CN109537044B - Preparation method of calcium pyrophosphate whisker, tricalcium phosphate whisker, preparation method and application thereof - Google Patents

Preparation method of calcium pyrophosphate whisker, tricalcium phosphate whisker, preparation method and application thereof Download PDF

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CN109537044B
CN109537044B CN201910070705.3A CN201910070705A CN109537044B CN 109537044 B CN109537044 B CN 109537044B CN 201910070705 A CN201910070705 A CN 201910070705A CN 109537044 B CN109537044 B CN 109537044B
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calcium
whisker
whiskers
pyrophosphate
tricalcium phosphate
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CN109537044A (en
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于宏兵
于显著
于晗
董恒
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Tianjin Fengxi Technology Co ltd
Nankai University
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Tianjin Fengxi Technology Co ltd
Nankai University
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Abstract

The application relates to the field of material preparation, in particular to a preparation method of calcium pyrophosphate whiskers, tricalcium phosphate whiskers and a preparation method and application thereof. The preparation method of the calcium pyrophosphate whisker comprises the following steps: the calcium salt complex slowly releases calcium ions in an alkaline environment and reacts with ammonium hydrogen phosphate to prepare the calcium phosphate. The calcium salt complex is placed in an alkaline environment, and calcium ions originally fixed in the complex are slowly released, so that the calcium ions and ammonium hydrogen phosphate are slowly combined to form calcium pyrophosphate with a whisker-shaped appearance. The calcium pyrophosphate with whisker-like morphology can be used for preparing tricalcium phosphate whiskers, so that tricalcium phosphate with the whisker-like morphology is obtained. The tricalcium phosphate crystal whisker can be prepared by adopting the calcium pyrophosphate crystal whisker.

Description

Preparation method of calcium pyrophosphate whisker, tricalcium phosphate whisker, preparation method and application thereof
Technical Field
The application relates to the field of material preparation, in particular to a preparation method of calcium pyrophosphate whiskers, tricalcium phosphate whiskers and a preparation method and application thereof.
Background
Tricalcium phosphate is the main component of human bones, and has the advantages of degradability, high biocompatibility, and the like, so the application range is wide.
Particularly, the printing material is one of ten printing consumables with the most potential in the three-dimensional printing industry, but the inherent brittleness of the tricalcium phosphate ceramic greatly limits the application of the tricalcium phosphate ceramic in the fields of orthopedics and the like.
Whisker toughening is one of the main means for improving ceramic brittleness, such as common SiC whisker toughened ceramic and the like, and the general whisker toughening can improve the ceramic strength by more than 2 times. However, the introduction of the second phase ceramic whiskers into the calcium phosphate matrix can affect the biological properties of the matrix. The calcium phosphate crystal whisker is used for biological artificial bone and the like to become the best choice, on one hand, the properties of the material such as osteogenesis are not influenced, and on the other hand, the strength of the material is also greatly improved.
Tricalcium phosphate whiskers are difficult to make, thus limiting their application.
Disclosure of Invention
In view of the above, an object of the embodiments of the present application is to provide a method for preparing calcium pyrophosphate whiskers, tricalcium phosphate whiskers, a method for preparing tricalcium phosphate whiskers, and an application thereof, so as to solve the above technical problems.
In a first aspect, an embodiment of the present application provides a method for preparing calcium pyrophosphate whiskers, including the following steps: the calcium salt complex slowly releases calcium ions in an alkaline environment and reacts with ammonium hydrogen phosphate to prepare the calcium phosphate.
The calcium salt complex is placed in an alkaline environment, and calcium ions originally fixed in the complex are slowly released, so that the calcium ions and ammonium hydrogen phosphate are slowly combined to form calcium pyrophosphate with a whisker-shaped appearance. The calcium pyrophosphate with whisker-like morphology can be used for preparing tricalcium phosphate whiskers, so that tricalcium phosphate with the whisker-like morphology is obtained.
In some embodiments of the present application, the calcium salt complex is prepared by reacting a calcium salt solution with citric acid.
Under an acidic environment, calcium ions are fixed by calcium salt in a complexing reaction mode, so that guarantee is provided for the subsequent preparation of calcium pyrophosphate with whisker-shaped morphology.
In some embodiments of the present application, the concentration of the calcium salt solution is the same as the concentration of the citric acid solution; optionally, the concentration of the calcium salt solution and the citric acid solution is 0.6-1.0 mol/L.
By selecting the concentration of the citric acid and calcium salt solution in the range of 0.6-1.0mol/L, sufficient calcium ions can be provided for the subsequent reaction.
In some embodiments of the present application, the slow release of calcium ions is achieved by reacting a calcium salt complex with urea such that calcium ions in the calcium salt complex are slowly released.
The urea not only provides an alkaline reaction environment for the calcium salt complex, but also can synthesize the calcium pyrophosphate whisker by a urea precipitation method. The method has simple operation and high synthesis rate.
In some embodiments of the present application, the mass of urea is 1.2-2.0 times the mass of the calcium salt.
By setting the mass selection of the urea to be 1.2-2.0 times of that of the calcium salt, the slow release of calcium ions in the system can be effectively ensured.
A preparation method of tricalcium phosphate whiskers comprises the following steps: preparing calcium pyrophosphate whisker by the preparation method of the calcium pyrophosphate whisker; grinding and mixing the prepared calcium pyrophosphate crystal whisker and calcium carbonate uniformly, and calcining at the temperature of 450-930 ℃; wherein the calcium carbonate is selected from micron-sized calcium carbonate or nano-sized calcium carbonate.
The tricalcium phosphate crystal whisker prepared from the calcium pyrophosphate crystal whisker prepared by the method can effectively ensure that the tricalcium phosphate crystal whisker with a crystal whisker-shaped morphology structure is obtained.
In some embodiments of the present application, the mass ratio of calcium pyrophosphate whiskers to calcium carbonate is 1: 0.4-0.6.
By selecting the mass ratio of the calcium pyrophosphate whisker to the calcium carbonate to be 1:0.4-0.6, the calcium pyrophosphate whisker and the calcium carbonate can be ensured to be fully reacted, so that sufficient tricalcium phosphate whisker is obtained, and higher synthesis rate is ensured.
In some embodiments of the present application, the calcination is performed by first calcining at 440-460 ℃ for 0.4-0.6 hours, then heating to 40-860 ℃ and maintaining the temperature for 0.4-0.6 hours, and finally heating to 920-940 ℃ and maintaining the temperature for 0.4-0.6 hours.
According to the calcining mode of the stage heating, the heating rates of the reaction raw materials in each stage are different, so that the reaction product is ensured to have a whisker-shaped morphology structure.
In a second aspect, embodiments of the present application provide tricalcium phosphate whiskers, which are prepared by the preparation method of tricalcium phosphate whiskers described above.
The tricalcium phosphate crystal whisker has a crystal whisker-shaped morphology structure and high conversion rate.
In a third aspect, the embodiments of the present application provide a use of the tricalcium phosphate whiskers described above in antibacterial agent carriers and ceramic toughening.
The tricalcium phosphate crystal whisker with the crystal whisker-shaped morphology structure can be effectively applied to ceramic toughening due to the special morphology structure of the tricalcium phosphate crystal whisker, and the toughness and the strength of the ceramic are greatly improved. Furthermore, the tricalcium phosphate whisker with the whisker-shaped morphology structure is used for the biological artificial bone, on one hand, the properties of the material such as osteogenesis and the like are not influenced, and on the other hand, the strength of the material is greatly improved. Because the tricalcium phosphate is the main component of human bones, has degradability and high biocompatibility, and the tricalcium phosphate crystal whisker can play a role in toughening and reinforcing, thereby being well applied to antibacterial agent carriers.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a scanning electron microscope image of tricalcium phosphate whiskers provided in the examples of the present application.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present application, it is noted that the terms "first", "second", and the like are used merely for distinguishing between descriptions and are not intended to indicate or imply relative importance.
The following are specific descriptions of the preparation method of calcium pyrophosphate whiskers, tricalcium phosphate whiskers, and the preparation method and application thereof in the examples of the present application.
The preparation method of the calcium pyrophosphate whisker provided by the embodiment of the application comprises the following steps:
the calcium salt complex slowly releases calcium ions in an alkaline environment and reacts with ammonium hydrogen phosphate to prepare the calcium phosphate.
The calcium salt complex is placed in an alkaline environment, and calcium ions originally fixed in the complex are slowly released, so that the calcium ions and ammonium hydrogen phosphate are slowly combined to form calcium pyrophosphate with a whisker-shaped appearance. The calcium pyrophosphate with whisker-like morphology can be used for preparing tricalcium phosphate whiskers, so that tricalcium phosphate with the whisker-like morphology is obtained.
Further, the calcium salt complex is prepared by reacting a calcium salt solution with citric acid.
Under an acidic environment, calcium ions are fixed by calcium salt in a complexing reaction mode, so that guarantee is provided for the subsequent preparation of calcium pyrophosphate with whisker-shaped morphology.
Further optionally, in some embodiments of the present application, the calcium salt may be selected from calcium chloride, calcium nitrate, and calcium acetate.
The calcium salt provides a calcium source for the subsequent preparation of calcium pyrophosphate with whisker-like morphology.
The citric acid isColorless translucent crystals or white granules or white crystalline powder, no odor, extremely acidic taste, and slight deliquescence in humid air. It may exist in the form of an anhydrate or monohydrate: when citric acid is crystallized from hot water, anhydrous compound is generated; crystallization in cold water produces the monohydrate. Upon heating to 78 deg.C, the monohydrate decomposes to give the anhydrous compound. Citric acid may also be dissolved in absolute ethanol at 15 degrees celsius. Citric acid is a tricarboxylic acid compound in structure and thus has similar physical and chemical properties to other carboxylic acids. Heating to 175 ℃ will decompose to produce carbon dioxide and water, leaving some white crystals. Citric acid is a strong organic acid with 3H groups+Can be ionized. Heating can decompose into various products, which react with acid, alkali, glycerol, etc.
In the embodiment of the application, citric acid plays a role in providing an acidic reaction environment for the calcium salt solution, and simultaneously, citric acid can perform a complex reaction with the calcium salt solution to fix calcium ions in a calcium salt complex, so as to provide a reaction raw material for the subsequent preparation of calcium pyrophosphate with a whisker-like morphology.
Further, when the citric acid and the calcium salt solution are reacted as described above, the concentration of the calcium salt solution is the same as that of the citric acid solution.
By selecting the concentrations of the citric acid and the calcium salt solution to be the same, it can be ensured that sufficient chemical reaction occurs between the citric acid and the calcium salt solution and sufficient calcium ions are fixed in the calcium salt complex.
Further, when the citric acid and the calcium salt solution are reacted as described above, the concentrations of the calcium salt solution and the citric acid solution are selected to be in the range of 0.6 to 1.0 mol/L.
By selecting the concentration of the citric acid and calcium salt solution in the range of 0.6-1.0mol/L, sufficient calcium ions can be provided for the subsequent reaction.
Further alternatively, when the citric acid and the calcium salt solution are reacted as described above, the concentrations of the calcium salt solution and the citric acid solution are selected to be in the range of 0.7 to 0.9 mol/L.
The concentration of the calcium salt solution and the citric acid solution is selected to be in the range of 0.7-0.9mol/L, so as to provide enough calcium ions for subsequent reaction.
Further, the slow release of calcium ions in an alkaline environment is achieved by reacting the calcium salt complex with urea so that the calcium ions in the calcium salt complex are slowly released.
Urea, also known as carbamide, is an organic compound consisting of carbon, nitrogen, oxygen and hydrogen and is a white crystal. Can react with acid to form salt. Has hydrolysis effect. Can carry out condensation reaction at high temperature to generate biuret, triuret and cyanuric acid. Heating to 160 deg.C to decompose, generating ammonia gas and changing into isocyanic acid. Urea is weakly alkaline.
The urea is adopted in the embodiment of the application, so that not only is an alkaline reaction environment provided for the calcium salt complex, but also the calcium pyrophosphate whisker can be synthesized by using a urea precipitation method. The method has simple operation and high synthesis rate.
Specifically, when urea is added to the above system, the reaction environment of the entire system is alkaline, and calcium ions in the calcium salt complex are slowly released in the alkaline environment and enter the reaction system in a free form.
Further, ammonium hydrogen phosphate is added to the reaction system, so that the slowly released calcium ions react with the ammonium hydrogen phosphate.
The inventors have found that, in the long-term study, calcium pyrophosphate is generally produced as a white powder when calcium ions react with ammonium hydrogen phosphate, and calcium pyrophosphate having a whisker-like morphology cannot be obtained. However, when calcium ions are slowly released from the reaction system, the calcium ions can react with ammonium hydrogen phosphate to form calcium pyrophosphate with whisker-like morphology. Therefore, the applicant creatively proposes to complex and fix calcium ions in an acidic environment, then slowly release the calcium ions in a calcium salt complex in an alkaline environment, and react the slowly released calcium ions with ammonium hydrogen phosphate, at this time, the calcium ions in the system are extremely small, and each time some calcium ions are slowly released, the calcium ions are quickly reacted with the ammonium hydrogen phosphate to form calcium pyrophosphate whiskers, and before the calcium ions are released again, the calcium ions released last time are reacted with the ammonium hydrogen phosphate to form whiskers, and the powdery calcium pyrophosphate is not formed in the system, so that the calcium pyrophosphate whiskers can be continuously formed in the system.
Furthermore, the mass of the urea is 1.2-2.0 times of that of the calcium salt.
By setting the mass selection of the urea to be 1.2-2.0 times of that of the calcium salt, the slow release of calcium ions in the system can be effectively ensured.
Further alternatively, the mass selection of urea mentioned above is set to be 1.5-1.8 times the mass of the calcium salt.
By setting the mass selection of the urea to be 1.5-1.8 times of the mass of the calcium salt, the slow release of calcium ions in the system can be further ensured.
Further, after adding urea, heating and reacting for 8-12 hours at 90-100 ℃.
Further alternatively, the reaction is heated at 95 ℃ to 98 ℃ for 10 hours after the urea is added.
The calcium pyrophosphate whisker and urea can be fully reacted at the temperature of 90-100 ℃, so that the calcium pyrophosphate with whisker-shaped morphology is ensured to be obtained.
Furthermore, before the urea is added, the calcium salt solution and the citric acid solution are uniformly stirred, so that the reaction effect can be effectively improved, and the reaction sufficiency is ensured.
The stirring may be performed by a method commonly used in the art. For example, manual stirring with a stirring bar or stirring with a stirrer.
Some embodiments of the present application also provide a method for preparing tricalcium phosphate whiskers, comprising the following steps:
preparing calcium pyrophosphate whiskers by the preparation method of the calcium pyrophosphate whiskers as described above;
the prepared calcium pyrophosphate whisker and calcium carbonate are ground and mixed evenly and then calcined at the temperature of 450-930 ℃.
The tricalcium phosphate crystal whisker prepared from the calcium pyrophosphate crystal whisker prepared by the method can effectively ensure that the tricalcium phosphate crystal whisker with a crystal whisker-shaped morphology structure is obtained.
Further, the calcium carbonate is selected from nano-scale calcium carbonate.
The nano calcium carbonate, also called nano calcium carbonate, has a particle size of 0.01-0.1 μm. Because of the superfine nano calcium carbonate particles, the crystal structure and the surface electronic structure of the nano calcium carbonate particles are changed, and the quantum size effect, the small size effect, the surface effect and the macroscopic quantum effect which are not possessed by the common calcium carbonate are generated.
The nano sodium carbonate selected in the preparation steps can effectively react with calcium pyrophosphate to generate tricalcium phosphate, and the whisker-shaped morphological characteristics of the tricalcium phosphate are not influenced, so that the tricalcium phosphate prepared by the reaction has whisker-shaped morphological characteristics, and the tricalcium phosphate whisker is prepared.
Further optionally, the calcium carbonate is selected from micron-sized calcium carbonate.
Further optionally, the micron-sized calcium carbonate has a selected particle size of several micrometers to several hundred micrometers.
The micron calcium carbonate can also react with calcium pyrophosphate to generate tricalcium phosphate, and the tricalcium phosphate prepared by the reaction has whisker-like morphological characteristics.
Further, the mass ratio of the calcium pyrophosphate whiskers to the calcium carbonate is 1: 0.4-0.6.
By selecting the mass ratio of the calcium pyrophosphate whisker to the calcium carbonate to be 1:0.4-0.6, the calcium pyrophosphate whisker and the calcium carbonate can be ensured to be fully reacted, so that sufficient tricalcium phosphate whisker is obtained, and higher synthesis rate is ensured.
Further optionally, the mass ratio of the calcium pyrophosphate whiskers to the calcium carbonate is 1: 0.45-0.55.
By selecting the mass ratio of the calcium pyrophosphate whisker to the calcium carbonate to be 1:0.4-0.6, the calcium pyrophosphate whisker and the calcium carbonate can be ensured to be fully reacted, so that sufficient tricalcium phosphate whisker is obtained, and higher synthesis rate is ensured.
Furthermore, before the calcium pyrophosphate whisker and the calcium carbonate are calcined, the calcium pyrophosphate whisker and the calcium carbonate are ground and uniformly mixed.
Through grinding and mixing the calcium pyrophosphate whiskers and the calcium carbonate uniformly before calcination, the reaction efficiency can be further improved, the conversion rate of the product is ensured, and errors caused by nonuniform mixing of reactants are avoided.
Further alternatively, in an alternative embodiment of the present application, the calcium pyrophosphate whiskers and the calcium carbonate are uniformly mixed by grinding before calcination, and optionally, the calcium pyrophosphate whiskers and the calcium carbonate are mixed by grinding in a water ball mill.
The calcium pyrophosphate whisker and the calcium carbonate raw material can be uniformly mixed by adopting a water ball milling mode for grinding and mixing, so that the calcium pyrophosphate whisker and the calcium carbonate are fully contacted and fully reacted during the subsequent calcination reaction of the calcium pyrophosphate whisker and the calcium carbonate.
Further alternatively, when the mixing is milled by means of a water ball mill, the mixing is carried out for 3 to 5 hours.
The calcium pyrophosphate whisker and the calcium carbonate raw material can be effectively and uniformly mixed by grinding and mixing for 3-5 hours in a water ball milling mode, so that the calcium pyrophosphate whisker and the calcium carbonate are ensured to be fully contacted and fully reacted during the subsequent calcination reaction of the calcium pyrophosphate whisker and the calcium carbonate.
Further alternatively, when the mixing is milled by means of a water ball mill, the mixing is carried out for 3.5 to 4.5 hours.
The calcium pyrophosphate whisker and the calcium carbonate raw material can be effectively and uniformly mixed by grinding and mixing for 3.5 to 4.5 hours in a water ball milling mode, so that the calcium pyrophosphate whisker and the calcium carbonate are ensured to be fully contacted and fully reacted during the subsequent calcination reaction of the calcium pyrophosphate whisker and the calcium carbonate.
Further, the mixture of the calcium pyrophosphate crystal whisker and the calcium carbonate is dried after water ball milling.
The drying can effectively remove the moisture in the mixture of the calcium pyrophosphate whiskers and the calcium carbonate, and further ensures that the reaction result cannot be influenced by the moisture when the calcium pyrophosphate whiskers and the mixture of the calcium carbonate react.
In other alternative embodiments of the present invention, when the mixture of calcium pyrophosphate whiskers and calcium carbonate is ground, other grinding methods commonly used in the art may also be selected.
It will be appreciated that when anhydrous grinding is used, there is no need to oven dry the mixture of calcium phosphate whiskers and calcium carbonate.
Furthermore, during calcination, the calcination is firstly carried out at 440-460 ℃ for 0.4-0.6 h, then the temperature is raised to 840-860 ℃ for heat preservation for 0.4-0.6 h, and finally the temperature is raised to 920-940 ℃ for heat preservation for 0.4-0.6 h.
According to the calcining mode of the stage heating, the heating rates of the reaction raw materials in each stage are different, so that the reaction product is ensured to have a whisker-shaped morphology structure.
Further alternatively, in the calcination, the calcination is performed for 0.5 hour at 450 ℃, then the temperature is raised to 850 ℃ and the temperature is kept for 0.5 hour, and finally the temperature is raised to 930 ℃ and the temperature is kept for 0.5 hour.
Some embodiments of the present application also provide tricalcium phosphate whiskers, which are prepared by the preparation method of tricalcium phosphate whiskers.
Furthermore, the shape of the tricalcium phosphate crystal whisker is in a crystal whisker shape.
Some embodiments of the present application also provide an application of the tricalcium phosphate whisker in antibacterial agent carriers and ceramic toughening.
The tricalcium phosphate whisker with the whisker-shaped morphology structure can be effectively applied to ceramic toughening due to the special morphology structure of the tricalcium phosphate whisker, and the toughness and the strength of the ceramic are greatly improved. Furthermore, the tricalcium phosphate whisker with the whisker-shaped morphology structure is used for the biological artificial bone, on one hand, the properties of the material such as osteogenesis and the like are not influenced, and on the other hand, the strength of the material is greatly improved.
Furthermore, as tricalcium phosphate is the main component of human bones, has degradability and high biocompatibility, the tricalcium phosphate whisker can play a role in toughening and reinforcing, and can be well applied to antibacterial agent carriers.
The features and properties of the present application are described in further detail below with reference to examples:
example 1
The tricalcium phosphate whisker provided by the embodiment is prepared according to the following steps:
mixing a calcium chloride solution with the concentration of 0.6mol/L and a citric acid solution with the same concentration, uniformly stirring, and then adding urea, wherein the content of the urea is 1.2 times that of the calcium chloride. Ammonium hydrogen phosphate was then added. Then heating at 90 ℃ for 10 hours to prepare the calcium pyrophosphate whisker.
Ball-milling and mixing the prepared calcium pyrophosphate crystal whisker and nano calcium carbonate, wherein the mass ratio of the calcium pyrophosphate crystal whisker to the nano calcium carbonate is 1: 0.5, ball milling with water for 4 hours, drying, calcining, keeping the temperature for half an hour at the calcining temperature of 450 ℃, keeping the temperature for half an hour at 850 ℃, and keeping the temperature for half an hour at 930 ℃.
Example 2
The tricalcium phosphate whisker provided by the embodiment is prepared according to the following steps:
mixing a calcium chloride solution with the concentration of 1.0mol/L and a citric acid solution with the same concentration, uniformly stirring, and then adding urea, wherein the content of the urea is 2.0 times of that of the calcium chloride. Ammonium hydrogen phosphate was then added. Then heating at 100 ℃ for 8 hours to prepare the calcium pyrophosphate whisker.
Ball-milling and mixing the prepared calcium pyrophosphate crystal whisker and nano calcium carbonate, wherein the mass ratio of the calcium pyrophosphate crystal whisker to the nano calcium carbonate is 1:0.4, ball milling with water for 3 hours, drying and calcining, wherein the calcining temperature is 440 ℃, the temperature is kept for half an hour, 840 ℃ is kept for half an hour, and 920 ℃ is kept for half an hour.
Example 3
The tricalcium phosphate whisker provided by the embodiment is prepared according to the following steps:
mixing a calcium chloride solution with the concentration of 0.7mol/L and a citric acid solution with the same concentration, uniformly stirring, and then adding urea, wherein the content of the urea is 1.5 times that of the calcium chloride. Ammonium hydrogen phosphate was then added. Then heating at 95 ℃ for 12 hours to prepare the calcium pyrophosphate whisker.
Ball-milling and mixing the prepared calcium pyrophosphate crystal whisker and nano calcium carbonate, wherein the mass ratio of the calcium pyrophosphate crystal whisker to the nano calcium carbonate is 1: 0.55, ball milling with water for 5 hours, drying, calcining, keeping the temperature for half an hour at 460 ℃, keeping the temperature for half an hour at 860 ℃, and keeping the temperature for half an hour at 940 ℃.
Example 4
The tricalcium phosphate whisker provided by the embodiment is prepared according to the following steps:
mixing a calcium chloride solution with the concentration of 0.9mol/L and a citric acid solution with the same concentration, uniformly stirring, and then adding urea, wherein the content of the urea is 1.8 times that of the calcium chloride. Ammonium hydrogen phosphate was then added. Then heating at 98 ℃ for 11 hours to prepare the calcium pyrophosphate whisker.
Ball-milling and mixing the prepared calcium pyrophosphate crystal whisker and nano calcium carbonate, wherein the mass ratio of the calcium pyrophosphate crystal whisker to the nano calcium carbonate is 1:0.45, ball milling with water for 3.5 hours, drying, calcining, keeping the temperature at 455 ℃ for half an hour, keeping the temperature at 855 ℃ for half an hour, and keeping the temperature at 935 ℃ for half an hour.
Example 5
The tricalcium phosphate whisker provided by the embodiment is prepared according to the following steps:
mixing a calcium chloride solution with the concentration of 0.9mol/L and a citric acid solution with the same concentration, uniformly stirring, and then adding urea, wherein the content of the urea is 1.8 times that of the calcium chloride. Ammonium hydrogen phosphate was then added. Then heating at 97 deg.C for 9 hours to obtain calcium pyrophosphate crystal whisker.
Ball-milling and mixing the prepared calcium pyrophosphate crystal whisker and nano calcium carbonate, wherein the mass ratio of the calcium pyrophosphate crystal whisker to the nano calcium carbonate is 1: 0.46, water ball milling for 5.5 hours, drying and calcining, wherein the calcining temperature is 450 ℃, the heat preservation is carried out for half an hour, the heat preservation is carried out for 850 ℃, and the heat preservation is carried out for half an hour at 930 ℃.
Example 6
The tricalcium phosphate whisker provided by the embodiment is prepared according to the following steps:
mixing a calcium chloride solution with the concentration of 0.65mol/L and a citric acid solution with the same concentration, uniformly stirring, and then adding urea, wherein the content of the urea is 1.7 times that of the calcium chloride. Ammonium hydrogen phosphate was then added. Then heating at 97 deg.C for 9 hours to obtain calcium pyrophosphate crystal whisker.
Ball-milling and mixing the prepared calcium pyrophosphate crystal whisker and nano calcium carbonate, wherein the mass ratio of the calcium pyrophosphate crystal whisker to the nano calcium carbonate is 1: 0.41, ball milling with water for 5 hours, drying, calcining, keeping the temperature for half an hour at the calcining temperature of 450 ℃, keeping the temperature for half an hour at 850 ℃, and keeping the temperature for half an hour at 930 ℃.
The morphology structure of the tricalcium phosphate whiskers prepared in the embodiments 1 to 6 of the application is detected by adopting a scanning electron microscope. The results are shown in FIG. 1.
As can be seen from fig. 1, the tricalcium phosphate whiskers produced in examples 1 to 6 of the present application have whisker-like morphology. Therefore, the tricalcium phosphate crystal whisker can be effectively obtained by the preparation method of the tricalcium phosphate crystal whisker, and the method is simple to operate, high in yield and beneficial to industrial application.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (9)

1. A preparation method of calcium pyrophosphate whiskers is characterized by comprising the following steps:
the calcium salt complex slowly releases calcium ions in an alkaline environment and reacts with ammonium hydrogen phosphate to prepare the calcium phosphate.
2. The method for preparing calcium pyrophosphate whiskers as claimed in claim 1, wherein,
the calcium salt complex is prepared by reacting a calcium salt solution with a citric acid solution.
3. The method for preparing calcium pyrophosphate whiskers as claimed in claim 2, wherein,
the concentration of the calcium salt solution is the same as the concentration of the citric acid solution.
4. The method for preparing calcium pyrophosphate whiskers as claimed in claim 2, wherein,
the concentrations of the calcium salt solution and the citric acid solution are both 0.6-1.0 mol/L.
5. The method for preparing calcium pyrophosphate whiskers as claimed in claim 2, wherein,
the slow release of calcium ions is achieved by reacting the calcium salt complex with urea such that the calcium ions in the calcium salt complex are slowly released.
6. The method for preparing calcium pyrophosphate whiskers as claimed in claim 5, wherein,
the mass of the urea is 1.2-2.0 times of that of the calcium salt.
7. A preparation method of tricalcium phosphate whiskers is characterized by comprising the following steps:
preparing calcium pyrophosphate whiskers by the method for preparing calcium pyrophosphate whiskers as claimed in any one of claims 1 to 6;
grinding and mixing the prepared calcium pyrophosphate whisker and calcium carbonate uniformly, and calcining at the temperature of 450-930 ℃;
wherein the calcium carbonate is selected from micron-sized calcium carbonate or nano-sized calcium carbonate.
8. The method of preparing tricalcium phosphate whiskers of claim 7, wherein,
the mass ratio of the calcium pyrophosphate whiskers to the calcium carbonate is 1: 0.4-0.6.
9. The method of preparing tricalcium phosphate whiskers of claim 7, wherein,
during calcination, the mixture is firstly calcined at 440-460 ℃ for 0.4-0.6 h, then heated to 840-860 ℃ for heat preservation for 0.4-0.6 h, and finally heated to 920-940 ℃ for heat preservation for 0.4-0.6 h.
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