CN101423205B - Synthesis technique of beta-calcium orthophosphate - Google Patents
Synthesis technique of beta-calcium orthophosphate Download PDFInfo
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- CN101423205B CN101423205B CN2008102272202A CN200810227220A CN101423205B CN 101423205 B CN101423205 B CN 101423205B CN 2008102272202 A CN2008102272202 A CN 2008102272202A CN 200810227220 A CN200810227220 A CN 200810227220A CN 101423205 B CN101423205 B CN 101423205B
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Abstract
The invention discloses a synthesis technique used for a Beta-calcium phosphate material, comprising the steps as follows: quantitative polystyrene microspheres are added into concentrated sulfuric acid, sufficiently mixed and dispersed by ultrasonic, centrifuged, washed and dried, thus gaining vulcanized polystyrene microspheres; calcium nitrate solution is complexed with diammonium phosphate solution so as to lead the molar ratio of calcium and phosphorus in the complexed solution to be 1.4-1.6; the pH value of the solution is adjusted to be 8-10; furthermore, a surfactant (CTAB) and the vulcanized polystyrene microspheres are added in the complex so as to react sufficiently and gain a white substance which is washed, dried and calcined in a heating surface; subsequently, the white substance is heat-preserved for 2-4 hours at the temperature of 700-1000 DEG C and cooled with the furnace to gain the Beta-calcium phosphate powder. The synthesis technique adds the PS microspheres in the chemical reaction process to synthesize the Beta-calcium phosphate with the aperture and high purity, and has the advantages of simple process, strong repeatability, stable performance of the product, and the like.
Description
Technical field
The invention belongs to material science, especially a kind of synthetic method of beta-calcium phosphate material.
Background technology
Tricalcium phosphate (Tricalcium Phosphate) is called for short TCP, Ca
3(PO
4)
2Since 1980, (α-TCP, β-research TCP) causes numerous scholars' extensive concern to have biological degradability calcium phosphate material TCP.It has megathermal α mutually and two kinds mutually of the β of low temperature modification.The composition of TCP is the same with HAP, all contains CaO and P
2O
5Wherein, β-TCP is most widely used general.The crystal system of α phase is an oblique crystal, lattice parameter
Density is 2.86g/cm
3β is hexahedron mutually,
Density is 3.07g/cm3.The chemical property of β-TCP is similar to hydroxyapatite, solvability to water is big, solubleness in the aqueous solution and body fluid is HAP (solubleness: 1 μ m/) 10～15 times, can slowly be absorbed by body fluid, so, the degraded of TCP can provide abundanter Ca, P for the formation of new bone, can pass through metabolic pathway in vivo, promote new bone tissue to generate, and progressively be the new bone tissue displacement.This material has excellent biological compatibility, and biological degradability can directly combine with bone, is a kind of good bone renovating material.
The method for preparing the TCP powder has dry method.Dry method is promptly synthetic by solid state reaction, can make the good crystallization powder, but grain-size is bigger, often has dephasign to exist, and not only time-consuming but also easy pickup during grinding is therefore in the less employing in biological ceramics field.
Summary of the invention
At the problem that prior art exists, the object of the present invention is to provide the synthetic method of the beta-calcium phosphate material that a kind of technology is simple, repeatability is strong, product performance are stable.
For achieving the above object, the synthetic method of a kind of beta-calcium phosphate material of the present invention is specially:
1) polystyrene microsphere (PS microballoon) with set amount adds the vitriol oil, behind sufficient stirring and ultra-sonic dispersion, dries the polystyrene microsphere after obtaining vulcanizing by centrifugal, washing back again;
2) ca nitrate soln and ammonium dibasic phosphate solution are cooperated, calcium, phosphorus mol ratio proportioning value are 1.4～1.6 in the solution after feasible the cooperation;
3) pH value to 8～10 of regulator solution, and the polystyrene microsphere after adding tensio-active agent (CTAB) and the sulfuration;
4) after the abundant reaction, obtain white mass, with this white mass washing, oven dry, and calcine in process furnace, be incubated 2～4 hours down at 700 ℃～1000 ℃, furnace cooling obtains the beta-calcium phosphate powder.
Further, the concrete sulfidation of described step 1) polystyrene microsphere is: with the polystyrene microsphere (PS microballoon) of set amount, add the vitriol oil, stirred on the magnetic stirring apparatus 5～6 hours, and through ultra-sonic dispersion 0.5～1 hour, 2～3 times repeatedly; And behind centrifugal, absolute ethanol washing, dry.
Further, adopt ammoniacal liquor to regulate pH value in the described step 3).
Further, the preliminary treatment process of white mass is specially in the described step 4): wash with deionized water and dehydrated alcohol respectively, the product after the washing carries out 7～9 hours oven dry under 60 ℃～80 ℃.
Characteristics such as the present invention synthesizes and has aperture and the higher beta-calcium phosphate of purity by add the PS microballoon in chemical reaction process, and the PS microballoon is used for doing template, and it is simple to have technology, and repeatability is strong, and product performance are stable.
Description of drawings
Fig. 1 is the TG-DTA curve of powder among the embodiment 1;
Fig. 2 is the XRD curve of powder among the embodiment 1;
Fig. 3 is the SEM curve of powder among the embodiment 1;
Fig. 4 is the TEM curve of powder among the embodiment 1;
Fig. 5 is the XRD curve of powder among the embodiment 2;
Fig. 6 is the TEM curve of powder among the embodiment 2;
Fig. 7 is the XRD curve of powder among the embodiment 3;
Fig. 8 is the SEM curve of powder among the embodiment 3;
Embodiment
The present invention prepares in the TCP powder process at wet chemistry method, prepares the precursor of β-TCP by adding polystyrene microsphere (PS microballoon), and in the calcining by differing tempss such as 700 ℃～1000 ℃, and is 1.4～1.6 by the molar ratio that changes calcium phosphorus; Realize synthetic pure calcium phosphate powder.
The PS template is by using the pure nitrocalcite (Ca (NO of chemical analysis
3)
2) and Secondary ammonium phosphate ((NH
4)
2HPO
4) reaction, add tensio-active agent (CTAB) and ammoniacal liquor (NH in the reaction process
3H
2O), ammoniacal liquor is used for the pH value of conditioned reaction solution, the PS microballoon is used for doing template, earlier nitrocalcite and Secondary ammonium phosphate are made into the solution of certain concentration, tensio-active agent (CTAB) and polystyrene (PS) are joined in the ca nitrate soln, ammonium dibasic phosphate solution joins in the above-mentioned solution slowly, Ca/P ratio is 1.4～1.6 in the reaction formula, meanwhile pH value to 8～10 of conditioned reaction solution will be reacted burning and will be put on the magnetic stirring apparatus, make that reaction is even and it is complete to carry out.After question response is complete and even, as seen adularescent precipitates in the reaction flask, wash with deionized water and dehydrated alcohol respectively, product after the washing is put into baking oven, under 60 ℃～80 ℃, carry out oven dry in 7～9 hours, product after the oven dry finally obtains the bata-tricalcium phosphate powder 700 ℃～1000 ℃ calcinings.
The present invention is by adding the PS microballoon, change calcium phosphorus mol ratio and calcining temperature, obtaining a kind of novel bone alternate material that has the controlled tricalcium phosphate pure phase of pore size.
Embodiment 1:
The prescription of each component is as shown in table 1, takes by weighing an amount of PS microballoon, adds the vitriol oil, stirred 5 hours on the magnetic stirring apparatus, and through ultra-sonic dispersion half hour, 2-3 time repeatedly.Behind centrifugal, absolute ethanol washing, dry, standby.Take by weighing nitrocalcite and diammonium hydrogen phosphate is made into saturated solution, Secondary ammonium phosphate splashed into slowly the ratio of calcium and phosphorus proportioning is 1.5:1 in the ca nitrate soln, the PS microballoon after the adding sulfuration simultaneously and the pH value of Surfactant CTAB ammoniacal liquor conditioned reaction are about 9, stir on the magnetic stirring apparatus, ageing behind the sufficient reacting, through centrifugal, dehydrated alcohol repetitive scrubbing, 70 ℃ of oven dry in the drying baker are fired to 700 ℃, 800 ℃, 850 ℃ and are incubated 3 hours respectively.
Table 1: the prescription of each component
Embodiment 2:
Take by weighing an amount of PS microballoon, add the vitriol oil, stirred 6 hours on the magnetic stirring apparatus, through ultra-sonic dispersion half hour, 2-3 time repeatedly.Behind centrifugal, absolute ethanol washing, dry, standby.Take by weighing nitrocalcite and diammonium hydrogen phosphate is made into saturated solution, calcium phosphorus mol ratio proportioning is 1.4:1, the PS microballoon after the adding sulfuration simultaneously and the pH value of Surfactant CTAB ammoniacal liquor conditioned reaction are about 8.5, stir on the magnetic stirring apparatus, ageing behind the sufficient reacting, through centrifugal, dehydrated alcohol repetitive scrubbing, 70 ℃ of oven dry in the drying baker are fired to 700 ℃, 800 ℃, 850 ℃ and are incubated 3 hours respectively.
Embodiment 3:
Take by weighing an amount of PS microballoon, add the vitriol oil, stirred 5 hours on the magnetic stirring apparatus, through ultra-sonic dispersion half hour, 2-3 time repeatedly.Behind centrifugal, absolute ethanol washing, dry, standby.Take by weighing nitrocalcite and Secondary ammonium phosphate is made into saturated solution, calcium phosphorus mol ratio proportioning is 1.6:1, the PS microballoon after the adding sulfuration simultaneously and the pH value of Surfactant CTAB ammoniacal liquor conditioned reaction are about 8, stir on the magnetic stirring apparatus, ageing behind the sufficient reacting, through centrifugal, dehydrated alcohol repetitive scrubbing, 70 ℃ of oven dry in the drying baker are fired to 700 ℃, 800 ℃, 900 ℃ and are incubated 3 hours respectively.
The characteristics such as the present invention synthesizes with aperture and the higher beta-calcium phosphate of purity by add the PS microballoon in chemical reaction process, and the PS microballoon is used for doing template, and it is simple to have technology, and repeatability is strong, and properties of product are stable.
Claims (4)
1. the synthetic method of a beta-calcium phosphate material is specially:
1) polystyrene microsphere (PS microballoon) with set amount adds the vitriol oil, behind sufficient stirring and ultra-sonic dispersion, dries the polystyrene microsphere after obtaining vulcanizing by centrifugal, washing back again;
2) ca nitrate soln and ammonium dibasic phosphate solution are cooperated, calcium, phosphorus mol ratio proportioning value are 1.4～1.6 in the solution after feasible the cooperation;
3) pH value to 8～10 of regulator solution, and the polystyrene microsphere after adding tensio-active agent and vulcanizing;
4) after the abundant reaction, obtain white mass, with this white mass washing, oven dry, and calcine in process furnace, be incubated 2～4 hours down at 700 ℃～1000 ℃, furnace cooling obtains the beta-calcium phosphate powder.
2. the synthetic method of beta-calcium phosphate material as claimed in claim 1, it is characterized in that, the concrete sulfidation of described step 1) polystyrene microsphere is: with the polystyrene microsphere (PS microballoon) of set amount, add the vitriol oil, stirred on the magnetic stirring apparatus 5～6 hours, through ultra-sonic dispersion 0.5～1 hour, 2～3 times repeatedly; And behind centrifugal, absolute ethanol washing, dry.
3. the synthetic method of beta-calcium phosphate material as claimed in claim 1 is characterized in that, adopts ammoniacal liquor to regulate the pH value in the described step 3).
4. the synthetic method of beta-calcium phosphate material as claimed in claim 1, it is characterized in that, the preliminary treatment process of white mass is specially in the described step 4): wash with deionized water and dehydrated alcohol respectively, the product after the washing carries out 7～9 hours oven dry under 60 ℃～80 ℃.
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| CN102556993B (en) * | 2012-01-06 | 2013-08-21 | 青岛科技大学 | Method of preparing hydroxyapatite with three-dimensional nanoflower structure |
| CN104445130B (en) * | 2014-11-27 | 2016-09-14 | 武汉理工大学 | A kind of mesoporous bata-tricalcium phosphate raw powder's production technology |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1278512A (en) * | 2000-07-25 | 2001-01-03 | 张友贵 | Production process of fine active calcium phosphate |
| CN101254910A (en) * | 2008-04-14 | 2008-09-03 | 北京化工大学 | Method for preparing calcium phosphate composite powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1278512A (en) * | 2000-07-25 | 2001-01-03 | 张友贵 | Production process of fine active calcium phosphate |
| CN101254910A (en) * | 2008-04-14 | 2008-09-03 | 北京化工大学 | Method for preparing calcium phosphate composite powder |
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