CN114804059A - Quasi-isometric fluorapatite nanocrystal and preparation method thereof - Google Patents
Quasi-isometric fluorapatite nanocrystal and preparation method thereof Download PDFInfo
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- 229910052587 fluorapatite Inorganic materials 0.000 title claims abstract description 48
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 title claims abstract description 41
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 40
- 229940077441 fluorapatite Drugs 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 22
- 239000001923 methylcellulose Substances 0.000 claims abstract description 22
- 235000010981 methylcellulose Nutrition 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- -1 fluoride ions Chemical class 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012620 biological material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 18
- 239000013078 crystal Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 14
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 229910052586 apatite Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052585 phosphate mineral Inorganic materials 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention provides a preparation method of a fluorapatite quasi-equiaxed nanocrystal and the prepared fluorapatite quasi-equiaxed nanocrystal. The preparation method comprises the following steps: (1) preparing a methyl cellulose aqueous solution with the concentration of 0.3-1 wt%; (2) dissolving a substance capable of providing phosphate ions and a substance capable of providing fluoride ions in the methyl cellulose aqueous solution obtained in the step (1); (3) adding an alkali solution into the mixed solution obtained in the step (2) to adjust the pH value; (4) and (4) adding the alkaline earth metal ion solution into the mixed solution obtained in the step (3) for reaction. The method has the advantages of simple operation, high product yield, environmental friendliness, easy realization of mass production and the like. The size of the fluorapatite quasi-equiaxed nanocrystal is less than 100nm, the length-diameter ratio is less than 2, the defect that the existing fluorapatite nanocrystal is always in a rod-shaped or linear shape is overcome, and the performance diversification and application scenes of the fluorapatite material are widened.
Description
Technical Field
The invention belongs to the technical field of biological materials, and particularly relates to a fluorapatite quasi-equiaxial nano-crystal and a preparation method thereof.
Background
Fluorapatite (general formula M) 5 (PO 4 ) 3 F, where M is an alkaline earth metal) is a class of phosphate minerals that is widely found in nature. Due to excellent biocompatibility, good physical/chemical stability, and strong strengthThe compound is widely applied to the fields of biological materials, fluorescent materials, solid-state lasers and the like. As is well known, the quality of the material performance depends greatly on the particle morphology of the material, and the material particles with different morphologies respectively have suitable application scenes. In addition, the nanometer effect derived from the nanometer particles can greatly enrich the performance of the material, so that various scholars have worked on the controllable synthesis of the fluorapatite nanometer material. The main current methods for synthesizing fluorapatite include solid-phase reaction method [1] Coprecipitation method [2] Sol-gel process [3] Hydrothermal process [4] And the like, wherein the nanoscale fluorapatite particles can be obtained by accurately adjusting reaction parameters in a liquid phase synthesis means.
During the liquid phase reaction, apatite tends to grow into hexagonal phase grains, and the hexagonal phase grains [001] The crystal orientation has a remarkable growth advantage, and the intrinsic crystal habit causes the liquid-phase obtained fluorapatite nano-crystals to be in a rod-shaped or linear shape. The phenomenon greatly limits the diversification of the performance of the fluorapatite material and greatly limits the application scene of the material. Therefore, the development of a method for synthesizing quasi-equiaxed apatite nanocrystals is of great significance to the further development of the materials.
[1]Nimai Pathak,Bhagyalaxmi Chundawat,Pratik Das,Pampa Modak,Brindaban Modak,Unraveling the site-specific energy transfer driven tunable emission characteristics of Eu 3+ &Tb 3+ co-doped Ca 10 (PO 4 ) 6 F 2 phosphors,RSC Adv.,2021,11,31421-31432.
[2]YiquanWu,JingDu,Robert L.Clark,Synthesis of Yb 3+ doped Sr 5 (PO 4 ) 3 F nanoparticles through co-precipitation,Materials Letters,107,2013,68-70.
[3]Karan Kumar Gupta,R.M.Kadam,N.S.Dhoble,S.P.Lochab,Vijay Singh,S.J.Dhoble,Photoluminescence,thermoluminescence and evaluation of some parameters of Dy 3+ activated Sr 5 (PO 4 ) 3 F phosphor synthesized by sol-gel method,Journal of Alloys and Compounds,688,2016,982-993.
[4]Zhihao Wang,Mengxiao Zhang,Jiao He,Yongan Tang,Tingchao He,Qiang Sun,Dianyuan Fan,YuWang,Strongly enhanced photoluminescence and X-ray excited optical luminescence of the hydrothermally crystallized(Sr,Mn) 5 (PO 4 ) 3 (F,Cl)nanorods by composition modulating,Journal of Alloys and Compounds,855,2021,157529.
Disclosure of Invention
Based on the above, the invention aims to provide the fluoride apatite quasi-equiaxed nanocrystal and the preparation method thereof. The quasi-isometric nano-crystal of the fluorapatite is a hexagonal quasi-isometric nano-crystal, the size of the nano-crystal is less than 100nm, the length-diameter ratio of the nano-crystal is less than 2, and the performance diversity of the fluorapatite material is widened; and the reaction operation is simple, the yield is high, and the method is green and pollution-free.
The technical scheme for achieving the purpose is as follows.
A preparation method of a fluorapatite quasi-equiaxed nanocrystal comprises the following steps: (1) preparing a methyl cellulose aqueous solution with the concentration of 0.3-1 wt%; (2) dissolving a substance capable of providing phosphate ions and a substance capable of providing fluoride ions in the methyl cellulose aqueous solution obtained in the step (1); (3) adding an alkali solution into the mixed solution obtained in the step (2) to adjust the pH value; (4) and (4) adding an alkaline earth metal ion solution into the mixed solution obtained in the step (3) for reaction to obtain the equiaxed fluorapatite nano-crystal.
In some of these embodiments, the substance capable of providing phosphate ions in step (2) is selected from at least one of phosphate ion hydrated or non-hydrated salts.
In some embodiments, the substance capable of providing fluoride ions in step (2) is selected from at least one of fluoride ion hydrate or non-hydrate salts.
In some of the embodiments, the substance capable of providing phosphate ions in step (2) is selected from Na 3 PO 4 、Na 2 HPO 4 、NaH 2 PO 4 、K 3 PO 4 、K 2 HPO 4 、KH 2 PO 4 At least one of (1).
In some embodiments, the substance capable of providing fluoride ions in step (2) is selected from NH 4 F. At least one of NaF and KF.
In some of these embodiments, the molar ratio of phosphate ions to fluoride ions is 3: 1.
in some of these embodiments, the molar ratio of alkaline earth metal ions to fluoride ions is 5: 1.
in some of these embodiments, the alkali solution of step (3) is selected from NaOH, KOH, NH 4 At least one of OH;
in some of these embodiments, the pH of step (3) is 5-12.
In some of the embodiments, the alkaline earth metal ion solution in step (4) is at least one of a soluble organic acid salt or an inorganic acid salt solution of magnesium, calcium, strontium, and barium.
In some of these embodiments, the alkaline earth metal ion solution of step (4) is a strontium acetate solution.
In some of the embodiments, the reaction temperature in the step (4) is 25 ℃ to 70 ℃, and the reaction time is 0.5 to 72 hours.
In some of these embodiments, the temperature in step (4) is from 25 ℃ to 55 ℃ and the reaction time is from 0.5 to 48 hours.
In some of these embodiments, the temperature in step (4) is from 25 ℃ to 45 ℃ and the reaction time is from 0.5 to 10 hours.
The invention also provides the quasi-isometric nano-crystal of the fluorapatite, which is prepared according to the preparation method.
In some of these embodiments, the fluoroapatite equiaxed nanocrystals have a size of less than 100nm and an aspect ratio of less than 2.
The invention also provides application of the fluorapatite quasi-equiaxial nano-crystalline in the fields of biological materials, fluorescent materials and solid-state lasers.
The preparation method of the fluoroapatite quasi-isometric nanocrystalline is obtained by optimization, and the preparation method fully utilizes the surface adsorption effect of the methylcellulose on the crystal grains to realize the synthesis of the fluoroapatite quasi-isometric nanocrystalline. The inventor finds that methylcellulose can effectively control the one-dimensional growth of apatite, when the methylcellulose is introduced into a reaction system, a layer of methylcellulose molecules can be adsorbed on the surface of formed fluorapatite crystal nuclei, the methylcellulose molecule layer can effectively reduce the diffusion of ions to the crystal nuclei, and the one-dimensional growth of the crystal nuclei along the predominant growth crystal orientation is hindered, so that the product is quasi-isometric nanocrystals: on one hand, the methyl cellulose does not contain any group with strong complexing ability, namely the methyl cellulose is not selectively adsorbed on a certain crystal face of a crystal but is uniformly adsorbed on all directions of a crystal grain, so that the growth of the crystal grain is limited in all directions, and the equiaxed crystal grain is obtained; on the other hand, the methyl cellulose is dissolved in water to form sol, which can effectively slow down the diffusion of ions, thereby reducing the growth rate of crystal grains and leading the product to still keep the nano-form after the chemical reaction is carried out for a long time. The method has the advantages of simple operation, high product yield, environmental friendliness, easy realization of mass production and the like.
The size of the fluorapatite quasi-hexagonal equiaxial nano-crystal prepared by the method is less than 100nm, the length-diameter ratio is less than 2, the defect that the existing fluorapatite nano-crystal is always in a rod-shaped or linear shape is overcome, the performance diversification and application scenes of the fluorapatite material are widened, and the fluorapatite quasi-hexagonal equiaxial nano-crystal has wider application in the fields of biological materials, fluorescent materials and solid-state lasers.
Drawings
FIG. 1 is a diagram of the quasi-equiaxed nanocrystalline morphology of fluorapatite prepared in example 1.
Figure 2 is a diagram of the quasi-equiaxed nanocrystalline morphology of fluorapatite prepared in example 2.
FIG. 3 is a morphology chart of the fluorapatite nanoparticles prepared in comparative example 1.
FIG. 4 is a morphology chart of the fluorapatite nanoparticles prepared in example 2.
Detailed Description
Experimental procedures according to the invention, in which no particular conditions are specified in the following examples, are generally carried out under conventional conditions, or under conditions recommended by the manufacturer. The various chemicals used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The present invention will be described with reference to specific examples.
Example 1
The embodiment provides a preparation method of a fluoroapatite quasi-isometric nanocrystal, which comprises the following specific steps:
1. weighing 0.3g of methylcellulose, dispersing in 100mL of deionized water, and stirring for 1h to obtain a light yellow colloidal liquid;
2. 3mmol of ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 Analytically pure) powder with 1mmol of ammonium fluoride (NH) 4 F) Putting the powder into the colloidal liquid obtained in the step 1 in sequence, and uniformly stirring for 10 min;
3. slowly adding 4 mol/L dropwise into the mixed solution obtained in the step 2 while stirring -1 Until the pH value of the mixed solution reaches 5;
4. weighing 5mmol strontium acetate (Sr (CH)) 3 COO) 2 Analytically pure) powder, and is stirred and dissolved in 20mL of deionized water;
5. slowly dripping the strontium acetate solution obtained in the step (4) into the mixed solution with the pH adjusted in the step (3) while stirring to obtain milky white liquid;
6. continuously stirring the milky white liquid obtained in the step 5 at room temperature for 5 hours;
7. repeatedly centrifuging, cleaning methyl cellulose attached to the product, and drying to obtain Sr 5 (PO 4 ) 3 F quasi-equiaxed nanocrystals.
Sr obtained by preparation in this example 5 (PO 4 ) 3 The quasi-equiaxed F nanocrystals, all having a size less than 50nm and an aspect ratio less than 2, can be called quasi-equiaxed nanocrystals, as shown in FIG. 1.
Example 2
The embodiment provides a preparation method of a fluoroapatite quasi-isometric nanocrystal, which comprises the following specific steps:
1. weighing 0.6g of methylcellulose, dispersing in 100mL of deionized water, and stirring for 1h to obtain a light yellow colloidal liquid;
2. 3mmol of ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 Analytically pure) powder with 1mmol of ammonium fluoride (NH) 4 F) Putting the powder into the colloidal liquid obtained in the step 1 in sequence, and uniformly stirring for 10 min;
3. slowly adding 4 mol/L dropwise into the mixed solution obtained in the step 2 while stirring -1 Until the pH value of the mixed solution reaches 8;
4. weighing 5mmol strontium acetate (Sr (CH)) 3 COO) 2 Analytically pure) powder, and is stirred and dissolved in 20mL of deionized water;
5. slowly dripping the obtained strontium acetate solution into the mixed solution with the pH adjusted in the step (3) while stirring to obtain milky white liquid;
6. continuously stirring the milky white liquid obtained in the step 5 for 5 hours;
7. repeatedly centrifuging, cleaning methyl cellulose attached to the product, and drying to obtain Sr 5 (PO 4 ) 3 F quasi equiaxial nano crystal.
As shown in FIG. 2, the obtained Sr produced in this example 5 (PO 4 ) 3 The size of the F quasi-equiaxial nano-crystals is less than 50nm, the length-diameter ratio is also less than 2, and the F quasi-equiaxial nano-crystals are called quasi-equiaxial crystals.
Comparative example 1
This comparative example provides a method for preparing fluorapatite nanoparticles, which, compared to example 1, does not use methylcellulose to participate in the reaction, and comprises the following specific steps:
1. 3mmol of ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 Analytically pure) powder with 1mmol of ammonium fluoride (NH) 4 F) Dissolving the powder in 100mL of deionized water successively to obtain a transparent solution;
2. slowly adding 4 mol. L dropwise into the mixed solution obtained in the step 1 while stirring -1 Until the pH value of the mixed solution reaches 5;
3. weighing 5mmol strontium acetate (Sr (CH)) 3 COO) 2 Analytically pure) powder, and is stirred and dissolved in 20mL of deionized water;
4. slowly dripping the obtained strontium acetate solution into the mixed solution with the pH adjusted in the step (2) while stirring to obtain milky white liquid;
5. continuously stirring the milky white liquid obtained in the step 4 for 5 hours;
6. repeatedly centrifuging, cleaning methyl cellulose attached to the product, and drying to obtain Sr 5 (PO 4 ) 3 And F, nano particles.
As shown in FIG. 3, the product prepared in this comparative example has a length of 40-500nm, a diameter of about 40nm, an aspect ratio of about 1-12, and mostly nanorods. It shows that no methyl cellulose is used to participate in the reaction, no adsorbate is around the crystal grain, the crystal grain grows up according to the intrinsic growth dominance direction, finally, the nano rod is formed, and the length even reaches the submicron level.
Comparative example 2
Compared with the preparation method of the example 1, the preparation method of the fluorapatite nano-particles uses carboxymethyl cellulose to replace methyl cellulose to participate in the reaction, and comprises the following specific steps:
1. weighing 0.3g of carboxymethyl cellulose, dispersing in 100mL of deionized water, and stirring for 1h to obtain a light yellow colloidal liquid;
2. 3mmol of ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 Analytically pure) powder with 1mmol of ammonium fluoride (NH) 4 F) Putting the powder into the colloidal liquid obtained in the step 1 in sequence, and uniformly stirring for 10 min;
3. slowly adding 4 mol/L dropwise into the mixed solution obtained in the step 2 while stirring -1 Until the pH value of the mixed solution reaches 5;
4. weighing 5mmol strontium acetate (Sr (CH)) 3 COO) 2 Analytically pure) powder, and is stirred and dissolved in 20mL of deionized water;
5. slowly dripping the obtained strontium acetate solution into the mixed solution with the pH adjusted in the step (3) while stirring to obtain milky white liquid;
6. continuously stirring the milky white liquid obtained in the step 5 for 5 hours;
7. repeatedly centrifuging, cleaning carboxymethyl cellulose attached to the product, and drying to obtain Sr 5 (PO 4 ) 3 And F, obtaining a product.
As can be seen from FIG. 4, the product particles prepared in this comparative example were strongly agglomerated and had clearly exhibited the morphology of nanorods, i.e., an aspect ratio greater than 2. The result shows that the carboxymethyl cellulose generates selective adsorption on the particles due to the existence of carboxyl, the carboxymethyl cellulose is not uniformly coated on the surfaces of the particles, so that the products grow in an oriented mode, and the carboxyl and the particles have strong adsorption capacity, so that the particles are seriously agglomerated.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being described in the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. A preparation method of a fluorapatite quasi-equiaxed nanocrystal is characterized by comprising the following steps: (1) preparing a methyl cellulose aqueous solution with the concentration of 0.3-1 wt%; (2) dissolving a substance capable of providing phosphate ions and a substance capable of providing fluoride ions in the methyl cellulose aqueous solution obtained in the step (1); (3) adding an alkali solution into the mixed solution obtained in the step (2) to adjust the pH value; (4) and (4) adding an alkaline earth metal ion solution into the mixed solution obtained in the step (3) for reaction to obtain the equiaxed fluorapatite nano-crystal.
2. The method for preparing quasi-equiaxed nanocrystals of fluorapatite according to claim 1, wherein the substance capable of providing phosphate ions in step (2) is selected from at least one of hydrated or non-hydrated salts of phosphate ions;
and/or the substance capable of providing the fluoride ions is selected from at least one of fluoride ion hydrated or non-hydrated salts.
3. The method of preparing a quasi-equiaxed nanocrystal of fluoroapatite according to claim 2, wherein the phosphate ion providing substance of step (2) is selected from Na 3 PO 4 、Na 2 HPO 4 、NaH 2 PO 4 、K 3 PO 4 、K 2 HPO 4 、KH 2 PO 4 At least one of; the substance capable of providing fluoride ions is selected from NH 4 F. At least one of NaF and KF.
4. The method of preparing a fluoroapatite equiaxed nanocrystal according to claim 1, wherein the molar ratio of phosphate ions to fluoride ions is 3: 1-30: 1; and/or the molar ratio of the alkaline earth metal ions to the fluoride ions is 5: 1.
5. the method of preparing quasi-equiaxed nanocrystals of fluorapatite as defined in claim 1, wherein the alkali solution in step (3) is selected from NaOH, KOH, NH 4 At least one of OH;
and/or the pH value is 5-12.
6. The method for preparing quasi-equiaxed nanocrystals of fluorapatite according to claim 1, wherein the alkaline earth metal ion solution in step (4) is at least one of a soluble organic acid salt or an inorganic acid salt solution of magnesium, calcium, strontium, barium.
7. The method for preparing quasi-equiaxed nanocrystals of fluorapatite according to claim 1, wherein the reaction temperature in step (4) is 25-70 ℃ and the reaction time is 0.5-72 h.
8. The quasi-equiaxed nano-crystalline fluorapatite prepared by the preparation method according to any one of claims 1 to 7.
9. The fluoroapatite equiaxed nanocrystals according to claim 8, wherein the dimensions of the fluoroapatite equiaxed nanocrystals are less than 100nm and the aspect ratio is less than 2.
10. Use of the fluoroapatite equiaxed nanocrystals according to claim 8 or 9 in the fields of biomaterials, fluorescent materials and solid-state lasers.
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Citations (8)
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| US20060257306A1 (en) * | 2005-05-10 | 2006-11-16 | Pentax Corporation | Nanoparticles of calcium phosphate compound, dispersion liquid thereof and method of production thereof |
| CN103977450A (en) * | 2014-05-14 | 2014-08-13 | 常州大学 | Calcium phosphate bone cement and preparation method thereof |
| JP2015093825A (en) * | 2013-11-14 | 2015-05-18 | 三菱製紙株式会社 | Method for manufacturing strontium (carbonate) fluorapatite and fine particles thereof |
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2022
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| US4157378A (en) * | 1973-01-11 | 1979-06-05 | Colgate Palmolive Company | Process for preparing fluorapatite |
| US5534244A (en) * | 1989-05-24 | 1996-07-09 | Tung; Ming S. | Methods and compositions for mineralizing and/or fluoridating calcified tissues with amorphous strontium compounds |
| JPH08239250A (en) * | 1995-03-03 | 1996-09-17 | Bio Matsupu Kk | Bioabsorbable cured material and its production |
| US6013591A (en) * | 1997-01-16 | 2000-01-11 | Massachusetts Institute Of Technology | Nanocrystalline apatites and composites, prostheses incorporating them, and method for their production |
| US20060257306A1 (en) * | 2005-05-10 | 2006-11-16 | Pentax Corporation | Nanoparticles of calcium phosphate compound, dispersion liquid thereof and method of production thereof |
| CN1843902A (en) * | 2006-04-21 | 2006-10-11 | 华南理工大学 | Meso-porous nanometer particle of calcium phosphate, its preparation method and application |
| JP2015093825A (en) * | 2013-11-14 | 2015-05-18 | 三菱製紙株式会社 | Method for manufacturing strontium (carbonate) fluorapatite and fine particles thereof |
| CN103977450A (en) * | 2014-05-14 | 2014-08-13 | 常州大学 | Calcium phosphate bone cement and preparation method thereof |
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