329.6A patent/CN105477681A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101879332A (en) * | 2010-07-13 | 2010-11-10 | 北京大学 | Polyether-ether-ketone composite material containing fluorapatite and titanium dioxide and preparation method thereof |
| CN104947008A (en) * | 2015-05-21 | 2015-09-30 | 太原理工大学 | Preparation method of carbon fiber reinforced magnesium matrix composite |
| CN105040146A (en) * | 2015-09-11 | 2015-11-11 | 江苏锦宇环境工程有限公司 | Preparing method for electrostatic spinning lignin/cellulose acetate nanometer composite material |
Non-Patent Citations (2)
| Title |
|---|
| 孙红霞: "多孔镁的制备及镁合金表面磷酸钙涂层的研究", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》 * |
| 李育仁: "静电纺丝制备二氧化钛基复合纳米材料及其光催化性质研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107137773A (en) * | 2017-05-19 | 2017-09-08 | 广州迈普再生医学科技有限公司 | Three-dimensional porous composite of fiber base for Bone Defect Repari and preparation method thereof and products formed |
| CN107137773B (en) * | 2017-05-19 | 2020-04-07 | 广州迈普再生医学科技股份有限公司 | Fiber-based three-dimensional porous composite material for bone repair, preparation method thereof and molded product |
| CN110616388A (en) * | 2019-10-16 | 2019-12-27 | 上海晶维材料科技有限公司 | Preparation method of anti-pulverization block getter |
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Application publication date: 20160413 |