CN113526477A - Preparation method for converting hydroxyapatite nanospheres into micron rods - Google Patents

Preparation method for converting hydroxyapatite nanospheres into micron rods Download PDF

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CN113526477A
CN113526477A CN202110720050.7A CN202110720050A CN113526477A CN 113526477 A CN113526477 A CN 113526477A CN 202110720050 A CN202110720050 A CN 202110720050A CN 113526477 A CN113526477 A CN 113526477A
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焦华
周雪蕊
赵康
汤玉斐
靳洁晨
张鑫媛
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Xian University of Technology
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Abstract

The invention relates to a preparation method for converting hydroxyapatite nanospheres into micron rods, belonging to the technical field of biological ceramic materials. The method adopts calcium chloride (CaCl)2) As the calcium salt, diammonium hydrogen phosphate ((NH)4)2HPO4) As a phosphate, oxalic acid (C) was added2H2O4·2H2O), obtaining an HA precursor solution by rotary evaporation reaction under the high-concentration alkaline condition; and washing the precursor powder with water and alcohol, drying in vacuum, and calcining at high temperature to successfully prepare the hydroxyapatite with different morphologies. The synthesis process of the invention mainly takes common inorganic salt and simple reagent as main materials, and has low cost, simple and easy operation and heavy weightGood renaturation, high synthetic performance and good stability, is suitable for large-scale production and can promote the commercialization process of the biological ceramic material.

Description

Preparation method for converting hydroxyapatite nanospheres into micron rods
Technical Field
The invention belongs to the technical field of biological ceramic materials, and particularly relates to a preparation method for converting hydroxyapatite nanospheres into micron rods.
Background
Hydroxyapatite (Ca)10(PO4)6(OH)2HA) is an inorganic constituent of human bones and teeth, HAs good biocompatibility and bioactivity, and HAs been clinically used for the repair of bone defects. It can form osseointegration with living tissue of the human body by a bone conduction mechanism. In addition, HA is also of interest in other non-biological areas, such as catalysis and water treatment. The use of hydroxyapatite materials depends largely on their structure, size and morphology. Currently, HA with different morphologies HAs been prepared for different application areas. For example, chinese patent CN100441503C discloses a method for preparing nano HA by ionothermal synthesis. Firstly, calcium nitrate and phosphate are selected as reaction raw materials, secondly, the mass ratio of the calcium nitrate to the ionic liquid is controlled to be 1 (3-20), after the calcium nitrate and the ionic liquid are uniformly stirred and mixed, concentrated ammonia water is added to adjust the pH value, and then the hydrothermal reaction is carried out, so that the HA with the particle size of 10-100nm can be obtained. Chinese patent CN101343054B uses EDTA as template agent, and calcium hydroxide, diammonium hydrogen phosphate, ammonium bicarbonate and phosphoric acid as reaction raw materials to synthesize HA with a diameter of 0.5-6.0 μm and petal-shaped or granular outer layer. Chinese patent CN 1903706A adopts a chemical precipitation method to prepare HA slurry by using calcium nitrate tetrahydrate and diammonium hydrogen phosphate as raw materials, then ammonium bicarbonate is added for spray drying, and the HA hollow microspheres are prepared through subsequent heat treatment. Chinese patent CN 101172592A uses water soluble calcium salt and acid phosphate as raw materials, adds additive N, N-dimethyl formamide, and prepares HA micron tube after hydrothermal treatment. Chinese patent CN104220102B prepares HA which can contain macropores for new bone to grow in and HAs rich lamellar porous pore walls by arranging the orientation, diameter and distribution of polymer fibers in a mold in advance and adopting freeze drying.
The above-prepared HA ceramic powders have complicated preparation methods and low preparation yields. The HA biological ceramic powder material which is prepared by the method HAs the advantages of simple preparation process, good repeatability, low cost, no toxicity and harm of products and suitability for large-scale production HAs very important strategic significance and urgent practical value.
Disclosure of Invention
The invention aims to provide a preparation method for converting hydroxyapatite nanospheres into micron rods, and researches an HA ceramic powder which is simple in preparation process, low in cost and uniform and controllable in components.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method for converting hydroxyapatite nanospheres into micron rods comprises the following steps:
step 1, preparing a calcium salt solution: weighing 28.036gCaCl2Adding 100mL of deionized water into a beaker, and stirring until the deionized water is completely dissolved to obtain a calcium salt solution;
step 2, preparing an oxalic acid solution: weighing 6.335gC2H2O4·2H2Adding 70mL of deionized water into the solution, and stirring the solution until the solution is completely dissolved to obtain a colorless and transparent oxalic acid solution;
step 3, preparing a mixed solution: weighing 20.009g (NH)4)2HPO4Adding the obtained solution into the oxalic acid solution obtained in the step 2, and stirring the solution until the solution is completely dissolved to obtain a mixed solution;
step 4, preparing an alkaline solution: weighing 20.833g of NaOH powder, adding a small amount of the weighed NaOH powder into 50mL of deionized water for multiple times, and uniformly stirring to obtain an alkaline solution;
step 5, sequentially adding the mixed solution and the alkaline solution obtained in the steps 3 and 4 into the calcium salt solution obtained in the step 1, and uniformly stirring to obtain a white emulsion which is an HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into an eggplant-shaped bottle, performing rotary evaporation reaction under certain parameters, centrifugally washing, and performing vacuum drying to obtain HA precursor powder;
and 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and setting different calcining temperatures to convert the hydroxyapatite nanospheres into the micron rods.
Preferably, the stirring process in the steps 1, 2, 3, 4 and 5 is performed by using a magnetic stirrer, and the stirring time is 5-30 min.
Preferably, the NaOH powder is added into the deionized water in the step 4 in 5-10 times.
Preferably, the conditions of rotary evaporation in step 6 are as follows: rotationally steaming at 78MPa and 55 ℃ for 60-100min, and then rotationally steaming at 72MPa and 60 ℃ for 100-150 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the vacuum drying time is 24-36 h.
Preferably, the calcining temperature in the step 7 is respectively selected from 500 ℃, 600 ℃, 700 ℃ and 800 ℃, and the calcining time is 120 min.
The invention has the beneficial effects that:
the invention provides a preparation method and a process for transforming HA nanospheres into micron rods, which adopt calcium chloride (CaCl)2) As a calcium source, diammonium hydrogen phosphate ((NH)4)2HPO4) Adding oxalic acid as phosphate, performing rotary evaporation reaction under the action of a strong base system to obtain an HA precursor, and performing vacuum drying and calcination temperature control to successfully prepare HA with different shapes. The method HAs the advantages of low cost, simplicity, easy implementation, good repeatability, high performance and good stability of the synthesized HA material, is suitable for large-scale production, and can promote the commercialization process of the biological ceramic material.
Drawings
Fig. 1 is a process flow chart of a preparation method for converting hydroxyapatite nanospheres into nanorods.
FIG. 2 is an X-ray diffraction pattern of the HA material prepared in example 2 of the present invention.
FIG. 3 is a high power scanning electron micrograph of the HA material prepared in example 2 of the present invention.
FIG. 4 is a scanning electron micrograph of HA material prepared according to example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method for converting hydroxyapatite nanospheres into micron rods, which comprises the following specific operation steps as shown in a process flow chart of figure 1:
step 1, preparing a calcium salt solution: 28.036g of CaCl were weighed2Adding 100mL of deionized water into a beaker, and stirring for 10-30min by using a magnetic stirrer to obtain a calcium salt solution;
step 2, preparing an oxalic acid solution: weighing 6.335g C2H2O4·2H2Adding 70mL of deionized water into the solution, and stirring the solution for 5 to 15min by using a magnetic stirrer to obtain a colorless and transparent oxalic acid solution;
step 3, preparing a mixed solution: weighing 20.009g (NH)4)2HPO4Adding the oxalic acid solution obtained in the step 2, and stirring for 10-30min by using a magnetic stirrer until the oxalic acid solution is completely dissolved to obtain a mixed solution;
step 4, preparing an alkaline solution: weighing 20.833g of NaOH powder, adding the weighed NaOH powder into 50mL of deionized water for 5-10 times, and stirring for 20-30min by using a magnetic stirrer to obtain an alkaline solution;
step 5, adding the mixed solution obtained in the step 3 into the calcium salt solution obtained in the step 1, stirring for 10-20min by using a magnetic stirrer, adding the alkaline solution obtained in the step 4, and continuing stirring for 10-30min by using the magnetic stirrer to obtain a white emulsion which is an HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into a eggplant-shaped bottle, and performing rotary evaporation at 78MPa and 55 ℃ for 60-100min, and then performing rotary evaporation at 72MPa and 60 ℃ for 100-150 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the vacuum drying time is 24-36 h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature in the air to obtain HA with different morphologies. The calcining temperature is 500 ℃, 600 ℃, 700 ℃, 800 ℃, and the high-temperature calcining time is 120 min.
Example 1:
step 1, preparing a calcium salt solution: weighing 28.036g CaCl2Adding 100mL of deionized water into a beaker, and stirring for 10min by using a magnetic stirrer to obtain a calcium salt solution;
step 2, preparing an oxalic acid solution: weighing 6.335g C2H2O4·2H2Adding 70mL of deionized water into the solution, and stirring the solution for 5min by using a magnetic stirrer to obtain a colorless and transparent oxalic acid solution;
step 3, preparing a mixed solution: weighing 20.009g (NH)4)2HPO4Adding the oxalic acid solution obtained in the step 2, and stirring for 10min by using a magnetic stirrer to obtain a mixed solution;
step 4, preparing an alkaline solution: weighing 20.833g of NaOH powder, adding the weighed NaOH powder into 50mL of deionized water for 5 times, and stirring for 20min by using a magnetic stirrer to obtain an alkaline solution;
step 5, adding the mixed solution obtained in the step 3 into the calcium salt solution obtained in the step 1, stirring for 10min by using a magnetic stirrer, adding the alkaline solution obtained in the step 4, and continuing stirring for 10min by using the magnetic stirrer to obtain uniform white emulsion which is HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into an eggplant-shaped bottle, and performing rotary evaporation at 78MPa and 55 ℃ for 60min and then performing rotary evaporation at 72MPa and 60 ℃ for 100 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the vacuum drying time is 24 h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature in the air to obtain HA with different morphologies. The calcining temperature is 500 ℃, 600 ℃, 700 ℃, 800 ℃, and the high-temperature calcining time is 120 min.
Example 2:
step 1, preparing a calcium salt solution: 28.036g of CaCl were weighed2Adding 100mL of deionized water into a beaker, and stirring for 15min by using a magnetic stirrer to obtain a calcium salt solution;
step 2, preparing an oxalic acid solution: weighing 6.335g C2H2O4·2H2O and 70mL of deionized water are added, and the mixture is stirred for 10min by a magnetic stirrer to obtain colorlessA transparent oxalic acid solution;
step 3, preparing a mixed solution: weighing 20.009g (NH)4)2HPO4Adding the oxalic acid solution obtained in the step 2, and stirring for 15min by using a magnetic stirrer to obtain a mixed solution;
step 4, preparing an alkaline solution: weighing 20.833g of NaOH powder, adding the weighed NaOH powder into 50mL of deionized water for 6 times, and stirring for 25min by using a magnetic stirrer to obtain an alkaline solution;
step 5, adding the mixed solution obtained in the step 3 into the calcium salt solution obtained in the step 1, stirring for 15min by using a magnetic stirrer, adding the alkaline solution obtained in the step 4, and continuing stirring for 15min by using the magnetic stirrer to obtain uniform white emulsion which is HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into a eggplant-shaped bottle, and performing rotary evaporation at 78MPa and 55 ℃ for 70min and then performing rotary evaporation at 72MPa and 60 ℃ for 110 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the vacuum drying time is 24 h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature in the air to obtain HA with different morphologies. The calcining temperature is 500 ℃, 600 ℃, 700 ℃, 800 ℃, and the high-temperature calcining time is 120 min.
Example 3:
step 1, preparing a calcium salt solution: 28.036g of CaCl were weighed2Adding 100mL of deionized water into a beaker, and stirring for 20min by using a magnetic stirrer to obtain a calcium salt solution;
step 2, preparing an oxalic acid solution: weighing 6.335g C2H2O4·2H2Adding 70mL of deionized water into the solution, and stirring the solution for 15min by using a magnetic stirrer to obtain a colorless and transparent oxalic acid solution;
step 3, preparing a mixed solution: weighing 20.009g (NH)4)2HPO4Adding the oxalic acid solution obtained in the step 2, and stirring for 20min by using a magnetic stirrer to obtain a mixed solution;
step 4, preparing an alkaline solution: weighing 20.833g of NaOH powder, adding the weighed NaOH powder into 50mL of deionized water for 7 times, and stirring for 30min by using a magnetic stirrer to obtain an alkaline solution;
step 5, adding the mixed solution obtained in the step 3 into the calcium salt solution obtained in the step 1, stirring for 20min by using a magnetic stirrer, adding the alkaline solution obtained in the step 4, and continuing stirring for 20min by using the magnetic stirrer to obtain uniform white emulsion which is HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into a eggplant-shaped bottle, and performing rotary evaporation at 78MPa and 55 ℃ for 80min and then performing rotary evaporation at 72MPa and 60 ℃ for 120 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the vacuum drying time is 24 h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature in the air to obtain HA with different morphologies. The calcining temperature is 500 ℃, 600 ℃, 700 ℃, 800 ℃, and the high-temperature calcining time is 120 min.
Example 4:
step 1, preparing a calcium salt solution: 28.036g of CaCl were weighed2Adding 100mL of deionized water into a beaker, and stirring for 30min by using a magnetic stirrer to obtain a calcium salt solution;
step 2, preparing an oxalic acid solution: weighing 6.335g C2H2O4·2H2Adding 70mL of deionized water into the solution, and stirring the solution for 5min by using a magnetic stirrer to obtain a colorless and transparent oxalic acid solution;
step 3, preparing a mixed solution: weighing 20.009g (NH)4)2HPO4Adding the oxalic acid solution obtained in the step 2, and stirring for 25min by using a magnetic stirrer to obtain a mixed solution;
step 4, preparing an alkaline solution: weighing 20.833g of NaOH powder, adding the weighed NaOH powder into 50mL of deionized water for 8 times, and stirring for 20min by using a magnetic stirrer to obtain an alkaline solution;
step 5, adding the mixed solution obtained in the step 3 into the calcium salt solution obtained in the step 1, stirring for 10min by using a magnetic stirrer, adding the alkaline solution obtained in the step 4, and continuing stirring for 25min by using the magnetic stirrer to obtain uniform white emulsion which is HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into an eggplant-shaped bottle, and performing rotary evaporation at 78MPa and 55 ℃ for 90min and then performing rotary evaporation at 72MPa and 60 ℃ for 130 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the vacuum drying time is 36 h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature in the air to obtain HA with different morphologies. The calcining temperature is 500 ℃, 600 ℃, 700 ℃, 800 ℃, and the high-temperature calcining time is 120 min.
Example 5:
step 1, preparing a calcium salt solution: 28.036g of CaCl were weighed2Adding 100mL of deionized water into a beaker, and stirring for 30min by using a magnetic stirrer to obtain a calcium salt solution;
step 2, preparing an oxalic acid solution: weighing 6.335g C2H2O4·2H2Adding 70mL of deionized water into the solution, and stirring the solution for 10min by using a magnetic stirrer to obtain a colorless and transparent oxalic acid solution;
step 3, preparing a mixed solution: weighing 20.009g (NH)4)2HPO4Adding the oxalic acid solution obtained in the step 2, and stirring for 25min by using a magnetic stirrer until the oxalic acid solution is completely dissolved to obtain a mixed solution;
step 4, preparing an alkaline solution: weighing 20.833g of NaOH powder, adding the weighed NaOH powder into 50mL of deionized water for 9 times, and stirring for 25min by using a magnetic stirrer to obtain an alkaline solution;
step 5, adding the mixed solution obtained in the step 3 into the calcium salt solution obtained in the step 1, stirring for 15min by using a magnetic stirrer, adding the alkaline solution obtained in the step 4, and continuing stirring for 30min by using the magnetic stirrer to obtain uniform white emulsion which is HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into a eggplant-shaped bottle, and performing rotary evaporation at 78MPa and 55 ℃ for 100min and then performing rotary evaporation at 72MPa and 60 ℃ for 140 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the vacuum drying time is 36 h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature in the air to obtain HA with different morphologies. The calcining temperature is 500 ℃, 600 ℃, 700 ℃, 800 ℃, and the high-temperature calcining time is 120 min.
Example 6:
step 1, preparing a calcium salt solution: 28.036g of CaCl were weighed2Adding 100mL of deionized water into a beaker, and stirring for 30min by using a magnetic stirrer to obtain a calcium salt solution;
step 2, preparing an oxalic acid solution: weighing 6.335g C2H2O4·2H2Adding 70mL of deionized water into the solution, and stirring the solution for 15min by using a magnetic stirrer to obtain a colorless and transparent oxalic acid solution;
step 3, preparing a mixed solution: weighing 20.009g (NH)4)2HPO4Adding the oxalic acid solution obtained in the step 2, and stirring for 30min by using a magnetic stirrer to obtain a mixed solution;
step 4, preparing an alkaline solution: weighing 20.833g of NaOH powder, adding the weighed NaOH powder into 50mL of deionized water by 10 times, and stirring for 30min by using a magnetic stirrer to obtain an alkaline solution;
step 5, adding the mixed solution obtained in the step 3 into the calcium salt solution obtained in the step 1, stirring for 20min by using a magnetic stirrer, adding the alkaline solution obtained in the step 4, and continuing stirring for 30min by using the magnetic stirrer to obtain uniform white emulsion which is HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into an eggplant-shaped bottle, and performing rotary evaporation at 78MPa and 55 ℃ for 100min and then performing rotary evaporation at 72MPa and 60 ℃ for 150 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the vacuum drying time is 36 h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature in the air to obtain HA with different morphologies. The calcining temperature is 500 ℃, 600 ℃, 700 ℃, 800 ℃, and the high-temperature calcining time is 120 min.
The HA material prepared in example 2 of the present invention was subjected to X-ray diffraction analysis (XRD) (as shown in fig. 2), and it can be seen from the XRD that the characteristic peak of HA appeared in the material under high temperature calcination at 500 ℃, 600 ℃, 700 ℃, 800 ℃, and the diffraction peak corresponded to the standard card of HA, and the prepared HA material had good crystallinity and substantially no impurity phase, so it can be concluded that the HA material was successfully prepared by the present invention.
By analyzing the morphology of the HA material prepared in example 2 of the present invention by using a Scanning Electron Microscope (SEM) (as shown in fig. 3), it can be seen that the morphology of the HA material gradually changes from a nanosphere to a nanorod as the calcination temperature increases. Under the calcination conditions of 500 ℃ and 600 ℃, HA is uniformly distributed in a nanometer spherical shape, HA begins to be converted from the nanometer spherical shape to the micron rod at 700 ℃, and the formation of the HA micron rod can be obviously observed at 800 ℃. The method of the invention is proved to successfully realize the conversion of the HA nanospheres to the microrods.
The method adopts calcium chloride (CaCl)2) As the calcium salt, diammonium hydrogen phosphate ((NH)4)2HPO4) As a phosphate, oxalic acid (C) was added2H2O4·2H2O), obtaining an HA precursor solution by rotary evaporation reaction under the high-concentration alkaline condition; and washing the precursor powder with water and alcohol, drying in vacuum, and calcining at high temperature to successfully prepare the hydroxyapatite with different morphologies. The method mainly takes common inorganic salt and simple reagents as main materials in the synthesis process, has the advantages of low cost, simplicity, easy implementation, good repeatability, high synthesis performance and good stability, is suitable for large-scale production, and can promote the commercialization process of the biological ceramic material.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (5)

1. A preparation method for converting hydroxyapatite nanospheres into micron rods is characterized by comprising the following steps:
step 1, preparing a calcium salt solution: weighing 28.036gCaCl2Adding 100mL of deionized water into a beaker, and stirring until the deionized water is completely dissolved to obtain a calcium salt solution;
step 2, preparing an oxalic acid solution: weighing 6.335gC2H2O4·2H2Adding 70mL of deionized water into the solution, and stirring the solution until the solution is completely dissolved to obtain a colorless and transparent oxalic acid solution;
step 3, preparing a mixed solution: weighing 20.009g (NH)4)2HPO4Adding the obtained solution into the oxalic acid solution obtained in the step 2, and stirring the solution until the solution is completely dissolved to obtain a mixed solution;
step 4, preparing an alkaline solution: weighing 20.833g of NaOH powder, adding a small amount of the weighed NaOH powder into 50mL of deionized water for multiple times, and uniformly stirring to obtain an alkaline solution;
step 5, sequentially adding the mixed solution and the alkaline solution obtained in the steps 3 and 4 into the calcium salt solution obtained in the step 1, and uniformly stirring to obtain a white emulsion which is an HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into an eggplant-shaped bottle, performing rotary evaporation reaction under certain parameters, centrifugally washing, and performing vacuum drying to obtain HA precursor powder;
and 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and setting different calcining temperatures to convert the hydroxyapatite nanospheres into the micron rods.
2. The method for preparing hydroxyapatite nanospheres transformed into nanorods according to claim 1, wherein the stirring process in the steps 1, 2, 3, 4 and 5 is performed by using a magnetic stirrer, and the stirring time is 5-30 min.
3. The method for preparing hydroxyapatite nanospheres to convert to nanorods according to claim 1, wherein the process of adding NaOH powder into deionized water in step 4 is divided into 5-10 times.
4. The method for preparing hydroxyapatite nanospheres transformed into nanorods according to claim 1, wherein the conditions of rotary evaporation in step 6 are as follows: rotationally steaming at 78MPa and 55 ℃ for 60-100min, and then rotationally steaming at 72MPa and 60 ℃ for 100-150 min; during centrifugal washing, firstly washing with ultrapure water for 3 times, and then washing with absolute ethyl alcohol for 3 times; the vacuum drying time is 24-36 h.
5. The method for preparing hydroxyapatite nanospheres transformed into nanorods according to claim 1, wherein the calcining temperature in step 7 is selected from 500 ℃, 600 ℃, 700 ℃, 800 ℃ respectively, and the calcining time is 120 min.
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