CN108264373A - The preparation method of medical reinforced porous biological ceramic material - Google Patents

The preparation method of medical reinforced porous biological ceramic material Download PDF

Info

Publication number
CN108264373A
CN108264373A CN201810115411.3A CN201810115411A CN108264373A CN 108264373 A CN108264373 A CN 108264373A CN 201810115411 A CN201810115411 A CN 201810115411A CN 108264373 A CN108264373 A CN 108264373A
Authority
CN
China
Prior art keywords
parts
ceramic material
biological ceramic
reinforced porous
porous biological
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201810115411.3A
Other languages
Chinese (zh)
Inventor
付主枝
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201810115411.3A priority Critical patent/CN108264373A/en
Publication of CN108264373A publication Critical patent/CN108264373A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • 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
    • A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
    • 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
    • A61L27/10—Ceramics or glasses
    • 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
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • 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
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61L27/14—Macromolecular materials
    • A61L27/20—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/636—Polysaccharides or derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/40—Porous or lightweight materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • C04B2235/3472—Alkali metal alumino-silicates other than clay, e.g. spodumene, alkali feldspars such as albite or orthoclase, micas such as muscovite, zeolites such as natrolite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • C04B2235/3481—Alkaline earth metal alumino-silicates other than clay, e.g. cordierite, beryl, micas such as margarite, plagioclase feldspars such as anorthite, zeolites such as chabazite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density

Abstract

The invention discloses the preparation methods of medical reinforced porous biological ceramic material, the technique is by lauryl amine base sodium sulfonate, ammonium chloride, iron oxide, hydroxypropyl methyl cellulose, polysiloxanes, thiodipropionic acid dilauryl cinnamic acid ester etc. carries out compressive reaction, add the organic components of lubricant and antifoaming agent making material, then ball-milling technology is utilized by hydroxyapatite, baryta fledspar, lepidolite, the mixture of raw material such as diatomite are ground, it is dry, activation, cross screening and choosing, prepare ceramic masterbatch, above-mentioned organic components and ceramic masterbatch are further subjected to progressive sintering step by step, finally it is granulated using twin-screw extrusion technology, vacuum dehydration, plastotype, high pressure steam sterilization and etc. medical reinforced porous biological ceramic material is prepared.The medical reinforced porous biological ceramic material being prepared, safe and non-toxic, density is gently, porous breathable is good, compression strength is high, has preferable application prospect.

Description

The preparation method of medical reinforced porous biological ceramic material
Technical field
The present invention relates to this technical fields of material, are related specifically to the preparation of medical reinforced porous biological ceramic material Method.
Background technology
As inorganic porous product for clinical purposes, for example, by calcining or being sintered the more of bioceramic acquisition Hole ceramics are known.However, when being used in the application of the shelf such as rebuild for live body bone tissue, prosthetic material or the like When, due to such porous ceramics show it is hard but it is crisp the shortcomings that, so always have after surgery due to slight collision and Cause the danger of damage.In addition, in field of surgery, processing and change the shape of porous ceramics come match live body bone tissue by The shape of the part of damage is also difficult.Further, since 10 years or more extended time cycle are required in some cases, Until it is substituted completely by live body bone, so keeping the danger for causing adverse effect by its damage during the period.So In order to avoid the risk of above-mentioned adverse effect to greatest extent, this invention address that research medical reinforced porous biological ceramic material Material is combined by optimizing various material combinations and proportioning, is optimized to simplify to prepare and be tempted so that the bioceramic material being prepared Reduce brittleness on the basis of hard, and it is safe and non-toxic, density is light, porous breathable is good, compression strength is high, have preferable Application prospect.
Invention content
In order to solve the above technical problems, the invention discloses the preparation method of medical reinforced porous biological ceramic material, The technique is by lauryl amine base sodium sulfonate, ammonium chloride, iron oxide, hydroxypropyl methyl cellulose, polysiloxanes, thiodipropionic acid dilauryl Cinnamic acid ester etc. carries out compressive reaction, adds the organic components of lubricant and antifoaming agent making material, then will using ball-milling technology The mixture of raw material such as hydroxyapatite, baryta fledspar, lepidolite, diatomite are ground, dry, activating, crossing screening and choosing, prepare Above-mentioned organic components and ceramic masterbatch are further carried out progressive sintering step by step, finally utilize twin-screw extrusion skill by ceramic masterbatch Art is granulated, vacuum dehydration, plastotype, high pressure steam sterilization and etc. medical reinforced porous biological ceramic material is prepared Material.The medical reinforced porous biological ceramic material being prepared, safe and non-toxic, density is light, porous breathable is good, pressure resistance Degree is high, has preferable application prospect.
The purpose of the present invention can be achieved through the following technical solutions：
The preparation method of medical reinforced porous biological ceramic material, includes the following steps：
(1) by 3-8 parts of lauryl amine base sodium sulfonate, 1-6 parts of ammonium chloride, 3-6 parts of iron oxide, hydroxypropyl methyl cellulose 4-6 Compressive reaction, reaction temperature are carried out in 1-3 parts of part, 3-4 parts of polysiloxanes, thiodipropionic acid dilauryl cinnamic acid ester mixed injection Muffle furnaces It is 105 DEG C to spend, and pressure is set as 8MPa, sustained response 5h, then adds in 1-3 parts of lubricant, 1-2 parts of antifoaming agent, lasting to stir 50min, reduction of blood pressure in high-speed to normal pressure, heat preservation are spare；
(2) by 1-4 parts of 4-9 parts of hydroxyapatite, 3-7 parts of baryta fledspar, 6-9 parts of lepidolite, diatomite mixing, ball milling 20- It is 24 hours, then continuous drying at a temperature of 70-80 DEG C in electric vacunm drying case, after being completely dried in inert gas flow Sieving, sealing are spare；
(3) three-step approach sintering will be carried out in the reactant of step (1) and the sieving of step (2) injection vacuum sintering furnace, First step sintering keeps the temperature 30min, second step is sintered with 5 DEG C/min's with the heating rate of 10 DEG C/min to 100-110 DEG C of heat preservation Heating rate is warming up to 130-135 DEG C, keeps the temperature 30min, and third step sintering keeps the temperature 12-18h controlled at 150-160 DEG C；
(4) the reaction paste injection double screw extruder in step (3) is squeezed, obtains masterbatch；
(5) by the masterbatch in step (4) through vacuum dehydration, plastotype, high pressure steam sterilization, 65 DEG C of dryings, pack up into Product.
Preferably, the lubricant in the step (1) is ethylene glycol, polyethylene glycol, silicone oil, one kind in glycerine or several Kind.
Preferably, the antifoaming agent in the step (1) is octadecyl alcolol stearate and triethanolamine stearate mass ratio 1:1 Mixed liquor.
Preferably, the inert gas in the step (2) is argon gas.
Preferably, the mesh size of crossing in the step (2) is 7000 mesh.
Preferably, in the step (4) double-screw extruder screw temperature be 180-200 DEG C, rotating speed for 500-700 turn/ Minute.
Preferably, to be increased to 450mmHg in 1min, dewatering time is the vacuum meter parameter in the step (5) 90sec。
Preferably, the high pressure steam sterilization parameter in the step (5) is pressure 103.4kPa, and 121.3 DEG C of temperature sterilizes Time is 20min.
Compared with prior art, the present invention advantage is：
(1) preparation method of medical reinforced porous biological ceramic material of the invention is by lauryl amine base sodium sulfonate, chlorination Ammonium, iron oxide, hydroxypropyl methyl cellulose, polysiloxanes, thiodipropionic acid dilauryl cinnamic acid ester etc. carry out compressive reaction, addition profit The organic components of lubrication prescription and antifoaming agent making material, then using ball-milling technology by hydroxyapatite, baryta fledspar, lepidolite, silicon The mixture of raw material such as diatomaceous earth are ground, dry, activating, crossing screening and choosing, prepare ceramic masterbatch, further have unit by above-mentioned Part and ceramic masterbatch carry out progressive sintering step by step, be finally granulated using twin-screw extrusion technology, vacuum dehydration, plastotype, height Pressure steam sterilizing and etc. medical reinforced porous biological ceramic material is prepared.The medical reinforced porous life being prepared Object ceramic material, safe and non-toxic, density is gently, porous breathable is good, compression strength is high, has preferable application prospect.
(2) medical reinforced porous biological ceramic material feedstock of the invention is easy to get, is simple for process, suitable for large-scale industry Change and use, it is highly practical.
Specific embodiment
The technical solution of invention is described in detail with reference to specific embodiment.
Embodiment 1
(1) by 3 parts of lauryl amine base sodium sulfonate, 1 part of ammonium chloride, 3 parts of iron oxide, 4 parts of hydroxypropyl methyl cellulose, poly- silica Compressive reaction is carried out in 1 part of 3 parts of alkane, thiodipropionic acid dilauryl cinnamic acid ester mixed injection Muffle furnace, reaction temperature is 105 DEG C, pressure 8MPa, sustained response 5h are set as by force, 1 part of ethylene glycol, 1 part of antifoaming agent is then added in, persistently stirs 50min, reduction of blood pressure in high-speed is extremely Normal pressure, heat preservation is spare, and wherein antifoaming agent is octadecyl alcolol stearate and triethanolamine stearate mass ratio 1:1 mixed liquor；
(2) 4 parts of hydroxyapatite, 3 parts of baryta fledspar, 6 parts of lepidolite, 1 part of diatomite are mixed, ball milling 20 hours, then It is continuous drying at a temperature of 70-80 DEG C in electric vacunm drying case, it is sieved in an argon stream after being completely dried, crossing mesh size is 7000 mesh, sealing are spare；
(3) three-step approach sintering will be carried out in the reactant of step (1) and the sieving of step (2) injection vacuum sintering furnace, First step sintering keeps the temperature 30min, second step is sintered with 5 DEG C/min's with the heating rate of 10 DEG C/min to 100-110 DEG C of heat preservation Heating rate is warming up to 130-135 DEG C, keeps the temperature 30min, and third step sintering keeps the temperature 12h controlled at 150-160 DEG C；
(4) the reaction paste injection double screw extruder in step (3) is squeezed, double-screw extruder screw temperature is 180 DEG C, rotating speed is 500 revs/min, obtains masterbatch；
(5) by the masterbatch in step (4) through vacuum dehydration, plastotype, high pressure steam sterilization, 65 DEG C of dryings, pack up into Product, wherein vacuum meter parameter are pressure to be increased to 450mmHg, dewatering time 90sec, high pressure steam sterilization parameter in 1min 103.4kPa, 121.3 DEG C of temperature, sterilization time 20min.
The performance test results of medical reinforced porous biological ceramic material obtained are as shown in table 1.
Embodiment 2
(1) by 5 parts of lauryl amine base sodium sulfonate, 3 parts of ammonium chloride, 4 parts of iron oxide, 4 parts of hydroxypropyl methyl cellulose, poly- silica Compressive reaction is carried out in 1 part of 3 parts of alkane, thiodipropionic acid dilauryl cinnamic acid ester mixed injection Muffle furnace, reaction temperature is 105 DEG C, pressure 8MPa, sustained response 5h are set as by force, 2 parts of polyethylene glycol, 1 part of antifoaming agent is then added in, persistently stirs 50min, reduction of blood pressure in high-speed To normal pressure, heat preservation is spare, and wherein antifoaming agent is octadecyl alcolol stearate and triethanolamine stearate mass ratio 1:1 mixed liquor；
(2) 5 parts of hydroxyapatite, 4 parts of baryta fledspar, 7 parts of lepidolite, 2 parts of diatomite are mixed, ball milling 21 hours, then It is continuous drying at a temperature of 70-80 DEG C in electric vacunm drying case, it is sieved in an argon stream after being completely dried, crossing mesh size is 7000 mesh, sealing are spare；
(3) three-step approach sintering will be carried out in the reactant of step (1) and the sieving of step (2) injection vacuum sintering furnace, First step sintering keeps the temperature 30min, second step is sintered with 5 DEG C/min's with the heating rate of 10 DEG C/min to 100-110 DEG C of heat preservation Heating rate is warming up to 130-135 DEG C, keeps the temperature 30min, and third step sintering keeps the temperature 14h controlled at 150-160 DEG C；
(4) the reaction paste injection double screw extruder in step (3) is squeezed, double-screw extruder screw temperature is 190 DEG C, rotating speed is 600 revs/min, obtains masterbatch；
(5) by the masterbatch in step (4) through vacuum dehydration, plastotype, high pressure steam sterilization, 65 DEG C of dryings, pack up into Product, wherein vacuum meter parameter are pressure to be increased to 450mmHg, dewatering time 90sec, high pressure steam sterilization parameter in 1min 103.4kPa, 121.3 DEG C of temperature, sterilization time 20min.
The performance test results of medical reinforced porous biological ceramic material obtained are as shown in table 1.
Embodiment 3
(1) by 6 parts of lauryl amine base sodium sulfonate, 5 parts of ammonium chloride, 5 parts of iron oxide, 5 parts of hydroxypropyl methyl cellulose, poly- silica Compressive reaction is carried out in 2 parts of 4 parts of alkane, thiodipropionic acid dilauryl cinnamic acid ester mixed injection Muffle furnaces, reaction temperature is 105 DEG C, pressure 8MPa, sustained response 5h are set as by force, 2 parts of silicone oil, 2 parts of antifoaming agent is then added in, persistently stirs 50min, reduction of blood pressure in high-speed is to normal Pressure, heat preservation is spare, and wherein antifoaming agent is octadecyl alcolol stearate and triethanolamine stearate mass ratio 1:1 mixed liquor；
(2) 7 parts of hydroxyapatite, 6 parts of baryta fledspar, 8 parts of lepidolite, 3 parts of diatomite are mixed, ball milling 22 hours, then It is continuous drying at a temperature of 70-80 DEG C in electric vacunm drying case, it is sieved in an argon stream after being completely dried, crossing mesh size is 7000 mesh, sealing are spare；
(3) three-step approach sintering will be carried out in the reactant of step (1) and the sieving of step (2) injection vacuum sintering furnace, First step sintering keeps the temperature 30min, second step is sintered with 5 DEG C/min's with the heating rate of 10 DEG C/min to 100-110 DEG C of heat preservation Heating rate is warming up to 130-135 DEG C, keeps the temperature 30min, and third step sintering keeps the temperature 16h controlled at 150-160 DEG C；
(4) the reaction paste injection double screw extruder in step (3) is squeezed, double-screw extruder screw temperature is 190 DEG C, rotating speed is 600 revs/min, obtains masterbatch；
(5) by the masterbatch in step (4) through vacuum dehydration, plastotype, high pressure steam sterilization, 65 DEG C of dryings, pack up into Product, wherein vacuum meter parameter are pressure to be increased to 450mmHg, dewatering time 90sec, high pressure steam sterilization parameter in 1min 103.4kPa, 121.3 DEG C of temperature, sterilization time 20min.
The performance test results of medical reinforced porous biological ceramic material obtained are as shown in table 1.
Embodiment 4
(1) by 8 parts of lauryl amine base sodium sulfonate, 6 parts of ammonium chloride, 6 parts of iron oxide, 6 parts of hydroxypropyl methyl cellulose, poly- silica Compressive reaction is carried out in 3 parts of 4 parts of alkane, thiodipropionic acid dilauryl cinnamic acid ester mixed injection Muffle furnaces, reaction temperature is 105 DEG C, pressure 8MPa, sustained response 5h are set as by force, 3 parts of glycerine, 2 parts of antifoaming agent is then added in, persistently stirs 50min, reduction of blood pressure in high-speed is extremely Normal pressure, heat preservation is spare, and wherein antifoaming agent is octadecyl alcolol stearate and triethanolamine stearate mass ratio 1:1 mixed liquor；
(2) 9 parts of hydroxyapatite, 7 parts of baryta fledspar, 9 parts of lepidolite, 4 parts of diatomite are mixed, ball milling 24 hours, then It is continuous drying at a temperature of 70-80 DEG C in electric vacunm drying case, it is sieved in an argon stream after being completely dried, crossing mesh size is 7000 mesh, sealing are spare；
(3) three-step approach sintering will be carried out in the reactant of step (1) and the sieving of step (2) injection vacuum sintering furnace, First step sintering keeps the temperature 30min, second step is sintered with 5 DEG C/min's with the heating rate of 10 DEG C/min to 100-110 DEG C of heat preservation Heating rate is warming up to 130-135 DEG C, keeps the temperature 30min, and third step sintering keeps the temperature 18h controlled at 150-160 DEG C；
(4) the reaction paste injection double screw extruder in step (3) is squeezed, double-screw extruder screw temperature is 200 DEG C, rotating speed is 700 revs/min, obtains masterbatch；
(5) by the masterbatch in step (4) through vacuum dehydration, plastotype, high pressure steam sterilization, 65 DEG C of dryings, pack up into Product, wherein vacuum meter parameter are pressure to be increased to 450mmHg, dewatering time 90sec, high pressure steam sterilization parameter in 1min 103.4kPa, 121.3 DEG C of temperature, sterilization time 20min.
The performance test results of medical reinforced porous biological ceramic material obtained are as shown in table 1.
Comparative example 1
(1) by 3 parts of lauryl amine base sodium sulfonate, 1 part of ammonium chloride, 3 parts of iron oxide, 4 parts of hydroxypropyl methyl cellulose, poly- silica It is reacted in 3 parts of mixed injection Muffle furnaces of alkane, reaction temperature is 105 DEG C, sustained response 5h, then adds in 1 part of ethylene glycol, disappears 1 part of infusion persistently stirs 50min, and heat preservation is spare, and wherein antifoaming agent is octadecyl alcolol stearate and triethanolamine stearate quality Than 1:1 mixed liquor；
(2) 4 parts of hydroxyapatite, 3 parts of baryta fledspar, 6 parts of lepidolite, 1 part of diatomite are mixed, ball milling 20 hours, then It is continuous drying at a temperature of 70-80 DEG C in electric vacunm drying case, it is sieved in an argon stream after being completely dried, crossing mesh size is 7000 mesh, sealing are spare；
(3) three-step approach sintering will be carried out in the reactant of step (1) and the sieving of step (2) injection vacuum sintering furnace, First step sintering keeps the temperature 30min, second step is sintered with 5 DEG C/min's with the heating rate of 10 DEG C/min to 100-110 DEG C of heat preservation Heating rate is warming up to 130-135 DEG C, keeps the temperature 30min, and third step sintering keeps the temperature 12h controlled at 150-160 DEG C；
(4) the reaction paste injection double screw extruder in step (3) is squeezed, double-screw extruder screw temperature is 180 DEG C, rotating speed is 500 revs/min, obtains masterbatch；
(5) by the masterbatch in step (4) through vacuum dehydration, plastotype, high pressure steam sterilization, 65 DEG C of dryings, pack up into Product, wherein vacuum meter parameter are pressure to be increased to 450mmHg, dewatering time 90sec, high pressure steam sterilization parameter in 1min 103.4kPa, 121.3 DEG C of temperature, sterilization time 20min.
The performance test results of medical reinforced porous biological ceramic material obtained are as shown in table 1.
Comparative example 2
(1) by 8 parts of lauryl amine base sodium sulfonate, 6 parts of ammonium chloride, 6 parts of iron oxide, 6 parts of hydroxypropyl methyl cellulose, poly- silica Compressive reaction is carried out in 3 parts of 4 parts of alkane, thiodipropionic acid dilauryl cinnamic acid ester mixed injection Muffle furnaces, reaction temperature is 105 DEG C, pressure 8MPa, sustained response 5h are set as by force, 3 parts of glycerine, 2 parts of antifoaming agent is then added in, persistently stirs 50min, reduction of blood pressure in high-speed is extremely Normal pressure, heat preservation is spare, and wherein antifoaming agent is octadecyl alcolol stearate and triethanolamine stearate mass ratio 1:1 mixed liquor；
(2) 9 parts of hydroxyapatite, 7 parts of baryta fledspar, 9 parts of lepidolite, 4 parts of diatomite are mixed, ball milling 24 hours, then The continuous drying rear sieving at a temperature of 70-80 DEG C in electric vacunm drying case, it is 7000 mesh to cross mesh size, and sealing is spare；
(3) three-step approach sintering will be carried out in the reactant of step (1) and the sieving of step (2) injection vacuum sintering furnace, First step sintering keeps the temperature 30min, second step is sintered with 5 DEG C/min's with the heating rate of 10 DEG C/min to 100-110 DEG C of heat preservation Heating rate is warming up to 130-135 DEG C, keeps the temperature 30min, and third step sintering keeps the temperature 18h controlled at 150-160 DEG C；
(4) the reaction paste injection double screw extruder in step (3) is squeezed, double-screw extruder screw temperature is 200 DEG C, rotating speed is 700 revs/min, obtains masterbatch；
(5) by the masterbatch in step (4) through vacuum dehydration, plastotype, high pressure steam sterilization, 65 DEG C of dryings, pack up into Product, wherein vacuum meter parameter are pressure to be increased to 450mmHg, dewatering time 90sec, high pressure steam sterilization parameter in 1min 103.4kPa, 121.3 DEG C of temperature, sterilization time 20min.
The performance test results of medical reinforced porous biological ceramic material obtained are as shown in table 1.
By the medical reinforced porous biological ceramic material obtained of embodiment 1-4 and comparative example 1-2 respectively into line density, Bending strength, hardness, cytotoxicity (animal) this several performance tests.
Table 1
The present invention medical reinforced porous biological ceramic material preparation method by lauryl amine base sodium sulfonate, ammonium chloride, Iron oxide, hydroxypropyl methyl cellulose, polysiloxanes, thiodipropionic acid dilauryl cinnamic acid ester etc. carry out compressive reaction, addition lubrication Agent and the organic components of antifoaming agent making material, then using ball-milling technology by hydroxyapatite, baryta fledspar, lepidolite, diatom The mixture of raw material such as soil are ground, dry, activating, crossing screening and choosing, ceramic masterbatch are prepared, further by above-mentioned organic components With ceramic masterbatch carry out progressive sintering step by step, be finally granulated using twin-screw extrusion technology, vacuum dehydration, plastotype, high pressure Steam sterilizing and etc. medical reinforced porous biological ceramic material is prepared.The medical reinforced porous biology being prepared Ceramic material, safe and non-toxic, density is gently, porous breathable is good, compression strength is high, has preferable application prospect.The present invention Medical reinforced porous biological ceramic material feedstock be easy to get, be simple for process, suitable for heavy industrialization use, it is highly practical.
The foregoing is merely the embodiment of the present invention, are not intended to limit the scope of the invention, every to utilize this hair The equivalent structure or equivalent flow shift that bright description is made directly or indirectly is used in other relevant technology necks Domain is included within the scope of the present invention.

Claims (8)

1. the preparation method of medical reinforced porous biological ceramic material, which is characterized in that include the following steps：
(1) by 3-8 parts of lauryl amine base sodium sulfonate, 1-6 parts of ammonium chloride, 3-6 parts of iron oxide, 4-6 parts of hydroxypropyl methyl cellulose, poly- Compressive reaction is carried out in 1-3 parts of 3-4 parts of siloxanes, thiodipropionic acid dilauryl cinnamic acid ester mixed injection Muffle furnaces, reaction temperature is 105 DEG C, pressure is set as 8MPa, sustained response 5h, then adds in 1-3 parts of lubricant, 1-2 parts of antifoaming agent, lasting to stir 50min, reduction of blood pressure in high-speed to normal pressure, heat preservation are spare；
(2) 4-9 parts of hydroxyapatite, 3-7 parts of baryta fledspar, 6-9 parts of lepidolite, 1-4 parts of diatomite are mixed, ball milling 20-24 is small When, it is then continuous drying at a temperature of 70-80 DEG C in electric vacunm drying case, after being completely dried in inert gas flow mistake Sieve, sealing are spare；
(3) will the reactant of step (1) and the sieving of step (2) injection vacuum sintering furnace in carry out three-step approach sintering, first Step sintering keeps the temperature 30min, second step is sintered with the heating of 5 DEG C/min with the heating rate of 10 DEG C/min to 100-110 DEG C of heat preservation Speed is warming up to 130-135 DEG C, keeps the temperature 30min, and third step sintering keeps the temperature 12-18h controlled at 150-160 DEG C；
(4) the reaction paste injection double screw extruder in step (3) is squeezed, obtains masterbatch；
(5) masterbatch in step (4) is got product through vacuum dehydration, plastotype, high pressure steam sterilization, 65 DEG C of dryings, packaging.
2. the preparation method of medical reinforced porous biological ceramic material according to claim 1, which is characterized in that described Lubricant in step (1) is one or more of ethylene glycol, polyethylene glycol, silicone oil, glycerine.
3. the preparation method of medical reinforced porous biological ceramic material according to claim 1, which is characterized in that described Antifoaming agent in step (1) is octadecyl alcolol stearate and triethanolamine stearate mass ratio 1:1 mixed liquor.
4. the preparation method of medical reinforced porous biological ceramic material according to claim 1, which is characterized in that described Inert gas in step (2) is argon gas.
5. the preparation method of medical reinforced porous biological ceramic material according to claim 1, which is characterized in that described Mesh size of crossing in step (2) is 7000 mesh.
6. the preparation method of medical reinforced porous biological ceramic material according to claim 1, which is characterized in that described Double-screw extruder screw temperature is 180-200 DEG C in step (4), and rotating speed is 500-700 revs/min.
7. the preparation method of medical reinforced porous biological ceramic material according to claim 1, which is characterized in that described Vacuum meter parameter in step (5) is is increased to 450mmHg, dewatering time 90sec in 1min.
8. the preparation method of medical reinforced porous biological ceramic material according to claim 1, which is characterized in that described High pressure steam sterilization parameter in step (5) is pressure 103.4kPa, 121.3 DEG C of temperature, sterilization time 20min.
CN201810115411.3A 2018-02-06 2018-02-06 The preparation method of medical reinforced porous biological ceramic material Withdrawn CN108264373A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810115411.3A CN108264373A (en) 2018-02-06 2018-02-06 The preparation method of medical reinforced porous biological ceramic material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810115411.3A CN108264373A (en) 2018-02-06 2018-02-06 The preparation method of medical reinforced porous biological ceramic material

Publications (1)

Publication Number Publication Date
CN108264373A true CN108264373A (en) 2018-07-10

Family

ID=62773525

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810115411.3A Withdrawn CN108264373A (en) 2018-02-06 2018-02-06 The preparation method of medical reinforced porous biological ceramic material

Country Status (1)

Country Link
CN (1) CN108264373A (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6364981A (en) * 1986-09-03 1988-03-23 三菱化学株式会社 Manufacture of porous ceramic sintered body
CN1712070A (en) * 2004-06-25 2005-12-28 中南大学 Production of gene carrier and use thereof
US20060199876A1 (en) * 2005-03-04 2006-09-07 The University Of British Columbia Bioceramic composite coatings and process for making same
CN1850293A (en) * 2006-04-26 2006-10-25 卢建熙 Medical reinforced porous biological ceramic, its preparing method and use
CN102316911A (en) * 2009-02-10 2012-01-11 阿祖瑞博有限公司 Bone-regeneration material based on the combination of monetite and other biologically actived calcium and silicon compound
CN103341206A (en) * 2013-06-09 2013-10-09 四川大学 Calcium phosphate/collagen/bone-like apatite three-level bionic bone tissue engineering scaffold and preparation method thereof
CN106587937A (en) * 2016-12-07 2017-04-26 苏州洛特兰新材料科技有限公司 High-strength carbon fiber based composite ceramic material and preparation method thereof
CN106999356A (en) * 2014-10-02 2017-08-01 波利皮得有限公司 Composition and method for treating and preventing surgical site infection

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6364981A (en) * 1986-09-03 1988-03-23 三菱化学株式会社 Manufacture of porous ceramic sintered body
CN1712070A (en) * 2004-06-25 2005-12-28 中南大学 Production of gene carrier and use thereof
US20060199876A1 (en) * 2005-03-04 2006-09-07 The University Of British Columbia Bioceramic composite coatings and process for making same
CN1850293A (en) * 2006-04-26 2006-10-25 卢建熙 Medical reinforced porous biological ceramic, its preparing method and use
CN102316911A (en) * 2009-02-10 2012-01-11 阿祖瑞博有限公司 Bone-regeneration material based on the combination of monetite and other biologically actived calcium and silicon compound
CN103341206A (en) * 2013-06-09 2013-10-09 四川大学 Calcium phosphate/collagen/bone-like apatite three-level bionic bone tissue engineering scaffold and preparation method thereof
CN106999356A (en) * 2014-10-02 2017-08-01 波利皮得有限公司 Composition and method for treating and preventing surgical site infection
CN106587937A (en) * 2016-12-07 2017-04-26 苏州洛特兰新材料科技有限公司 High-strength carbon fiber based composite ceramic material and preparation method thereof

Similar Documents

Publication Publication Date Title
WO2018072679A1 (en) Biomimetic biomineralized artificial bone repair material and preparation method therefor and use thereof
CN106999635A (en) Repair of cartilage graft support and its manufacture method
CN109718197B (en) Magnetic injectable hydrogel, preparation method and application
KR100807108B1 (en) Preparation method of porous ?-tricalcium phosphate granules
CN110721346B (en) Biological 3D printing ink and preparation method thereof
CN105705171B (en) Pass through the raw body material substance for naturally be crosslinked reinforcing its rubber properties physical property and its manufacturing method and application method of collagen and sodium hyaluronate
CN105949690A (en) Quickly-formed high-strength hydrogel and preparation method thereof
CN102895215A (en) Cellulose and red alga polysaccharide plant empty capsule and raw material composition and preparation method thereof
CN104844810A (en) Pulullan-human-like collagen hydrogel and preparation method thereof
CN107032775A (en) A kind of nanometer hydroxyapatite, dicalcium silicate composite boilogical ceramic and its preparation method and application
CN106110395A (en) A kind of bone repairing support with selfreparing, antibiotic effect and preparation method thereof
CN106866128A (en) A kind of bioceramic material and preparation method
CN108264373A (en) The preparation method of medical reinforced porous biological ceramic material
CN109205581A (en) A kind of preparation method of the composite hydroxylapatite powder with photo-thermal Synergistic antimicrobial performance
CN104984387A (en) Honeycomb bracket material for bone tissue engineering and preparation method of honeycomb bracket
BRPI0819960B1 (en) tissue repair devices prepared from fish scales and methods for preparing them
CN106747566A (en) A kind of preparation method of new mg-doped bioceramic porous material
CN102895703A (en) Decalcified bone matrix material and preparation method thereof
Zainuddin et al. Conceptual framework of hydroxyapatite for damaged skull through design approach
CN102805879A (en) Preparation method for biogenic fluorinated porcine hydroxyapatite (FPHA) bone substitution material
CN104984401A (en) Preparation method of temperature-sensitive hydrogel/tricalcium phosphate material
CN102660049A (en) Method and device for preparing temperature-induced reversible color-changing bacterial cellulose composite membrane
CN106924090B (en) A kind of preparation and application of the immobilized lysozyme toothpaste of multistage hole bioactive glass
CN107998387A (en) A kind of medical porous Al (OH)3The preparation method and applications of adjuvant
CN108178622A (en) Add the preparation method of the composite bioceramic material of mineral collagen

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20180710

WW01 Invention patent application withdrawn after publication