CN113526477B - 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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CN113526477B
CN113526477B CN202110720050.7A CN202110720050A CN113526477B CN 113526477 B CN113526477 B CN 113526477B CN 202110720050 A CN202110720050 A CN 202110720050A CN 113526477 B CN113526477 B CN 113526477B
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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, and belongs to the technical field of biological ceramic materials. Calcium chloride (CaCl 2) is used as a calcium salt, diammonium hydrogen phosphate ((NH 4) 2HPO 4) is used as a phosphate, oxalic acid (C2H2O4.2H2O) is added, and HA precursor solution is obtained through rotary evaporation reaction under high-concentration alkaline conditions; washing precursor powder with water and alcohol, vacuum drying, and calcining at high temperature to obtain hydroxyapatite with different morphology. The synthesis process of the invention mainly uses common inorganic salt and simple reagent, has 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.

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 (PO 4 ) 6 (OH) 2 HA) is an inorganic constituent of human bones and teeth, HAs good biocompatibility and bioactivity, and HAs been clinically used for repairing bone defects. It can form bone-joining with human living tissue through bone conduction mechanism. In addition, HA is also of great importance in other non-biological fields, such as catalysis and water treatment. The application of hydroxyapatite materials is mainly dependent on their structure, size and morphology. At present, HA with different morphologies HAs been prepared for different application fields. For example, chinese patent CN100441503C discloses a method for preparing nanometer HA by ion thermal synthesis. Firstly, calcium nitrate and phosphate are selected as reaction raw materials, then the mass ratio of the calcium nitrate to the ionic liquid is controlled to be 1 (3-20), and after being stirred and mixed uniformly, ammonia is addedAfter the pH value is regulated by water, the HA with the particle size of 10-100nm can be obtained by hydrothermal reaction. Chinese patent CN101343054B uses EDTA as a template agent and calcium hydroxide, diammonium 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, adopts calcium nitrate tetrahydrate and diammonium phosphate as raw materials to prepare HA slurry, then adds ammonium bicarbonate for spray drying, and prepares the HA hollow microspheres through subsequent heat treatment. Chinese patent CN 101172592A uses water-soluble calcium salt and acid phosphate as raw materials, and adds N, N-dimethylformamide as additive, and then the HA micro-tube is obtained after hydrothermal treatment. Chinese patent CN104220102B prepared a macroporous HA capable of accommodating new bone ingrowth and having abundant lamellar porous walls by arranging polymer fibers in advance in a mold for orientation, diameter and distribution, and freeze drying.
The preparation method of the HA ceramic powder prepared by the method is too complex, and the preparation yield is low. The HA biological ceramic powder material which HAs simple preparation process, good repeatability, low cost, no toxicity or harm of the product and suitability for large-scale production is researched, and 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 HA ceramic powder with simple preparation process, low cost and uniform and controllable components.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method for converting the hydroxyapatite nanospheres into the micro rods comprises the following steps:
step 1, preparing a calcium salt solution: 28.036g CaCl was weighed 2 Adding 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 oxalic acid solution: weigh 6.335gC 2 H 2 O 4 ·2H 2 Adding 70mL of deionized water, and stirring until the solution is completely dissolved to obtain colorless and transparent oxalic acid solution;
step 3, preparing a mixed solution: 20.009g (NH) 4 ) 2 HPO 4 Adding the mixture into the oxalic acid solution obtained in the step 2, and stirring until the mixture 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, adding the mixed solution and the alkaline solution obtained in the step 3 and the step 4 into the calcium salt solution obtained in the step 1 in sequence, 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, centrifuging, 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 enable the hydroxyapatite nanospheres to be converted 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 5-30min.
Preferably, the NaOH powder is added into the deionized water in the step 4 for 5-10 times.
Preferably, the conditions of rotary evaporation in the step 6 are as follows: spin-steaming at 55deg.C under 78MPa for 60-100min, and spin-steaming at 60deg.C under 72MPa for 100-150min; during centrifugal washing, ultrapure water is firstly used for washing 3 times, and then absolute ethyl alcohol is used for washing 3 times; the vacuum drying time is 24-36h.
Preferably, the calcination temperature in the step 7 is 500 ℃, 600 ℃,700 ℃,800 ℃ and the calcination time is 120min.
The beneficial effects of the invention are as follows:
the invention provides a preparation method and a process for converting HA nanospheres into micron rods, which adopts calcium chloride (CaCl) 2 ) As a calcium source, diammonium phosphate ((NH) 4 ) 2 HPO 4 ) As phosphate, oxalic acid is added under the action of strong alkali systemAnd (3) obtaining an HA precursor by utilizing a rotary evaporation reaction, and successfully preparing HA with different morphologies by vacuum drying and controlling the calcination temperature. The method HAs the advantages of low cost, simplicity, easiness in 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 micro rods.
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 microscope image of the HA material prepared in example 2 of the present invention.
Fig. 4 is a low power scanning electron microscope image of the HA material prepared in example 2 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
The preparation method for converting hydroxyapatite nanospheres into micron rods provided by the invention, as shown in a process flow chart of fig. 1, comprises the following specific operation steps:
step 1, preparing a calcium salt solution: 28.036g CaCl was weighed 2 Adding 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 oxalic acid solution: weigh 6.335g C 2 H 2 O 4 ·2H 2 Adding 70mL of deionized water, and stirring for 5-15min by using a magnetic stirrer to obtain colorless transparent oxalic acid solution;
step 3, preparing a mixed solution: 20.009g (NH) 4 ) 2 HPO 4 Adding the mixture into the oxalic acid solution obtained in the step 2, and stirring the mixture for 10 to 30 minutes by using a magnetic stirrer until the mixture 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 continuously stirring for 10-30min by using the magnetic stirrer to obtain a white emulsion which is the HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into an eggplant-shaped bottle, performing rotary steaming for 60-100min at 78MPa and 55 ℃, and performing rotary steaming for 100-150min at 72MPa and 60 ℃; during centrifugal washing, ultrapure water is firstly used for washing 3 times, and then absolute ethyl alcohol is used for washing 3 times; the vacuum drying time is 24-36h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature under air to obtain HA with different morphologies. The calcination temperature is 500 ℃, 600 ℃,700 ℃,800 ℃ and the high-temperature calcination time is 120min.
Example 1:
step 1, preparing a calcium salt solution: 28.036g CaCl was weighed 2 Adding 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 oxalic acid solution: weigh 6.335g C 2 H 2 O 4 ·2H 2 Adding 70mL of deionized water, and stirring for 5min by using a magnetic stirrer to obtain colorless transparent oxalic acid solution;
step 3, preparing a mixed solution: 20.009g (NH) 4 ) 2 HPO 4 Adding the mixture into the oxalic acid solution obtained in the step 2, and stirring the mixture for 10 minutes 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 continuously stirring for 10min by using the magnetic stirrer to obtain a uniform white emulsion which is the HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into an eggplant-shaped bottle, performing rotary steaming for 60min at 78MPa and 55 ℃, and performing rotary steaming for 100min at 72MPa and 60 ℃; during centrifugal washing, ultrapure water is firstly used for washing 3 times, and then absolute ethyl alcohol is used for washing 3 times; the vacuum drying time was 24h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature under air to obtain HA with different morphologies. The calcination temperature is 500 ℃, 600 ℃,700 ℃,800 ℃ and the high-temperature calcination time is 120min.
Example 2:
step 1, preparing a calcium salt solution: 28.036g CaCl was weighed 2 Adding 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 oxalic acid solution: weigh 6.335g C 2 H 2 O 4 ·2H 2 Adding 70mL of deionized water, and stirring for 10min by using a magnetic stirrer to obtain colorless transparent oxalic acid solution;
step 3, preparing a mixed solution: 20.009g (NH) 4 ) 2 HPO 4 Adding the mixture into the oxalic acid solution obtained in the step 2, and stirring the mixture for 15 minutes 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 continuously stirring for 15min by using the magnetic stirrer to obtain a uniform white emulsion which is the HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into an eggplant-shaped bottle, performing rotary steaming for 70min at 78MPa and 55 ℃, and performing rotary steaming for 110min at 72MPa and 60 ℃; during centrifugal washing, ultrapure water is firstly used for washing 3 times, and then absolute ethyl alcohol is used for washing 3 times; the vacuum drying time was 24h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature under air to obtain HA with different morphologies. The calcination temperature is 500 ℃, 600 ℃,700 ℃,800 ℃ and the high-temperature calcination time is 120min.
Example 3:
step 1, preparing a calcium salt solution: 28.036g CaCl was weighed 2 Adding 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 oxalic acid solution: weigh 6.335g C 2 H 2 O 4 ·2H 2 Adding 70mL of deionized water, and stirring for 15min by using a magnetic stirrer to obtain colorless transparent oxalic acid solution;
step 3, preparing a mixed solution: 20.009g (NH) 4 ) 2 HPO 4 Adding the mixture into 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 continuously stirring for 20min by using the magnetic stirrer to obtain a uniform white emulsion which is the HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into an eggplant-shaped bottle, performing rotary steaming for 80min at 78MPa and 55 ℃, and performing rotary steaming for 120min at 72MPa and 60 ℃; during centrifugal washing, ultrapure water is firstly used for washing 3 times, and then absolute ethyl alcohol is used for washing 3 times; the vacuum drying time was 24h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature under air to obtain HA with different morphologies. The calcination temperature is 500 ℃, 600 ℃,700 ℃,800 ℃ and the high-temperature calcination time is 120min.
Example 4:
step 1, preparing a calcium salt solution: 28.036g CaCl was weighed 2 In beakersAdding 100mL of deionized water, and stirring for 30min by using a magnetic stirrer to obtain a calcium salt solution;
step 2, preparing oxalic acid solution: weigh 6.335g C 2 H 2 O 4 ·2H 2 Adding 70mL of deionized water, and stirring for 5min by using a magnetic stirrer to obtain colorless transparent oxalic acid solution;
step 3, preparing a mixed solution: 20.009g (NH) 4 ) 2 HPO 4 Adding the mixture into the oxalic acid solution obtained in the step 2, and stirring the mixture for 25 minutes 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 continuously stirring for 25min by using the magnetic stirrer to obtain a uniform white emulsion which is the HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into an eggplant-shaped bottle, performing rotary steaming for 90min at 78MPa and 55 ℃, and performing rotary steaming for 130min at 72MPa and 60 ℃; during centrifugal washing, ultrapure water is firstly used for washing 3 times, and then absolute ethyl alcohol is used for washing 3 times; the vacuum drying time was 36h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature under air to obtain HA with different morphologies. The calcination temperature is 500 ℃, 600 ℃,700 ℃,800 ℃ and the high-temperature calcination time is 120min.
Example 5:
step 1, preparing a calcium salt solution: 28.036g CaCl was weighed 2 Adding 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 oxalic acid solution: weigh 6.335g C 2 H 2 O 4 ·2H 2 Adding 70mL of deionized water, and stirring for 10min by using a magnetic stirrer to obtain colorless transparent oxalic acid solution;
step 3, preparing a mixed solution: 20.009g (NH) 4 ) 2 HPO 4 Adding the mixture into the oxalic acid solution obtained in the step 2, and stirring the mixture for 25 minutes by using a magnetic stirrer until the mixture 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 continuously stirring for 30min by using the magnetic stirrer to obtain a uniform white emulsion which is the HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into an eggplant-shaped bottle, performing rotary steaming for 100min at 78MPa and 55 ℃, and performing rotary steaming for 140min at 72MPa and 60 ℃; during centrifugal washing, ultrapure water is firstly used for washing 3 times, and then absolute ethyl alcohol is used for washing 3 times; the vacuum drying time was 36h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature under air to obtain HA with different morphologies. The calcination temperature is 500 ℃, 600 ℃,700 ℃,800 ℃ and the high-temperature calcination time is 120min.
Example 6:
step 1, preparing a calcium salt solution: 28.036g CaCl was weighed 2 Adding 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 oxalic acid solution: weigh 6.335g C 2 H 2 O 4 ·2H 2 Adding 70mL of deionized water, and stirring for 15min by using a magnetic stirrer to obtain colorless transparent oxalic acid solution;
step 3, preparing a mixed solution: 20.009g (NH) 4 ) 2 HPO 4 Adding the mixture into the oxalic acid solution obtained in the step 2, and stirring the mixture for 30 minutes 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 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 continuously stirring for 30min by using the magnetic stirrer to obtain a uniform white emulsion which is the HA precursor solution;
step 6, transferring the HA precursor solution obtained in the step 5 into an eggplant-shaped bottle, performing rotary steaming for 100min at 78MPa and 55 ℃, and performing rotary steaming for 150min at 72MPa and 60 ℃; during centrifugal washing, ultrapure water is firstly used for washing 3 times, and then absolute ethyl alcohol is used for washing 3 times; the vacuum drying time was 36h.
And 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and calcining at high temperature under air to obtain HA with different morphologies. The calcination temperature is 500 ℃, 600 ℃,700 ℃,800 ℃ and the high-temperature calcination time is 120min.
The HA material prepared in example 2 of the present invention was subjected to X-ray diffraction analysis (XRD) (as shown in fig. 2), from which it can be seen that characteristic peaks of HA appear in the material upon calcination at high temperatures of 500 ℃, 600 ℃,700 ℃,800 ℃, the diffraction peaks of which correspond to standard cards of HA, and the prepared HA material HAs a good crystallinity and is substantially free of impurity phases, so that it can be concluded that the HA material was successfully prepared by the present invention.
Analysis of the morphology of the HA material prepared in example 2 of the present invention (as shown in fig. 3) using Scanning Electron Microscopy (SEM) shows that the morphology of the HA material gradually changes from nanospheres to nanorods as the calcination temperature increases. Under the calcination condition of 500 ℃ and 600 ℃, HA is uniformly distributed in a nanosphere shape, HA starts to be converted from the nanospheres to the micron rods at 700 ℃, and the formation of the HA micron rods can be obviously observed at 800 ℃. The method provided by the invention can successfully realize the conversion from HA nanospheres to micron rods.
The method adopts calcium chloride (CaCl) 2 ) As calcium salt, diammonium phosphate ((NH) 4 ) 2 HPO 4 ) Oxalic acid (C) was added as phosphate 2 H 2 O 4 ·2H 2 O), under the high-concentration alkaline condition, carrying out rotary evaporation reaction to obtain an HA precursor solution; washing precursor powder with water and alcohol, vacuum drying, and calcining at high temperature to obtain hydroxyapatite with different morphology. The synthesis process of the invention mainly uses common inorganic salt and simple reagent, has 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 foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.

Claims (3)

1. The preparation method for converting the hydroxyapatite nanospheres into the micro rods is characterized by comprising the following steps of:
step 1, preparing a calcium salt solution: 28.036g CaCl was weighed 2 Adding 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 oxalic acid solution: weigh 6.335gC 2 H 2 O 4 ·2H 2 Adding 70mL of deionized water, and stirring until the solution is completely dissolved to obtain colorless and transparent oxalic acid solution;
step 3, preparing a mixed solution: 20.009g (NH) 4 ) 2 HPO 4 Adding the mixture into the oxalic acid solution obtained in the step 2, and stirring until the mixture 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, adding the mixed solution and the alkaline solution obtained in the step 3 and the step 4 into the calcium salt solution obtained in the step 1 in sequence, 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, centrifuging, washing, and performing vacuum drying to obtain HA precursor powder;
the rotary evaporation conditions in the step 6 are as follows: spin-steaming at 55deg.C under 78MPa for 60-100min, and spin-steaming at 60deg.C under 72MPa for 100-150min; during centrifugal washing, ultrapure water is firstly used for washing 3 times, and then absolute ethyl alcohol is used for washing 3 times; the vacuum drying time is 24-36h;
step 7, placing the HA precursor powder obtained in the step 6 in a muffle furnace, and setting different calcining temperatures to enable the hydroxyapatite nanospheres to be converted into the micron rods;
the calcination temperature in the step 7 is respectively 500 ℃, 600 ℃,700 ℃,800 ℃ and the calcination time is 120min.
2. The method for preparing the hydroxyapatite nanospheres converted into the micro rods 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 5-30min.
3. The method for preparing the hydroxyapatite nanospheres from the micro rods according to claim 1, wherein the process of adding the NaOH powder into the deionized water in the step 4 is divided into 5 to 10 times.
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