CN114956026A - Method for synthesizing calcium phosphate powder by precise atom pairing suspension - Google Patents
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Abstract
The invention provides a method for synthesizing calcium phosphate powder by precise atom pairing suspension, which comprises the following steps: calibrating the purity of the calcium source body and the phosphorus source body; calculating the theoretical dosage ratio of the calcium source body and the phosphorus source body according to the theoretical calcium atom number and the theoretical phosphorus atom number of the calcium source body and the theoretical calcium atom number and the theoretical phosphorus atom number of the target powder, and calculating the actual dosage of the calcium source body and the phosphorus source body by combining the calibrated purity; preparing a calcium source solution and a phosphorus source solution according to the actual dosage of the calcium source and the phosphorus source; stirring, mixing and suspending the calcium source solution and the phosphorus source solution for chemical reaction to obtain milky white suspension; curing the suspension to obtain raw powder; and calcining and granulating the raw powder to obtain the target powder. The technical scheme of the invention can synthesize the high-purity and high-quality calcium phosphate powder.
Description
Technical Field
The invention relates to the field of chemical synthesis of inorganic materials and medical biomaterials, in particular to a method for synthesizing calcium phosphate powder by precise atom pairing suspension.
Background
Calcium phosphate materials are a class of biological materials which are physically and chemically stable, biocompatible, degradable and absorbable and can promote tissue regeneration, represented by degradable beta-tricalcium phosphate (beta-TCP) and non-degradable Hydroxyapatite (HA), become one of the most widely applied biological materials in the world, are especially incomparable to other materials in the aspect of hard tissue injury repair, and are mainly used as bone repair materials, surgical implants, cell and drug carriers, implant coatings, surface treatment and the like. As the purity and the impurity content of the medical calcium phosphate material can directly influence the quality and the performance of products, the requirement of the raw material is very high, at present, China completely depends on import, a detection standard sample is basically blank, and the industrial development is seriously influenced.
The preparation of calcium phosphate powder can be divided into dry process and wet process, the former includes mechanochemical synthesis and solid phase synthesis, and the latter includes traditional chemical precipitation, sol-gel and micro-emulsion. The products of the mechanochemical synthesis method have uneven particle size distribution and easy agglomeration, the mechanical treatment time is long, the energy consumption is high, and the abrasion of the grinding medium can cause pollution to the products. The product of the solid phase synthesis method has coarse crystal grains, is easy to agglomerate, has uneven composition and is often accompanied with impurity generation. Impurities are easily introduced into the product of the traditional chemical precipitation method, the appearance is uneven, and the product is easy to agglomerate. The sol-gel method has long reaction time, some raw materials are organic substances and are harmful to human beings, and a large number of micropores exist in gel and can generate shrinkage in the drying process. The microemulsion method has complex process and high cost, and some raw materials are not environment-friendly.
Therefore, there is a need for an improved process for preparing calcium phosphate powder, which can obtain calcium phosphate powder with high purity and high quality while avoiding the problems of the above-mentioned preparation method.
Disclosure of Invention
The invention aims to provide a method for synthesizing calcium phosphate powder by accurate atom pairing suspension, which is used for carrying out atom pairing on fed materials and accurately regulating and controlling a process so as to realize the high-purity and high-quality targets of the calcium phosphate powder.
In order to achieve the purpose, the invention provides a method for synthesizing calcium phosphate powder by precise atom pairing suspension, which comprises the following steps:
calibrating the purity of the calcium source body and the phosphorus source body;
calculating the theoretical dosage ratio of the calcium source body to the phosphorus source body according to the theoretical calcium atom number and the theoretical phosphorus atom number of the calcium source body and the theoretical calcium atom number and the theoretical phosphorus atom number of the target powder to be synthesized;
calculating the actual dosage of the calcium source body and the phosphorus source body according to the theoretical dosage ratio of the calcium source body and the phosphorus source body and the calibrated purity of the calcium source body and the phosphorus source body, and preparing a calcium source body solution and a phosphorus source body solution;
stirring, mixing and suspending the calcium source solution and the phosphorus source solution for chemical reaction to obtain milky white suspension;
curing the suspension to obtain raw powder;
and calcining and granulating the raw powder to obtain the target powder.
Optionally, the calcium source comprises at least one of calcium nitrate, calcium carbonate, calcium acetate, calcium chloride, calcium hydroxide, and calcium diethanolate.
Optionally, the phosphorus source comprises at least one of monoammonium phosphate, trimethyl phosphate, triethyl phosphate, trisodium phosphate, and phosphoric acid.
Optionally, the method of calibrating the purity of the calcium source and the phosphorus source comprises at least one of inductively coupled plasma and atomic emission spectrometry, inductively coupled plasma and mass spectrometry, atomic absorption spectrometry, and X-ray diffraction.
Optionally, the theoretical dosage ratio of the calcium source body to the phosphorus source body is calculated by the formula:
the theoretical use amount ratio is (the theoretical molecular weight of the calcium source body is the theoretical number of calcium atoms of the target powder body/the theoretical number of calcium atoms of the calcium source body)/(the theoretical molecular weight of the phosphorus source body is the theoretical number of phosphorus atoms of the target powder body/the theoretical number of phosphorus atoms of the phosphorus source body).
Optionally, the calculation formula of the actual usage amount of the calcium source body and the phosphorus source body is as follows:
the actual consumption of the calcium source is the theoretical consumption of the calcium source/the purity of the calcium source;
and the actual consumption of the phosphorus source is the theoretical consumption of the phosphorus source/the purity of the phosphorus source.
Optionally, the calcium source and the phosphorus source are prepared into the calcium source solution and the phosphorus source solution by using a liquid medium, and the liquid medium is pure water or deionized water.
Optionally, the step of suspending the calcium source solution and the phosphorus source solution by stirring to mix them for chemical reaction comprises:
putting the whole amount of the calcium source solution into a reaction device, and then dropwise adding the phosphorus source solution while fully stirring and mixing to form milky white suspension.
Optionally, the dropping speed is 1ml/min to 1000ml/min, and the stirring speed is 10rpm to 1000 rpm.
Optionally, during the stirring, mixing and suspending chemical reaction, acid and alkali regulating solution is dripped to control the pH value of the reaction solution.
Optionally, when the target powder is tricalcium phosphate, the pH value is kept between 6 and 7; when the target powder is hydroxyapatite, the pH value is maintained to be not less than 9.
Optionally, during the stirring, mixing and suspending chemical reaction, the temperature of the reaction solution is kept at 20-80 ℃.
Optionally, during the stirring, mixing and suspending chemical reaction, adding pure metal and/or metal compound to obtain the target powder containing metal ions.
Optionally, the metal ions include at least one of gold, silver, copper, iron, magnesium, zinc, strontium, titanium, tantalum, manganese, and molybdenum.
Optionally, the step of obtaining the raw meal comprises:
curing the suspension at a set temperature and a set stirring speed to obtain a precipitate;
and (3) recovering the precipitate by adopting a filtering method and/or a centrifuging method, and drying to obtain the raw powder.
Optionally, the filtration method adopts a filtration membrane with a pore diameter of 0.1-20 μm for negative pressure suction filtration; the centrifugation method adopts the speed of 200 rpm-10000 rpm for centrifugation for 10 min-120 min; and drying the precipitate for 10-100 h at 30-80 ℃ to form the raw powder.
Optionally, the step of obtaining the target powder includes:
calcining the raw powder to obtain a cooked powder;
and granulating the cooked powder by adopting a roller hedging grinding process to obtain the target powder.
Optionally, the calcination temperature is 600-1200 ℃, and the calcination time is 0.5-10 h.
Optionally, in the roller impact grinding process, the cooked powder is granulated by using hard grinding balls and/or soft grinding balls, the hard grinding balls are made of at least one of alumina and dopants thereof, zirconia and dopants thereof, and yttria and dopants thereof, and the soft grinding balls are made of at least one of medical organic silica gel, ultra-high molecular weight polyethylene and polymethyl methacrylate.
Optionally, the diameters of the hard grinding balls and the soft grinding balls are 1 mm-100 mm, and at least two hard grinding balls and/or soft grinding balls with different diameters are proportioned for grinding and granulating.
Optionally, during the granulation of the cooked powder by the roller impact grinding process, a grinding medium is added, wherein the grinding medium comprises water and/or oil.
Optionally, the particle size of the target powder is 0.01 μm to 1000 μm.
Compared with the prior art, the method for synthesizing the calcium phosphate powder through precise atom pairing suspension is an original method, the theoretical dosage ratio of the calcium source body and the phosphorus source body is calculated according to the theoretical calcium atom quantity and the theoretical phosphorus atom quantity of the calcium source body and the theoretical calcium atom quantity and the theoretical phosphorus atom quantity of the target powder, the actual dosage of the calcium source body and the phosphorus source body is calculated by combining the calibrated calcium source body and phosphorus source body purity, and then corresponding calcium source body solution and phosphorus source body solution are prepared, so that atom pairing precise feeding is carried out on the calcium source body and the phosphorus source body, and a foundation is laid for synthesizing high-purity target powder; in addition, in the process of suspending the calcium source solution and the phosphorus source solution through stirring and mixing, the synthesis parameters are accurately regulated and controlled, and the chemical reaction is ensured to develop towards the expected direction; and the raw powder is obtained by adopting a fine curing process, and is granulated by adopting a roller hedging grinding process after the raw powder is calcined, so that the quality of the target powder is improved, and the requirements of customers are met. Therefore, the method for synthesizing the calcium phosphate powder by accurate atom pairing suspension can synthesize the calcium phosphate powder with high purity and high quality, so that the calcium phosphate powder reaches the international medical grade standard (the purity is more than or equal to 95 percent) and even meets the requirement of a higher detection standard sample (the purity is more than or equal to 99.5 percent).
Drawings
Fig. 1 is a flow chart of a method for synthesizing calcium phosphate powder by precise atom pairing suspension according to an embodiment of the present invention.
Detailed Description
In order to make the objects, advantages and features of the present invention more clear, the method for synthesizing calcium phosphate powder by precise atom pairing suspension proposed by the present invention is further described in detail below. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.
An embodiment of the present invention provides a method for synthesizing calcium phosphate powder by precise atom pairing suspension, referring to fig. 1, where fig. 1 is a flowchart of a method for synthesizing calcium phosphate powder by precise atom pairing suspension according to an embodiment of the present invention, and the method for synthesizing calcium phosphate powder by precise atom pairing suspension includes:
step S1, calibrating the purity of calcium source and phosphorus source;
step S2, calculating the theoretical dosage ratio of the calcium source body and the phosphorus source body according to the theoretical calcium atom number and the theoretical phosphorus atom number of the calcium source body and the theoretical calcium atom number and the theoretical phosphorus atom number of the target powder to be synthesized;
step S3, calculating the actual consumption of the calcium source body and the phosphorus source body according to the theoretical consumption ratio of the calcium source body and the phosphorus source body and the calibrated purity of the calcium source body and the phosphorus source body, and preparing a calcium source body solution and a phosphorus source body solution;
step S4, stirring, mixing and suspending the calcium source solution and the phosphorus source solution for chemical reaction to obtain milky white suspension;
step S5, curing the suspension to obtain raw powder;
and step S6, calcining and granulating the raw powder to obtain the target powder.
First, according to step S1, the purity of the calcium source and the phosphorus source is calibrated.
The calcium source body provides calcium atoms required for synthesizing the target powder, and the phosphorus source body provides phosphorus atoms required for synthesizing the target powder.
The target powder can be tricalcium phosphate, hydroxyapatite or the like.
The calcium source comprises at least one of calcium compounds such as calcium nitrate, calcium carbonate, calcium acetate, calcium chloride, calcium hydroxide and calcium diethanolate. The phosphorus source comprises at least one of phosphorus-containing compounds such as ammonium dihydrogen phosphate, trimethyl phosphate, triethyl phosphate, trisodium phosphate and phosphoric acid.
The purity of the calcium source body and the purity of the phosphorus source body can be accurately calibrated by adopting a high-precision detection means, wherein the detection means comprises at least one of methods of inductively coupled plasma and atomic emission spectrometry, inductively coupled plasma and mass spectrometry, atomic absorption spectrometry, X-ray diffraction method and the like.
Due to the fact that impurities exist in the purchased or self-made calcium source body and phosphorus source body, the purity of the calcium source body and phosphorus source body is accurately calibrated, the actual consumption of the calcium source body and phosphorus source body is more accurately calculated subsequently, and the concentration of the prepared calcium source body solution and phosphorus source body solution is more accurate.
Further, the calcium source and the phosphorus source may be purchased or manufactured by oneself in a solid or liquid state.
According to step S2, calculating the theoretical usage ratio of the calcium source and the phosphorus source required for synthesizing the target powder according to the theoretical calcium atom number and the theoretical phosphorus atom number of the calcium source and the phosphorus source and the theoretical calcium atom number and the theoretical phosphorus atom number of the target powder required for synthesizing.
The theoretical calcium atom number and the theoretical phosphorus atom number of the target powder can be obtained according to the chemical formula of the target powder. For example, if the target powder is tricalcium phosphate, the molecular formula is Ca 3 (PO 4 ) 2 Then the theoretical number of calcium atoms and the theoretical number of phosphorus atoms are 3 and 2, respectively. If the target powder is hydroxyapatite, the molecular formula is Ca 5 (PO4) 3 (OH), then the theoretical number of calcium atoms and the theoretical number of phosphorus atoms are 5 and 3, respectively.
The calculation formula of the theoretical dosage of the calcium source body and the phosphorus source body is as follows:
the theoretical dosage ratio of the calcium source body to the phosphorus source body (theoretical molecular weight of the calcium source body, theoretical number of calcium atoms in the target powder body/theoretical number of calcium atoms in the calcium source body)/(theoretical molecular weight of the phosphorus source body, theoretical number of phosphorus atoms in the target powder body/theoretical number of phosphorus atoms in the phosphorus source body) is represented by formula (1);
and the theoretical dosage ratio of the calcium source body to the phosphorus source body can be calculated by the following formula:
the theoretical dosage ratio of the calcium source body to the phosphorus source body is equal to the theoretical dosage of the calcium source body/the theoretical dosage of the phosphorus source body in a formula (2);
therefore, when the theoretical amount of the calcium source is known, the theoretical amount of the phosphorus source can be obtained by calculation according to the above formula (1) and formula (2).
The above calculation formula is for the solid calcium source and the solid phosphorus source.
According to step S3, calculating the actual usage amounts of the calcium source and the phosphorus source according to the theoretical usage ratio of the calcium source and the phosphorus source and the calibrated purity of the calcium source and the phosphorus source, and preparing a calcium source solution and a phosphorus source solution.
The calculation formula of the actual dosage of the calcium source body and the phosphorus source body is as follows:
the actual consumption of the calcium source is the theoretical consumption of the calcium source/the purity of the calcium source;
and the actual consumption of the phosphorus source is the theoretical consumption of the phosphorus source/the purity of the phosphorus source.
The above calculation formula is for the solid calcium source and the solid phosphorus source.
And, the theoretical amount and the actual amount of the above formula are referred to as theoretical weight and actual weight, respectively.
And respectively preparing the calcium source solution and the phosphorus source solution by adopting a liquid medium and taking actual dosage as the calcium source solution and the phosphorus source solution, wherein the liquid medium can be pure water or deionized water.
And if the purchased or self-made calcium source body and the phosphorus source body are solids, measuring the required weight of the calcium source body and the phosphorus source body, and preparing the calcium source body solution and the phosphorus source body solution with accurate concentrations by adopting the liquid medium.
If the purchased or self-made calcium source body and the phosphorus source body are liquid, the actual dosage of the calcium source body and the phosphorus source body can be calculated according to the calibrated concentration of the calcium source body and the phosphorus source body, and the liquid medium is adopted to dilute the calcium source body solution and the phosphorus source body solution into the calcium source body solution and the phosphorus source body solution with accurate concentration.
The error between the actual concentration and the theoretical concentration of the prepared calcium source solution and the phosphorus source solution is-0.1%.
According to step S4, the calcium source solution and the phosphorus source solution are mixed by stirring to suspend the chemical reaction, so as to obtain a milky white suspension.
The step of suspending the calcium source solution and the phosphorus source solution by stirring and mixing a chemical reaction comprises: first, the calcium source solution prepared in the step S3 is placed in a reaction apparatus by a manual and/or mechanical method; and then, dropwise adding the phosphorus source solution into the reaction device by a manual and/or mechanical method until the phosphorus source solution is completely added. The whole dropping process of the phosphorus source solution is carried out in a continuous stirring and uniformly mixing state, so that the calcium source and the phosphorus source can fully and chemically react to obtain the milky suspension.
And intelligently and accurately regulating and controlling the influencing factors of the chemical reaction so as to ensure that the chemical reaction develops according to the expected target direction. Wherein the influencing factors comprise pH value, temperature, dropping speed of the phosphorus source solution, stirring speed of the chemical reaction solution and the like.
And if the target powder is tricalcium phosphate, controlling the pH value required by the chemical reaction solution to be 6-7. If the target powder is hydroxyapatite, the pH value required by the chemical reaction solution is not less than 9. The pH value error of the chemical reaction solution is controlled to be-0.1.
In the stirring, mixing and suspending chemical reaction process, acid-base regulating solution is dripped to control the pH value of the reaction solution, and the acid-base regulating solution can be alkalescent solution such as ammonia water. It should be noted that the added acid-base adjusting solution should not contain phosphorus and calcium elements, so as not to affect the formation of the target powder.
In addition, in the stirring, mixing and suspending chemical reaction process, the temperature of the chemical reaction solution can be accurately controlled to be 20-80 ℃, and the error is controlled to be-0.5 ℃.
Moreover, the dropping speed of the phosphorus source solution is 1ml/min to 1000ml/min, and the error is-0.01 percent to 0.01 percent; the stirring speed of the chemical reaction solution is 10rpm to 1000rpm, and the error is controlled to be-1 to 1 percent.
In addition, in the process of chemical reaction between the calcium source solution and the phosphorus source solution, pure metal and/or metal compound particles can be added to obtain target powder containing metal ions, so that the sintering degree, the antibacterial property, the tissue regeneration promoting capability and the like of the powder can be adjusted.
The metal ions of the pure metal and the metal compound include at least one of gold, silver, copper, iron, magnesium, zinc, strontium, titanium, tantalum, manganese, molybdenum, and the like.
The suspension is subjected to aging treatment according to step S5 to obtain raw powder.
The method comprises the following steps: firstly, curing the suspension at a set temperature and a set stirring speed to obtain a precipitate; then, the precipitate is recovered by a filtration method and/or a centrifugation method, and is dried by baking to obtain the dried raw powder. The set temperature is 20-80 ℃, and the set stirring speed is 10-1000 rpm.
The filtration method adopts a filtration membrane with the aperture of 0.1-20 mu m for negative pressure suction filtration; the centrifugation method adopts the speed of 200 rpm-10000 rpm to carry out centrifugation for 10 min-120 min; and drying the precipitate at the temperature of 30-80 ℃ for 10-100 h to ensure that the precipitate is completely dehydrated to obtain the raw powder.
And according to the step S6, calcining and granulating the raw powder to obtain the target powder.
The method comprises the following steps: firstly, calcining the raw powder, and removing residual organic matters and/or volatile substances to obtain chemically stable cooked powder, wherein chemical components of the cooked powder reach a set target; and then, granulating the cooked powder by adopting a roller opposite impact grinding process to obtain the target powder with the required particle size.
Wherein the calcining temperature is 600-1200 ℃, and the calcining time is 0.5-10 h.
In the roller hedging grinding process, grinding balls with different sizes, different hardness and different proportions and the cooked powder are filled into a grinding tank, and the grinding balls collide with each other and with the inner wall of the grinding tank through the rotation of the grinding tank, so that agglomerated powder particles are dispersed, and the requirement on the particle size of the expected powder is met.
And in order to meet different manufacturing processes and different product requirements, the cooked powder is granulated by adjusting at least one of the size ratio of the grinding balls, the ratio of the soft balls to the hard balls, the ratio of the grinding speed, the ratio of the grinding time and the ratio of the grinding medium, so as to achieve the expected target.
The hard grinding ball is made of at least one of alumina and its dopant, zirconia and its dopant, yttria and its dopant, etc. The soft grinding ball is made of at least one of medical organic silica gel, ultra-high molecular weight polyethylene, polymethyl methacrylate and the like.
The diameter of the hard grinding balls and the soft grinding balls can be 1 mm-100 mm; and, the cooked powder may be ground and granulated by using at least two kinds of the hard grinding balls and/or the soft grinding balls with different diameters, and the ratio of the hard grinding balls and/or the soft grinding balls with different diameters includes, but is not limited to, 1:1 to 1: 10.
The ratio of the soft grinding balls to the hard grinding balls includes, but is not limited to, 0: 1-1: 10.
The grinding speed includes but is not limited to 50 rpm-50000 rpm, and the grinding time includes but is not limited to 10 min-100 h.
In the roller impact grinding granulation process, grinding media with different viscosities can be added into the grinding tank, and the grinding media can comprise low-viscosity water and/or high-viscosity oil and the like, so that the powder particles are uniformly stressed in the grinding process, and the target powder with more uniform particle size is obtained.
After the grinding is completed, filtering and drying are performed to remove the grinding medium, so as to obtain the target powder with the desired particle size.
The particle size of the target powder can be 0.01-1000 μm.
The preparation of the target powder is tricalcium phosphate (molecular formula is Ca) 3 (PO 4 ) 2 ) For example, the method for synthesizing calcium phosphate powder by precise atom pairing suspension is described as follows:
step S1, calcium nitrate tetrahydrate (molecular formula is Ca (NO)) 3 ) 2 ·4H 2 O) as the calcium source, ammonium dihydrogen phosphate (molecular formula is (NH) 4 ) 2 HPO 4 ) As a phosphorus source. The purity of the calcium nitrate tetrahydrate and the purity of the ammonium dihydrogen phosphate are calibrated by adopting an inductive coupling plasma and an atomic emission spectrometry, and the purity calibration results of the calcium nitrate tetrahydrate and the purity calibration results of the ammonium dihydrogen phosphate are respectively 98.50% and 99.60%. The theoretical molecular weights of calcium nitrate tetrahydrate and ammonium dihydrogen phosphate are 236.15g/mole and 132.06g/mole, respectively.
The chemical reaction of the calcium nitrate tetrahydrate and the ammonium dihydrogen phosphate in the synthesis of the tricalcium phosphate is as follows:
3Ca(NO 3 ) 2 ·4H 2 O+2(NH 4 ) 2 HPO 4 +2NH 4 OH→Ca 3 (PO 4 ) 2 +6NH 4 NO 3 +14H 2 O
wherein NH 4 OH is acid-base regulating liquid.
Step S2, Ca according to the molecular formula of tricalcium phosphate 3 (PO 4 ) 2 Theoretical synthesis requires 3 calcium atoms and 2 phosphorus atoms per molecule of tricalcium phosphate. The theoretical number of calcium atoms of calcium nitrate tetrahydrate is 1 and the theoretical number of phosphorus atoms of ammonium dihydrogen phosphate is 1, i.e. 3 molecules of calcium nitrate tetrahydrate and 2 molecules of ammonium dihydrogen phosphate are needed for theoretically synthesizing each molecule of tricalcium phosphate.
Therefore, according to the formula for calculating the theoretical usage ratio of the calcium source body to the phosphorus source body, the theoretical usage ratio of the calcium source body to the phosphorus source body (theoretical molecular weight of calcium nitrate tetrahydrate, theoretical number of calcium atoms in tricalcium phosphate/theoretical number of calcium atoms in calcium nitrate tetrahydrate)/(theoretical molecular weight of ammonium dihydrogen phosphate)/(theoretical number of phosphorus atoms in ammonium dihydrogen phosphate) is (236.15, 3/1)/(132.06, 2/1) is 708.45/264.12 is 2.68.
Assuming that the theoretical amount of calcium nitrate tetrahydrate (i.e., calcium nitrate tetrahydrate without impurities) required is 100g, the theoretical amount of ammonium dihydrogen phosphate (i.e., ammonium dihydrogen phosphate without impurities) is 100/2.68-37.31 g.
And step S3, calculating the actual dosage of the calcium source body and the phosphorus source body.
The actual dosage of the calcium nitrate tetrahydrate is 100 percent/98.50 percent/the purity of the calcium nitrate tetrahydrate is 101.53 g.
The actual amount of ammonium hydrogen phosphate used is 37.31/99.6% purity of the theoretical amount of ammonium hydrogen phosphate used is 37.46 g.
Preparing a calcium nitrate tetrahydrate solution and an ammonium dihydrogen phosphate solution by adopting pure water and respectively preparing the calcium nitrate tetrahydrate solution and the ammonium dihydrogen phosphate solution with actual using amounts, wherein the concentrations of the calcium nitrate tetrahydrate solution and the ammonium dihydrogen phosphate solution are both 60 wt%.
And step S4, filling the whole amount of calcium nitrate tetrahydrate solution into a reaction device, and then dripping ammonium dihydrogen phosphate solution until the ammonium dihydrogen phosphate solution is completely dripped to form milky suspension. Wherein the temperature of the solution in the reaction device is controlled at 60 ℃, and the pH value of the solution in the reaction device is controlled at 6.5; and during the reaction, stirring the solution in the reaction apparatus at a speed of 300 rpm; and the dropping speed of the ammonium dihydrogen phosphate solution is controlled at 50 ml/min.
And step S5, curing the milky white suspension for 70 hours in the environment with set temperature, set stirring speed and pH value, and generating a large amount of precipitates after stopping stirring.
Centrifuging at 2000rpm for 2 hr to obtain cheese-like precipitate, and oven drying at 70 deg.C for 48 hr to obtain raw powder.
And step S6, mechanically and/or manually grinding the raw powder, and calcining for 2 hours at 900 ℃ to obtain cooked powder. And then carrying out opposite impact grinding and granulation for 24 hours by adopting a roller to obtain tricalcium phosphate powder with the grain diameter of 3.5 microns +/-0.05 microns.
According to the method for synthesizing the calcium phosphate powder by the precise atomic pairing suspension, the theoretical dosage ratio of the calcium source body and the phosphorus source body is calculated according to the theoretical calcium atom quantity of the calcium source body, the theoretical phosphorus atom quantity of the phosphorus source body and the theoretical calcium atom quantity and the theoretical phosphorus atom quantity of the target powder, the actual dosage of the calcium source body and the phosphorus source body is calculated by combining the calibrated calcium source body and phosphorus source body purity, and then the corresponding calcium source body solution and phosphorus source body solution are prepared, so that the calcium source body and the phosphorus source body are subjected to atomic pairing precise feeding, and a foundation is laid for synthesizing the high-purity target powder. In the process of suspending the calcium source solution and the phosphorus source solution through stirring and mixing, the synthesis parameters are accurately regulated and controlled, and the chemical reaction is ensured to develop towards the expected direction. The raw powder is obtained by adopting a fine curing process, and is granulated by adopting a roller hedging grinding process after the raw powder is calcined, so that the quality of the target powder is improved, and the requirements of customers are met. Therefore, the method for synthesizing the calcium phosphate powder by accurate atom pairing suspension can synthesize high-purity and high-quality calcium phosphate powder, so that the calcium phosphate powder reaches the international medical standard (the purity is more than or equal to 95 percent) and even meets the higher requirement of a detection standard sample.
The above description is only for the purpose of describing the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are within the scope of the appended claims.
Claims (22)
1. A method for synthesizing calcium phosphate powder by precise atom pairing suspension is characterized by comprising the following steps:
calibrating the purity of the calcium source body and the phosphorus source body;
calculating the theoretical dosage ratio of the calcium source body to the phosphorus source body according to the theoretical calcium atom number and the theoretical phosphorus atom number of the calcium source body, the theoretical calcium atom number and the theoretical phosphorus atom number of the target powder to be synthesized;
calculating the actual dosage of the calcium source body and the phosphorus source body according to the theoretical dosage ratio of the calcium source body and the phosphorus source body and the calibrated purity of the calcium source body and the phosphorus source body, and preparing a calcium source body solution and a phosphorus source body solution;
stirring, mixing and suspending the calcium source solution and the phosphorus source solution for chemical reaction to obtain milky white suspension;
curing the suspension to obtain raw powder;
and calcining and granulating the raw powder to obtain the target powder.
2. The method for synthesizing calcium phosphate powder by precise atomic pairing suspension according to claim 1, wherein the calcium source comprises at least one of calcium nitrate, calcium carbonate, calcium acetate, calcium chloride, calcium hydroxide, and calcium diethanolate.
3. The method for synthesizing calcium phosphate powder by precise atom pairing suspension of claim 1, wherein the phosphorus source comprises at least one of ammonium dihydrogen phosphate, trimethyl phosphate, triethyl phosphate, trisodium phosphate, and phosphoric acid.
4. The method for synthesizing calcium phosphate powder by precise atomic pairing suspension according to claim 1, wherein the method for calibrating the purity of the calcium source and the phosphorus source comprises at least one of inductively coupled plasma and atomic emission spectrometry, inductively coupled plasma and mass spectrometry, atomic absorption spectrometry, and X-ray diffraction.
5. The method for synthesizing calcium phosphate powder by precise atom pairing suspension according to claim 1, wherein the theoretical dosage ratio of the calcium source body and the phosphorus source body is calculated by the formula:
the theoretical dosage ratio is (theoretical molecular weight of the calcium source body, theoretical number of calcium atoms of the target powder body/theoretical number of calcium atoms of the calcium source body)/(theoretical molecular weight of the phosphorus source body, theoretical number of phosphorus atoms of the target powder body/theoretical number of phosphorus atoms of the phosphorus source body).
6. The method for synthesizing calcium phosphate powder by precise atom pairing suspension according to claim 1, wherein the calculation formula of the actual dosage of the calcium source body and the phosphorus source body is as follows:
the actual consumption of the calcium source is the theoretical consumption of the calcium source/the purity of the calcium source;
and the actual consumption of the phosphorus source is the theoretical consumption of the phosphorus source/the purity of the phosphorus source.
7. The method for synthesizing calcium phosphate powder by precise atomic pairing suspension according to claim 1, wherein the calcium source and the phosphorus source are prepared into the calcium source solution and the phosphorus source solution by using a liquid medium, and the liquid medium is pure water or deionized water.
8. The method for synthesizing calcium phosphate powder by precise atomic pairing suspension according to claim 1, wherein the step of mixing the calcium source solution and the phosphorus source solution by stirring to mix and suspend the chemical reaction comprises:
and (3) placing the calcium source solution into a reaction device, dropwise adding the phosphorus source solution into the reaction device, and fully stirring and mixing while dropwise adding to form milky suspension.
9. The method for synthesizing calcium phosphate powder by precise atom pairing suspension according to claim 8, wherein the dropping speed is 1ml/min to 1000ml/min, and the stirring speed is 10rpm to 1000 rpm.
10. The method for synthesizing calcium phosphate powder by precise atomic pairing suspension according to claim 1, wherein during the stirring, mixing and suspending chemical reaction, acid and alkali regulating solution is dripped to control the pH value of the reaction solution.
11. The method for synthesizing calcium phosphate powder by precise atom pairing suspension according to claim 10, wherein when the target powder is tricalcium phosphate, the pH value is maintained between 6 and 7; when the target powder is hydroxyapatite, the pH value is maintained to be not less than 9.
12. The method for synthesizing calcium phosphate powder by accurate atomic pairing suspension according to claim 1, wherein the temperature of the reaction solution is maintained at 20-80 ℃ during the stirring, mixing and suspending chemical reaction.
13. The method for synthesizing calcium phosphate powder by accurate atomic pairing suspension according to claim 1, wherein pure metal and/or metal compound is added during the stirring, mixing and suspending chemical reaction process to obtain target powder containing metal ions.
14. The method for synthesizing calcium phosphate powder by precise atomic pairing suspension according to claim 13, wherein the metal ions comprise at least one of gold, silver, copper, iron, magnesium, zinc, strontium, titanium, tantalum, manganese, and molybdenum.
15. The method of synthesizing calcium phosphate powder with precise atomic pairing suspension according to claim 1, wherein the step of obtaining the green powder comprises:
curing the suspension at a set temperature and a set stirring speed to obtain a precipitate;
and recovering the precipitate by adopting a filtering method and/or a centrifuging method, and drying to obtain the raw powder.
16. The method for synthesizing calcium phosphate powder by precise atom pairing suspension as claimed in claim 15, wherein the filtration method adopts a filtration membrane with a pore size of 0.1-20 μm for negative pressure suction filtration; the centrifugation method adopts the speed of 200 rpm-10000 rpm for centrifugation for 10 min-120 min; and drying the precipitate for 10-100 h at 30-80 ℃ to form the raw powder.
17. The method of synthesizing calcium phosphate powder by precise atomic pairing suspension according to claim 1, wherein the step of obtaining the target powder comprises:
calcining the raw powder to obtain a cooked powder;
and granulating the cooked powder by adopting a roller hedging grinding process to obtain the target powder.
18. The method for synthesizing calcium phosphate powder by precise atom pairing suspension according to claim 17, wherein the calcination temperature is 600-1200 ℃ and the calcination time is 0.5-10 h.
19. The method for synthesizing calcium phosphate powder by precise atomic pairing suspension according to claim 17, wherein the roller impact grinding process uses hard grinding balls and/or soft grinding balls to granulate the calcined powder, the hard grinding balls are made of at least one of alumina and its dopant, zirconia and its dopant, and yttria and its dopant, and the soft grinding balls are made of at least one of medical organic silica gel, ultra-high molecular weight polyethylene, and polymethyl methacrylate.
20. The method for synthesizing calcium phosphate powder by precise atomic pairing suspension according to claim 19, wherein the diameter of the hard grinding ball and the soft grinding ball is 1mm to 100mm, and the hard grinding ball and/or the soft grinding ball with at least two different diameters are used for grinding and granulating.
21. The method for synthesizing calcium phosphate powder by precise atomic pairing suspension according to claim 17, wherein a grinding medium is added during the granulation of the calcined powder by the tumbling-impact grinding process, and the grinding medium comprises water and/or oil.
22. The method for synthesizing calcium phosphate powder by precise atom pairing suspension according to claim 1, wherein the particle size of the target powder is 0.01 μm to 1000 μm.
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