CN117142447A - Preparation method of uniformly dispersed alpha-tricalcium phosphate - Google Patents
Preparation method of uniformly dispersed alpha-tricalcium phosphate Download PDFInfo
- Publication number
- CN117142447A CN117142447A CN202210566396.0A CN202210566396A CN117142447A CN 117142447 A CN117142447 A CN 117142447A CN 202210566396 A CN202210566396 A CN 202210566396A CN 117142447 A CN117142447 A CN 117142447A
- Authority
- CN
- China
- Prior art keywords
- tricalcium phosphate
- powder
- temperature
- alpha
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 70
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 46
- 239000002086 nanomaterial Substances 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000010791 quenching Methods 0.000 claims abstract description 14
- 230000000171 quenching effect Effects 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 239000011575 calcium Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 11
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 11
- 229940095079 dicalcium phosphate anhydrous Drugs 0.000 claims description 11
- 239000001506 calcium phosphate Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 235000011089 carbon dioxide Nutrition 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 4
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 4
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000005054 agglomeration Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 17
- 239000002639 bone cement Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000019739 Dicalciumphosphate Nutrition 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 and preferably Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 1
- 229940038472 dicalcium phosphate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[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 XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 description 1
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
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
-
- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The application belongs to the technical field of biomedical materials, and particularly relates to a preparation method of uniformly dispersed alpha-tricalcium phosphate. The preparation method of the uniformly dispersed alpha-tricalcium phosphate is characterized by comprising the following steps of: 1) The calcium carbonate and the calcium hydrophosphate are uniformly mixed according to the mol ratio of (2-2.5) 1, and the volume ratio of the powder to the organic solvent is 1: adding an organic solvent in the proportion of (1-3), grinding by adopting a low-temperature dispersion nano material preparation dispersing machine to obtain powder A, calcining the powder A at 800-1000 ℃ for 1-2h, and cooling along with a furnace to obtain beta-TCP; 2) Preparing powder B by dispersing the nano material at low temperature of beta-TCP, 3) placing the powder B in a muffle furnace, heating to 1100-1200 ℃, preserving heat for 2-48h, taking out, and quenching to room temperature to obtain the alpha-TCP. The alpha-tricalcium phosphate particles prepared by the method are uniformly dispersed, do not generate agglomeration, have good fluidity, and can reduce the temperature of converting beta-tricalcium phosphate into alpha-tricalcium phosphate.
Description
Technical Field
The application belongs to the technical field of biomedical materials, and particularly relates to a preparation method of uniformly dispersed alpha-tricalcium phosphate.
Background
Calcium phosphate is a constituent of bone, and contains: hydroxyapatite, beta-tricalcium phosphate (beta-TCP), alpha-tricalcium phosphate (alpha-TCP), dicalcium phosphate, tetracalcium phosphate, each component having different characteristics, wherein alpha-TCP is widely used in bone cements due to its hydration. Although the alpha-TCP and the beta-TCP have the same chemical components, the density and the solubility of the alpha-TCP and the beta-TCP are different, so that the biological performance and the clinical application of the alpha-TCP are different, the beta-TCP has long setting time, and the alpha-TCP cannot be applied to injectable calcium phosphate bone cement, and the alpha-TCP is usually selected clinically.
The preparation method of the alpha-TCP is mainly a high-temperature solid-phase reaction method, a chemical precipitation method and the like, and the alpha-TCP in the market is generally low in purity and high in price, which results in the preparation of the alpha-TCP in a laboratory by researchers in the field of bone cement. The low purity of alpha-TCP is generally due to incomplete conversion of beta-TCP to alpha-TCP or the reversible conversion of the alpha-TCP portion to beta-TCP during cooling, and thus it is important to solve the problem of low purity of alpha-TCP during the preparation process.
Disclosure of Invention
The application aims to provide a preparation method of uniformly dispersed alpha-tricalcium phosphate, which aims to solve the problems of low purity and easy agglomeration in the existing alpha-TCP preparation process.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
the inventor of the present application surprisingly found that by dispersing the powder of tricalcium phosphate in a low-temperature dispersing nanomaterial dispersing machine, by dispersing, pressurizing and cooling the beta-tricalcium phosphate in the low-temperature dispersing nanomaterial dispersing machine, the prepared alpha-tricalcium phosphate powder is uniformly distributed and does not agglomerate, the temperature at which the beta-tricalcium phosphate is converted into the alpha-tricalcium phosphate can be reduced, and the prepared alpha-tricalcium phosphate has better compressive strength, and may cause surface defects of alpha-tricalcium phosphate crystals in the pressurizing process, thereby affecting the performance of the alpha-tricalcium phosphate.
The application provides a preparation method of uniformly dispersed alpha-tricalcium phosphate, which is characterized by comprising the following steps:
1) The calcium carbonate and the calcium hydrophosphate are uniformly mixed according to the mol ratio of (2-2.5) 1, and the volume ratio of the powder to the organic solvent is 1: adding an organic solvent in the proportion of (1-3), grinding by adopting a low-temperature dispersion nano material preparation dispersing machine to obtain powder A, calcining the powder A at 900-1000 ℃ for 1-2h, and cooling along with a furnace to obtain beta-TCP;
2) Placing the beta-TCP low-temperature dispersed nano material into a dispersing machine to prepare powder B;
3) And (3) placing the powder B in a muffle furnace, heating to 1100-1200 ℃, preserving heat for 2-48h, taking out, and quenching to room temperature to obtain the alpha-TCP.
Preferably, the organic solvent is selected from one or more of ethanol, acetone, acetonitrile, butanol and isopropanol, and preferably, the organic solvent is ethanol.
Preferably, the low-temperature dispersion nano material preparation disperser in the step 1) applies 5-10Mpa pressure at 2-8 ℃ for 0.5-1.5h, the flow rate of liquid inlet is 0.6-1.2L/h when applying pressure, preferably, 6Mpa pressure is applied, the temperature is 6 ℃ for 1h, and the flow rate of liquid inlet is 1L/h when applying pressure.
Preferably, the low-temperature dispersion nanomaterial preparation disperser in step 2) applies 10-20Mpa pressure at 2-8 ℃ for 0.5-1.5h, preferably 14Mpa pressure at 6 ℃ for 1h.
Preferably, the liquid inlet flow rate is 0.6-1.2L/h when the pressure is applied.
Preferably, the cooling mode of the step 3) is selected from one or more of air cooling, dry ice cooling and nitrogen cooling, and preferably, the cooling mode is selected from dry ice cooling.
Preferably, the temperature rising rate of the step 3) is 5-10 ℃/min.
Preferably, 1) calcium carbonate and dibasic calcium phosphate are added in an amount of 2:1, adding alcohol in a volume ratio of 1:2, placing the mixture in a low-temperature dispersing nano material preparation dispersing machine, applying 6Mpa pressure to disperse to obtain powder A, dispersing 1h, wherein the liquid inlet flow rate is 1L/h when the temperature is 6 ℃, placing the powder A in a muffle furnace at 900 ℃ to calcine for 1h, and cooling along with the furnace to obtain beta-TCP;
2) Adding beta-TCP into a low-temperature dispersion nano material preparation disperser, applying 14Mpa pressure at 6 ℃ for dispersing for 1h to obtain powder B.
3) And (3) placing the powder B in a muffle furnace, heating to 1150 ℃ at a heating rate of 5 ℃/min, preserving heat for 5 hours, taking out, and quenching in dry ice to room temperature to obtain the alpha-TCP.
The application also provides alpha-tricalcium phosphate.
Compared with the prior art, the application has the beneficial effects that:
1) The particles are uniformly dispersed, no agglomeration is generated, and the fluidity is good.
2) The alpha-tricalcium phosphate has high purity, does not produce beta-tricalcium phosphate, and has stable crystal form.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present application, the present application will be further described with reference to the following specific examples. It will be appreciated by persons skilled in the art that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
JN-02FS low-temperature dispersing nano material preparation dispersing machine, guangzhou energy-accumulating nano biotechnology Co., ltd
Example 1
As an example of the method for preparing α -tricalcium phosphate described in the present application, the method for preparing α -tricalcium phosphate described in the present embodiment includes the steps of:
1) With calcium carbonate (CaCO) 3 ) And dibasic calcium phosphate (CaHPO) 4 •2H 2 O) to 2:1, adding absolute ethyl alcohol in a volume ratio of 1:2 to obtain a mixture, placing the mixture into a low-temperature dispersion nano material preparation disperser, applying 10Mpa pressure at 8 ℃ with a liquid inlet flow rate of 1L/h, dispersing for 1 hour, placing the powder into a muffle furnace at 900 ℃ for calcination for 1 hour, and cooling along with the furnace to obtain powder A;
2) Adding the powder A into a low-temperature dispersion nano material preparation disperser, applying 20Mpa pressure, and dispersing for 1h at a liquid inlet flow rate of 1L/h at a temperature of 8 ℃ to obtain powder B;
3) And (3) placing the powder B in a muffle furnace, heating to 1150 ℃ at a heating rate of 5 ℃/min, preserving heat for 5 hours, taking out, and quenching in air to room temperature.
Example 2
As an example of the method for preparing α -tricalcium phosphate described in the present application, the method for preparing α -tricalcium phosphate described in the present embodiment includes the steps of:
1) With calcium carbonate (CaCO) 3 ) And dibasic calcium phosphate (CaHPO) 4 •2H 2 O) to 2:1, adding absolute ethyl alcohol in a volume ratio of 1:2 to obtain a mixture, placing the mixture into a low-temperature dispersion nano material preparation disperser, applying 6Mpa pressure, wherein the flow rate of liquid inlet is 1L/h when the pressure is applied, the temperature is 6 ℃, calcining the powder in a muffle furnace at 900 ℃ for 1h after dispersing for 1h, and cooling along with the furnace to obtain powder A;
2) Adding the powder A into a low-temperature dispersion nano material preparation disperser, applying 14Mpa pressure, wherein the liquid inlet flow rate is 1L/h when the pressure is applied, and dispersing for 1h at the temperature of 6 ℃ to obtain powder B;
3) And (3) placing the powder B in a muffle furnace, heating to 1150 ℃ at a heating rate of 5 ℃/min, preserving heat for 5 hours, taking out, and quenching in air to room temperature.
Example 3
As an example of the method for preparing α -tricalcium phosphate described in the present application, the method for preparing α -tricalcium phosphate described in the present embodiment includes the steps of:
1) With calcium carbonate (CaCO) 3 ) And dibasic calcium phosphate (CaHPO) 4 •2H 2 O) to 2:1, adding absolute ethyl alcohol in a volume ratio of 1:2 to obtain a mixture, placing the mixture into a low-temperature dispersion nano material preparation disperser, applying 5Mpa pressure, wherein the flow rate of liquid inlet is 1L/h when the pressure is applied, dispersing at 2 ℃ for 1 hour, and then placing into a muffle furnace at 900 ℃ for calcination for 1 hour, and cooling along with the furnace to obtain powder A;
2) Adding the powder A into a low-temperature dispersion nano material preparation disperser, applying 10Mpa pressure, and dispersing for 1h at 2 ℃ at a liquid inlet flow rate of 1L/h to obtain powder B;
3) And (3) placing the powder B in a muffle furnace, heating to 1150 ℃ at a heating rate of 5 ℃/min, preserving heat for 5 hours, taking out, and quenching in air to room temperature.
Example 4
As an example of the method for preparing α -tricalcium phosphate described in the present application, the method for preparing α -tricalcium phosphate described in the present embodiment includes the steps of:
1) With calcium carbonate (CaCO) 3 ) And dibasic calcium phosphate (CaHPO) 4 •2H 2 O) to 2:1, adding absolute ethyl alcohol in a volume ratio of 1:2 to obtain a mixture, placing the mixture into a low-temperature dispersion nano material preparation disperser, applying 6Mpa pressure, wherein the flow rate of liquid inlet is 1L/h when the pressure is applied, the temperature is 6 ℃, calcining the powder in a muffle furnace at 900 ℃ for 1h after dispersing for 1h, and cooling along with the furnace to obtain powder A;
2) Adding the powder A into a low-temperature dispersion nano material preparation disperser, applying 14Mpa pressure, wherein the liquid inlet flow rate is 1L/h when the pressure is applied, and dispersing for 1h at the temperature of 6 ℃ to obtain powder B;
3) And (3) placing the powder B in a muffle furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min, preserving heat for 5 hours, taking out, and quenching in air to room temperature.
Example 5
As an example of the method for preparing α -tricalcium phosphate described in the present application, the method for preparing α -tricalcium phosphate described in the present embodiment includes the steps of:
1) With calcium carbonate (CaCO) 3 ) And dibasic calcium phosphate (CaHPO) 4 •2H 2 O) to 2:1, adding absolute ethyl alcohol in a volume ratio of 1:2 to obtain a mixture, placing the mixture into a low-temperature dispersion nano material preparation disperser, applying 6Mpa pressure, wherein the flow rate of liquid inlet is 1L/h when the pressure is applied, the temperature is 6 ℃, placing the powder into a muffle furnace at 900 ℃ for calcination for 1h after dispersing for 1.5h, and cooling along with the furnace to obtain powder A;
2) Adding the powder A into a low-temperature dispersion nano material preparation disperser, applying 14Mpa pressure, and dispersing for 1.5h at a temperature of 1L/h at a liquid inlet flow rate of 6 ℃ to obtain powder B;
3) And (3) placing the powder B in a muffle furnace, heating to 1200 ℃ at a heating rate of 5 ℃/min, preserving the heat for 5 hours, taking out, and quenching in air to room temperature.
Comparative example 1
The preparation method of the alpha-tricalcium phosphate comprises the following steps:
1) With calcium carbonate (CaCO) 3 ) And dibasic calcium phosphate (CaHPO) 4 •2H 2 O) to 2:1, adding absolute ethyl alcohol in a volume ratio of 1:2 to obtain a mixture, grinding the mixture by a planetary ball mill, placing the powder in a muffle furnace at 900 ℃ for calcination for 1h, and cooling the powder along with the furnace to obtain powder A;
2) And (3) placing the powder A in a muffle furnace, heating to 1350 ℃ at a heating rate of 5 ℃/min, preserving the heat for 5 hours, taking out, and quenching in air to room temperature.
The comparative example uses a common solid phase synthesis to prepare alpha-tricalcium phosphate.
Comparative example 2
1) With calcium carbonate (CaCO) 3 ) And dibasic calcium phosphate (CaHPO) 4 •2H 2 O) to 2:1, adding absolute ethyl alcohol in a volume ratio of 1:2 to obtain a mixture, placing the mixture into a low-temperature dispersion nano material preparation disperser, applying 2Mpa pressure at 6 ℃, wherein the flow rate of feed liquid is 1L/h when the pressure is applied, calcining the powder in a muffle furnace at 900 ℃ for 1h after dispersing for 1h, and cooling along with the furnace to obtain powder A;
2) Adding the powder A into a low-temperature dispersion nano material preparation disperser, applying 6Mpa pressure, wherein the liquid inlet flow rate is 1L/h when the pressure is applied, and dispersing for 1h at the temperature of 6 ℃ to obtain powder B;
3) And (3) placing the powder B in a muffle furnace, heating to 1150 ℃ at a heating rate of 5 ℃/min, preserving heat for 5 hours, taking out, and quenching in air to room temperature.
This comparative example is substantially the same as example 2, except that the pressure applied by the low-temperature dispersion nanomaterial preparation dispenser is different.
Comparative example 3
1) With calcium carbonate (CaCO) 3 ) And dibasic calcium phosphate (CaHPO) 4 •2H 2 O) to 2:1, adding absolute ethyl alcohol in the volume ratio of powder to alcohol of 1:2 to obtain a mixture, placing the mixture into a low-temperature dispersing nano material preparation dispersing machine, applying 6Mpa pressure and the temperature of 6 DEG CThe flow rate of liquid inlet is 1L/h when pressure is applied, after the liquid is dispersed for 1h, the powder is placed in a muffle furnace at 900 ℃ for calcination for 1h, and the powder A is obtained after cooling along with the furnace;
2) Adding the powder A into a low-temperature dispersion nano material preparation disperser, applying 14Mpa pressure, and dispersing for 1h at a temperature of 6 ℃ at a liquid inlet flow rate of 1L/h to obtain powder B;
3) And (3) placing the powder B in a muffle furnace, heating to 1250 ℃ at a heating rate of 5 ℃/min, preserving the heat for 5 hours, taking out, and quenching in air to room temperature.
This comparative example is substantially the same as example 2 except that the temperature is raised to 1250 ℃ in step 3).
Comparative example 4
The preparation method of the alpha-tricalcium phosphate comprises the following steps:
1) With calcium carbonate (CaCO) 3 ) And dibasic calcium phosphate (CaHPO) 4 •2H 2 O) to 2:1, adding absolute ethyl alcohol in a volume ratio of 1:2 to obtain a mixture, placing the mixture into a low-temperature dispersion nano material preparation disperser, applying 6Mpa pressure, wherein the flow rate of liquid inlet is 1L/h when the pressure is applied, the temperature is 12 ℃, placing the powder into a muffle furnace at 900 ℃ for calcination for 1h after dispersing for 1h, and cooling along with the furnace to obtain powder A;
2) Adding the powder A into a low-temperature dispersion nano material preparation disperser, applying 14Mpa pressure, wherein the liquid inlet flow rate is 1L/h when the pressure is applied, and dispersing for 1h at 12 ℃ to obtain powder B;
3) And (3) placing the powder B in a muffle furnace, heating to 1150 ℃ at a heating rate of 5 ℃/min, preserving heat for 5 hours, taking out, and quenching in air to room temperature.
This comparative example is substantially the same as example 2, except that the temperature of the low-temperature dispersion nanomaterial preparation dispenser of step 2) and step 3) is 12 ℃.
The following tests were performed on the α -tricalcium phosphate prepared in examples 1-5, comparative examples 1-4:
1. measurement of particle size: microscopic morphology of the alpha-tricalcium phosphate sample prepared under different reaction conditions is observed by using a jsm-6460lv scanning electron microscope, a small amount of sample is dissolved into absolute ethyl alcohol for oscillation by using a BT-9300s laser particle size distribution instrument, and the particle size distribution condition of the sample is analyzed. The particle size distribution is shown in Table 1:
as can be seen by a scanning electron microscope, the α -tricalcium phosphate prepared in examples 1-5 is uniformly dispersed, no agglomeration is generated, the particles are loose, and the fluidity is good, the low-temperature dispersion nanomaterial preparation disperser is adopted to uniformly distribute the particle size of the sample and prevent the α -tricalcium phosphate from agglomerating, the conventional stationary phase is adopted to synthesize the α -tricalcium phosphate in comparative example 1, the product is agglomerated, the pressure in the low-temperature dispersion nanomaterial preparation disperser in comparative example 2 is lower than the pressure of the application, the agglomeration is also generated, the pressure in the low-temperature dispersion nanomaterial preparation disperser is prevented within a certain range, the agglomeration is determined by increasing the temperature of step 3) in comparative example 3 to 1250 ℃, the agglomeration is determined by pressurizing the β -tricalcium phosphate at a low temperature, the temperature of the β -tricalcium phosphate to be converted into the α -tricalcium phosphate is reduced, the temperature of the low-tricalcium phosphate preparation disperser in comparative example 4 is 12 ℃, and the prepared α -tricalcium phosphate is agglomerated, which indicates that the temperature of the low-temperature nanomaterial preparation disperser in the preparation process affects the agglomeration. The temperature of the low temperature dispersion nanomaterial preparation disperser, the applied pressure and the temperature of the beta-tricalcium phosphate converted into alpha-tricalcium phosphate can influence the dispersibility of the prepared alpha-tricalcium phosphate.
2. X-ray diffraction analysis
Analysis of tricalcium phosphate prepared in examples 1 to 5 and comparative examples 1 to 3 by a D/Max-3B type X-ray diffractometer, respectively, revealed that the X-ray diffraction patterns of α -tricalcium phosphate prepared in examples 1 to 5 were only α -tricalcium phosphate, which indicated that the α -tricalcium phosphate prepared in examples 1 to 5 was a highly ordered lattice structure, contained no other substances, and that the X-ray diffraction patterns of α -tricalcium phosphate prepared in comparative examples 1 to 3 were spiked at other positions than 30.00 degrees, indicating that the α -tricalcium phosphate prepared in comparative examples 1 to 3 contained impurities.
3. Compressive Strength
The calcium phosphate powders of examples 1 to 5 and comparative examples 1 to 4 were mixed with the curing liquid in proportion, respectively, and blended with a spatula for 30 seconds to form a uniform bone cement paste, filled into a stainless steel cylinder mold having a diameter of 6mm and a height of 12mm, and compacted by applying a pressure of 0.7MPa, and the prepared cylinder sample was packed into a glass tube having a diameter of 6.5mm and a height of 13mm, and then placed in an environment having a temperature of 37℃and a relative humidity of 100% for curing for 3 days, and then the compressive strength of the sample was measured by a universal material tester at a loading rate of 1mm/min, and the results are shown in Table 2.
4. Coagulation time
The setting time of bone cement was determined using gilmo (gilcore) two-needle method. Represented by the initial setting time and final setting time of the bone cement. I.e. a needle with a relatively light mass (w=113.4 g) and a relatively large cross-sectional area (d=2.13 mm) was used for determining the initial setting time; another needle with a heavier mass (w=453.6 g) and a smaller cross-sectional area (d=1.06 mm) was used to determine the final set time. The initial setting time and the final setting time were respectively obtained as the time at which the puncture mark was not left by the thick and thin needle, and the results are shown in Table 2.
TABLE 2
The above results show that the grinding mode during the preparation of the alpha-tricalcium phosphate has an effect on the performance of the bone cement containing the alpha-tricalcium phosphate due to the reaction pressure, and the bone cement containing the alpha-tricalcium phosphate prepared in examples 1-5 has good compressive strength and setting time.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the scope of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present application.
Claims (10)
1. A method for preparing tricalcium phosphate which is uniformly dispersed, which is characterized by comprising the following steps:
1) The calcium carbonate and the calcium hydrophosphate are uniformly mixed according to the mol ratio of (2-2.5) 1, and the volume ratio of the powder to the organic solvent is 1: adding an organic solvent in the proportion of (1-3), grinding by adopting a low-temperature dispersion nano material preparation dispersing machine to obtain powder A, calcining the powder A at 800-1000 ℃ for 1-2h, and cooling along with a furnace to obtain beta-TCP;
2) Placing beta-TCP in a low-temperature dispersing nano material preparation dispersing machine for low-temperature pressurized dispersion to obtain powder B;
3) And (3) placing the powder B in a muffle furnace, heating to 1100-1200 ℃, preserving heat for 2-48h, taking out, and quenching to room temperature to obtain the alpha-TCP.
2. The method for preparing α -tricalcium phosphate as claimed in claim 1, wherein the organic solvent is one or more selected from ethanol, acetone, acetonitrile, butanol, and isopropanol, and preferably the organic solvent is ethanol.
3. The method for preparing alpha-tricalcium phosphate as claimed in claim 1, wherein the low-temperature dispersion nanomaterial preparation disperser in step 1) applies 5-10Mpa pressure at 2-8 ℃ for 0.5-1.5h, and the liquid inlet flow rate is 0.6-1.2L/h when the pressure is applied, preferably, 6Mpa pressure, 6 ℃ for 1h, and 1L/h when the pressure is applied.
4. The method for preparing α -tricalcium phosphate as claimed in claim 1, wherein the low-temperature dispersion nanomaterial preparation disperser in step 2) applies 10-20Mpa pressure at 2-8 ℃ for 0.5-1.5h.
5. The method for producing α -tricalcium phosphate as claimed in claim 4, wherein the inflow rate is 0.6 to 1.2L/h when the pressure is applied.
6. The method for preparing α -tricalcium phosphate as claimed in claim 4, wherein the pressure of 14Mpa is applied at a temperature of 6 ℃ for a dispersion time of 1h.
7. The method for producing α -tricalcium phosphate as claimed in claim 1, wherein the cooling means in step 3) is selected from one or more of air cooling, dry ice cooling, nitrogen cooling, preferably the cooling means is selected from dry ice cooling.
8. The method for producing α -tricalcium phosphate as claimed in claim 1, wherein the temperature rising rate of step 3) is 5 to 10 ℃/min.
9. The method for producing α -tricalcium phosphate as claimed in claim 1, wherein,
1) Calcium carbonate and dibasic calcium phosphate in 2:1, adding alcohol in a volume ratio of 1:2, placing the mixture in a low-temperature dispersing nano material preparation dispersing machine, applying 6Mpa pressure to disperse to obtain powder A, dispersing for 1h at a temperature of 6 ℃, wherein the flow rate of feed liquid is 1L/h when the mixture is pressurized, placing the powder A in a muffle furnace at 900 ℃ to calcine for 1h, and cooling along with the furnace to obtain beta-TCP;
2) Adding beta-TCP into a low-temperature dispersion nano material preparation disperser, applying 14Mpa pressure at 6 ℃ for dispersing for 1h to obtain powder B;
3) And (3) placing the powder B in a muffle furnace, heating to 1150 ℃ at a heating rate of 5 ℃/min, preserving heat for 5 hours, taking out, and quenching in dry ice to room temperature to obtain the alpha-TCP.
10. An α -tricalcium phosphate prepared by the method for preparing α -tricalcium phosphate as claimed in any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210566396.0A CN117142447A (en) | 2022-05-24 | 2022-05-24 | Preparation method of uniformly dispersed alpha-tricalcium phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210566396.0A CN117142447A (en) | 2022-05-24 | 2022-05-24 | Preparation method of uniformly dispersed alpha-tricalcium phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117142447A true CN117142447A (en) | 2023-12-01 |
Family
ID=88906745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210566396.0A Pending CN117142447A (en) | 2022-05-24 | 2022-05-24 | Preparation method of uniformly dispersed alpha-tricalcium phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117142447A (en) |
-
2022
- 2022-05-24 CN CN202210566396.0A patent/CN117142447A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Duxson et al. | Understanding the relationship between geopolymer composition, microstructure and mechanical properties | |
| Tampieri et al. | Sintering and characterization of HA and TCP bioceramics with control of their strength and phase purity | |
| KR100436817B1 (en) | Reactive tricalcium phosphate compositions and uses | |
| Joseph Nathanael et al. | Enhanced mechanical strength of hydroxyapatite nanorods reinforced with polyethylene | |
| Lee et al. | Synthesis and hydration study of Portland cement components prepared by the organic steric entrapment method | |
| Liu et al. | Effect of crystal seeding on the hydration of calcium phosphate cement | |
| Cai et al. | Large-scale and fast synthesis of nano-hydroxyapatite powder by a microwave-hydrothermal method | |
| DE102021107273A1 (en) | Method for the production of granular silicon carbide by two-frequency microwave | |
| Kang et al. | Effects of polycarboxylate ether (PCE)-based superplasticizer on the dissolution and subsequent hydration of calcium oxide (CaO) | |
| CN106164019A (en) | The method preparing zirconium oxide Quito phase ceramics composite | |
| CN111138186B (en) | Alpha-tricalcium phosphate biological ceramic material and preparation method thereof | |
| Guan et al. | Performance of magnesium hydroxide gel at different alkali concentrations and its effect on properties of magnesium oxysulfate cement | |
| Zhao et al. | Rheology of cement pastes with calcium carbonate polymorphs | |
| Liao et al. | Synthesis and mechanism of tetracalcium phosphate from nanocrystalline precursor | |
| CN117142447A (en) | Preparation method of uniformly dispersed alpha-tricalcium phosphate | |
| Xie et al. | Effect of acid-activator characteristics on the early hydration behavior and properties of metakaolin-based geopolymer | |
| Bohner et al. | Effect of thermal treatments on the reactivity of nanosized tricalcium phosphate powders | |
| Romeo et al. | Synthesis of tetracalcium phosphate from mechanochemically activated reactants and assessment as a component of bone cements | |
| Andriotis et al. | Preparation and characterization of bioceramics produced from calcium phosphate cements | |
| Wang et al. | Low temperature preparation of α-tricalcium phosphate and its mechanical properties | |
| Li et al. | Novel two-step sintering and in situ bonding method for fabrication of ZrP2O7 ceramics | |
| CN107720764B (en) | Method for preparing high-purity superfine tricalcium silicate powder by wet chemical method | |
| CN1230210C (en) | Method for making biologic composite materials of nanometer hydroxyapatite/polyamide series for medical use | |
| CN105948012A (en) | Method for preparing beta-tricalcium phosphate crystal material under low temperature condition | |
| Panzavolta et al. | Optimization of a biomimetic bone cement: role of DCPD |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |