KR20170109371A - Synthesis of Calcium Phosphate Derived from Calcined Eggshell and Phosphoric Acid Solution - Google Patents
Synthesis of Calcium Phosphate Derived from Calcined Eggshell and Phosphoric Acid Solution Download PDFInfo
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- KR20170109371A KR20170109371A KR1020160033405A KR20160033405A KR20170109371A KR 20170109371 A KR20170109371 A KR 20170109371A KR 1020160033405 A KR1020160033405 A KR 1020160033405A KR 20160033405 A KR20160033405 A KR 20160033405A KR 20170109371 A KR20170109371 A KR 20170109371A
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- phosphoric acid
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- egg shell
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 58
- 210000003278 egg shell Anatomy 0.000 title claims abstract description 35
- 102000002322 Egg Proteins Human genes 0.000 title claims abstract description 30
- 108010000912 Egg Proteins Proteins 0.000 title claims abstract description 30
- 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 description 31
- 239000001506 calcium phosphate Substances 0.000 title claims description 27
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims description 24
- 235000011010 calcium phosphates Nutrition 0.000 title claims description 24
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 2
- 239000000843 powder Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- 230000008859 change Effects 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 238000001308 synthesis method Methods 0.000 claims 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 abstract description 19
- 229910052588 hydroxylapatite Inorganic materials 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 17
- 239000011575 calcium Substances 0.000 abstract description 12
- 239000000376 reactant Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 235000019731 tricalcium phosphate Nutrition 0.000 abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 3
- 241000208340 Araliaceae Species 0.000 abstract 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 abstract 2
- 235000003140 Panax quinquefolius Nutrition 0.000 abstract 2
- 235000008434 ginseng Nutrition 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052586 apatite Inorganic materials 0.000 description 4
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- -1 ammonia ions Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 3
- 229940078499 tricalcium phosphate Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000560 biocompatible material Substances 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 235000013601 eggs Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005445 natural material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241000272525 Anas platyrhynchos Species 0.000 description 1
- 241000272814 Anser sp. Species 0.000 description 1
- 241000242757 Anthozoa Species 0.000 description 1
- 241000271566 Aves Species 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000272534 Struthio camelus Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011738 major mineral Substances 0.000 description 1
- 235000011963 major mineral Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Medical Uses (AREA)
Abstract
In the present invention, a heat-treated egg shell is used as a starting material for synthesizing a ginseng calcium-based material such as hydroxyapatite or tribasic calcium phosphate, and a normal temperature reaction and a solution process for mixing an egg shell and a phosphoric acid solution are used. Control the crystal phase and particle shape of ginseng calcium by varying concentration and pH. In the process of mixing egg shell powder and phosphoric acid solution having high surface area at room temperature, a vigorous exothermic reaction proceeded and the crystal phase was changed by a subsequent heat treatment. All reactants at room temperature showed a Ca 3 (PO 4 ) 2 phase, except for the sample with a pH of 0.69. Samples using 40 wt% phosphoric acid solution successfully synthesized HA through heat treatment at 800 ℃, while samples using 60 wt% phosphoric acid solution produced HA by heat treatment at 1150 ℃. It has been confirmed that the pH value greatly affects the microstructure of the room temperature reactants and the heat treated samples, and the particle size is inversely proportional to the pH value of the solution.
Description
The present invention relates to a method for synthesizing calcium phosphate, and more particularly, to a novel method for synthesizing calcium phosphate by using a heat-treated egg shell powder as a starting material and reacting with a phosphate solution having a controlled concentration and pH at room temperature.
Biomaterials are materials that are stable, reliable, and economical, as well as materials that can be used to replace parts of the body or complement the function in a physiologically acceptable manner. In the meantime, tri-calcium phosphate (TCP) and hydroxyapatite (HA) have been studied as biocompatible materials. Apatite is a major mineral constituting hard tissues such as bones and teeth in the human body. Bio-mineralization of apatite is a self-remodeling process driven by osteoblasts and proteins. These materials are used as mediators that integrate with living tissues using apatite implanted on the surface. Due to their high biocompatibility, they are often referred to as biomaterials. Calcium phosphate type ceramics usually have low mechanical strength. For this reason, HA is used in combination with other materials such as coating with titanium metal (Japanese Patent Laid-Open No. 2010-113971, Laid-open Patent Application No. 2012-14307), and studies are under way to compensate for the disadvantages of HA.
Despite the bioavailability of HA, the production of HA is currently not in place in Korea, and almost all of it depends on imports. Imported HA depends on burning raw materials such as corals and animal bones by using petroleum etc., so that it is not excellent in quality such as failing to realize the color of white, and the manufacturing cost is high, and the raw material of the burning process There is a disadvantage in that harmful components that leak from petroleum such as petroleum can be contained in apatite.
Therefore, there is a need to develop a method for producing a high-quality biocompatible material from a natural raw material in a more economical manner. In addition, it is urgent to develop advanced technology that can control the crystal phase, particle size and shape while using a simpler process in the production of calcium phosphate.
SUMMARY OF THE INVENTION The present invention has been made in view of the above technical background, and an object of the present invention is to provide a method for synthesizing calcium phosphate through a room temperature reaction and a solution process from a natural material.
Another object of the present invention is to provide a process for controlling the phase transition and the particle morphology in the production of calcium phosphate by a reaction at room temperature and a solution process.
Other objects and technical features of the present invention will be more specifically described in the following detailed description.
In order to achieve the above object, the present invention provides a method for producing a pure CaO powder, comprising the steps of: Adjusting the pH value to a range of 0.05 to 6 in consideration of the concentration of the phosphoric acid solution after preparing the phosphoric acid solution; Mixing the CaO powder and the phosphoric acid solution at room temperature to react; And a step of heat-treating the reactant at room temperature of the CaO powder and the phosphoric acid solution to change the crystal phase, and a method for synthesizing calcium phosphate using the egg shell and the phosphoric acid solution.
The pH of the phosphoric acid solution can be adjusted by adding 10 to 70 wt% of ammonia solution in consideration of the concentration of the phosphoric acid solution. By changing the pH value, the concentration of the phosphoric acid solution can be varied within a range of 20 to 80 wt% have.
In the present invention, the phosphoric acid solution and the egg shell powder may be mixed in a weight ratio of 1: 0.5 to 1: 5, and the reactant obtained by mixing the CaO powder and the phosphoric acid solution obtained from the egg shell at room temperature may be 400 to 1200 Lt; 0 > C for 2 to 5 hours to change the crystal phase.
According to the present invention, calcium phosphate material can be synthesized through heat treatment after reacting at a room temperature with a phosphoric acid solution using egg shell, which is a natural material.
Particularly, there is an advantage that the crystal phase and the particle shape of the calcium phosphate material can be changed by simultaneously controlling the concentration and the pH of the phosphoric acid solution.
The present invention can produce calcium phosphate of high quality through a reaction at a room temperature and a solution process at a low cost, thereby enabling development of a biomaterial related field such as hydroxyapatite.
FIG. 1 is a TEM photograph of egg shell powder subjected to heat treatment and ball milling,
Figure 2 shows the XRD patterns of the 60 wt% phosphoric acid solution samples at 800 < 0 &
FIG. 3 shows the XRD patterns of the 40 wt%
4 is a SEM photograph of samples (b, d, f, h) at room temperature reactants (a, c, e, g) and samples annealed at 800 ° C for a mixture of 40 wt%
5 is a SEM photograph of a mixture of 60 wt% phosphoric acid solution samples (b, d, f, h) at room temperature reactants (a, c, e, g)
The present invention proposes a method of synthesizing calcium phosphate through a room temperature reaction and a solution process. Specifically, the present invention uses a shell egg (egg shell) of birds or poultry as a starting material, and mixes a phosphoric acid solution whose pH value is adjusted to produce a calcium phosphate material such as hydroxyapatite.
Egg shells used in the present invention can be eggs, such as chicken, duck, goose, and ostrich. Eggshells are used in the examples of the present invention. Egg shells can be converted to pure CaO powder through a simple heat treatment process. Therefore, calcium phosphate such as calcium tertiary phosphate (TCP) or hydroxyapatite can be synthesized through a simple solution process using egg shell.
In the present invention, it is preferable to obtain a nano-sized CaO powder having a large specific surface area by pulverization after heat treatment. For this purpose, the egg shell can be heat-treated at a temperature in the range of 700 to 900 ° C, and wet ball milling can be performed using alcohol. The egg shell powder thus obtained has a high surface area of 31.6 m 2 / g and has a high reactivity with the phosphoric acid solution, and the egg shell powder and phosphoric acid solution undergo intense exothermic reaction during mixing at room temperature. The reaction between the railing and the phosphoric acid solution at room temperature can change the crystal phase through subsequent heat treatment and various calcium phosphate can be synthesized by changing the concentration and pH of the phosphoric acid solution.
For example, by changing the pH value, the degree of exothermic reaction can be changed when the egg shell and the phosphoric acid solution are reacted at room temperature, and the resulting calcium phosphate crystal phase can be controlled. These results are advantageous in that the crystal phase of calcium phosphate can be changed in combination with the concentration of the phosphoric acid solution and the subsequent heat treatment process, and the size and shape of the finally produced calcium phosphate particles can be controlled as desired.
Specifically, in the present invention, the amount of ammonia ions used to adjust the pH of the phosphoric acid solution influenced the microstructure of the room temperature reactant and the heat-treated sample, and the particle size was inversely proportional to the amount of ammonia ions. In addition, all of the reactants at room temperature showed a Ca 3 (PO 4 ) 2 phase, except for the sample with a pH of 0.69. Samples using phosphoric acid solution of 40 wt% concentration successfully synthesized HA through heat treatment at 800 ° C, whereas samples using phosphoric acid solution of 60 wt% showed beta-TCP phase at 800 ° C heat treatment, HA was generated in the heat treatment.
Hereinafter, the technical characteristics and effects of the present invention will be described in more detail with reference to preferred embodiments.
Example - Egg shell Synthesis of calcium phosphate used
The washed egg shells were heat-treated at a temperature of 900 캜 for 4 hours in the air. The heat - treated egg shells were milled by wet ball milling. The wet ball mill was performed with zirconia balls for 24 hours using isopropyl alcohol (IPA, 99.5%, Daejung Chemicals & Metals CO., LTD, Korea) as a solvent. The volume ratio of heat - treated egg shell and IPA was 1: 1. The pulverized powder was dried at 80 DEG C for 48 hours. The dried egg shell powder was mixed with the phosphoric acid solution to conduct the main reaction for HA formation.
Two concentrations of phosphoric acid solution of 40 wt% and 60 wt% were used. The phosphoric acid solution was prepared by mixing phosphoric acid (85 wt% in H 2 O, DC Chemical Co. Ltd., Korea) with DI water and ammonia solution (29% NH 3 in H 2 O, JUNSEI, Japan) . The pH of the phosphoric acid solution was adjusted in consideration of the water contained in the reactant, and the prepared phosphoric acid solution and the corresponding pH were shown in Table 1.
The prepared phosphoric acid solution was mixed with the dried egg shell powder at a weight ratio of 1: 1.5. After mixing, all the samples were dried at room temperature, and then the dried mixture powder was heated at 3 ° C / min and heat-treated at 400 ° C to 1150 ° C for 4 hours.
Crystalline phase formation of the synthesized powder was confirmed by X-ray diffraction (X'pert-pro MPD, PANalytical, Netherlands). Morphological characteristics were investigated using a field emission scanning electron microscope (FE-SEM, S-4800, Hitachi, Japan) and a transmission electron microscope (TEM, JEM-2100F, JEOL, Japan).
The ball mill and the heat treated powder showed a particle size of about 20 nm. FIG. 1 shows a TEM photograph and an electron diffraction (SAD) pattern. CaO is shown as a black part, and the picture (b) below is an enlargement of the above picture (a). As a result of SAD analysis, a ring pattern of CaO was observed, and this result shows the nano characteristics of the powder. TEM analysis showed blurry materials around the powder. This is thought to be amorphous hydrate due to the reaction between powder and water.
Due to the high specific surface area of the egg shell powder during the room temperature mixing process, an exothermic reaction occurred between the powder and the phosphoric acid solution. In the pH adjusted solution with ammonia solution, no exothermic reaction was observed at the initial stage of contact with the powder, and a strong exothermic reaction was observed after 1 to 3 minutes. This exothermic reaction occurred strongly as the amount of ammonia added increased. It is believed that the ammonia ion reacts with the powder to form Ca (OH) 2 , which reacts with phosphorus ions in the solution, resulting in a violent reaction between the precursors.
Crystalline phase change with concentration and pH of phosphoric acid solution
Table 2 shows the crystal phase analysis results of the XRD patterns for the samples reacted at room temperature and at various temperatures.
The sample with the concentration of 40wt% was CaHPO 4 , whereas the sample with the concentration of 60wt% was Ca 3 (PO 4 ) 2 except for pH 0.69. This difference in crystallinity is due to the heat generated during the exothermic process. Each sample also showed a small amorphous peak. Ca 4 O (PO 4 ) 2 was formed as the main crystal phase in the sample using the pH 0.69 phosphoric acid solution, which is thought to be caused by the high temperature caused by the exothermic reaction. After the heat treatment at 400 ℃, all the samples showed Ca 4 O (PO 4 ) 2 phase and only the samples synthesized with the phosphoric acid solution of 40wt% without adding ammonia showed an exception. Samples synthesized with 40wt% phosphoric acid solution showed different crystallinity depending on the pH depending on the amount of ammonia solution added.
The XRD patterns for the samples synthesized with the phosphoric acid solution of 60 wt% and 40 wt% concentration are shown in Fig. 2 and Fig. 3, respectively.
The XRD patterns of the powders synthesized by heat treatment at 800 ℃ showed that the 60wt% samples exhibited a similar pattern, while the 40wt% samples varied significantly in peak intensity. At 40wt% concentration, the ammonia solution reacts with the powder more vigorously and generates a large amount of Ca (OH) 2 , which is considered to have a peak intensity directly proportional to the amount of ammonia added. The samples of 40wt% showed HA phase at 800 ℃ and complete phase transition of Ca (OH) 2 at 1150 ℃.
On the other hand, 60wt% of samples showed β-TCP crystalline phase at 800 ℃ and HA crystalline phase at 1150 ℃. It has been reported that tetra-calcium phosphate (Ca 4 O (PO 4 ) 2 ) is a basic substance of calcium phosphate and is structurally related to HA. This fact suggests that acid-base reaction between calcium phosphate- Lt; RTI ID = 0.0 > HA. ≪ / RTI > It is believed that the lack of P ions in the 60wt% sample produced unstable mesophases like the β-TCP crystalline phase.
Change of particle shape according to concentration and pH of phosphoric acid solution
The microstructure of the samples reacted at room temperature and the samples heat-treated at 800 ° C are shown in FIGS. 4 and 5, respectively. All the samples reacted at room temperature show sticky and plate - like particles. Samples synthesized by changing pH of 40wt% phosphoric acid solution showed intermediate shapes of rod and spherical particles while samples synthesized with 60wt% phosphoric acid solution showed flake and flake particles. The samples annealed at 800 ℃ without changing the pH value showed no grain growth of the grains and the grain size was rather reduced. Grain growth was observed in samples annealed at 800 ℃ when ammonia was added and pH was changed.
The pH change in the 40wt% phosphoric acid solution sample changed the particle shape to irregular particles, which was the most severe at 0.5 pH samples. Increasing the pH value decreased the particle size of the synthesized powder. In 60wt% phosphoric acid solution samples, particle shape was transferred to needle - like particles as pH was increased. From these results, it can be confirmed that the ammonia ion has an important influence on the microstructure and crystal phase of the room temperature reactants and the heat treated samples, and in particular, the particle size is inversely proportional to the pH value.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, Modified, modified, or improved.
Claims (8)
Adjusting the pH value in the range of 0.05 to 6 in consideration of the concentration of the phosphoric acid solution after preparing the phosphoric acid solution,
Mixing the CaO powder and the phosphoric acid solution at room temperature to react; And
And a step of heat treating the reaction product at room temperature of the CaO powder and the phosphoric acid solution to change the crystal phase
Calcium phosphate synthesis method using egg shell and phosphate solution.
Wherein the pH of the phosphoric acid solution is adjusted by adding 10 to 70 wt% of ammonia solution in consideration of the concentration of the phosphoric acid solution.
Wherein the concentration of the phosphoric acid solution is in the range of 20 to 80 wt%.
Wherein the mixing ratio of the phosphoric acid solution to the egg shell is in the range of 1: 0.5 to 1: 5 by weight.
Wherein the reaction product obtained by mixing CaO powder and phosphoric acid solution obtained from egg shell at room temperature is heat-treated at 400 to 1200 ° C. for 2 to 5 hours, thereby synthesizing calcium phosphate using egg shell and phosphoric acid solution.
Wherein the eggshell is pulverized by a wet ball milling process.
Wherein the egg shell heat treatment is performed at a temperature in the range of 700 to 900 ° C.
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| KR102094987B1 (en) * | 2019-07-12 | 2020-03-31 | 주식회사 휴덴스 | Synthetic bone graft material manufacturing device |
| CN111085158A (en) * | 2019-12-23 | 2020-05-01 | 暨南大学 | Method for preparing defluorination water purifying agent by using eggshells and application thereof |
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| KR100783587B1 (en) | 2007-01-19 | 2007-12-11 | 인하대학교 산학협력단 | Preparation method of beta-tricalcium phosphate powders and compacts thereof |
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| KR102094987B1 (en) * | 2019-07-12 | 2020-03-31 | 주식회사 휴덴스 | Synthetic bone graft material manufacturing device |
| WO2021010548A1 (en) * | 2019-07-12 | 2021-01-21 | 주식회사 휴덴스 | Apparatus for manufacturing alloplastic bone graft material |
| CN111085158A (en) * | 2019-12-23 | 2020-05-01 | 暨南大学 | Method for preparing defluorination water purifying agent by using eggshells and application thereof |
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