CN108793845A - A kind of calcium phosphate bioactive ceramics and preparation method thereof - Google Patents

A kind of calcium phosphate bioactive ceramics and preparation method thereof Download PDF

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CN108793845A
CN108793845A CN201810732793.4A CN201810732793A CN108793845A CN 108793845 A CN108793845 A CN 108793845A CN 201810732793 A CN201810732793 A CN 201810732793A CN 108793845 A CN108793845 A CN 108793845A
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叶露穗
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    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/001Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing unburned clay
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/12Phosphorus-containing materials, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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    • C04B38/00Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/10Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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    • C04B2111/00241Physical properties of the materials not provided for elsewhere in C04B2111/00
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    • C04B2111/00379Materials containing oriented fillers or elements the oriented elements being fibres
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Abstract

A kind of calcium phosphate bioactive ceramics of present invention proposition and preparation method thereof, it is respectively formed pore structure on two opposite sides of calcium phosphate bioactive ceramics, and the hole connection setting on two sides, with larger contact area, improve its bioactivity ability, and the bioactive ceramics are prepared using cleverly method, make the pore structure self-assembling formation formed thereon, is conducive to improve its bioactivity ability.

Description

A kind of calcium phosphate bioactive ceramics and preparation method thereof
Technical field
The present invention relates to field of biomedical materials, and in particular to a kind of calcium phosphate bioactive ceramics and its preparation side Method.
Background technology
Bioactive materials with " active repair function " and " controlling biological response characteristic " are just as currently and not Carry out the important development direction of hard tissue repair.The concept of bioactivity is proposed that Hench was in postgraduate in 1969 by Hench earliest It is found when object glass:Bio-vitric is given birth on interface with the chemical keyness bonding of bon e formation, i.e. this proposition material after being implanted into bone The active concept of object, next year, this concept gained public acceptance in the world.It is that one kind can be in material that Hench, which defines bioactive materials, Special biological respinse is induced on interface, this reaction leads to the biomaterial that chemical bonding is formed between tissue and material.It is raw Object active ceramic refers to just the ceramic material that chemical bonding can be formed with live body bone tissue, live body soft tissue.Typical biology is living Property ceramics mainly include bioactivity glass and series of calcium phosphate bioactive ceramics.With modern medicine, biology and material supply section The concept of development, bioactivity obtains continuous infiltration and development.In Present clinical application, people are not intended merely to material can be with group It knits and combines closely to form bone bonding, and it is desirable that material promotes the ability of tissue growth with the differentiation of inducing peripheral histocyte. For osseous tissue renovating material, not being intended merely to implantation material can be bonded with bon e formation bone, it is also desirable to which being implanted into material has soon The function of speed induction bone tissue regeneration and reparation, that is, have good bioactivity and induction ostosis ability.
It can accelerate organization healing and regeneration with the active implant of good biological, realize defect or lesion bone tissue again It is raw to rebuild, to reach permanent rehabilitation.The 1980s mid-term, " organizational project " method propose using material as controlled release carrier, The appositional growth factor and active somatic cell extracorporeal culture form live body device, and then are implanted into vivo, it can be achieved that biomaterial induces The biological function of regeneration.However the cell injuring model technical sophistication involved in organizational engineering, required growth factor Expensive, patient personalized to be selected with drug dose difficult, and the series of problems such as storage, transport significantly limit it and face Bed promotes and applies.Therefore, by materialogy optimization design, control biomaterial chemical composition, bionical tissue microstructure carry out Material biological nature/function assessment research, and then exploitation can control activation, regulation and control body skeletonization response characteristic, induce bone tissue Regeneration, the bioactive materials of " with active repair function " are with important market value and potential applicability in clinical practice.
Biomaterial is that its surface/interface is contacted with biotic environment first after implanting, biological activity and its table Face/interface is directly related.Combination of the chemical reaction that material surface occurs between implant and host bone is extremely important.Research It has been shown that, existing two kinds of typical bioactive materials:Bioactivity glass and porous calcium phosphate ceramic, with being bonded all for bone The biochemical reaction that is occurred in vivo by material surface formed bone like apatite layer again with ossified keyness bonding, This illustrates that the surface characteristic of biomaterial plays vital regulating and controlling effect, the surface/interface of material for its bioactivity And its behavior is directly related with the osteoinductive of material.Existing calcium phosphate biological ceramic, due to having and chemistry as bone photo Ingredient and the performances such as biodegradable, it is always the focal selection object of bone renovating material, however is sintered by conventional ceramic Often bioactivity is insufficient for the micron grain ceramics that technology makes, and is unable to Effective Regulation body skeletonization response characteristic, rapid induction Bone tissue regeneration is rebuild, its clinical application effect is affected.Therefore, in order to assign the better bioactivity of material and self-bone grafting Property, Recent study person proposes the optimization design by material itself, such as optimizes its pore structure and refiner material crystal grain is (nanocrystalline Grain) etc. approach can improve the bioactivity and osteoinductive of material.Unique " nano effect ", such as small ruler possessed by nano material Tempting application prospect of the characteristics such as very little effect, high-specific surface area, surface/interface effect in field of tissue engineering technology.However, although mesh It is preceding have it is numerous about synthesis, preparation and evaluation calcium phosphate nano particle, the research report of particle, in related application, nanometer Calcium phosphate material mostly in a dispersed form, such as nano particle, particle, or in the form of the second phase doped and compounded in other bases Among body material (such as high molecular material, collagen etc.), and prepare the nanocrystalline calcium phosphate biological active ceramic material of block shape by The bottleneck in always its development and application is restricted in sintering process.Therefore by process for modifying surface, ceramic surface it is compound, apply It is uniform to cover a composition of layer, there is the calcium phosphate nano biological active ceramic material of stable structure, superior performance important exploitation to answer With value.
Invention content
A kind of calcium phosphate bioactive ceramics of present invention proposition and preparation method thereof, the two of calcium phosphate bioactive ceramics It is respectively formed pore structure, and the hole connection setting on two sides on a opposite side, with larger contact area, carries Its high bioactivity ability, and the bioactive ceramics are prepared using cleverly method, keep the pore structure formed thereon natural It is formed, is conducive to improve its bioactivity ability.
The technical proposal of the invention is realized in this way:
A kind of calcium phosphate bioactive ceramics, including calcium phosphate ceramic matrix, two of the calcium phosphate ceramic matrix are opposite Side on be distributed with several holes, the centre of the calcium phosphate ceramic matrix is equipped with blended fabric, the calcium phosphate ceramic matrix two The hole of side is connected to by blended fabric, and the blended fabric is that biological reactive phosphate base continuous glass fibre and polylactic acid are fine The blended fabric of dimension.
The present invention is further arranged to, and the single fiber diameter of the bioactivity phosphate base continuous glass fibre is 7~17 μm.
A kind of preparation method of calcium phosphate bioactive ceramics, includes the following steps:
Step 1:After various raw materials are crushed, water is added to be uniformly mixed so as to obtain pug, the pug after the mixing is at thick liquid State;
Step 2:Prepare the mold of side opening on one, the bottom of the mold is evenly distributed with several stomatas, in the mold Above-mentioned blended fabric is spread in bottom, then pug is poured into mold;
Step 3:Air-blowing device is connected in the downside of mold, the air-blowing device blasts gas into mold by stomata Body, air-blowing time are 4-8 hours, and air-blowing frequency is to blast a gas in 5 minutes, and the speed for blasting gas is 0.2m/min, The temperature for blasting gas is 40-80 degrees Celsius;
Step 4:It after air-blowing, after the pug in mold is cooled and shaped, is demoulded, obtains side and be equipped with blended knit Object, the other side form the semi-finished product in hole, and hole is connected to the both sides setting of semi-finished product;
Step 5:Semi-finished product are inverted into mold, then pug is poured into mold;
Step 6:Air-blowing device is connected in the downside of mold, the air-blowing device blasts gas into mold by stomata Body, air-blowing time are 4-8 hours, and air-blowing frequency is to blast a gas in 5 minutes, and the speed for blasting gas is 0.2m/min, The temperature for blasting gas is 40-80 degrees Celsius;
Step 7:After air-blowing, after the pug in mold is cooled and shaped, is demoulded, obtains to both sides and be equipped with hole, Centre is equipped with the finished product ceramics of blended fabric, and the hole of both sides is connected to by intermediate blended fabric.
The present invention is further arranged to, the raw material by weight, 20-30 parts of Chongqing Ci Ba clays, ferrallite 15-30 parts, 10-20 parts of lateritic nickel ore, 3-10 parts of dolomite, 5-10 parts of HIGH-PURITY SILICON, 8-15 parts of bone meal, 1-5 parts of diatomite, phosphoric acid 1-5 parts of calcium powder, 5-10 parts of far infrared ceramic powder, 0.5-3 parts of nano-titanium oxide, 0.5-2 parts of boron nitride, carboxymethyl chitosan 0.5-2 parts, 0.01-0.05 parts of nano zine oxide, 0.01-0.05 parts of nano-stannic oxide.
The present invention is further arranged to, and in step (1), is specially by the crushing of each raw material:By Chongqing Ci Ba clays, iron Alumina, lateritic nickel ore, diatomite and bone meal mix, and carry out ball milling, obtain the first mixture;By dolomite, HIGH-PURITY SILICON, Boron nitride, nano-titanium oxide and nano-stannic oxide mix, and carry out ball milling, obtain the second mixture;By phosphoric acid calcium powder, Far infrared ceramic powder, carboxymethyl chitosan and nano zine oxide mix, and obtain third mixture.
The present invention is further arranged to, and in step (1), described plus water mixing is specially:By first mixture It is added to the water, after mixing, is then added second mixture, after mixing, the third mixture is added, obtains pug.
Above-mentioned technical proposal is used, beneficial effects of the present invention are:
(1) calcium phosphate bioactive ceramics provided by the present invention, it is simple in structure, on two opposite side respectively Pore structure, and the hole connection setting on two sides are formed, with larger contact area, improves its bioactivity ability, And the centre of ceramics is equipped with blended fabric layer, can play the role of reinforcing integral ceramic structure intensity;
(2) preparation method of a kind of calcium phosphate bioactive ceramics provided by the present invention, by the side for blasting gas Method forms pore structure on ceramics, and during blasting gas, and blended fabric, which can play, evenly dispersed blasts gas Effect, so that the hole formed on ceramics is uniformly distributed, it is this blast gas by way of self-assembling formation hole, can be further Improve the bioactivity ability of ceramics.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention without having to pay creative labor, may be used also for those of ordinary skill in the art With obtain other attached drawings according to these attached drawings.
Fig. 1 is the structural schematic diagram of calcium phosphate bioactive of the present invention ceramics;
Fig. 2 is one of the structural schematic diagram of calcium phosphate bioactive ceramics preparation facilities of the present invention;
Fig. 3 is the second structural representation of calcium phosphate bioactive ceramics preparation facilities of the present invention.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, those of ordinary skill in the art are obtained every other without creative efforts Embodiment shall fall within the protection scope of the present invention.
The present invention will be described by following reference chart 1-3:
A kind of calcium phosphate bioactive ceramics, including calcium phosphate ceramic matrix 1, two phases of the calcium phosphate ceramic matrix 1 To side on be distributed with several holes 2, the centre of the calcium phosphate ceramic matrix 1 is equipped with blended fabric 3, the calcium phosphate ceramic base The hole of 1 both sides of body is connected to by blended fabric 3, the blended fabric 3 be biological reactive phosphate base continuous glass fibre with The blended fabric 3 of acid fiber by polylactic.
Wherein, the single fiber diameter of the bioactivity phosphate base continuous glass fibre is 7~17 μm.
A kind of preparation method of calcium phosphate bioactive ceramics, includes the following steps:
Step 1:After various raw materials are crushed, water is added to be uniformly mixed so as to obtain pug, the pug after the mixing is at thick liquid State;
Step 2:Prepare the mold 4 of side opening on one, the bottom of the mold 4 is evenly distributed with several stomatas, in the mold 4 Bottom spread above-mentioned blended fabric 3, then pug is poured into mold 4;
Step 3:In the downside of mold 4 connection air-blowing device 5, the air-blowing device 5 is blasted by stomata into mold 4 Gas, air-blowing time are 4-8 hours, and air-blowing frequency is to blast a gas in 5 minutes, and the speed for blasting gas is 0.2m/ Min, the temperature for blasting gas are 40-80 degrees Celsius;
Step 4:It after air-blowing, after the pug in mold 4 is cooled and shaped, is demoulded, obtains side equipped with blended Fabric 3, the other side form the semi-finished product in hole, and hole is connected to the both sides setting of semi-finished product;
Step 5:Semi-finished product are inverted into mold 4, then pug is poured into mold 4;
Step 6:In the downside of mold 4 connection air-blowing device 5, the air-blowing device 5 is blasted by stomata into mold 4 Gas, air-blowing time are 4-8 hours, and air-blowing frequency is to blast a gas in 5 minutes, and the speed for blasting gas is 0.2m/ Min, the temperature for blasting gas are 40-80 degrees Celsius;
Step 7:After air-blowing, after the pug in mold 4 is cooled and shaped, is demoulded, obtains to both sides and be equipped with hole, Centre is equipped with the finished product ceramics of blended fabric 3, and the hole of both sides is connected to by intermediate blended fabric 3.
Wherein, the raw material by weight, 20-30 parts of Chongqing Ci Ba clays, 15-30 parts of ferrallite, lateritic nickel ore 10-20 parts, 3-10 parts of dolomite, 5-10 parts of HIGH-PURITY SILICON, 8-15 parts of bone meal, 1-5 parts of diatomite, 1-5 parts of phosphoric acid calcium powder, far infrared 5-10 parts of line ceramic powder, 0.5-3 parts of nano-titanium oxide, 0.5-2 parts of boron nitride, 0.5-2 parts of carboxymethyl chitosan, nano zine oxide 0.01-0.05 parts, 0.01-0.05 parts of nano-stannic oxide.
Wherein, in step (1), it is specially by the crushing of each raw material:By Chongqing Ci Ba clays, ferrallite, lateritic nickel ore, silicon Diatomaceous earth and bone meal mix, and carry out ball milling, obtain the first mixture;By dolomite, HIGH-PURITY SILICON, boron nitride, nano oxidized Titanium and nano-stannic oxide mix, and carry out ball milling, obtain the second mixture;By phosphoric acid calcium powder, far infrared ceramic powder, Carboxymethyl chitosan and nano zine oxide mix, and obtain third mixture.
Wherein, in step (1), described plus water mixing is specially:First mixture is added to the water, after mixing, Then it is added second mixture, after mixing, the third mixture is added, obtains pug.
Above-mentioned technical proposal is used, beneficial effects of the present invention are:
1, calcium phosphate bioactive ceramics provided by the present invention, it is simple in structure, on two opposite side respectively Pore structure, and the hole connection setting on two sides are formed, with larger contact area, improves its bioactivity ability, And the centre of ceramics is equipped with 3 layers of blended fabric, can play the role of reinforcing integral ceramic structure intensity;
2, the preparation method of a kind of calcium phosphate bioactive ceramics provided by the present invention, the method by blasting gas Pore structure is formed on ceramics, and during blasting gas, blended fabric 3 can play the evenly dispersed gas that blasts Effect, so that the hole formed on ceramics is uniformly distributed, it is this blast gas by way of self-assembling formation hole, can further carry The bioactivity ability of high ceramics.
Above-described is only presently preferred embodiments of the present invention, is not intended to limit the invention, all the present invention's Within spirit and principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.

Claims (6)

1. a kind of calcium phosphate bioactive ceramics, it is characterised in that:Including calcium phosphate ceramic matrix, the calcium phosphate ceramic matrix Several holes are distributed on two opposite sides, the centre of the calcium phosphate ceramic matrix is equipped with blended fabric, calcium phosphate pottery The hole of porcelain basal body both sides is connected to by blended fabric, the blended fabric be biological reactive phosphate base continuous glass fibre with The blended fabric of acid fiber by polylactic.
2. a kind of calcium phosphate bioactive ceramics according to claim 1, it is characterised in that:The bioactivity phosphoric acid The single fiber diameter of alkali continuous glass fibre is 7~17 μm.
3. a kind of preparation method of calcium phosphate bioactive ceramics, which is characterized in that include the following steps:
Step 1:After various raw materials are crushed, water is added to be uniformly mixed so as to obtain pug, the pug after the mixing is at thick liquid condition;
Step 2:Prepare the mold of side opening on one, the bottom of the mold is evenly distributed with several stomatas, in the bottom of the mold The blended fabric as described in claims 1-2 is spread, then pug is poured into mold;
Step 3:Air-blowing device is connected in the downside of mold, the air-blowing device blasts gas into mold by stomata, The air-blowing time is 4-8 hours, and air-blowing frequency is to blast a gas in 5 minutes, and the speed for blasting gas is 0.2m/min, blasts gas The temperature of body is 40-80 degrees Celsius;
Step 4:It after air-blowing, after the pug in mold is cooled and shaped, is demoulded, obtains side and be equipped with blended fabric, The other side forms the semi-finished product in hole, and hole is connected to the both sides setting of semi-finished product;
Step 5:Semi-finished product are inverted into mold, then pug is poured into mold;
Step 6:Air-blowing device is connected in the downside of mold, the air-blowing device blasts gas into mold by stomata, The air-blowing time is 4-8 hours, and air-blowing frequency is to blast a gas in 5 minutes, and the speed for blasting gas is 0.2m/min, blasts gas The temperature of body is 40-80 degrees Celsius;
Step 7:After air-blowing, after the pug in mold is cooled and shaped, is demoulded, obtain to both sides and be equipped with hole, it is intermediate Finished product ceramics equipped with blended fabric, and the hole of both sides is connected to by intermediate blended fabric.
4. a kind of preparation method of calcium phosphate bioactive ceramics according to claim 3, it is characterised in that:The original Expect by weight, 20-30 parts of Chongqing Ci Ba clays, 15-30 parts of ferrallite, 10-20 parts of lateritic nickel ore, 3-10 parts of dolomite, 5-10 parts of HIGH-PURITY SILICON, 8-15 parts of bone meal, 1-5 parts of diatomite, 1-5 parts of phosphoric acid calcium powder, 5-10 parts of far infrared ceramic powder, nano oxygen Change 0.5-3 parts of titanium, 0.5-2 parts of boron nitride, 0.5-2 parts of carboxymethyl chitosan, 0.01-0.05 parts of nano zine oxide, nano-silica Change 0.01-0.05 parts of tin.
5. a kind of preparation method of calcium phosphate bioactive ceramics according to claim 4, it is characterised in that:In step (1) in, it is specially by the crushing of each raw material:Chongqing Ci Ba clays, ferrallite, lateritic nickel ore, diatomite and bone meal are blended in one It rises, carries out ball milling, obtain the first mixture;Dolomite, HIGH-PURITY SILICON, boron nitride, nano-titanium oxide and nano-stannic oxide are mixed It is combined, carries out ball milling, obtain the second mixture;By phosphoric acid calcium powder, far infrared ceramic powder, carboxymethyl chitosan and nanometer Zinc oxide mixes, and obtains third mixture.
6. a kind of preparation method of calcium phosphate bioactive ceramics according to claim 5, it is characterised in that:In step (1) in, described plus water mixing is specially:First mixture is added to the water, after mixing, second mixing is then added Object after mixing, is added the third mixture, obtains pug.
CN201810732793.4A 2018-07-05 2018-07-05 A kind of calcium phosphate bioactive ceramics and preparation method thereof Withdrawn CN108793845A (en)

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