CN1171644C - Preparation method of wollastone/tricalcium phosphate composite bio-active material - Google Patents
Preparation method of wollastone/tricalcium phosphate composite bio-active material Download PDFInfo
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- CN1171644C CN1171644C CNB02110848XA CN02110848A CN1171644C CN 1171644 C CN1171644 C CN 1171644C CN B02110848X A CNB02110848X A CN B02110848XA CN 02110848 A CN02110848 A CN 02110848A CN 1171644 C CN1171644 C CN 1171644C
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- tricalcium phosphate
- wollastonite
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Abstract
The present invention relates to a preparation method of compounding grammite /tricalcium phosphate biologic material, which belongs to the field of biologic material. The present invention is characterized in that Na2SiO3 or silicon collosol is taken as a silicon source, Ca(NO3)2, CaCl2 or Ca(OH)2 is taken as a calcium source, and the material as the silicon source and the material as the calcium source are respectively prepared into solution with a certain concentration and pH value; a right amount of beta-tricalcium phosphate (beta-TCP) is added to the calcic solution, and the beta-tricalcium phosphate disperses evenly; then, a uniformly mixed precipitated substance of a calcium silicate hydrate and beta-TCP powder is prepared by a chemical coprecipitation method; the precipitated substance is washed, baked and calcined at a temperature of 800 to 900DEG C to obtain the grammite and compounding beta-TCP powder; the compounding beta-TCP powder is processed by granulating and dry pressing for forming; the formed granules are sintered at an air temperature of 1300 to 1400 DEG C for 2 to 5 hours to obtain the compounding grammite/ tricalcium phosphate biological ceramic. The components in the compounding biologic material prepared by the method of the present invention can be adjusted according to different needs, particularly the formation of an in situ porous structure is easy for the tissues, blood vessels, etc. to grow in the structure.
Description
Technical field
The present invention relates to the preparation method of wollastonite/tricalcium phosphate composite biological material, belong to technical field of biological material, be mainly used in filling up, repair and rebuilding of human body hard tissue in the biomedicine (skeleton and tooth).
Background technology
The A-W glass ceramics of people such as T.Kokubo invention is the best biological active ceramic material of present known mechanical property.Wollastonite is as one of two kinds of crystallite phases in the A-W glass ceramics (another kind is an apatite), and not only the mechanical property to the A-W glass ceramics has significant contribution, and also has very high biological activity simultaneously.T.Kokubo is studying CaO-SiO
2-P
2O
5Point out behind the system bioactivity glass: the various bioactive materials of tool difference in functionality can be at CaO-SiO
2Develop on the basis of base bio-vitric.In view of this, technical field of biological material scholar begins to abandon " phosphorus is essential component in the biomaterial " this traditional view, then to wollastonite ceramics and CaO-SiO
2Be that biomaterials such as bio-vitric are studied.
P.N.De Aza etc. considers that biomaterial implants the carrying at initial stage and growing into of the tissue in the agglutination, and design has prepared before a kind of the implantation fine and close and implant the in-situ pore-formed composite biological material in back.In this composite biological material, one is the wollastonite (Wollastonite) of biologically active mutually, and another then is a biodegradable tricalcium phosphate (TCP) mutually.In the composite biological material preparation, place platinum crucible to be heated to 1500 ℃ in 2 hours wollastonite and tricalcium phosphate, obtain uniform liquid phase, reduce to 1410 ℃ with 3 ℃/minute speed then, reduce to 1390 ℃ with 0.5 ℃/hour speed again.Zhi Bei composite biological material has by wollastonite and tricalcium phosphate interlaminate and the accurate spherical congruent melting structure that forms thus.In simulated body fluid and human saliva soak test, calcium silicates in this kind wollastonite/tricalcium phosphate composite biological material is optionally disappeared molten, form the original position loose structure, and tricalcium phosphate wherein changes into apatite low-crystallinity, tool tricalcium phosphate false appearance.At the later stage of test, in the solution because Ca
2+And HPO
4 2-Supersaturation also cause the deposition of hydroxyapatite layer at material surface.This shows that above-mentioned wollastonite/tricalcium phosphate composite biological material has the advantage of good biological activity and original position formation loose structure.
But, above-mentioned also have following shortcoming by designs such as P.N.De Aza preparation wollastonite/tricalcium phosphate composite biological material: temperature higher (1390-1500 ℃) in the ceramic post sintering process, time is grown (greater than 40 hours), so the preparation process energy consumption is big, and the cost height.In addition, because molding in advance, thereby the design of the form of sample also is restricted.
Summary of the invention
The preparation method that the purpose of this invention is to provide a kind of wollastonite/tricalcium phosphate composite biological material.The method is according to different needs, can regulate the ratio of wollastonite and tricalcium phosphate in the composite; In the Composite Preparation process, the tricalcium phosphate of adding can be regulated and control its granular size and form, particle size distribution etc.; Because molding in advance, thereby the form design limit of sample is less; Wollastonite/tricalcium phosphate composite biological material biological activity the height of preparation can form the hydroxyapatite layer that contains carbonate on its surface very soon in simulated body fluid soaks; Especially the formation of original position loose structure be very beneficial for organizing, the growing into of blood vessel etc.
The present invention prepares wollastonite/tricalcium phosphate composite biological material and comprises two steps: the one, and the composite granule of preparation wollastonite and tricalcium phosphate, the 2nd, the sintering of composite granule.Concrete technical scheme is as follows: with Na
2SiO
3Or Ludox is silicon source, Ca (NO
3)
2Or CaCl
2, Ca (OH)
2Be the calcium source, be mixed with certain density solution respectively, wherein, siliceous solution pH value is greater than 13.0, calcic solution pH value 12.0-13.0, and its pH value or use a strong aqua ammonia, or use KOH, or regulate with NaOH solution.Ca
2+, Si
4+Concentration between the 0.1-0.5 mol, Ca
2+/ Si
4+=1.0; By the volume ratio of the β-TCP that designs with the wollastonite of expection generation, (β-TCP) powder body joins above-mentioned containing in the calcium solution, and powerful stirring or ultra-sonic dispersion make it even with an amount of bata-tricalcium phosphate; Then, siliceous drips of solution is joined in the suspension of intensively stirred calcic and β-TCP powder, generate the calcium silicate hydrate of white and the mixed uniformly precipitate of β-TCP powder body, continue stirring into product after being added dropwise to complete, the one-tenthization time is 12-24 hour; Sucking filtration is removed solution then, uses the deionized water through ammonia adjusting pH value (pH=11.0-12.0) repeatedly to clean white depositions, after the reuse dehydrated alcohol repeatedly washes white depositions, is placed in the baking oven, dries through 24 hours in 80-120 ℃; Calcined 1-2 hour, and obtained wollastonite and β-TCP composite granule for 800-900 ℃; With the dehydrated alcohol is ball-milling medium, and with powder body ball milling 12-24 hour, 80-120 ℃ through oven dry in 24 hours; Add the PVA quality and be the solution of 1% dry powder preparation, behind the powder body mix homogeneously, cross the pelletize of 40-100 order mesh screen; Preforming under 10-20MPa is again through static pressure such as 200MPa; 1300-1400 ℃ of air atmosphere, 2-5 hour pressureless sintering obtain wollastonite/tricalcium phosphate composite biological material.
Fig. 1 is that wollastonite/tricalcium phosphate composite biological material soaks the SEM image that different time rear surface pattern changes in simulated body fluid.When composite biological material soaked one day in simulated body fluid after, its surface was covered (Fig. 1-(B)) by bobbles shape sedimentary deposit, and the EDS of Fig. 2 the analysis showed that, this sedimentary deposit chemical analysis is Ca and P (Fig. 2-(B)); In the time of 3 days, Ca, P " bobbles " thereby interconnect makes sedimentary deposit become fine and close (Fig. 1-(C)); During by 7 days, it is fine and close more that sedimentary deposit becomes, and have new spherical depositional fabric to generate on compacted zone again.When biomaterial was carried out the external biological activity rating, it was according to being in simulated body fluid soaks, and speed that biomaterial surface hydroxyapatite sedimentary deposit forms, grows and sedimentary deposit are to the situation of biomaterial surface covering.The wollastonite of Fig. 1/tricalcium phosphate composite biological material surface hydroxyl apatite sedimentary deposit forms, the speed of growth is fast, and can very fast complete covering surfaces, and this illustrates that this wollastonite/tricalcium phosphate composite biological material has good biological activity.
Fig. 3 is wollastonite/tricalcium phosphate composite biological material soaks different time in simulated body fluid after, the situation that Ca, Si, P concentration change in the simulated body fluid.The Ca ion concentration was rising in 28 days that soak always, and just soaking rose after 3 days just tends to be steady; The Si ion concentration rose very fast at initial 3 days that soak, after this tend to be steady.The P ion concentration is soaking at the beginning just sharply decline, and is almost nil during by 7 days.This be because: in the initial stage of soaking, Ca in the solution, P ion concentration are saturated with respect to hydroxyapatite, and are unsaturated to wollastonite, so wollastonite is optionally dissolved, form the original position loose structure, discharge Ca, Si ion, Si ion polymerization heavily again forms the silicon gel.On the other hand, the rising of Ca ion concentration has further increased the degree of supersaturation of hydroxyapatite in the solution, and the silicon gel provides good nucleation site, thereby apatite layer deposits simultaneously at specimen surface, and this shows as the rapid decline of P ion concentration.The deposition of apatite layer has hindered Ca, Si ion from sample freely spreading to simulated body fluid, thereby has suppressed the further dissolving of wollastonite to a certain extent.At this moment, Ca, Si ion concentration tend to be steady.
Fig. 4 is wollastonite/tricalcium phosphate composite biological material soaks different time in simulated body fluid after, the situation of change of pH value in the simulated body fluid.Be soaked in wollastonite/tricalcium phosphate composite biological material the 28 day time of simulated body fluid, the pH value of simulated body fluid rises to 7.66 from initial 7.25, and this is because the Ca in the biomaterial
2+With H in the simulated body fluid
+The cause that exchange, simulated body fluid do not upgrade always.In people or animal body, body fluid is not arrhea moving the renewal, and the pH value around the implant can maintain within the normal level fully.
Fig. 5, Fig. 6 are wollastonite/tricalcium phosphate composite biological material soaks different time in simulated body fluid after, its surface are carried out the result of thin film X-ray diffraction (TF-XRD) and fourier infrared conversion spectrum (FTIR) analysis.By above test as can be known, wollastonite/tricalcium phosphate composite biological material (WT (0)) soaks after 1 day in simulated body fluid, its surface has formed the lower hydroxyapatite layer that contains carbonate of degree of crystallinity, because the characteristic diffraction peak (2 θ=32 ° and 26 °) of hydroxyapatite in the TF-XRD collection of illustrative plates, occurred, and PO also arranged respectively on the FTIR collection of illustrative plates
4 3-(1100cm
-1), CO
3 2-(1400-1550cm
-1), OH
-(2500-3700cm
-1) absworption peak; Along with the prolongation of soak time, the diffracted intensity of above-mentioned sedimentary deposit increases gradually, and the information of wollastonite/tricalcium phosphate substrate weakens gradually to nothing, and this thickness that shows the hydroxyapatite sedimentary deposit is in continuous increase.
The composite biological material of method preparation provided by the invention can be regulated each component in the composite according to different needs; Especially the formation of original position loose structure be very beneficial for organizing, the growing into of blood vessel etc.Therefore, the wollastonite/tricalcium phosphate composite biological material of method provided by the invention preparation can be applicable to human body hard tissue (bone and tooth) reparation, fill up and rebuild.
Description of drawings
Fig. 1 wollastonite/tricalcium phosphate composite material soaks surface scan ultramicroscope (SEM) morphology analysis behind the different time before immersion and in simulated body fluid.(A), (B) (C), (D) represent respectively: before soaking and soak 1,3,7 day surperficial SEM image.
Fig. 2 wollastonite/tricalcium phosphate composite material soaks surface energy spectrometer (EDS) component analysis after 14 days before immersion and in simulated body fluid.
Fig. 3 wollastonite/tricalcium phosphate composite material soaks different time in simulated body fluid after, inductively coupled plasma-atomic emission spectrum (ICP-AES) component analysis of Ca, Si, P concentration change in the simulated body fluid.Abscissa is a soak time, and unit is a natural law; Ordinate is a concentration of element, and unit is mM.
Fig. 4 wollastonite/tricalcium phosphate composite material soaks different time in simulated body fluid after, the situation that pH value changes in the simulated body fluid.Abscissa is a soak time, and unit is a natural law; Ordinate is a pH value.
Fig. 5 wollastonite/tricalcium phosphate composite material soaks different time in simulated body fluid after, its surface film X-ray diffraction (TF-XRD) is analyzed collection of illustrative plates.Zero represents apatite among the figure.
Fig. 6 wollastonite/tricalcium phosphate composite material soaks different time in simulated body fluid after, its surperficial fourier infrared conversion spectrum (FTIR) is analyzed collection of illustrative plates.
The specific embodiment
The invention will be further described below in conjunction with example, but only be confined to embodiment by no means.
Operating procedure is as follows
(1) with 124.85 gram analytical pure Ca (NO
3)
24H
2O joins in the appropriate amount of deionized water, is stirred to the dissolving clarification, adds proper ammonia, regulator solution pH value to 12.0, and this moment, the volume of solution was 1.25 liters;
(2) 38 gram β-TCP powder body are joined above-mentioned Ca (NO
3)
2In the solution, the powerful stirring 30 minutes is uniformly dispersed so that add powder body;
(3) with 145.55 gram analytical pure Na
2SiO
39H
2O joins in the appropriate amount of deionized water, is stirred to the dissolving clarification, is equipped with 1.25 liters of solution, and recording its pH value is 13.40;
(4) the powerful stirring is equipped with good Ca (NO
3)
2And β-TCP powder body suspension, simultaneously with above-mentioned Na
2SiO
3Drips of solution is added to wherein, generates the precipitation of calcium silicate hydrate and β-TCP uniform mixing; Wait to be added dropwise to complete, continue to stir 12 hours, so that reaction is carried out fully;
(5) sucking filtration removes solution, uses deionized water, the dehydrated alcohol repeated multiple times cleaning reaction gained precipitation of regulating pH value to 12.0 through ammonia, then in baking oven in 80 ℃, through oven dry in 24 hours;
(6) in calcining furnace, under the air atmosphere, 900 ℃ obtain wollastonite/tricalcium phosphate composite powder through calcining in 2 hours; With the dehydrated alcohol is ball-milling medium, ball milling calcium silicate powder 24 hours, then in baking oven in 80 ℃, through 24 hours the oven dry;
(7) in wollastonite/tricalcium phosphate composite powder, cross 100 order mesh screen pelletizes after adding the PVA quality and be 1% PVA solution mix homogeneously.Under 10MPa, with above-mentioned powder body pre-molding, again in the inferior static pressure of 200MPa;
(8) under the air atmosphere, 1400 ℃, the 2 hours above-mentioned samples of sintering, obtain wollastonite/tricalcium phosphate composite material;
The composite of preparation soaked respectively in simulated body fluid 1,3,7,14,21,28 day, and specimen surface pattern, composition, structural change are shown in Fig. 4,5,6.
In the wollastonite/tricalcium phosphate composite biological material of present embodiment preparation, the volume ratio design between wollastonite and the tricalcium phosphate is at 60: 40, and between the two ratio should reach designing requirement in the last product.Because reaction is to carry out, continue into change after drips of solution adds, and deionized water is regulated pH value through ammonia, Ca when this all helps reacting when cleaning calcium silicate hydrate under strong basicity (pH＞12.0) condition
2+Abundant deposition, prevented Ca in the washing process effectively
2+Loss.
The simulated body fluid immersion test is the result show, wollastonite/tricalcium phosphate composite biological material has good biological activity, and particularly the formation of original position loose structure is particularly important.This is because biomaterial then need have certain mechanical property if any carrying in early days what implant; When the original position loose structure formed, interface bond strength between organism and the embedded material had then been strengthened in growing into of blood capillary and tissue again, thereby more helped carrying, was beneficial to the reconstruction and the healing of tissue.Therefore, the wollastonite/tricalcium phosphate composite biological material of method provided by the invention preparation can be applicable to human body hard tissue (bone and tooth) reparation, fill up and rebuild.
Claims (7)
1. the preparation method of wollastonite/tricalcium phosphate composite biological material comprises the preparation of wollastonite/tricalcium phosphate composite powder and two processing steps of sintering of composite granule, it is characterized in that:
(1) preparation of composite granule comprises
1. first compound concentration is the Ca between the 0.1-0.5 mol respectively
2+/ Si
4+Solution that=1.0 strong basicity is siliceous and calcareous solution;
2. press the volume ratio of wollastonite/tricalcium phosphate, β-TCP powder body is joined and contains in the calcium solution, and brute force stirs or ultra-sonic dispersion is even;
3. siliceous drips of solution is added in the suspension of the powerful calcic that stirs and β-TCP powder body, generate the calcium silicate hydrate and the β-mixed uniformly precipitate of TCP powder body of white, after being added dropwise to complete, continue to stir the one-tenthization product;
4. sucking filtration is removed solution, and using the pH that regulates through ammonia is the washed with de-ionized water white depositions of 11-12, after the reuse dehydrated alcohol cleans, dries through 24 hours in 80-120 ℃; And 800-900 ℃ of calcining 1-2 hour after ball milling, pulverizing, filtration obtain wollastonite/calcium phosphate composite granule;
(2) sintering of composite granule comprises
1. in the wollastonite/calcium phosphate composite granule of above-mentioned preparation, add the PVA quality and be the solution of 1% PVA dry powder preparation, mix the back evenly, cross the pelletize of 40-100 order mesh screen;
2. preforming is after the 200MPa isostatic compaction, and wollastonite/tricalcium phosphate composite material is made in pressureless sintering in 2-5 hour under the 1300-1400 ℃ of air conditions.
2. by the preparation method of the described wollastonite of claim 1/tricalcium phosphate composite biological material, it is characterized in that siliceous solution is with Na
2SiO
3Or Ludox is the silicon source; Calcareous solution is with Ca (NO
3)
2Or CaCl
2, Ca (OH)
2Be the calcium source.
3. by the preparation method of claim 1 or 2 described wollastonite/tricalcium phosphate composite biological materials, it is characterized in that described siliceous solution pH value is greater than 13.0; Calcareous solution pH value 12.0-13.0; PH value is or uses strong aqua ammonia, or uses KOH, or regulate with NaOH solution.
4. by the preparation method of the described wollastonite of claim 1/tricalcium phosphate composite biological material, the volume ratio that it is characterized in that wollastonite/tricalcium phosphate is 60: 40.
5. by the preparation method of the described wollastonite of claim 1/tricalcium phosphate composite biological material, it is characterized in that into the change response time is 12-24 hour.
6. by the preparation method of the described wollastonite of claim 1/tricalcium phosphate composite biological material, it is characterized in that described calcining back composite granule warp is a ball-milling medium with the dehydrated alcohol, in 80-120 ℃, dried in 24 hours after 12-24 hour.
7. by the preparation method of the described wollastonite of claim 1/tricalcium phosphate composite biological material, it is characterized in that described wollastonite/preformed pressure of tricalcium phosphate powder body is 10-20MPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402099C (en) * | 2006-09-15 | 2008-07-16 | 浙江理工大学 | Method for preparing fibroin/calcium phosphate composite material regulated and controlled by silicon |
| RU2743834C1 (en) * | 2020-04-06 | 2021-02-26 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for producing porous bioceramic wollastonite |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293017C (en) * | 2004-10-28 | 2007-01-03 | 中国科学院上海硅酸盐研究所 | Bredigites biological ceramic and preparation method and application thereof |
| 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 |
| CN101041089B (en) * | 2007-04-28 | 2013-11-06 | 中国科学院上海硅酸盐研究所 | Compound biological material of compact high-strength titanium silicidation/calcium silicate and preparation method thereof |
| CN101367525B (en) * | 2008-09-19 | 2011-08-03 | 中国科学院上海硅酸盐研究所 | Sodium calcium silicate biological material, preparation method and uses thereof |
| CN102139124A (en) * | 2011-01-20 | 2011-08-03 | 胡钢锋 | Degradable composite calcium phosphate bone cement composition and preparation method and application thereof |
| CN108569896B (en) * | 2018-03-21 | 2021-04-06 | 山东大学 | Calcium polyphosphate/wollastonite biological composite ceramic material and preparation method thereof |
-
2002
- 2002-02-09 CN CNB02110848XA patent/CN1171644C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402099C (en) * | 2006-09-15 | 2008-07-16 | 浙江理工大学 | Method for preparing fibroin/calcium phosphate composite material regulated and controlled by silicon |
| RU2743834C1 (en) * | 2020-04-06 | 2021-02-26 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for producing porous bioceramic wollastonite |
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