KR100593262B1 - Methods for the manufacturing of apatite powders - Google Patents

Abstract

The present invention relates to a method for producing apatite, and more particularly, to a method for producing apatite having various shapes, sizes, and porosities. The present invention provides a method for preparing apatite by aging a mixed aqueous solution containing calcium salt and phosphate. The aging step of the present invention can be carried out simultaneously with the supply of gas, the gas being fed affects the apatite particle shape, particle size and specific surface area. According to the present invention, it is possible to prepare apatite particles having various shapes and sizes.

Apatite, Intermediate Reactant, Honeycomb Porous Plate, Needle, Plate, Gas

Description

Apatite powder manufacturing method {METHODS FOR THE MANUFACTURING OF APATITE POWDERS}

FIG. 1A is a view schematically showing a reaction apparatus for preparing apatite according to an embodiment of the present invention, and FIG. 1B is a flowchart illustrating a method for preparing apatite according to an embodiment of the present invention.

2 is an X-ray diffraction pattern for each powder obtained by varying aging time according to the present invention.

3a and 3b are scanning electron micrographs of the powder obtained through the aging process of 10 minutes and 12 hours of the powder obtained by varying the aging time of FIG.

4A and 4B are X-ray diffraction patterns and scanning electron micrographs of hydroxide apatite prepared by supplying carbon dioxide gas according to an embodiment of the present invention, respectively.

5A and 5B are X-ray diffraction patterns and scanning electron micrographs of hydroxide apatite prepared by supplying oxygen gas, respectively, according to an embodiment of the present invention.

6A and 6B are X-ray diffraction patterns and scanning electron micrographs of hydroxide apatite prepared by supplying oxygen gas, respectively, according to an embodiment of the present invention.

7A and 7B are X-ray diffraction patterns and scanning electron micrographs of hydroxide apatite prepared by supplying nitrogen gas according to an embodiment of the present invention, respectively.

8A and 8B are X-ray diffraction patterns and scanning electron micrographs of Mg ion-added apatite hydroxides prepared by supplying oxygen gas, respectively, according to an embodiment of the present invention.

9A and 9B are X-ray diffraction patterns and scanning electron micrographs of hydroxyapatite added with TiO ₂ powder prepared by supplying nitrogen gas, respectively, according to an embodiment of the present invention.

<Brief description of the symbols in the drawings>

100: reaction device 110: reaction vessel

120: supply gas tank 130: atmosphere gas tank

150: gas blower 160: heater

The present invention relates to a method for producing apatite, and more particularly, to a method for producing apatite having various shapes, sizes, and porosities.

Apatite is known as a material having high biocompatibility, and a typical example of the hydroxide apatite is Ca ₁₀ (PO ₄ ) ₆ (OH) _2-x nH ₂ O (0 ≦ n ≦ 2.5, 0 ≦ _x ≦ 2.5). It is expressed as In the detailed description of the present invention described below, apatite includes a carbonate group (CO ₃ ^2- ), an oxygen group (O ₂ ⁻ ), and a fluorine group (F ⁻ ) in place of a hydroxyl group (OH _⁻ ) in the chemical formula of the apatite hydroxide and the apatite hydroxide. ), a chlorine group (Cl ^- anions, etc.) is used as a general term for a substituted form.

Apatite is in the limelight as an artificial bone graft because the substances and components that make up the bones of the human body are very similar. In addition, apatite is a reinforcing material for ceramics, fillers for bone defects, exchangers for heavy metal ions, fillers for column chromatography, biopolymers such as proteins and nucleic acids, adsorption materials for amino acids, antibacterial and deodorizing materials, and a wide variety of fields. Is being applied.

However, apatite is required to have a suitable particle shape and particle size for each application in order to provide the properties for the application. In addition, the pore size and pore volume also play an important role in the expression of properties of apatite.

For example, apatite as an implantable artificial bone material requires very high strength. Suchanek et al. Published a paper published in the Journal of the Korean Ceramic Society (vol 80, pp 2805-2813) to prepare fiber-reinforced apatite by mixing needle-like apatite particles with spherical apatite particles. Has been presented. Another method of preparing acicular apatite particles is U. S. Patent No. 6,228, 339 to Ota et al.

It is preferable that the apatite used as a bone filler or a reinforcing material such as plastic or rubber is made of plate-shaped particles. An example of a method of manufacturing such plate-shaped apatite is disclosed in Japanese Patent Laid-Open No. 2002-274821.

In order to impregnate apatite with proteins or medicines and deliver them to the human body, porous plate-shaped particles containing small pores are required. U. S. Patent No. 6,558, 703 shows an example of a method for producing such porous plate-shaped apatite.

Apatite, which is used as an antibacterial and deodorizing material, provides a large specific surface area to facilitate adsorption of malodorous components, and it is sometimes desirable to contain a catalyst material therein for decomposition or sterilization thereof as necessary. An example of a method of use in such a field is disclosed in US Patent Publication No. 2002-0031489 and Japanese Patent Publication No. 2000-167410. US Patent Publication No. 2002-0031489 discloses a method for producing apatite having a high porosity by substituting some calcium ions of apatite with magnesium (Mg) and the like, and Japanese Patent Laid-Open No. 2000-167410 A porous apatite-titanium oxide complex which simultaneously performs adsorption and photolysis functions is proposed. In the Japanese Laid-Open Patent, apatite increases the adsorption characteristics of odor molecules, and titanium oxide serves to decompose odor molecules adsorbed through a photocatalytic reaction.

As such, it is very important for the apatite to have various particle sizes, particle shapes and specific surface areas depending on the application.

Conventionally used methods for preparing acicular apatite include hydrothermal synthesis and solid reaction. As an example, Japanese Patent Laid-Open No. 5-17110 proposes a method for synthesizing acicular apatite powder by heat-treating apatite, calcium phosphate and dicalcium phosphate in the presence of an alkali metal salt at a temperature range of 800 ° C to 1200 ° C. have. As another example, US Patent No. 6,228,339 described above first mixes a raw material such as calcium oxide in acicular beta calcium phosphate (β-Ca (PO ₃ ) ₂ ) powder, and then heat-treats at a temperature range of 800 ° C. to 1200 ° C. The method for producing needle-like apatite powder is disclosed in Japanese Patent Application Laid-Open Nos. 2-141500 and 4-16600, wherein urea is added to an aqueous solution containing calcium salt and phosphate, and is prepared at 90 ° C to 180 ° C. A method of synthesizing acicular apatite by hydrothermal synthesis in the temperature range is proposed.

On the other hand, the hydrothermal synthesis method is mainly used as a manufacturing method of plate-shaped apatite. For example, U.S. Patent No. 5,427,754 proposes a method for hydrothermally synthesizing the plate-shaped apatite powder under a pressure of 1 to 200 kgf / cm ² , Japanese Patent Laid-Open No. 10-45405 is a mixed aqueous solution of phosphate and calcium salt A method for producing a plate-shaped apatite by adding amine compounds such as fatty acid amines to hydrothermal synthesis is proposed.

Thus, conventionally, the production of acicular or plate-shaped apatite particles has been mainly relied on the solid reaction method and the hydrothermal synthesis method. However, these conventional methods have many problems.

The solid state reaction method has a problem in that the heat-treatment temperature is about 800 ° C to 1200 ° C, so that the particles produced are large enough to reach several tens of micrometers, and the complex subsequent processes such as mixing, calcining, and pulverization after the reaction must be involved. Could not be an advantageous way.

Hydrothermal synthesis, on the other hand, generally involves the use of an amorphous precipitated calcium phosphate (Calcium Phosphate) in an autoclave at a temperature range of about 150 to 250 ° C., requiring a two step process of precipitation and hydrothermal synthesis. The two additives had to be mixed together and the process itself was complicated, resulting in mass production problems.

It is an object of the present invention to provide a process for preparing apatite powders having various particle sizes, particle shapes and specific surface areas.

In order to achieve the above technical problem, the present invention, in the method for producing apatite powder, providing a mixed aqueous solution containing calcium salt and phosphate, reacting the calcium salt and phosphate in the aqueous solution having a different phase from the apatite It provides a method for producing an apatite comprising the step of producing an intermediate reactant, the step of aging the aqueous solution to synthesize the apatite powder from the intermediate reactant and the slurry precipitated in the aqueous solution.

In the present invention, the intermediate reactant is preferably dicalcium phosphate dihydrate. In the present invention, the calcium salt is calcium hydroxide, the phosphate is preferably phosphoric acid. The aging step of the present invention can be carried out at 5 ~ 90 ℃. Apatite powder having a plate-like particle shape can be produced by the method of the present invention.

In order to achieve the above technical problem, the present invention also provides a mixed aqueous solution containing calcium salt and phosphate, synthesizing calcium phosphate compound while supplying gas into the aqueous solution and drying the synthesized calcium phosphate compound It provides a method for producing apatite comprising the step of.

In the present invention, the synthesis step may include producing an intermediate reactant by reacting calcium salt with phosphate in the aqueous solution and synthesizing a calcium phosphate compound from the intermediate reactant. In the present invention, the intermediate product may be dicalcium phosphate dihydrate.

In the present invention, the calcium salt may include at least one salt selected from the group consisting of calcium nitrate, calcium carbonate, calcium chloride, calcium hydroxide and calcium acetate. In addition, the phosphate may include at least one salt selected from the group consisting of phosphoric acid, sodium monophosphate, sodium diphosphate, potassium monophosphate, potassium diphosphate, ammonium monophosphate and ammonium diphosphate. . In the present invention, the mixed aqueous solution is at least one oxide selected from the group consisting of magnesium ions, barium ions and strontium ions, titanium dioxide, manganese oxide, vanadium oxide and copper oxide, silver, platinum and At least one metal selected from the group consisting of palladium, or the mixed aqueous solution may further include at least one ion selected from the group consisting of fluorine ions, chlorine ions and carbonate ions.

The gas supplied in the synthesis step of the present invention may include at least one gas selected from the group consisting of helium, argon, hydrogen, oxygen, nitrogen and carbon dioxide. In the precipitation step of the present invention, the mixed aqueous solution is preferably maintained at about 5 ℃ to about 90 ℃. In the present invention, the mixed aqueous solution is preferably maintained at pH 3.0 to 14.0. In the present invention, the aqueous solution preferably has a molar ratio of calcium to phosphorus in the range of about 1 to about 10.

In the present invention, the providing of the mixed aqueous solution may include stirring the aqueous solution containing calcium salt, stirring the aqueous solution containing phosphate, and mixing the aqueous calcium salt solution with the aqueous phosphate solution. In the phosphate stirring step, one or more gases selected from the group consisting of helium, argon, hydrogen, oxygen, nitrogen, and carbon dioxide may be supplied.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

1A schematically illustrates the structure of a reaction device 100 used in the method of the present invention.

Referring to FIG. 1A, the reaction apparatus 100 of the present invention includes a reaction vessel 110, a supply gas tank 120, an atmosphere gas tank 130, a gas blower 150, and a heater 160. . In addition, the reaction apparatus 100 includes a pH meter 144 and a thermometer 146 and a stirrer 142 loaded for measuring the pH of the aqueous solution 140, measuring the temperature, and stirring the aqueous solution.

The supply gas tank 120 supplies the stored compressed gas into the aqueous solution. A gas blower 150 is provided at the bottom of the reaction vessel 110 so that the gas to be supplied may be uniformly supplied to the aqueous solution in the reaction vessel. The gas blower 150 is connected to the supply gas tank 120 through a gas inlet 116 and a gas inlet conduit 121. The gas inlet conduit 121 is provided with an on / off valve 124 and a regulator 122 to control the supply and supply flow rate of the gas to be supplied.

The aqueous solution 140 in the reaction vessel 110 is maintained at a constant temperature by the heater 160 provided on the bottom and / or side of the reaction vessel (110). As the heater 160, a conventional one having a heating wire 162 therein may be used.

The reaction apparatus 100 of the present invention further includes a device for supplying an atmosphere gas to prevent the gas such as CO ₂ existing in the atmosphere from being dissolved in the aqueous solution 140. In the present invention, the atmosphere gas in the atmosphere gas tank 130 is supplied to the reaction vessel 110 through the regulator 132, the control valve 134. The atmosphere gas is introduced into the reaction vessel through the gas inlet 112 and discharged into the atmosphere through the gas outlet 114. In the present invention, N ₂ gas is preferably used as the atmosphere gas.

1B is a flowchart illustrating a method of preparing apatite of the present invention.

Referring to Figure 1b, first, the calcium salt aqueous solution is stirred in a separate vessel (S100). The type of calcium salt usable in the present invention is not limited, such as calcium nitrate (Ca (NO ₃ ) ₂ ), calcium carbonate (CaCO ₃ ), calcium chloride (CaCl ₂ ), calcium hydroxide (Ca (OH) ₂ ), or calcium acetate (Ca (CH ₃ COO) ₂ ) and the like can be used. The calcium salt may be used by mixing one or more kinds. The calcium salt is stirred at room temperature for a suitable time.

The aqueous solution of phosphate is stirred separately from the aqueous solution of calcium salt (S200). The type of phosphate used in the present invention is not limited, and for example, phosphoric acid (H ₃ PO ₄ ), monobasic sodium phosphate (NaH ₂ PO ₄ ), dibasic sodium phosphate (Na ₂ HPO ₄ ), monobasic potassium phosphate ( KH ₂ PO ₄ ), dipotassium phosphate (K ₂ HPO ₄ ), ammonium monophosphate (NH ₄ H ₂ PO ₄ ) or diammonium phosphate ((NH ₄ ) ₂ HPO ₄ ) and the like may be used. In the present invention, the phosphate may be used by mixing one or more kinds.

The stirring step S200 may be performed in the reaction vessel 110 of FIG. 1A or may be performed in a separate vessel. Gas of a certain flow rate may be continuously supplied from the supply gas tank 120 as necessary to facilitate stirring. The gas is preferably supplied with the same kind of gas supplied in the aging step described later. In addition, when stirring the aqueous calcium salt solution, a material for improving the properties of the apatite to be finally prepared, for example, a material for controlling particle growth or performing a catalytic function may be added and stirred together. The additive material may be alkaline earth metal ions such as magnesium ions (Mg ²⁺ ), barium ions (Ba ²⁺ ), strontium ions (Sr ²⁺ ) or titanium dioxide (TiO ₂ ), manganese oxide (MnO), vanadium oxide ( Oxides such as V ₂ O ₅ ), copper oxide (CuO), or metals of silver (Ag), platinum (Pt), and palladium (Pd) may be used. The additive material may be used by mixing one or more kinds. In addition, anions such as fluoride ions (F ⁻ ), chlorine ions (Cl ⁻ ), and carbonates (CO 3 ^2- ) may be added to improve apatite deodorization performance and / or to improve biocompatibility when used in the human body.

Subsequently, the calcium salt aqueous solution and the phosphate aqueous solution are mixed in the reaction vessel 110 (S300). The ratio of calcium salt and phosphate of the mixed aqueous solution thus prepared may be appropriately selected. For example, the stoichiometric molar ratio of Ca / P in the preparation of hydroxide apatite is about 1.67, but aqueous solutions having a value greater than or less than the molar ratio may be used in the present invention. In the present invention, the molar ratio is preferably in the range of about 1 to 10. If the molar ratio of Ca / P is less than 1, secondary phases such as calcium phosphate remain in the dried powder. If the molar ratio is greater than 10, calcium salts are present in the precipitate, which makes it difficult to produce pure apatite. In addition, when the production reaction of the calcium phosphate compound containing apatite is slow in the aging step (S500) to be described later, the molar ratio is changed during the process due to the addition of calcium ions or phosphate ions into the mixed aqueous solution to promote the reaction. You can also

The reaction of calcium salt and phosphate in the aqueous solution is started by the above mixing step (S300), and as a result of the reaction, a hydrate such as dicalcium phosphate dihydrate (hereinafter referred to as 'DCPD') is an intermediate reactant. It is generated as (S400).

The intermediate reactant produced by the reaction is determined according to the type of calcium salt and phosphate used. For example, the DCPD forming reaction may be represented by the following reaction formula.

Subsequently, a aging step (S500) for synthesizing the calcium phosphate compound from the intermediate reactant is performed. Reaction to generate apatite from the DCPD in the aging step (S500) can be represented by the following scheme.

Calcium phosphate compound produced through the aging step (S500) of the present invention is in addition to apatite monocalcium phosphate (Ca ₂ P ₂ O ₇ ), tricalcium phosphate (Ca ₂ P ₂ O ₇ ) and hexacalcium phosphate (Ca ₄ P ₂ O ₇ ). In the present invention, the ratio of the secondary phase and apatite including monocalcium phosphate, tricalcium phosphate and tetracalcium phosphate in the precipitated calcium phosphate compound may be appropriately selected in consideration of the process conditions described below.

The aging step S400 may be performed at various temperature ranges. Since the temperature of the aqueous solution 140 in the present invention affects the reaction rate and the size of the particles, it may be appropriately selected according to the desired particle size. Preferred reaction temperatures in the present invention are from about 5 ° C to about 90 ° C.

Aging time in the aging step (S500) is related to the type of calcium phosphate compound to be produced and should be appropriately selected in consideration of this. According to an embodiment of the present invention, when the reaction time is less than 10 minutes, pure apatite may be formed because the content of an intermediate reactant such as DCPD is high in the precipitate slurry and a secondary phase such as monocalcium phosphate (Ca ₂ P ₂ O ₇ ) is present. Difficult to obtain On the other hand, the aging time affects the amount of precipitation and the size of the particles. According to an embodiment of the invention an increase in aging time results in an increase in particle size. Therefore, the aging time in the present invention can be appropriately selected according to the desired particle size. However, the reaction time of 48 hours or more is insignificant in practical terms because the effect on the size, yield, etc. of the particles is insignificant.

The pH of the mixed aqueous solution in the aging step (S500) is preferably maintained in the range of 3.0 to 14.0. The pH of the aqueous solution is related to the type of calcium phosphate compound precipitated. For example, in the case of hydroxide apatite, pure apatite is not obtained at pH lower than 3.0.

The above-described aging step (S500) may be carried out in the state of being maintained in the reaction vessel 110 or at the same time as the stirring by the stirrer 142, the gas of a constant flow rate from the supply gas tank 120 into the aqueous solution It may be performed while feeding. This is another important feature of the present invention. As described above, the apatite is required to have a variety of shapes, sizes and specific surface areas depending on the application field, and the inventors of the present invention, by supplying any gas into the aqueous solution in the aging step (S500), the particle shape of the apatite produced It has been found that the particle size and specific surface area can be controlled in various ways.

Feed gases usable in the present invention include helium (He), argon (Ar), hydrogen (H ₂ ), oxygen (O ₂ ), nitrogen (N ₂ ) or carbon dioxide (CO ₂ ), and these gases are mixed It may be supplied. In addition, since the flow rate of the gas injected in the aging step (S500) of the present invention affects the production rate of the calcium phosphate compound including apatite, it may be appropriately selected in consideration of various process conditions. For example, according to the results of experiments with a mixed aqueous solution of 900cc according to the present invention, when the gas flow rate is 100cc / min or less, the effect of the gas supply on the particle generation is minimal, at 2000cc / min or more evaporation of the aqueous solution is reproducible powder Was difficult to synthesize. Of course, in selecting the gas flow rate, the amount of the aqueous solution in the reaction vessel and the content of calcium salt and phosphate in the aqueous solution should be considered together.

When the reaction is complete, the precipitated slurry is dried (S600). Drying may use a freeze drying method carried out at -50 ° C to -100 ° C and about 50 mTorr or less. The freeze-drying method is preferable in that fine powder can be obtained because the aggregation and growth of particles can be suppressed. On the other hand, when a powder having a large particle size is desired, a conventional drying method, that is, a method of drying at a temperature of 25 ° C. to 200 ° C. and normal pressure may be used. The manufacturing of the apatite is completed by the drying step (S600).

Hereinafter, various aspects of the present invention described above will be described in more detail with reference to preferred embodiments.

Example 1 is an example showing the apatite generation mechanism of the present invention described above.

Example 1

36.689 g of calcium hydroxide (Ca (OH) ₂ ) was mixed with 450 cc of distilled water and stirred at room temperature for about 30 minutes to prepare an aqueous calcium hydroxide solution. The distilled water used in the examples described below, including the present embodiment, is treated with decarbonation by blowing nitrogen gas in a process of cooling to room temperature after boiling at 100 ° C. to remove carbon dioxide. will be.

In the reaction vessel 110 of FIG. 1A, 31.131 g of phosphoric acid (H ₃ PO ₄ ) was mixed with 450 cc of distilled water and stirred at room temperature for 30 minutes to prepare an aqueous solution of phosphoric acid. Subsequently, the prepared calcium hydroxide aqueous solution was rapidly injected into the reaction vessel 110, mixed with the aqueous solution of phosphoric acid, aged, and the precipitated slurry was dried. The temperature of the aqueous solution was maintained at 30 ℃ in the aging step. In order to observe the phase change of the reactants during the aging process, the experiment was performed at different aging times.

FIG. 2 is an X-ray diffraction pattern for each powder obtained by varying the aging time at a aging temperature of 30 ° C. for 10 minutes, 40 minutes, 1 hour, 2 hours, 12 hours, 24 hours, 36 hours, and 48 hours.

As can be seen from the depicted diffraction pattern, a peak of high intensity indicating the (020) plane of DCPD was detected when the aging time was 2 hours or less, while the peak of apatite hydroxide was hardly detected. From this, it was confirmed that crystalline DCPD was first formed as an intermediate product before the apatite was formed by the reaction of phosphate and calcium salt. As the aging time passed 12 hours, the DCPD peak was remarkably decreased, and the DCPD peak could not be detected in the powder obtained by aging for 24 hours.

3A and 3B are scanning electron micrographs of powders obtained through a aging process of 10 minutes and 12 hours at a aging temperature of 30 ° C., respectively. The powder aged for 10 minutes from Figure 3a consists of coarse DCPD particles of several tens to hundreds of microns, it can be seen that the fine apatite particles are growing on the surface of the DCPD particles. The fine particles grew into plate-shaped particles as shown in FIG. 3B after 12 hours of aging.

Through the present embodiment it can be confirmed that calcium salt and phosphate in the aqueous solution is first produced DCPD according to Scheme 1 and then precipitated as hydroxide apatite.

Examples 2 to 8 below show examples of various changes in the particle shape, particle size, and specific surface area of the apatite produced according to the gas supply and the supply gas type.

Example 2

A mixed aqueous solution was prepared by mixing a calcium hydroxide aqueous solution and a phosphoric acid aqueous solution under the same conditions as in Example 1 above.

In the aging step, the aqueous solution was maintained for 48 hours at the temperature of 30 ℃ and 80 ℃. In addition, to determine the effect of drying conditions on the particle size, the case of freeze drying at a temperature of −50 ° C. and a pressure of 6 mTorr and a case of atmospheric drying at a temperature of 150 ° C. were compared.

Particle shape, particle size and specific surface data for the above four conditions are shown in Table 1. The specific surface area was measured using the ASAP2010 instrument which is a BET measuring instrument of Micromeritics, USA.

As shown in Table 1, a plate-like powder could be obtained regardless of the aging temperature and the drying method. When the reaction temperature is aged for 48 hours at 30 ℃ and freeze-dried specimens, the particle size reaches about 1 ~ 2.4㎛, it can be seen that the specific surface area is 75.2 m ² / g. As the aging temperature increased, the particle size increased and the specific surface area decreased. The same tendency was observed even when the drying temperature was increased.

Example 3

31.131 g of phosphoric acid (H ₃ PO ₄ ) is mixed with 450 cc distilled water in a reaction vessel 110 of FIG. 1A, and carbon dioxide (CO ₂ ) gas is blown at 500 cc / min and stirred at room temperature for 30 minutes to calcium phosphate An aqueous solution was prepared. Subsequently, the calcium hydroxide aqueous solution prepared in the same manner as in Example 2 was rapidly injected into the reaction vessel 110, mixed with the aqueous phosphoric acid solution, and aged. In the aging process, carbon dioxide gas was continuously injected at a flow rate of 500 cc / min. The precipitated slurry was then dried to prepare an apatite powder. Aging and drying were carried out under the same conditions as in Example 2 to determine the effect of the aging temperature and drying temperature on the particle size of the resulting hydroxide apatite.

Particle shape, particle size, and specific surface area data for each condition are shown in Table 1.

From Table 1, it can be seen that as the aging temperature increases, the particle size increases and the specific surface area decreases. Through freeze-drying, particles having a smaller particle size and a larger specific surface area can be obtained.

4A and 4B show X-ray diffraction patterns and scanning electron micrographs of lyophilized specimens at a aging temperature of 30 ° C. during the above four conditions. It can be seen from the diffraction pattern of FIG. 4A that the precipitate consists of pure hydroxide apatite. On the other hand, although not shown, when the aging time was maintained for 24 hours or less unlike the present example, it was confirmed from the X-ray diffraction pattern that secondary phases such as monocalcium phosphate (Ca ₂ P ₂ O ₇ ) remain in the precipitate. It can be seen from FIG. 4B that porous plate-shaped apatite particles having a honeycomb structure having a pore diameter of about 100 to 300 nm are produced. The specific surface area of this powder was about 181 m ² / g.

Example 4

The experiment was carried out under the same conditions as in Example 3 except that the feed gas was changed to oxygen (O ₂ ). The apatite particles produced in this example were acicular. As in Example 3, the apatite particle size and specific surface data obtained under four conditions are shown in Table 1.

5A and 5B are X-ray diffraction patterns and scanning electron micrographs of the freeze-dried specimens maintained at aging temperature of 30 ° C., and confirmed that needle-like apatite having a length of about 300 to 400 nm and a thickness of 50 to 70 nm was produced. Can be. The specific surface area of this powder was 78.3 m ² / g.

Example 5

The experiment was carried out under the same conditions as in Example 3 except for changing the feed gas to hydrogen (H ₂ ). The apatite produced in this example was acicular particles. 6A and 6B are X-ray diffraction patterns and scanning electron micrographs of the freeze-dried specimens maintained at a aging temperature of 30 ° C., respectively, to confirm that needle-shaped apatite having a length of about 500 to 600 nm and a thickness of 80 to 120 nm was produced. have. The specific surface area of this powder was 55.1 m ² / g. From Table 1, it can be seen that the influence of the aging temperature and the drying temperature on the particle size and the specific surface area shows the same tendency as in Example 3.

<Example 6>

The experiment was carried out under the same conditions as in Example 3 except that the feed gas was changed to nitrogen (N ₂ ). In this example, very large plate-shaped apatite particles were produced. 7A and 7B show that the plate-shaped apatite having a width of about 1 to 2 μm and a thickness of about 50 nm is generated by X-ray diffraction patterns and scanning electron micrographs of the lyophilized specimens at a aging temperature of 30 ° C., respectively. . The specific surface area of this powder was 87.2 m ² / g.

<Example 7>

The experiment was carried out under the same conditions as in Example 3 except that the feed gas was changed to helium (He). In this example, very large plate-shaped apatite particles were produced. It can be seen from Table 1 that the aging temperature is maintained at 30 ° C. and the freeze-dried specimen has a particle size of about 1 to 3 μm and a specific surface area of 70.6 m ² / g. As the aging temperature increases, the particle size increases about 10 times, and the specific surface area decreases significantly. The same tendency was observed even when the drying temperature was increased.

<Example 8>

The experiment was carried out under the same conditions as in Example 3 except that the supply gas was changed to argon (Ar). In this example, very large plate-shaped apatite particles were produced. It can be seen from Table 1 that the aging temperature is maintained at 30 ° C. and the freeze-dried specimen has a particle size of about 1 to 3 μm and a specific surface area of 65.3 m ² / g. As in the case of Example 7, the increase in the aging temperature showed a significant increase and decrease in particle size and specific surface area. Similar trends were observed when the drying temperature increased.

division Type of gas Aging temperature (℃) Freeze drying (less than 50 ℃, 6 mtorr) General drying (150 ℃) Particle shape Particle Size (㎛) Specific surface area (m ² / g) Particle shape Particle Size (㎛) Specific surface area (m ² / g) Example 2 No supply gas 30 Plate 1 to 2.4 75.2 Plate 5 to 11 4.2 80 7-13 8.4 11-21 3.1 Example 3 CO ₂ 30 Porous plate 0.1 to 0.3 181 Porous plate 0.9 to 1.6 59.7 80 2-3 78.5 3 to 5 34.9 Example 4 O ₂ 30 couch 0.3 to 0.4 78.3 couch 2-3 18.5 80 1 to 2 59.8 2-3 35.7 Example 5 H ₂ 30 couch 0.5 to 0.6 55.1 couch 3 to 4 38.6 80 3 to 5 42.3 6-10 11.8 Example 6 N ₂ 30 Plate 1 to 2 87.2 Plate 5 to 10 6.2 80 6 to 13 9.7 8 to 20 4.2 Example 7 He 30 Plate 1 to 3 70.6 Plate 6 to 11 4.5 80 12-25 1.4 15-31 1.2 Example 8 Ar 30 Plate 1 to 3 65.3 Plate 5 to 12 3.8 80 11-21 2.3 13-22 2.7

On the other hand, in order to make it suitable for the deodorization, antibacterial, biomaterials, etc. of an apatite powder as mentioned above, it is preferable that a substance, such as another ion, an oxide or a metal, is contained in a powder. Examples 9 and 10 below describe examples of producing such apatite powder using the method of the present invention.

Example 9

In an aqueous phosphate solution, about 9.23 g of Mg (NO ₃ ) ₂ .6H ₂ O (About 8 mol% Mg ion with respect to calcium ions) was charged to the reaction vessel and stirred. Subsequently, the stirred calcium hydroxide aqueous solution was injected into the reaction vessel to prepare a mixed aqueous solution, and aged for 48 hours while supplying oxygen gas. The slurry obtained after the reaction was lyophilized. Other conditions were the same as in Example 4.

X-ray diffraction patterns and scanning electron micrographs of the apatite powder thus obtained are shown in FIGS. 8A and 8B, respectively. As shown, acicular apatite particles of about 100 to 200 nm in length and 20 to 40 nm in thickness were obtained according to this example. Compared with Example 4 described above, it can be seen that the effect of inhibiting apatite grain growth can be obtained due to the addition of magnesium ions.

On the other hand, it was confirmed that tricalcium phosphate (Ca ₃ (PO ₄ ) ₂ ) phase was formed when magnesium ions were added 20 mol% or more with respect to calcium ions. Therefore, in order to obtain pure apatite powder, it is preferable that the amount of calcium ions added does not exceed 20 mol%.

<Example 10>

49.84 g (50 wt%) of titanium oxide (TiO ₂ ) was charged to an aqueous phosphate solution and stirred. Subsequently, a stirred aqueous solution of calcium hydroxide was injected into the reaction vessel to prepare a mixed aqueous solution, and then aged for 48 hours while supplying nitrogen gas. The slurry obtained after the reaction was lyophilized. Other experimental conditions were the same as in Example 6.

9A and 9B show X-ray diffraction patterns and scanning electron micrographs of the apatite powder thus prepared. As shown, spherical apatite / titanium oxide mixed powder having a diameter of about 30 to 120 nm could be obtained.

In order to use the apatite / titanium oxide mixed powder for the purpose of deodorization or the like, it is preferable that 10 wt% or more of titanium dioxide is added. This is because, when the amount of titanium dioxide added is 10 wt% or less, the photolysis efficiency is significantly lowered. In addition, unlike Example 9, when the content of the added titanium dioxide is 80wt% or more, it was confirmed that secondary phases such as monocalcium phosphate (Ca ₂ P ₂ O ₇ ) remain. Therefore, for the production of pure apatite, the content of titanium dioxide is preferably maintained at 80wt% or less.

From Examples 2 to 10 described above, it can be seen that the shape and particle size of the particles are affected depending on whether the gas is supplied or the type of the gas. However, this is difficult to explain clearly. However, according to the present invention, since the apatite phase is produced via the intermediate reactant, it is estimated that the supplied gas affects the growth of the apatite particles generated on the surface of the DCPD to change the shape and size of the particles.

The above-described embodiments do not limit the scope of the present invention, but are merely exemplary for implementing the present invention. Although the specific embodiments described above relate to a process for preparing hydroxide apatite, those skilled in the art will appreciate that the method of the above described embodiments does not require special technical considerations to extend throughout the apatite, and the two or more feed gases Even in the case of using the present invention, it will be difficult to understand and practice that the desired change in particle shape and particle size may occur.

According to the method of the present invention, the apatite is characterized in that it first forms an intermediate reaction product such as DCPD from calcium salts and phosphates, and then is reprecipitated. Therefore, it is possible to control the size and shape of the particles in this process, it is possible to manufacture apatite particles having a variety of shapes and sizes depending on the gas supply or the type of the supply gas.

In addition, according to the production method of the present invention by controlling the reaction temperature and drying conditions it can be obtained apatite powder having a variety of porosity and specific surface area. Therefore, according to the method of the present invention, it is possible to provide an apatite having physical properties that meet the specifications required for a particular application.

Accordingly, the present invention is suitable for acicular or plate-shaped apatite particles, bone fillers and plate-shaped apatite particles for use as rubber and paper fillers required for high-strength apatite composites for human implants, proteins or pharmaceutical products to be supplied to the human body. Porous apatite particles having a honeycomb structured porous apatite particles and various metal ions and anions or various catalysts that can be used as antibacterial and deodorizing materials can be provided.

Claims (18)

In the apatite powder production method, Providing a mixed aqueous solution comprising calcium salt and phosphate; Reacting the calcium salt and the phosphate salt in the aqueous solution to produce an intermediate reactant having a phase different from that of the apatite; Aging the aqueous solution at 5 to 90 ° C. to synthesize apatite powder from the intermediate reactant; And Apatite manufacturing method comprising the step of drying the slurry precipitated in the aqueous solution. The method of claim 1, Wherein said intermediate reactant is dicalcium phosphate dihydrate. The method of claim 1, The calcium salt is calcium hydroxide, and the phosphate is phosphoric acid manufacturing method. delete The method of claim 1, The apatite powder is apatite manufacturing method having a plate-like particle shape. Providing a mixed aqueous solution comprising calcium salt and phosphate; Synthesizing the calcium phosphate compound while supplying gas into the aqueous solution; And Apatite production method comprising the step of drying the synthesized calcium phosphate compound. The method of claim 6, The synthesis step Reacting the calcium salt with phosphate in the aqueous solution to produce an intermediate reactant; And Comprising the step of synthesizing the calcium phosphate compound from the intermediate reactant. The method of claim 7, wherein Wherein said intermediate product is dicalcium phosphate dihydrate. The method of claim 6, The calcium salt is an apatite production method comprising at least one salt selected from the group consisting of calcium nitrate, calcium carbonate, calcium chloride, calcium hydroxide and calcium acetate. The method of claim 6, The phosphate is apatite preparation comprising at least one salt selected from the group consisting of phosphoric acid, sodium monophosphate, sodium diphosphate, potassium monophosphate, potassium diphosphate, ammonium monophosphate and ammonium diphosphate Way. The method of claim 6, The mixed aqueous solution further comprises at least one ion selected from the group consisting of magnesium ions, barium ions and strontium ions. The method of claim 6, The mixed aqueous solution further comprises at least one ion selected from the group consisting of fluorine ions, chlorine ions and carbonate ions. The method of claim 6, The mixed aqueous solution further comprises at least one oxide selected from the group consisting of titanium dioxide, manganese oxide, vanadium oxide and copper oxide. The method of claim 6, The mixed aqueous solution further comprises at least one metal selected from the group consisting of silver, platinum and palladium. The method of claim 6, Providing the mixed aqueous solution is Stirring the aqueous solution containing the calcium salt; Stirring the aqueous solution containing phosphate; And Apatite manufacturing method comprising the step of mixing the aqueous solution of calcium salt to the aqueous solution of phosphate. The method of claim 15, The stirring step of the aqueous solution of phosphate is apatite manufacturing method that is stirred while supplying at least one gas selected from the group consisting of helium, argon, hydrogen, oxygen, nitrogen and carbon dioxide to the aqueous solution containing phosphate. The method according to claim 15 or 16, In the phosphate stirring step, the phosphate aqueous solution is selected from the group consisting of magnesium ion, barium ion, strontium ion, fluorine ion, chlorine ion, carbonate ion, titanium dioxide, manganese oxide, vanadium oxide, copper oxide, silver, platinum and palladium. And at least one catalytic material. The method of claim 6, The gas is apatite manufacturing method comprising at least one gas selected from the group consisting of helium, argon, hydrogen, oxygen, nitrogen and carbon dioxide.

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