CN103466581B - Method for preparing hollow hexagonal-prism-shaped hydroxyapatite crystal - Google Patents
Method for preparing hollow hexagonal-prism-shaped hydroxyapatite crystal Download PDFInfo
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Abstract
The invention relates to a method for preparing a hollow hexagonal-prism-shaped hydroxyapatite crystal, belonging to the field of ceramic materials. The method is characterized by comprising the steps of preparing an aqueous solution containing L-glutamic acid, disodium hydrogen phosphate and sodium hydroxide, sequentially adding yttrium nitrate, calcium nitrate and urea, uniformly stirring, then, pouring into a hydrothermal kettle until the loaded rate of the hydrothermal kettle is 90%, carrying out two-step hydrothermal reaction, then, carrying out furnace cooling, filtrating, washing, and drying, thereby obtaining the hollow hexagonal-prism-shaped hydroxyapatite crystal. The method for preparing the hollow hexagonal-prism-shaped hydroxyapatite crystal, disclosed by the invention, is simple, and the prepared crystal has broad application prospects in the fields of surface adsorption, catalysis, drug carrier, composites and the like.
Description
Technical field
The present invention relates to a kind of preparation method of hollow hexa-prism hydroxyapatite crystal, belong to stupalith field.
Background technology
Hydroxyapatite and human body hard tissue, as bone is similar with the inorganic components of tooth, have a wide range of applications in bio-medical field as stupalith, concrete application comprises the bone substitute materials of the packing material of Cranial defect position, the top coat of artificial skelecton metallic substance and the position that do not stress, the use properties of this type of material and the structure of hydroxyapatite crystal have substantial connection, and therefore researchist develops many methods to prepare hydroxyapatite crystal.In most widely used chemical precipitation method, hydro-thermal reaction method is a kind of simple, the easy to operate method of technique, prepare granular, corynebacterium or fibrous hydroxyapatite crystal mainly through the regulation and control nucleution and growth behavior of crystal in water-heat process, can use as the wild phase of the carrier of sorbent material, catalyzer and medicine and matrix material.
Although the preparation method of hydroxyapatite crystal is a lot, the Patent data with the hydroxyapatite crystal aspect of hollow structure is less.Chinese patent CN101172592A discloses and utilizes in water-heat process the method for adding DMF to prepare hydroxyapatite micrometre tube, internal diameter 450 ~ 550 nanometer, external diameter 1000 ~ 1200 nanometer, and length is 30 ~ 50 microns.Chinese patent CN101786615 A discloses that to utilize in water-heat process the method for adding organic amine to prepare diameter be 20 ~ 80 nanometers, the hydroxyapatite nano pipe of long 1 ~ 20 micron.These two kinds of methods adopt chemical reagent to have certain toxicity, larger size also have developed it in biomedical and other industrial application.Disclose in Chinese patent CN101428779A and in reaction soln, add disodium ethylene diamine tetraacetate and after adjust ph, adopt the method for hydro-thermal reaction to prepare the hydroxyapatite with hollow structure, the nanometer hexa-prism crystal wherein prepared is closed at both ends, limits medicine and the equimolecular loading process of catalyzer.Aforesaid method there is no method and effectively regulates and controls hydroxyapatite size, pattern and structure, and these character are to the physical and chemical performance of crystal, as surface adsorption, catalysis and and matrices of composite material between the performance such as bonding strength have significant impact.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of hollow hexa-prism hydroxyapatite crystal, this method has required device simple, the reagent safety selected and can the advantage such as structure of Effective Regulation crystal.
For achieving the above object, the technical solution adopted in the present invention is as follows:
Step 1. is prepared containing 0.091 mole of often liter of Pidolidone, the aqueous solution of Sodium phosphate dibasic and 0.039 mole of often liter of sodium hydroxide, after stirring at room temperature makes it dissolve completely, add Yttrium trinitrate successively again, nitrocalcite and urea, it is 0.056 mole often liter that configuration obtains urea-containing concentration, calcium ion and ruthenium ion total concn are the mixing solutions of 0.026 mole often liter, wherein ruthenium ion concentration is 0.004 ~ 0.013 mole often liter, calcium ion concn is 0.022 ~ 0.013 mole often liter, the ratio of the volumetric molar concentration that the concentration changing Sodium phosphate dibasic makes the volumetric molar concentration of phosphoric acid hydrogen radical ion and calcium ion and ruthenium ion total is 0.92:1 ~ 1.11:1,
The mixing solutions stirred is transferred in stainless steel autoclave by step 2., and filling rate is 90%, and under 100oC, process is warming up to 160oC ~ 180oC again in 24 hours and is cooled to room temperature after processing 24 hours;
The reaction product that step 2 is obtained by reacting by step 3. after filtration, washing and dry, prepare hollow hexa-prism hydroxyapatite crystal.
In preparation process, provide phosphoric acid hydrogen radical ion by Sodium phosphate dibasic, provide calcium ion by nitrocalcite, provide ruthenium ion by Yttrium trinitrate.The hollow hexa-prism hydroxyapatite crystal with constructional feature is prepared by changing calcium ion and the total concn of ruthenium ion and the temperature of the ratio of phosphoric acid hydrogen radical ion concentration, the concentration of ruthenium ion or hydro-thermal reaction.Concentration wherein by changing Sodium phosphate dibasic regulates the total concn of calcium ion and ruthenium ion and the ratio of phosphoric acid hydrogen radical ion concentration; When changing the concentration of ruthenium ion, also the concentration of corresponding change calcium ion is constant to guarantee the total concn of calcium ion and ruthenium ion.
Beneficial effect of the present invention is: the device prepared needed for crystal is simple and easy, and utilize reagent cheap and easy to get as reactant, production cost is low.Selected chemical reagent safety, toxicity are little, and environmental pollution is few.Can the structure of conveniently regulating and controlling crystal by the selection of processing condition.
Accompanying drawing explanation
Fig. 1 is hollow hexa-prism hydroxyapatite crystal X-ray powder diffraction figure prepared by the embodiment of the present invention 1.
Fig. 2 is hollow hexa-prism hydroxyapatite crystal SEM electron scanning micrograph prepared by the embodiment of the present invention 1.
Fig. 3 is hollow hexa-prism hydroxyapatite crystal SEM electron scanning micrograph prepared by the embodiment of the present invention 2.
Fig. 4 is hollow hexa-prism hydroxyapatite crystal SEM electron scanning micrograph prepared by the embodiment of the present invention 3.
Fig. 5 is hollow hexa-prism hydroxyapatite crystal SEM electron scanning micrograph prepared by the embodiment of the present invention 4.
Embodiment
Embodiment 1
1) preparation is containing the aqueous solution of 0.091 mole of often liter of Pidolidone, 0.024 mole of often liter of Sodium phosphate dibasic and 0.039 mole of often liter of sodium hydroxide, after stirring at room temperature makes it dissolve completely, add Yttrium trinitrate, nitrocalcite and urea successively again, make its concentration be respectively 0.004,0.022 and 0.056 mole often liter;
2) by the solution stirring of step 1) evenly after transfer in stainless steel autoclave, filling rate is 90%, and under 100oC, process is warming up to 160oC again in 24 hours and is cooled to room temperature after processing 24 hours;
3) by step 2) reaction product that obtains after filtration, washing and dry, prepare hollow hexa-prism hydroxyapatite crystal.
Product is accredited as hydroxyapatite (see figure 1) through X-ray powder diffraction.SEM scanning electronic microscope testing product pattern (see figure 2).
Embodiment 2
1) preparation is containing the aqueous solution of 0.091 mole of often liter of Pidolidone, 0.024 mole of often liter of Sodium phosphate dibasic and 0.039 mole of often liter of sodium hydroxide, after stirring at room temperature makes it dissolve completely, add Yttrium trinitrate, nitrocalcite and urea successively again, make its concentration be respectively 0.013,0.013 and 0.056 mole often liter;
2) by the solution stirring of step 1) evenly after transfer in stainless steel autoclave, filling rate is 90%, and under 100oC, process is warming up to 160oC again in 24 hours and is cooled to room temperature after processing 24 hours;
3) by step 2) reaction product that obtains after filtration, washing and dry, prepare hollow hexa-prism hydroxyapatite crystal.
Product is accredited as hydroxyapatite and a small amount of yttrium phosphate through X-ray powder diffraction.SEM scanning electronic microscope testing product pattern (see figure 3).
Embodiment 3
1) preparation is containing the aqueous solution of 0.091 mole of often liter of Pidolidone, 0.029 mole of often liter of Sodium phosphate dibasic and 0.039 mole of often liter of sodium hydroxide, after stirring at room temperature makes it dissolve completely, add Yttrium trinitrate, nitrocalcite and urea successively again, make its concentration be respectively 0.004,0.022 and 0.056 mole often liter;
2) by the solution stirring of step 1) evenly after transfer in stainless steel autoclave, filling rate is 90%, and under 100oC, process is warming up to 160oC again in 24 hours and is cooled to room temperature after processing 24 hours;
3) by step 2) reaction product that obtains after filtration, washing and dry, prepare hollow hexa-prism hydroxyapatite crystal.
Product is accredited as hydroxyapatite through X-ray powder diffraction.SEM scanning electronic microscope testing product pattern (see figure 4).
Embodiment 4
1) preparation is containing the aqueous solution of 0.091 mole of often liter of Pidolidone, 0.024 mole of often liter of Sodium phosphate dibasic and 0.039 mole of often liter of sodium hydroxide, after stirring at room temperature makes it dissolve completely, add Yttrium trinitrate, nitrocalcite and urea successively again, make its concentration be respectively 0.004,0.022 and 0.056 mole often liter;
2) by the solution stirring of step 1) evenly after transfer in stainless steel autoclave, filling rate is 90%, and under 100oC, process is warming up to 180oC again in 24 hours and is cooled to room temperature after processing 24 hours;
3) by step 2) reaction product that obtains after filtration, washing and dry, prepare hollow hexa-prism hydroxyapatite crystal.
Product is accredited as hydroxyapatite through X-ray powder diffraction.SEM scanning electronic microscope testing product pattern (see figure 5).
Claims (1)
1. a preparation method for hollow hexa-prism hydroxyapatite crystal, is characterized in that comprising the following steps:
Step 1. is prepared containing 0.091 mole of often liter of Pidolidone, the aqueous solution of Sodium phosphate dibasic and 0.039 mole of often liter of sodium hydroxide, after stirring at room temperature makes it dissolve completely, add Yttrium trinitrate successively again, nitrocalcite and urea, it is 0.056 mole often liter that configuration obtains urea-containing concentration, calcium ion and ruthenium ion total concn are the mixing solutions of 0.026 mole often liter, wherein ruthenium ion concentration is 0.004 ~ 0.013 mole often liter, calcium ion concn is 0.022 ~ 0.013 mole often liter, the ratio of the volumetric molar concentration that the concentration changing Sodium phosphate dibasic makes the volumetric molar concentration of phosphoric acid hydrogen radical ion and calcium ion and ruthenium ion total is 0.92:1 ~ 1.11:1,
The mixing solutions stirred is transferred in stainless steel autoclave by step 2., and filling rate is 90%, and under 100oC, process is warming up to 160oC ~ 180oC again in 24 hours and is cooled to room temperature after processing 24 hours;
The reaction product that step 2 is obtained by reacting by step 3. after filtration, washing and dry, prepare hollow hexa-prism hydroxyapatite crystal.
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