CN115285957B - Method for preparing hydroxyapatite powder by non-aqueous precipitation process - Google Patents
Method for preparing hydroxyapatite powder by non-aqueous precipitation process Download PDFInfo
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- CN115285957B CN115285957B CN202210928398.XA CN202210928398A CN115285957B CN 115285957 B CN115285957 B CN 115285957B CN 202210928398 A CN202210928398 A CN 202210928398A CN 115285957 B CN115285957 B CN 115285957B
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- 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
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention discloses a method for preparing hydroxyapatite powder by a non-aqueous precipitation process, which comprises the following steps: step one: dissolving a calcium source and a phosphorus source in a nonaqueous solvent according to a certain proportion, and preparing a precursor mixed solution by heating, stirring and mixing; step two: promoting the precursor mixed solution in the step one in a certain way to obtain precipitation slurry through precipitation reaction; step three: and step two, removing and recovering the solvent from the precipitation slurry, drying to obtain a dry precipitation material, and grinding to obtain hydroxyapatite powder. The invention has the outstanding characteristics of simple process, low synthesis temperature, low control requirement, short preparation period, green pollution-free property and the like, thereby having wide application prospect.
Description
Technical Field
The invention belongs to the technical field of inorganic material preparation, and particularly relates to a method for preparing hydroxyapatite powder by a non-aqueous precipitation process.
Background
The hydroxyapatite (abbreviated as HA or HAP) material HAs a series of advantages of good biocompatibility, bioactivity, bone conductivity, stability and the like due to similar chemical components with calcium phosphate in biological hard bone tissues, and can also form strong active connection with bones. The hydroxyapatite powder with high specific surface area is also beneficial to ion exchange and adsorption. Therefore, hydroxyapatite is one of the hot spots of current implant material research. Meanwhile, the hydroxyapatite is used as an important raw material of biomedical ceramic materials and is widely applied to the fields of medicine, sewage treatment, polluted soil restoration and the like. Hydroxyapatite powder is a raw material for preparing hydroxyapatite ceramic materials, and the performance and the application of the hydroxyapatite ceramic are greatly influenced by the properties of the hydroxyapatite powder. Therefore, the preparation of high-quality hydroxyapatite powder is a key for obtaining high-quality hydroxyapatite ceramic materials. The preparation of high-quality hydroxyapatite powder is also a hot spot for domestic and foreign research.
Common preparation methods of hydroxyapatite powder include a solid phase method, a chemical precipitation method, a self-combustion method, a hydrolytic sol-gel method, a microemulsion method and the like. The liquid phase preparation method of the hydroxyapatite powder has better and more controllable quality compared with the solid phase method. In the liquid phase preparation method of hydroxyapatite, a hydrothermal method and a hydrolytic sol-gel method are commonly used. The hydrothermal method and the hydrolytic sol-gel method have the characteristics of low reaction temperature, easy quality control and the like, but the hydrothermal method and the hydrolytic sol-gel method take water as a solvent, so that particle agglomeration is easy to cause. Although the hydroxyapatite ceramic has higher compressive strength, brittle fracture and fatigue fracture are easy to occur, and the hydroxyapatite particles in the ceramic sintered body are well crystallized and have the size of more than micrometers, which is far from natural bone apatite. From the bionics perspective, the nano state of the hydroxyapatite in the bone substitute should be maintained, so that the hydroxyapatite particles can only be selected to avoid agglomeration as far as possible when preparing the bone repair hydroxyapatite material.
Disclosure of Invention
The invention aims to provide a method for preparing hydroxyapatite powder by a non-aqueous precipitation process, which has stable performance, convenient operation and low cost.
In order to solve the technical problems, the technical scheme of the invention is as follows: a method for preparing hydroxyapatite powder by a non-aqueous precipitation process is characterized by comprising the following steps:
step one: dissolving a calcium source and a phosphorus source in a nonaqueous solvent according to a certain proportion, and mixing to prepare a precursor mixed solution;
step two: promoting the precursor mixed solution in the step one in a certain way to obtain precipitation slurry through precipitation reaction;
step three: and step two, removing and recovering the solvent from the precipitation slurry, drying to obtain a dry precipitation material, and grinding to obtain hydroxyapatite powder.
The calcium source in the first step is one of calcium acetate, calcium carbonate, calcium ethoxide, calcium hydroxide and calcium chloride; the phosphorus source is one of disodium hydrogen phosphate, diammonium hydrogen phosphate and dipotassium hydrogen phosphate; the nonaqueous solvent is an organic solvent containing hydroxyl groups.
The molar ratio of calcium to phosphorus in the first step is 1.50-3.00; the temperature of the heating and stirring is 60-90 ℃.
The organic solvent is one of glycerol, ethylene glycol, absolute ethyl alcohol, methanol, acetic acid, absolute acetic acid, formic acid and propionic acid.
And in the second step, one of oil bath heating, ultrasonic treatment, microwave treatment and accelerator initiation is adopted.
The heating temperature of the oil bath is 40-220 ℃ and the heating time is 2-36 h; the ultrasonic treatment frequency is 25KHz, 40KHz and 68KHz, and the ultrasonic treatment power is 500-2200W; the ultrasonic treatment time is 15-360 min; the microwave treatment power is 500-1350W, and the microwave treatment time is 2-60 min.
The promoter is one of formamide, dimethyl amide and triethanolamine.
The usage amount of the accelerator is 0.05-10% of the molar amount of the hydroxyapatite powder to be prepared.
The mode of removing and recycling in the third step is one of centrifugation, filtration, spin-drying, decompression and spraying.
The temperature of the drying process is 40-250 ℃.
The non-aqueous precipitation method provided by the invention is a simple and reliable synthesis method under mild conditions, the organic solvent system can not only avoid agglomeration caused by surface tension and polycondensation of water in the aqueous precipitation method, but also realize simple solvent separation, recovery and reuse, compared with the traditional preparation process for preparing the hydroxyapatite powder by using liquid phase, the preparation process effectively overcomes the agglomeration caused by taking water as a solvent, greatly shortens the production period, reduces the energy consumption of production, and has the excellent characteristics of simple process, low synthesis temperature, low control requirement, short preparation period, greenness, no pollution and the like.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is an XRD pattern of a sample prepared in example 1;
FIG. 3 is an XRD pattern for a sample prepared in example 2;
FIG. 4 is an XRD pattern for a sample prepared in example 3;
FIG. 5 is an XRD pattern for a sample prepared in example 4;
FIG. 6 is an XRD pattern for a sample prepared in example 5;
fig. 7 is an XRD pattern of a sample prepared in example 6.
Detailed Description
The invention will be described in further detail with reference to the drawings and the detailed description.
Example 1:
3.47g of calcium acetate and 4.22g of disodium hydrogen phosphate are respectively added into 35mL of glycerol, and after heating, stirring and dissolving at 90 ℃, the two are mixed to form a precursor mixed solution, the precursor mixed solution is subjected to oil bath for 2 hours at 90 ℃ to obtain a precipitate slurry, and after centrifugation, the main solvent is removed and recovered, the wet precipitate is dried and ground at 250 ℃ to obtain a sample.
Example 2:
3.30g of calcium chloride and 4.22g of disodium hydrogen phosphate are respectively added into 26mL of ethylene glycol, and the two are mixed to form a precursor mixed solution after being heated, stirred and dissolved at 60 ℃. Oil bath is carried out for 36 hours at 110 ℃ to obtain precipitation slurry, and after the main solvent is removed and recovered by filtration, the wet precipitation slurry is dried and ground at 200 ℃ to obtain a sample.
Example 3:
3.60g of calcium ethoxide and 4.22g of disodium hydrogen phosphate are respectively added into 23mL of absolute ethyl alcohol, and the two are mixed to form a precursor mixed solution after being heated, stirred and dissolved at 70 ℃. Oil bath is carried out for 2 hours at 70 ℃ to obtain precipitation slurry, and after spin-drying, removal and recovery of main solvent, the wet precipitation slurry is dried at 70 ℃ and ground to obtain a sample.
Example 4:
3.80g of calcium hydroxide and 4.22g of disodium hydrogen phosphate are respectively added into 20mL of acetic acid, and the mixture is heated, stirred and dissolved at 80 ℃ to form a precursor mixed solution. Ultrasonic treatment is carried out for 360min under the conditions of the frequency of 40KHz and the power of 500W, the sediment slurry is obtained, the main solvent is removed and recovered under the reduced pressure of 0.05MPa, and then the wet sediment is dried and ground at 80 ℃ to obtain the sample.
Example 5:
adding 4.00g of calcium acetate and 4.22g of disodium hydrogen phosphate into 18mL of anhydrous acetic acid respectively, heating, stirring and dissolving at 90 ℃ and then mixing the two to form a precursor mixed solution, carrying out microwave treatment for 2min under the power of 1350W to obtain a precipitate slurry, centrifuging to remove and recover a main solvent, and drying and grinding the wet precipitate at 250 ℃ to obtain a sample.
Example 6:
4.20g of calcium chloride and 4.22g of disodium hydrogen phosphate are respectively added into 16mL of anhydrous acetic acid, and the two are mixed to form a precursor mixed solution after being heated, stirred and dissolved at 60 ℃. Adding 0.1g of initiator formamide to obtain a precipitate slurry, filtering to remove and recycle the main solvent, and drying and grinding the wet precipitate at 200 ℃ to obtain a sample.
Example 7:
4.40g of calcium ethoxide and 4.22g of disodium hydrogen phosphate are respectively added into 15mL of glycerol, and the two are mixed to form a precursor mixed solution after being heated, stirred and dissolved at 70 ℃. Oil bath is carried out for 2 hours at 70 ℃ to obtain precipitation slurry, and after spin-drying, removal and recovery of main solvent, the wet precipitation slurry is dried at 70 ℃ and ground to obtain a sample.
Example 8:
adding 4.60g of calcium acetate and 4.22g of disodium hydrogen phosphate into 13mL of anhydrous acetic acid respectively, heating, stirring and dissolving at 90 ℃ and then mixing the two to form a precursor mixed solution, carrying out oil bath for 24 hours at 120 ℃ to obtain a precipitate slurry, centrifuging to remove and recover a main solvent, and drying and grinding the wet precipitate at 250 ℃ to obtain a sample.
Example 9:
adding 4.60g of calcium acetate and 3.93g of diammonium hydrogen phosphate into 35mL of glycerol respectively, heating, stirring and dissolving at 220 ℃, mixing the two to form a precursor mixed solution, carrying out oil bath for 2 hours at 220 ℃ to obtain a precipitate slurry, centrifuging to remove and recover a main solvent, and drying and grinding the wet precipitate at 250 ℃ to obtain a sample.
Example 10:
4.60g of calcium acetate and 2.69g of dipotassium hydrogen phosphate are respectively added into 35mL of glycerol, and the mixture is heated, stirred and dissolved at 40 ℃ to form a precursor mixed solution. Ultrasonic treatment is carried out for 15min at the frequency of 25KHz and the power of 2200W to obtain precipitate slurry, then the solvent is removed and recovered through spray drying, and the precipitate is ground to obtain a sample.
Example 11:
3.47g of calcium acetate and 4.22g of disodium hydrogen phosphate are respectively added into 35mL of ethanol, heated, stirred and dissolved at 60 ℃ and then mixed to form precursor mixed solution, the precursor mixed solution is subjected to microwave treatment for 60min under the power of 500W to obtain precipitate slurry, and after the main solvent is removed and recovered through centrifugation, the wet precipitate is dried and ground at 80 ℃ to obtain a sample.
Example 12:
3.47g of calcium acetate and 4.22g of disodium hydrogen phosphate are respectively added into 35mL of ethanol, the mixture is heated, stirred and dissolved at 60 ℃ and then mixed to form a precursor mixed solution, 0.2g of an initiator triethanolamine is added to obtain a precipitate slurry, the precipitate slurry is filtered and removed, and the main solvent is recovered, and then the wet precipitate is dried at 80 ℃ and ground to obtain a sample.
Claims (6)
1. A method for preparing hydroxyapatite powder by a non-aqueous precipitation process is characterized by comprising the following steps:
step one: dissolving a calcium source and a phosphorus source in a nonaqueous solvent according to a certain proportion, and preparing a precursor mixed solution by heating, stirring and mixing;
step two: promoting the precursor mixed solution in the step one in a certain way to obtain precipitation slurry through precipitation reaction;
step three: step two, removing and recovering solvent from the precipitation slurry, drying to obtain a dry precipitation material, and grinding to obtain hydroxyapatite powder;
the calcium source in the first step is one of calcium acetate, calcium carbonate, calcium ethoxide, calcium hydroxide and calcium chloride; the phosphorus source is one of disodium hydrogen phosphate, diammonium hydrogen phosphate and dipotassium hydrogen phosphate; the nonaqueous solvent is an organic solvent containing hydroxyl;
the organic solvent is one of glycerol, ethylene glycol, absolute ethyl alcohol, methanol, acetic acid, absolute acetic acid, formic acid and propionic acid;
the certain mode in the second step is one of oil bath heating, ultrasonic treatment, microwave treatment and accelerator initiation;
the heating temperature of the oil bath is 40-220 ℃ and the heating time is 2-36 h; the ultrasonic treatment frequency is 25KHz, 40KHz and 68KHz, and the ultrasonic treatment power is 500-2200W; the ultrasonic treatment time is 15-360 min; the microwave treatment power is 500-1350W, and the microwave treatment time is 2-60 min.
2. The method according to claim 1, characterized in that: the molar ratio of calcium to phosphorus in the first step is 1.50-3.00; the temperature of the heating and stirring is 60-90 ℃.
3. The method according to claim 1, characterized in that: the promoter is one of formamide, dimethyl amide and triethanolamine.
4. The method according to claim 1, characterized in that: the usage amount of the accelerator is 0.05-10% of the molar amount of the hydroxyapatite powder to be prepared.
5. The method according to claim 1, characterized in that: the mode of removing and recycling in the third step is one of centrifugation, filtration, spin-drying, decompression and spraying.
6. The method according to claim 1, characterized in that: the temperature of the drying process is 40-250 ℃.
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Citations (6)
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|---|---|---|---|---|
| CN1785797A (en) * | 2005-11-15 | 2006-06-14 | 清华大学 | Preparation method of non-agglomeration nano-grade hydroxy apatite |
| CN103785062A (en) * | 2014-02-07 | 2014-05-14 | 许自霖 | Bone repair material of coating hydroxyapatite and preparation method of bone repair material |
| CN106395782A (en) * | 2016-09-19 | 2017-02-15 | 常州大学 | Method for preparing mesoporous hydroxyapatite through combining microwave and gaseous diffusion |
| KR101794497B1 (en) * | 2017-06-27 | 2017-11-08 | 부산대학교 산학협력단 | Preparation method of noncrystalline network-hydroxyapatite using supersaturation-precipitation and preparation method of β-tricalcium phosphate |
| CN107746046A (en) * | 2017-11-14 | 2018-03-02 | 湖北工业大学 | A kind of method that Oil soluble hydroxy apatite nano particle is prepared based on non-aqueous system |
| RU2717064C1 (en) * | 2019-12-30 | 2020-03-17 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Method of producing spherical hydroxylapatite with controlled granulometric composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9758377B2 (en) * | 2015-06-29 | 2017-09-12 | Comsats Institute Of Information Technology | Extraction of hydroxyapatite from fish scales employing ionic liquids |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785797A (en) * | 2005-11-15 | 2006-06-14 | 清华大学 | Preparation method of non-agglomeration nano-grade hydroxy apatite |
| CN103785062A (en) * | 2014-02-07 | 2014-05-14 | 许自霖 | Bone repair material of coating hydroxyapatite and preparation method of bone repair material |
| CN106395782A (en) * | 2016-09-19 | 2017-02-15 | 常州大学 | Method for preparing mesoporous hydroxyapatite through combining microwave and gaseous diffusion |
| KR101794497B1 (en) * | 2017-06-27 | 2017-11-08 | 부산대학교 산학협력단 | Preparation method of noncrystalline network-hydroxyapatite using supersaturation-precipitation and preparation method of β-tricalcium phosphate |
| CN107746046A (en) * | 2017-11-14 | 2018-03-02 | 湖北工业大学 | A kind of method that Oil soluble hydroxy apatite nano particle is prepared based on non-aqueous system |
| RU2717064C1 (en) * | 2019-12-30 | 2020-03-17 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Method of producing spherical hydroxylapatite with controlled granulometric composition |
Non-Patent Citations (1)
| Title |
|---|
| A simple sol–gel technique for preparing hydroxyapatite nanopowders;Wang Feng et al.;《Materials Letters》;第917页Experimental部分,第918页TEM analyses部分 * |
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