CN1923752A - Composite organism ceramic material composed of apatite-wollastonite/beta-tricalcium phosphate - Google Patents
Composite organism ceramic material composed of apatite-wollastonite/beta-tricalcium phosphate Download PDFInfo
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- CN1923752A CN1923752A CN 200510021568 CN200510021568A CN1923752A CN 1923752 A CN1923752 A CN 1923752A CN 200510021568 CN200510021568 CN 200510021568 CN 200510021568 A CN200510021568 A CN 200510021568A CN 1923752 A CN1923752 A CN 1923752A
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- wollastonite
- tricalcium phosphate
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Abstract
The invention discloses a composite biological active ceramic material of Apatite-Wollastonite/beta-tricalcium phosphate (AW/beta-TCP), which comprises the following steps: adopting sol-gel process to prepare AW former powder; preparing TCP former powder through chemical sediment method; sieving TCP former powder through 60-order standard sieve; putting AW former powder and TCP former particle in the material mixing machine according to different proportion; adding certain rate corresponding to powder weight geoceric acid or naphthalene particle with grain size at 20-30 order; making 5wt% polyvinyl alcohol solution as adhesive; blending completely; moulding; drying; sintering to obtain porous product.
Description
Technical field
The invention belongs to ceramic and biomedical engineering field, relate to a kind of new system bone renovating material---phosphatic rock/wollastonite (AW)/bata-tricalcium phosphate (composite organism ceramic material of β-TCP).
Background technology
Nineteen eighty-two, Kokubo etc. develop contain phosphatic rock (A, apatite), (W, wollastonite) MgO-CaO-SiO2-P2O5 of crystalline phase and glassy phase is the AW biological active glass ceramic to wollastonite.A-W biological active glass ceramic biocompatibility is good, and is safe, nontoxic after goods implant, and do not have untoward reactions such as rejection, inflammation and tissue necrosis, has higher physical strength.Its biological activity is also very outstanding, can form apatite layer by surface chemical reaction at short notice after in its implanted body, thus with the body in-seam securely bonding be one, form synostosis.Since the last century the eighties, people have given great attention to biodegradation type calcium phosphate ceramic material and have carried out research more in depth.Bata-tricalcium phosphate (β-TCP, β-tricalcium phosphate) with good biocompatibility, bone conduction effect and biological degradability is noticeable especially.Its moiety is similar to the inorganic components in the biological bone, good biocompatibility, and dissolve the back that implants, and the Ca that dissolves, Pi (refer to whole free inorganic phosphate radical ions, as HPO
4 2-, H
2PO
4 -, PO
4 3-) enter the live body recycle system and form area of new bone then, lifeless implant dissolves disappearance gradually behind the certain hour, by lived area of new bone is replaced.β-TCP is better than hydroxyapatite (HA) on bone formation rate, is a kind of very ideal, sclerous tissues's impairment renovation material that potential applicability in clinical practice is very tempting.
As bone renovating material or tissue engineering bracket material, in order to promote the new bone material of growing into, material should have vesicular structure suitable, the simulating nature bone.The bone tissue engineering stent material porosity is high more to help growing into of cell and osseous tissue more, and still, the high porosity materials mechanical property is lower.Be the absorbable and degradable of comprehensive performance AW biological active glass ceramic excellent mechanical property, biological activity and β-TCP, the present invention adopts the compound β-TCP of AW to prepare AW/ β-TCP composite boilogical ceramic.The pore-creating agent relative quantity that adds when preparation AW/ β-TCP composite boilogical ceramic is lower, makes it than single AW or β-TCP relatively low initial porosity be arranged, thereby has higher initial mechanical intensity.After AW/ β-TCP composite boilogical ceramic is soaked or is implanted, by dissolving energy original position (in situ) pore-forming of dissolving phase β-TCP, for new bone growth provides abundant Ca
2+, Pi, on the basis of material pre-existent pore rate, increase the material porosity, for histocyte provides nutrition channel, be beneficial to growing into of osseous tissue and blood vessel.
Look into new by retrieval, Lin Kaili etc. have proposed calcium silicate/beta-tricalcium phosphate complex phase biological ceramics system in patent of invention " preparation method of porous calcium silicate/bata-tricalcium phosphate complex phase bioceramic material " (Shanghai Silicate Inst., Chinese Academy of Sciences, patent publication No. CN 1439618A); Huang Xiang etc. have proposed wollastonite/bata-tricalcium phosphate complex phase biological ceramics system in patent of invention " preparation method of wollastonite/tricalcium phosphate composite bio-active material " (Shanghai Silicate Inst., Chinese Academy of Sciences, patent publication No. CN 1171644C); And a large amount of reports have been mentioned hydroxyapatite/bata-tricalcium phosphate compound system, as: patents of invention such as Wang Chen " preparation method of hydroxyapatite and bata-tricalcium phosphate complex phase biological ceramics " (Tsing-Hua University, patent publication No. CN 1562873A).The above-mentioned tissue engineering bracket material that is reported as provides abundant selection scheme.
The present invention proposes the AW biological active glass ceramic that adopts biological activity and mechanical strength very excellent, with degradable mutually bata-tricalcium phosphate carry out compound, the preparation bone tissue engineering stent material, can improve the mechanical property of composite boilogical ceramic timbering material, in the immersion or the process that implants, increase porosity, give support controlled biological degradability mutually by β-CP simultaneously.By retrieval: domestic patent and the paper report that does not still have this system as bone renovating material or bone tissue engineer repair materials.
Summary of the invention
The objective of the invention is at the requirement of bone tissue engineering stent material biomaterial biological activity, mechanical strength, pore morphology and degradable characteristic, by phosphatic rock/wollastonite biological glass ceramic (AWGC) and degradable mutually bata-tricalcium phosphate (the compound preparation of β-TCP) has higher initial mechanical intensity, biological activity is excellent and biodegradable tissue engineering bracket material.
(β-TCP) preparation process of composite boilogical ceramic relates to phosphatic rock of the present invention/wollastonite biological glass ceramic (AWGC)/bata-tricalcium phosphate: adopt independently developed sol-gel method high reactivity, fine AW GC powder (number of patent application: 200510021184.0) or the AW powder and the β-TCP powder that adopt fusion process to obtain be that raw material (also can adopt without incinerating AW, β-TCP precursor powder), earlier with β-TCP powder granulation, again AW powder and β-TCP powder are carried out batch mixing by different ratios, and then interpolation pore-creating agent, compression molding behind the tackiness agent batch mixing obtains composite bioceramic material 1170 ℃ of calcinings.
The X diffraction analysis proves: the present invention is by the composite organism ceramic material of AW powder and β-even blend of TCP powder, moulding, pore-creating and preparation after optimal temperature (1170 ℃) calcining, new solid state reaction does not take place, and its crystalline structure is: phosphatic rock, β-wollastonite and bata-tricalcium phosphate three-phase coexistence.
Among the present invention, vesicular structure for the simulating nature bone, the present invention in the process of preparation porous ceramics, add stearic acid particle that particle size is 600～700 μ m or or the naphthalene particle as pore-creating agent, utilize the volatilization of pore-creating agent in ceramic body, to form macroscopic pores, be beneficial to growing into of osseous tissue; The dissolving of the original position of utilization β-TCP phase in the body fluid environment can further improve the material porosity, be beneficial to the growing into of cell, the circulation of body fluid; Because material can be in-situ pore-formed, so can reduce the initial mechanical intensity that the add-on of pore-creating agent improves material.Scanning electron microscope result shows: compound porous biological ceramics has suitable pore morphology: the mutual perforation macroscopic pores of 100～500 μ m has a large amount of micropores on the hole wall.
The NEW TYPE OF COMPOSITE bioactive ceramics of the present invention preparation has outstanding biological activity, can form the surface hydroxyl apatite layer fast in in-vitro simulated body fluid experiment, and the formation of the surface apatite layer bioactive item key that is material; Can stick fast, breed, break up at material surface through skeletonization direction inductive bone marrow stroma stem cell, show that novel bioactive glass-ceramic cell compatibility is good.
In the Application Areas of bone renovating material and bone tissue engineering stent material, the compound system material of the present invention's preparation has the following advantages:
1. (in the compound system of β-TCP), the AW biological active glass ceramic has very outstanding biological activity to phosphatic rock/wollastonite biological glass ceramic (AW GC)/bata-tricalcium phosphate, helps matrix material and implants between back and osseous tissue bone bonding closely takes place;
2.AW biological active glass ceramic is that mechanical strength is the highest in the lithotroph stupalith, the compound enhancing of AW biological glass ceramic has improved material mechanical performance greatly;
3. compound porous biological ceramics has suitable pore morphology: the mutual perforation macroscopic pores of 100～500 μ m have a large amount of micropores on the hole wall, and material will help the infiltration of body fluid in the body fluid environment by the lysigenous a large amount of micropores of original position.
4. can make the composite porous ceramic timbering material have controlled biological degradability and the required initial mechanical performance of material by control degradable phase bata-tricalcium phosphate adding proportion in the preparation process and by control pore-creating agent content adjustment apertures rate.
5. the tissue engineering bracket material porosity is high more helps growing into of cell and osseous tissue more, but increasing of material porosity will cause mechanical strength significantly to descend, and the porosity of existing bone renovating material is generally 45～55%; And the new system of the present invention preparation is owing to strengthen by AW GC mechanics wild phase, and porosity of porous material can be up to 70%, and the initial mechanical intensity of material reaches the timbering material requirement before implanting; Implant the back because the original position dissolving of material in body fluid also will further increase the porosity of material;
6. the compound system biological ceramics can form the surface biological apatite layer fast in body fluid or simulated body fluid environment, shows good biological activity; The material cell compatibility is good, helps cell in the sticking fast, breed, break up of its surface, and is suitable to bone tissue engineering stent material.
Description of drawings
The X diffracting spectrum of accompanying drawing 1 composite bio-active pottery
The scanning electron microscope picture of the ceramic porous timbering material of accompanying drawing 2 composite bio-actives
Embodiment
Example 1:
1. adopt independently developed sol-gel method to prepare high reactivity, fine AW GC precursor powder (number of patent application: 200510021184.0), basic step is: the fully hydrolysis in ethanol with tetraethoxy and triethyl phosphate earlier, inorganic salt with facile hydrolysis successively are dissolved in the organic reagent again, and make it to react with water, through hydrolysis and polycondensation process and form gel, pass through ageing, drying again, and remove remaining organism and moisture, make fine precursor powder in 500 ℃ of thermolysiss;
2.TCP the preparation of precursor powder: with deionized water with high-purity fine CaCO
3Reconcile into slurry.Under the ultrasonic agitation effect, splash into phosphoric acid solution under the normal temperature, react, will obtain the TCP presoma after washing of precipitate, the drying by Ca/P=1.5;
Phosphatic rock-wollastonite biological glass ceramic (AW GC)/β tricalcium phosphate (β-TCP) preparation of composite bio-active pottery:
3.1 60 mesh standard sieves are crossed in the TCP presoma granulation that step 2 obtains;
3.2 the AW precursor powder that step 1 is obtained and 3.1 gained TCP granular precursor material are by AW: TCP=70: 30 (wt%) mix in the V-type mixer, adding accounts for powder weight 30% again, particle diameter is 20～30 purpose stearic acid, add an amount of polyvinyl alcohol solution (5wt%) and make binding agent, carry out abundant mixing.
3.3 the material through abundant mixing is shape goods base substrates such as column, sheet, strip through pressure forming (forming pressure is), drying is 2 hours under 110 ℃.
3.4 3.3 resulting product base substrates are placed High Temperature Furnaces Heating Apparatus, between 250 ℃～450 ℃, slowly heat up, remove tackiness agent fully, avoid blank cracking, and make pore-creating agent burning volatilization residual macropore in matrix, and be rapidly heated then and under 1170 ℃, calcine 2h, obtain the ceramic porous timbering material of composite bio-active behind the furnace cooling, its crystalline structure is phosphatic rock, β-wollastonite and bata-tricalcium phosphate, the results are shown in accompanying drawing 1; Its pore morphology is: the macroscopic pores that 100～500 μ m connect mutually, have a large amount of micropores on the hole wall, and the results are shown in accompanying drawing 2;
Example 2:
1. adopt fusion process to prepare AW parent glass powder, basic step is: with MgO4.6, CaO44.9, SiO
234.2, P
2O
516.3, CaF
20.5 mixture (heavy scape per-cent) in platinum crucible in 1450 ℃ of fusing 2h, after quenching becomes frit then, pulverize, screening obtains glass powder;
2.TCP the preparation of precursor powder: the Ca (NO that adopts the TCP ratio of calcium and phosphorus
3)
2(NH
4)
2HPO
4Carry out the chemical precipitation reaction, it is 11～12 that ammoniacal liquor is regulated pH, and reaction 12h gets precursor powder after filtration, washing, the drying;
3. phosphatic rock-wollastonite biological glass ceramic (the AW GC)/bata-tricalcium phosphate (β-TCP) preparation of composite bio-active pottery: with the described consistent AW GC/ β-TCP composite bio-active pottery for preparing of example 1 step 3 method.
Claims (4)
1. a kind of composed of apatite-wollastonite/beta-tricalcium phosphate of the present invention (composite bioceramic material of AW GC/ β-TCP), it is characterized in that: 60 mesh standard sieves are crossed in β-TCP micro mist granulation, carry out batch mixing with AW GC micro mist by different ratios, add organic binder bond again, pore-creating agent carries out abundant mixing.Obtain the composed of apatite-wollastonite/beta-tricalcium phosphate (composite bioceramic material of AW GC/ β-TCP) through technologies such as moulding, calcinings;
2. (composite powder of AW GC/ β-TCP) is characterized in that: AW GC powder adopts sol-gel method or traditional fusion process to make to prepare composed of apatite-wollastonite/beta-tricalcium phosphate according to claim 1; β-TCP adopts chemical precipitation method preparation and granulation to cross 60 mesh standard sieves: carry out batch mixing by different ratioss such as AW: β-TCP mass percent 70: 30,60: 40,50: 50; Adding accounts for powder weight certain mass ratio, particle diameter is that 20～30 purpose stearic acid or naphthalene particle etc. are made pore-creating agent and add an amount of polyvinyl alcohol solution (5wt%) to make binding agent, carries out abundant mixing.
3. composed of apatite-wollastonite/beta-tricalcium phosphate (the preparation method of composite bioceramic material of AW GC/ β-TCP) according to claim 1, it is characterized in that: will be by the compound uniform mixing powder of right 2 gained, through in High Temperature Furnaces Heating Apparatus, removing tackiness agent after the pressure forming through low temperature calcination, and make pore-creating agent volatilization burning residual macropore in matrix, being rapidly heated obtains the ceramic porous timbering material of composite bio-active again to 1170 ℃ of calcining 2h;
4. a kind of new system bone tissue engineering stent material of the present invention: phosphatic rock-wollastonite (AW)/bata-tricalcium phosphate (ceramic porous timbering material of composite bio-active of β-TCP), crystalline structure is phosphatic rock, β-wollastonite and bata-tricalcium phosphate, microstructure is: macroscopical macropore that 100～500 μ m connect mutually has a large amount of micropores on the hole wall.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200510021568 CN1923752A (en) | 2005-08-30 | 2005-08-30 | Composite organism ceramic material composed of apatite-wollastonite/beta-tricalcium phosphate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000361A (en) * | 2010-11-02 | 2011-04-06 | 陕西科技大学 | Preparation method of HA (Hydroxyapatite)-beta-tricalcium phosphate-alumina three-phase composite bioceramic |
| CN102851664A (en) * | 2012-08-03 | 2013-01-02 | 华中科技大学 | Method for preparing hydroxy apatite biological ceramic coating containing fluorine |
| CN104721880A (en) * | 2015-02-11 | 2015-06-24 | 华东理工大学 | Beta-tricalcium phosphate/mesoporous biological glass composite scaffold as well as preparation method and application |
| CN104771782A (en) * | 2014-01-10 | 2015-07-15 | 东莞博捷生物科技有限公司 | Bone repair material beta-tricalcium phosphate and preparation method thereof |
| CN105999400A (en) * | 2016-07-14 | 2016-10-12 | 上海交通大学 | CS/beta-TCP (calcium silicate/beta-tricalcium phosphate) porous composite material for promoting osteogenesis and vasculogenesis and preparation method thereof |
| CN107847638A (en) * | 2014-12-29 | 2018-03-27 | 佰欧维恩图斯有限责任公司 | System and method for improving the delivering of osteoinductive molecule in Bone Defect Repari |
| CN109534681A (en) * | 2019-01-09 | 2019-03-29 | 福州大学 | A kind of preparation method of lithium bisilicate compound bio glass ceramics |
| WO2019179194A1 (en) * | 2018-03-21 | 2019-09-26 | 山东大学 | Calcium polyphosphate/wollastonite bio-composite ceramic material and preparation method therefor |
| CN116283344A (en) * | 2021-12-13 | 2023-06-23 | 富尔哥顿生技股份有限公司 | Method for producing porous composite material |
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2005
- 2005-08-30 CN CN 200510021568 patent/CN1923752A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000361A (en) * | 2010-11-02 | 2011-04-06 | 陕西科技大学 | Preparation method of HA (Hydroxyapatite)-beta-tricalcium phosphate-alumina three-phase composite bioceramic |
| CN102000361B (en) * | 2010-11-02 | 2013-07-24 | 陕西科技大学 | Preparation method of HA (Hydroxyapatite)-beta-tricalcium phosphate-alumina three-phase composite bioceramic |
| CN102851664A (en) * | 2012-08-03 | 2013-01-02 | 华中科技大学 | Method for preparing hydroxy apatite biological ceramic coating containing fluorine |
| CN104771782A (en) * | 2014-01-10 | 2015-07-15 | 东莞博捷生物科技有限公司 | Bone repair material beta-tricalcium phosphate and preparation method thereof |
| CN107847638A (en) * | 2014-12-29 | 2018-03-27 | 佰欧维恩图斯有限责任公司 | System and method for improving the delivering of osteoinductive molecule in Bone Defect Repari |
| CN104721880A (en) * | 2015-02-11 | 2015-06-24 | 华东理工大学 | Beta-tricalcium phosphate/mesoporous biological glass composite scaffold as well as preparation method and application |
| CN104721880B (en) * | 2015-02-11 | 2017-06-20 | 华东理工大学 | β tricalcium phosphates/mesoporous bioglass compound rest and preparation method and application |
| CN105999400A (en) * | 2016-07-14 | 2016-10-12 | 上海交通大学 | CS/beta-TCP (calcium silicate/beta-tricalcium phosphate) porous composite material for promoting osteogenesis and vasculogenesis and preparation method thereof |
| WO2019179194A1 (en) * | 2018-03-21 | 2019-09-26 | 山东大学 | Calcium polyphosphate/wollastonite bio-composite ceramic material and preparation method therefor |
| CN109534681A (en) * | 2019-01-09 | 2019-03-29 | 福州大学 | A kind of preparation method of lithium bisilicate compound bio glass ceramics |
| CN109534681B (en) * | 2019-01-09 | 2021-04-27 | 福州大学 | Preparation method of lithium disilicate composite bioglass ceramic |
| CN116283344A (en) * | 2021-12-13 | 2023-06-23 | 富尔哥顿生技股份有限公司 | Method for producing porous composite material |
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