CN1208281C - Preparation of porous calsium silicate/beta-tricalsium phosphate composite bio-ceramic materials - Google Patents
Preparation of porous calsium silicate/beta-tricalsium phosphate composite bio-ceramic materials Download PDFInfo
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- CN1208281C CN1208281C CN 03115941 CN03115941A CN1208281C CN 1208281 C CN1208281 C CN 1208281C CN 03115941 CN03115941 CN 03115941 CN 03115941 A CN03115941 A CN 03115941A CN 1208281 C CN1208281 C CN 1208281C
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Abstract
The present invention relates to a method for preparing porous calcium silicate/beta-tricalsium phosphate composite bio-ceramic materials with biological activity and degradability, which belongs to the field of biological materials. The present invention adopts a chemical method to prepare calcium silicate micro powder and beta-tricalcium phosphate micro powder which are used as raw materials, the calcium silicate micro powder and the beta-tricalcium phosphate micro powder are uniformly mixed according to the mass ratio of (10 to 90) to (99 to 1), organic or macromolecular pore forming agents are added, and the mass ratio of the organic or macromolecular pore forming agents to the composite micro powder is (3 to 7) to (6 to 4); after uniform mixing, porous material biscuits are obtained by dry pressing forming and gelatin mould casting forming; finally, the biscuits are calcined at 900 to 1200 DEG C for 1 to 5 hours to obtain the bio-ceramic materials. The porous bio-ceramic materials prepared by the present invention have good biological activity, degradability and mechanical strength, and proper porosity and pore diameter, and completely satisfy the requirements of repairing materials for hard tissue coloboma and cytoskeleton materials for culturing bone tissues in vitro. The present invention has the advantages of simple and easy technology and convenient generalization.
Description
Technical field
The present invention relates to a kind of preparation method, belong to technical field of biological material with porous calcium silicate/bata-tricalcium phosphate complex phase biological ceramics of good biological activity, degradation property and mechanical strength.
Background technology
In recent years, along with the continuous development of organizational engineering, the biomaterial especially medical hard tissue repair of lithotroph and replacement material is subjected to people's attention and attention day by day as the base mateiral of this discipline development.People discover, in this class material bata-tricalcium phosphate class biomaterial degradation property better but biological activity is low, and tricalcium silicate class biomaterial is in contrast, the biological activity performance is very good and degradation property is general.Therefore how to obtain a kind ofly have simultaneously preferably that the biomaterial of biological activity and degradation property becomes the problem of pendulum in face of people.
In addition, except the composition of biomaterial, the structure of biomaterial can directly have influence on the clinical application of this material to a great extent.Studies show that in the past, the aperture is suitable as hard tissue repairing material and cytoskeleton material most at the porous blocks biomaterial of 50-500 micron.The aperture the advantage of the porous biomaterial of this scope be help cell migration, tissue is grown into and thereby the fusion of material and biological tissue more effectively reaches the purpose of repairing the damaged and tissue reconstruction of tissue, can also strengthen so simultaneously planting material being stationed and stable.Therefore, in the organizational engineering research that developed rapidly in recent years, often utilize as cell carrier with porous support, utilize the degradability of material, allow cell in substrate material, grow and make up the biological tissue that contains this somatic cell gene information, again in the implant into body with repair deficiency tissue and organ.
P.N.de Aza (the Biomaterials of Spain San Diego university, 1997,18:1285) with Calucium Silicate powder and 60: 40 by volume mixed of tricalcium phosphate and place platinum crucible 2h to be heated to 1500 ℃, obtain uniform liquid phase, reduce to 1410 ℃ with the speed of 3 ℃/min then, reduce to 1390 ℃ with the speed of 0.5 ℃/h again.Prepare the composite bioceramic material that contains Calucium Silicate powder and tricalcium phosphate eutectic structure thus.This material has good class bone hydroxyapatite and forms ability in simulated body fluid and human saliva immersion test.But this method has following shortcoming: temperature higher (1390-1500 ℃) in the sintering process of pottery, and the time is grown (greater than 40 hours), so the preparation process energy consumption is big, the cost height.What use simultaneously that this method prepares is fine and close stupalith, is not suitable as the timbering material in the organizational project.
The eighties in 20th century Japan people such as Kokubo (J.Mater.Sci., 1986, the A-W glass that 21:536) works out be a kind of in glassy phase the glass-ceramic of precipitation of phosphorus lime stone and two kinds of crystalline phases of Calucium Silicate powder.This material has preferably mechanical mechanics property and biological activity but can not degrade.People's such as Kokubo research also confirms, CaO-SiO in simulated body fluid
2The base glass surface can form class bone hydroxyapatite layer, and CaO-P
2O
5The base glass surface does not have class bone hydroxyapatite to form.
Human chemical processes such as Huang Xiang are prepared Calucium Silicate powder/tricalcium phosphate composite powder, behind dry-pressing and the isostatic pressing in 1300-1400 ℃ down calcining make Calucium Silicate powder/tricalcium phosphate with 60: 40 volume ratio compound biological active ceramic materials (Chinese patent application number: 02110847.1).Because sintering temperature is much larger than the sintering temperature of Calucium Silicate powder and calcium phosphate, this method can't prepare the porous ceramics with macropore, and the material that obtains only contains a spot of micropore, and its aperture also only is the 1-2 micron.So little micropore is difficult to the material internals of growing into such as feasible tissue and blood vessel, is not suitable as the cytoskeleton material in the organizational project.In addition, this invention is not made clear and definite evaluation to the degradation property of the material that makes yet.
Summary of the invention
The objective of the invention is to go out a kind of through hole calcium silicate/beta-tricalcium phosphate complex phase bioceramic material good biological activity, degradability but also that have suitable mechanical strength, aperture and porosity that not only had by optimizing process exploitation.This material can be as sclerous tissues's impairment renovation material and external osseous tissue cultivation cytoskeleton material, to satisfy the needs of biomaterial development of new generation.
The present invention is realized by following proposal:
Calcium silicate micro power used in the present invention is with Ca (NO by chemical process
3)
24H
2O and Na
2SiO
39H
2O is that feedstock production obtains.Chinese patent 02137248.9 has been put down in writing the preparation method of this powder.Promptly prepare the Ca (NO of 0.1-1.0mol/L
3)
24H
2O and Na
2SiO
39H
2O solution, with etc. the material reaction of mol ratio, with Na
2SiO
3Solution adds Ca (NO
3)
2In the solution, material finishes and continue to stir 8-24 hour, filters and with deionized water and the residual Na of dehydrated alcohol thorough washing removal
+Ion, and the powder that obtains by oven dry behind ball milling in 800 ℃-1000 ℃ calcinings 1-3 hour, obtain β-CaSiO
4Micro mist.Bata-tricalcium phosphate micro mist used in the present invention also prepares by chemical process, concrete grammar can referring to document (Jarcho M, Bolen C H.J.Materials Sci, 1976,11:2027-2035).The granularity of above-mentioned Calucium Silicate powder and bata-tricalcium phosphate requires to be 100nm-150 μ m.
Be 10 by mass percentage: 90-99: 1 is mixed into composite micro-powder with calcium silicate micro power and bata-tricalcium phosphate micro mist.Select for use in the organic or macromolecular material such as PEG (polyoxyethylene glycol), PVA (polyvinyl alcohol), paraffin, polystyrene-divinylbenzene one or more as pore-forming material, its granularity requires to be the 50-700 micron.In mass ratio is 3: 7-6: 4 ratio with pore-forming material with composite micro-powder mix compound.
Can take following two kinds of forming methods afterwards,
First kind is dry pressing, and the PVA (polyvinyl alcohol) that promptly adds mass percent 1-5% concentration and be 1-10% in above-mentioned compound makes cakingagent, after mixing, in punching block with the pressure of 2-30MPa dry-pressing formed porous material biscuit of the present invention.
Second method is a gel moldings formed therefrom method, i.e. preparation earlier has the mixed aqueous solution of following mass percent concentration, the acrylamide of 10-30% (AM) monomer, the N of 0.5-10%, poly amic acid (PMAA-NH4) dispersion agent of N '-methylene-bisacrylamide (MBAM) linking agent and 5-10%, be 30 by volume: 70-60: 40 ratio mixes above-mentioned compound with mixed aqueous solution, the ammonium persulphate that adds mass percent 1-5%, add-on is volume percent 1-15%, the N that adds mass percent 1-5% again, N, N ', N '-Tetramethyl Ethylene Diamine (TEMED), add-on is volume percent 1-15%, stir mobile slurry preferably, pour slurry into plastics or gypsum mold inner gel moldings formed therefrom, and crosslinking reaction 1-10 hour of 30-80 ℃ of trigger monomer, the dry afterwards demoulding got porous material biscuit of the present invention.
Biscuit with two kinds of technology gained obtained porous material of the present invention in 1-5 hour 900-1200 ℃ of calcining at last.
The performance evaluation that present method makes porous material is as follows:
One, the mechanical strength of porous material
The porous material sample that the present invention obtains is tested ultimate compression strength on the accurate universal testing machine of AG-I of day island proper Tianjin company.The test speed of sample is 5.0mm/min, and the ultimate compression strength of the porous material that test shows the present invention obtains is in the 2-80MPa scope.
Two, the porosity of porous material and pore structure
We test porosity, applied optics microscopic examination pore morphology and pore distribution to the sample segment that the present invention obtains with Archimedes's method.The porosity of the porous material that test shows the present invention obtains is in the 40-85% scope; The size distribution in hole is evenly distributed, is communicated with 50-600 micron and hole.
Three, evaluated biological activity
The porous material that the present invention is obtained is earlier after deionized water and washing with acetone, carry out external solution biological activity test after drying.Solutions employed is human body simulation body fluid (SBF; SimulatedBody Fluid).SBF contains ion identical with human plasma and ionic group concentration.SBF consists of:
NaCl： 7.996g/L
NaHCO
3： 0.350g/L
KCl： 0.224g/L
K
2HPO
4.3H
2O： 0.228g/L
MgCl
2.6H
2O： 0.305g/L
HCl： 1.0mol/L
CaCl
2： 0.278g/L
Na
2SO
4： 0.071g/L
NH
2C(CH
2OH)
3： 6.057g/L
Porous material is in SBF, and reaction conditions is in 0.15g porous material, 30.0mL/day SBF, the 37 ℃ of thermostat containers.After respectively porous material being soaked 1,3,5 and 7 day, take out sample also through carrying out SEM, fourier infrared conversion spectrum (FTIR) and XRD test behind the deionized water wash, the result sees Fig. 2, Fig. 3 and Fig. 4 respectively.Biological activity test shows that porous calcium silicate/bata-tricalcium phosphate two-phase composite bioceramic material that the present invention obtains can generate class bone hydroxyapatite at spatial induction, thereby shows these material biologically actives.
Four, degradation property evaluation
With obtain composite porous first of the present invention after carry out the external degradation experimental evaluation after deionized water and washing with acetone, the oven dry.We are to soak the Ca that discharges behind the different time in 7.25 three (methylol) amido methane (Tris) buffered soln by this polyporous materials at pH value
2+Percentage composition or the weightlessness of the material degradation property of coming evaluating material.The result shows that the bata-tricalcium phosphate mass range soaks 7 days degradation rate at 10%-70% 5%-80% composite porous in the Tris damping fluid.
Description of drawings
By following accompanying drawing and in conjunction with to the detailed description that the present invention did, can understand content mentioned above better.If the mass percent of sample mesosilicic acid calcium accounts for 30%, the mass percent of bata-tricalcium phosphate accounts for 70%, and then the identified as samples of this component is designated as W3T7, and other roughly the same.Wherein,
Fig. 1 is respectively the SEM shape appearance figure before pure Calucium Silicate powder of the present invention (A) and pure bata-tricalcium phosphate (B) soak in SBF (human body simulation body fluid).
Fig. 2 is respectively that the porous composite boilogical ceramic of pure Calucium Silicate powder of the present invention (A), W7T3 (B), W5T5 (C), W3T7 (D) and pure bata-tricalcium phosphate (E) soaks the SEM figure after 1 day in SBF (human body simulation body fluid).
The porous material that Fig. 3 is respectively pure Calucium Silicate powder of the present invention (A) and W5T5 (B) soaks preceding, Fourier transform infrared spectroscopy (FTIR) figure of immersion after 1,3 and 7 day in SBF.
The porous material that Fig. 4 is respectively pure Calucium Silicate powder of the present invention (A) and W5T5 (B) soaks the XRD figure after the some time in SBF.
The composite porous opticmicroscope figure that Fig. 5 obtains for the present invention.
The result of synthesizing map 1-Fig. 4 is a class bone hydroxyapatite layer at the sedimentary new thing of the material surface of Fig. 2 mutually.The result of Fig. 2 shows that the biological activity of such composite porous ceramic is improved along with the increase of Calucium Silicate powder content.Even and the tool through hole of the pore distribution of the material that the present invention of display application as a result of Fig. 5 prepares.
Embodiment
Be embodiments of the invention below, but the present invention only limit to embodiment by no means.
Embodiment 1:
With sieve the back granularity the Calucium Silicate powder of 45-75 μ m and bata-tricalcium phosphate micro mist in 50: 50 ratio ball milling of mass ratio mix composite granule.In 60: 40 ratio of mass ratio, composite granule is mixed at the PEG powder of 315-630 μ m with the back granularity of sieving, adds mass percent and be 2% concentration and be 6% PVA solution and make cakingagent, transfer even after, dry-pressing formed in 14MPa, the demoulding gets the biscuit of porous material.
Biscuit is incubated 3 hours down at 1100 ℃ and makes porous material of the present invention.Record ultimate compression strength and be about 14MPa, porosity is about 55%, and 7 days degradation rate is about 27% in Tris buffered soln.
The porous material of gained was soaked in the SBF simulated body fluid 1,3,5 and 7 day, and the sample after will soaking carries out evaluated biological activity.Fig. 1, Fig. 2, Fig. 3 and Fig. 4 show that the porous biomaterial that the present invention prepares has superior bioactive.
Embodiment 2:
With sieve the back granularity the Calucium Silicate powder of 38-44 μ m and bata-tricalcium phosphate micro mist in 50: 50 ratio ball milling of mass ratio mix composite granule.In 40: 60 ratio of mass ratio, composite granule is mixed at the PEG powder of 315-630 μ m with the back granularity of sieving, adds mass percent and be 2% concentration and be 6% PVA solution and make cakingagent, transfer even after, dry-pressing formed in 14MPa, the demoulding gets the biscuit of porous material.
Biscuit is incubated 3 hours down at 1100 ℃ and makes porous material of the present invention.Record ultimate compression strength and be about 2.5MPa, porosity is about 75%, and 7 days degradation rate is about 30% in Tris buffered soln.
The evaluated biological activity of material is with embodiment 1.
Embodiment 3:
With sieve the back granularity the Calucium Silicate powder of 38-45 μ m and bata-tricalcium phosphate micro mist in 95: 5 ratio ball milling of mass ratio mix composite granule.70: 30 get material at the PVA powder of 300-600 μ m by mass ratio with the back granularity of sieving by composite granule and mix, get solid mixture.The preparation mass percent concentration is 20% AM, 2% MBAM and 8% PMAA-NH
4Mixed aqueous solution, 50: 50 by volume ratio mixes 10 gram solid mixtures with above-mentioned mixed aqueous solution, the ammonium persulphate that adds mass percent 3%, add-on is volume percent 6%, adds the TEMED of mass percent 3% again, add-on is a volume percent 8%, stir mobile slurry preferably, pour slurry into plastics or gypsum mold inner gel casting, and the crosslinking reaction of 60 ℃ of trigger monomers 3 hours, the dry afterwards demoulding got porous material biscuit of the present invention.
Biscuit is incubated the ultimate compression strength that made porous material of the present invention in 2 hours down at 1100 ℃ and is about 75MPa, porosity about 43%.7 days degradation rate is about 45% in Tris buffered soln.
The evaluated biological activity of material is with embodiment 1.
Embodiment 4:
With sieve the back granularity the Calucium Silicate powder of 38-45 μ m and bata-tricalcium phosphate micro mist in 20: 80 ratio ball milling of mass ratio mix composite granule.In 50: 50 ratio of mass ratio, composite granule is mixed at the PEG of 315-630 micron powder with the back granularity of sieving, adds mass percent and be 3% concentration and be 6% PVA solution and make cakingagent, transfer even after, dry-pressing formed in 14MPa, the demoulding gets the biscuit of porous material.The calcinating system of biscuit such as embodiment 1 make the about 5.6MPa of ultimate compression strength of porous material of the present invention, porosity about 65%.7 days degradation rate is about 16.3% in Tris buffered soln.
The evaluated biological activity of material is with embodiment 1.
Embodiment 5:
With sieve the back granularity the Calucium Silicate powder of 38-45 μ m and bata-tricalcium phosphate micro mist in 80: 20 ratio ball milling of mass ratio mix composite granule.In 50: 50 ratio of mass ratio, composite granule is mixed at the PEG of 150-200 micron powder with the back granularity of sieving, adds mass percent and be 3% concentration and be 6% PVA solution and make cakingagent, transfer even after, dry-pressing formed in 14MPa, the demoulding gets the biscuit of porous material.The calcinating system of biscuit such as embodiment 1 make the about 6MPa of ultimate compression strength of porous material of the present invention, porosity about 65%.7 days degradation rate is about 68% in Tris buffered soln.
The evaluated biological activity of material such as embodiment 1.
Claims (7)
1, the preparation method of the porous calcium silicate of a kind of biologically active and degradation property/bata-tricalcium phosphate complex phase bioceramic material comprises the preparation of calcium silicate micro power and bata-tricalcium phosphate micro mist, it is characterized in that:
(a) be calcium silicate micro power and bata-tricalcium phosphate micro mist to be mixed into composite micro-powder in 20: 80～95: 5 by mass ratio;
(b) select for use in polyoxyethylene glycol, polyvinyl alcohol, paraffin, the polystyrene-divinylbenzene one or more as pore-forming material, be 3 by mass ratio: 7-6: 4 ratio mixes pore-forming material with composite micro-powder;
(c) add mass percent 1-5% in the mixture of step (b) gained, concentration is the polyvinyl alcohol of 1-10%, and after mixing, with the dry-pressing formed one-tenth biscuit of the pressure of 2-30MPa, last biscuit was at 900-1200 ℃ of temperature lower calcination 1-5 hour in punching block.
2, press the preparation method of the porous calcium silicate/bata-tricalcium phosphate complex phase bioceramic material of described a kind of biologically active of claim 1 and degradation property, it is characterized in that the granularity of described Calucium Silicate powder and bata-tricalcium phosphate requires to be 45-75 μ m.
3, press the preparation method of the porous calcium silicate/bata-tricalcium phosphate complex phase bioceramic material of claim 1 or 2 described a kind of biologically actives and degradation property, the granularity that it is characterized in that described pore-forming material is the 50-700 micron.
4, the preparation method of the porous calcium silicate of a kind of biologically active and degradation property/bata-tricalcium phosphate complex phase bioceramic material comprises the preparation of calcium silicate micro power and bata-tricalcium phosphate micro mist, it is characterized in that:
(a) be calcium silicate micro power and bata-tricalcium phosphate micro mist to be mixed into composite micro-powder in 20: 80～95: 5 by mass ratio;
(b) select for use in polyoxyethylene glycol, polyvinyl alcohol, paraffin, the polystyrene-divinylbenzene one or more as pore-forming material, be 3 by mass ratio: 7-6: 4 ratio mixes pore-forming material with composite micro-powder;
(c) the preparation mass percent concentration is the mixed aqueous solution of 10-30% acrylamide monomer, 0.5-10%N, N '-methylene-bisacrylamide linking agent, 5-10% poly amic acid dispersion agent;
(d) be 30 by volume: 70-60: 40 ratio mixes the mixed powder of step (b) gained and the mixed aqueous solution of step (c) gained, adding mass percent is the ammonium persulphate of 1-5%, add-on is the 1-15% of volume percent, add the N that mass percent is 1-5% again, N, N ', N '-Tetramethyl Ethylene Diamine, add-on is the 1-15% of volume percent, obtain slurry after stirring, pour slurry into plastics or gypsum mold inner gel moldings formed therefrom, and crosslinking reaction 1-10 hour of 30-80 ℃ of trigger monomer, again with the biscuit of the dry demoulding at 900-1200 ℃ of temperature lower calcination 1-5 hour.
5, press the preparation method of the porous calcium silicate/bata-tricalcium phosphate complex phase bioceramic material of described a kind of biologically active of claim 4 and degradation property, it is characterized in that the granularity of described calcium silicate micro power and bata-tricalcium phosphate micro mist requires to be 45-75 μ m.
6, press the preparation method of the porous calcium silicate/bata-tricalcium phosphate complex phase bioceramic material of claim 4 or 5 described a kind of biologically actives and degradation property, the granularity that it is characterized in that described pore-forming material is the 50-700 micron.
7, the porous calcium silicate/bata-tricalcium phosphate complex phase bioceramic material of a kind of biologically active that makes according to the described method of one of claim 1-6 and degradation property is as sclerous tissues's impairment renovation material and external osseous tissue culturing cell timbering material.
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| CN100391418C (en) * | 2004-03-05 | 2008-06-04 | 中国科学院上海硅酸盐研究所 | Bioactive composite cytoskeleton made of degradable porous polyester/calcium silicate, prepn. method and use thereof |
| SE528360C2 (en) | 2004-09-10 | 2006-10-24 | Doxa Ab | Resorbable ceramic compositions intended for medical implants |
| CN100360191C (en) * | 2005-05-13 | 2008-01-09 | 中国科学院上海硅酸盐研究所 | Material of porous akermanite for support and its preparation process and application |
| CN100391901C (en) * | 2005-12-09 | 2008-06-04 | 中国科学院上海硅酸盐研究所 | Method for preparing calcium silicate/beta- tricalcium phosphate composite powder by two-step chemical precipitation method |
| CN100344581C (en) * | 2005-12-09 | 2007-10-24 | 中国科学院上海硅酸盐研究所 | Method for preparing calcium silicate/beta- tricalcium phosphate composite powder by in situ chemical precipitation method |
| TWI411595B (en) * | 2010-04-07 | 2013-10-11 | Univ Kaohsiung Medical | Process for preparing composition comprising porous ceramic with thermo-response hydrogel |
| CN101948277B (en) * | 2010-09-08 | 2012-11-14 | 广西大学 | Method for preparing light porous inorganic gelled material product from gel particles |
| CN102641523A (en) * | 2012-03-07 | 2012-08-22 | 中南大学 | Porous hydroxyapatite biological ceramic and preparation method thereof |
| CN106045568A (en) * | 2016-06-08 | 2016-10-26 | 甘肃迅美节能科技股份有限公司 | Method for preparing high polymer material micropore foam heat insulation tile piece |
| 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 |
| CN106390190A (en) * | 2016-11-07 | 2017-02-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Process for manufacturing alpha-tricalcium phosphate-alpha-calcium sulfate hemihydrates bone cement porous bracket through squashing method |
| CN109251024A (en) * | 2017-07-14 | 2019-01-22 | 上海蓝怡科技股份有限公司 | Porous calcium silicate/bata-tricalcium phosphate compound phase bioceramic preparation method |
| CN108395237B (en) * | 2018-03-02 | 2020-07-03 | 中国科学院上海硅酸盐研究所 | High-strength calcium silicophosphate biological ceramic material and preparation method thereof |
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