WO2013153749A1 - アパタイト結晶 - Google Patents
アパタイト結晶 Download PDFInfo
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- WO2013153749A1 WO2013153749A1 PCT/JP2013/001928 JP2013001928W WO2013153749A1 WO 2013153749 A1 WO2013153749 A1 WO 2013153749A1 JP 2013001928 W JP2013001928 W JP 2013001928W WO 2013153749 A1 WO2013153749 A1 WO 2013153749A1
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- 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
- C01B25/455—Phosphates containing halogen
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/321—Methods for converting an alkaline earth metal ortho-phosphate into another ortho-phosphate
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/14—Phosphates
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/66—Crystals of complex geometrical shape, e.g. tubes, cylinders
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- C—CHEMISTRY; METALLURGY
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2973—Particular cross section
- Y10T428/2975—Tubular or cellular
Definitions
- the present invention relates to a crystalline apatite applicable to a wide range of fields as a functional material.
- Non-Patent Document 1 a solid hexagonal columnar apatite single crystal is known.
- Apatite-based materials can be applied to various applications, and there is room for further improvement in shapes and components suitable for the applications.
- the present invention has been made in view of such circumstances, and an object thereof is to provide a new apatite crystal.
- an apatite crystal of an embodiment of the present invention has a general formula of M 2 5 (PO 4 ) 3 X (M 2 is at least selected from the group consisting of a divalent alkaline earth metal and Eu) One element, X represents at least one element or molecule selected from the group consisting of a halogen element and OH.)
- the single crystal is tube-shaped.
- the outer shape may be a hexagonal column, and the shape of the opening of the hole formed in the upper surface or the lower surface of the hexagonal column may be a hexagon. Thereby, an apatite crystal with a uniform tube thickness is obtained.
- the inner diameter of the hole may be 10 nm to 60 ⁇ m.
- the diameter may be 20 nm to 100 ⁇ m.
- the length in the longitudinal direction may be 50 nm to 4 mm.
- the transmittance for visible light may be 65% or more.
- a new apatite crystal can be formed.
- the apatite crystal according to the present embodiment is a tube-shaped single crystal.
- the apatite crystal has a general formula of M 2 5 (PO 4 ) 3 X (M 2 is at least one element selected from the group consisting of a divalent alkaline earth metal and Eu, and X is a halogen element and OH. Represents at least one element or molecule selected from the group).
- Alkaline earth metals are, for example, Ca, Sr, Ba, Ra, Mg, Be.
- the halogen element is, for example, F, Cl, Br, or I.
- Example 7 are methods for synthesizing chlorapatite single crystals.
- Examples 8 to 10 are methods for synthesizing a hydroxyapatite single crystal. Examples of the synthesis method include a flux method, a coprecipitation method, and a sol-gel method.
- Example 1 Flux method
- CaHPO 4 , CaCO 3 , and CaCl 2 are weighed so that the molar ratio of Ca: P: Cl is 5: 3: 1 and mixed uniformly.
- NaCl was added so that the chlorapatite concentration was 0.15 mol%, and the mixture was heated in a platinum crucible to 800 to 1100 ° C. at a heating rate of 100 to 500 ° C./h, and a synthesis temperature of 800 to 1100 ° C.
- the temperature is lowered from 800 to 1100 ° C. to 500 ° C. at a temperature drop rate of 5 to 300 ° C./h, and then cooled to room temperature by natural cooling.
- it is carefully washed with warm pure water (about 80 ° C.) to take out the chlorapatite single crystal.
- Example 2 Flux method
- CaHPO 4 , CaCO 3 , and CaCl 2 are weighed so that the molar ratio of Ca: P: Cl is 5: 3: 1 and mixed uniformly. Thereafter, a large amount of CaCl 2 was added, and the mixture was heated in a platinum crucible to 800 to 1100 ° C. at a heating rate of 100 to 500 ° C./h, synthesized at a synthesis temperature of 800 to 1100 ° C. for 48 hours, and then cooled down. The temperature is lowered from 800 to 1100 ° C. to 500 ° C. at 5 to 300 ° C./h, and then cooled to room temperature by natural cooling. After firing, it is carefully washed with warm pure water (about 80 ° C.) to take out the chlorapatite single crystal.
- Example 3 Flux method
- CaHPO 4 , CaCO 3 , SrCO 3 , CaCl 2 , SrCl 2 are weighed so that the molar ratio of Ca + Sr: P: Cl is 5: 3: 1 and uniformly mixed.
- SrCl 2 was added so that the chlorapatite concentration was 0.15 mol%, and the mixture was heated in a platinum crucible to 800 to 1100 ° C. at a heating rate of 100 to 500 ° C./h, and the synthesis temperature was 800 to 1100.
- the temperature is decreased from 800 to 1100 ° C. to 500 ° C. at a temperature decrease rate of 5 to 300 ° C./h, and then cooled to room temperature by natural cooling.
- it is carefully washed with warm pure water (about 80 ° C.) to take out the chlorapatite single crystal.
- Example 4 Flux method
- CaHPO 4 , CaCO 3 , MgCO 3 , CaCl 2 , and MgCl 2 are weighed so that the molar ratio of Ca + Mg: P: Cl is 5: 3: 1 and uniformly mixed.
- MgCl 2 was added so that the chlorapatite concentration was 0.15 mol%, and the mixture was heated in a platinum crucible to 800 to 1100 ° C. at a heating rate of 100 to 500 ° C./h, and a synthesis temperature of 800 to 1100 ° C. After being synthesized for 48 hours, the temperature is lowered from 800 to 1100 ° C. to 500 ° C. at a temperature drop rate of 5 to 300 ° C./h, and then cooled to room temperature by natural cooling. After firing, it is carefully washed with warm pure water (about 80 ° C.) to take out the chlorapatite single crystal.
- Example 5 Coprecipitation method
- calcium nitrate and calcium chloride are dissolved in pure water, phosphoric acid is dropped into the solution, and the pH is adjusted to 5 to 9 to form a precipitate (seed crystal).
- the seed crystal prepared by the coprecipitation method is grown as a seed crystal by the Czochralski method.
- a Ca 2 ClPO 4 concentration of 15 mol% is heated to 1200 ° C., the seed crystal is immersed in a high temperature solution, and gradually cooled from 1200 ° C. to 1050 ° C. While pulling up the crystal, a chloroapatite single crystal was obtained.
- Example 6 Sol-gel method
- phosphoric acid ethoxide total molar concentration of calcium and phosphorus; 0.05 mol / liter
- concentrated hydrochloric acid chlorine is 1 mol per 1 mol of calcium. 1 mol
- This solution was dried at 60 ° C. for 2 hours to remove distilled water to obtain seed crystals.
- the seed crystal prepared by the sol-gel method is grown as a seed crystal by the Czochralski method.
- a Ca 2 ClPO 4 concentration of 15 mol% is heated to 1200 ° C., the seed crystal is immersed in a high temperature solution, and gradually cooled from 1200 ° C. to 1050 ° C. While pulling up the crystal, a chloroapatite single crystal was obtained.
- Example 7 Sol-gel method
- phosphoric acid was further added (total molar concentration of calcium and phosphorus; 0.05 mol / liter) and stirred, and then concentrated hydrochloric acid was added.
- This solution was dried at 60 ° C. for 2 hours to remove distilled water to obtain seed crystals.
- the seed crystal prepared by the sol-gel method is grown as a seed crystal by the Czochralski method.
- a Ca 2 ClPO 4 concentration of 15 mol% is heated to 1200 ° C., the seed crystal is immersed in a high temperature solution, and gradually cooled from 1200 ° C. to 1050 ° C. While pulling up the crystal, a chloroapatite single crystal was obtained.
- Example 8 Coprecipitation method
- Single crystal precipitation by adding 0.5 mol / L phosphoric acid aqueous solution dropwise to 0.3 mol / L calcium hydroxide suspension and adjusting the pH to 5-9, taking care to form single crystals.
- a product seed crystal
- the seed crystal prepared by the coprecipitation method is grown as a seed crystal by the Czochralski method. Calcium hydroxide was heated to 1650 ° C., the seed crystal was immersed in a high-temperature solution, and the crystal was pulled up while gradually cooling from 1650 ° C. to 1000 ° C. to obtain a needle-like hydroxyapatite single crystal.
- Example 9 Hydrothermal synthesis method
- lactic acid is dissolved in 1 liter of water, then 22.11 g of calcium hydroxide is added, and 6.92 g of phosphoric acid is mixed and dissolved.
- the slurry thus prepared is filled in an autoclave and subjected to hydrothermal treatment at 165 ° C. for 5 hours.
- the treated slurry was filtered and dried to obtain a hydroxyapatite single crystal.
- Example 10 Sol-gel method
- 1.0 ⁇ 10 ⁇ 2 moles of calcium diethoxide is dissolved in 6.5 ml of ethylene glycol.
- a mixed solution of calcium diethoxide in ethylene glycol and triethyl phosphite is stirred for 2 hours to form a precipitate. It was heated at 200 ° C. for 2 hours to obtain a seed crystal.
- the seed crystal prepared by the sol-gel method is grown as a seed crystal by the Czochralski method.
- Calcium hydroxide was heated to 1650 ° C., the seed crystal was immersed in a high-temperature solution, and the crystal was pulled up while gradually cooling from 1650 ° C. to 1000 ° C. to obtain a needle-like hydroxyapatite single crystal.
- Example 11 Chlorine apatite single crystal (20 mg) is put in a platinum capsule (2.6 mm ⁇ , length 3.3 mm) together with 6.25 (mol / L) aqueous potassium hydroxide (KOH) (40 ⁇ l) and sealed.
- the hydrothermal treatment is performed under conditions of 100 MPa using water as a pressure medium in a test tube type autoclave. The heating rate is 20 ° C. per minute, the processing temperature is 400 ° C., and the processing time is constant for 48 hours. Thereby, a hydroxyapatite single crystal was obtained.
- Example 12 Chloroapatite single crystal (20 mg) is heated to 1300 ° C. and reacted in steam through steam for 2 weeks to convert it into a hydroxyapatite single crystal.
- FIG. 1 is an example of an X-ray diffraction pattern of a crystal prepared by the method of the example. As shown in FIG. 1, the crystal was a single layer of chlorapatite crystal Ca 5 (PO 4 ) 3 Cl.
- FIG. 2 is a photograph showing an example of a chloroapatite tube single crystal observed by SEM.
- the apatite single crystal according to the present embodiment has a tube shape, and the outer shape is a hexagonal column.
- the shape of the opening part of the hole formed in the upper surface or lower surface of a hexagonal column is a hexagon. Therefore, the thickness of the outer wall of the tube is almost uniform.
- the inner diameter of the hole in the opening of the tubular single crystal is about 10 nm to 60 ⁇ m.
- the diameter of the tubular single crystal is about 20 nm to 100 ⁇ m.
- the tube-shaped single crystal has a length in the longitudinal direction of about 50 nm to 4 mm.
- the tube-shaped single crystal has a transmittance of 65% or more with respect to visible light.
- the tube-like apatite single crystal can accommodate other substances inside, it can be applied to new applications. For example, (1) By filling the inside of the apatite single crystal with the Mg—Ni alloy, it can be used for a fuel cell as a hydrogen storage material. (2) By confining the gas molecule adsorbent inside the apatite single crystal, it can be used as a nanopore material. (3) By filling the inside of an apatite single crystal with an amino acid, it can be used as a biocolumn for separating and purifying DNA from cells.
- apatite single crystal By filling the inside of the apatite single crystal with a catalyst or enzyme, it can be used as a reaction field for a gas or solvent decomposition column or a bioreactor.
- a carbon nanotube or an organic material can be inserted into an apatite single crystal and used as a column for aligning the arrangement of the inserts.
- the tube-shaped apatite single crystal can be applied to the following uses depending on the shape and size. (6) By filling the inside of a tube-like apatite single crystal with a drug, it can be used as a drug delivery system. (7) Since the tubular apatite single crystal has a high aspect ratio, it can be used as a reinforcing material (reinforcing material) in a composite material. (8) It can be used as an atmospheric culture field utilizing the shape of a tube-like apatite single crystal. (9) It can be used as a terahertz light emitting device. (10) Application to applications using volume expansion / contraction inside the tube is possible.
- the apatite single crystal of the present invention can be used as various functional materials including phosphors.
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Abstract
Description
(実施例1:フラックス法)
はじめに、CaHPO4、CaCO3、CaCl2を、Ca:P:Clのモル比が5:3:1となるように計量し、均一混合する。その後、塩素アパタイト濃度が0.15mol%となるようにNaClを追加し、混合物を白金るつぼ中で800~1100℃まで昇温速度100~500℃/hで昇温させ、合成温度800~1100℃で48時間合成した後、降温速度5~300℃/hで800~1100℃から500℃まで降温させ、その後は自然冷却で常温まで冷却する。焼成後、温純水(約80℃)で丹念に洗浄し、塩素アパタイト単結晶を取り出す。
はじめに、CaHPO4、CaCO3、CaCl2を、Ca:P:Clのモル比が5:3:1となるように計量し、均一混合する。その後、多量のCaCl2を追加し、混合物を白金るつぼ中で800~1100℃まで昇温速度100~500℃/hで昇温させ、合成温度800~1100℃で48時間合成した後、降温速度5~300℃/hで800~1100℃から500℃まで降温させ、その後は自然冷却で常温まで冷却する。焼成後、温純水(約80℃)で丹念に洗浄し、塩素アパタイト単結晶を取り出す。
はじめに、CaHPO4、CaCO3、SrCO3,CaCl2,SrCl2を、Ca+Sr:P:Clのモル比が5:3:1となるように計量し、均一混合する。その後、塩素アパタイト濃度が0.15mol%となるようにSrCl2を追加し、混合物を白金るつぼ中で800~1100℃まで昇温速度100~500℃/hで昇温させ、合成温度800~1100℃で48時間合成した後、降温速度5~300℃/hで800~1100℃から500℃まで降温させ、その後は自然冷却で常温まで冷却する。焼成後、温純水(約80℃)で丹念に洗浄し、塩素アパタイト単結晶を取り出す。
はじめに、CaHPO4、CaCO3、MgCO3、CaCl2、MgCl2を、Ca+Mg:P:Clのモル比が5:3:1となるように計量し、均一混合する。その後、塩素アパタイト濃度が0.15mol%となるようMgCl2を追加し、混合物を白金るつぼ中で800~1100℃まで昇温速度100~500℃/hで昇温させ、合成温度800~1100℃で48時間合成した後、降温速度5~300℃/hで800~1100℃から500℃まで降温させ、その後は自然冷却で常温まで冷却する。焼成後、温純水(約80℃)で丹念に洗浄し、塩素アパタイト単結晶を取り出す。
はじめに、純水に硝酸カルシウム、塩化カルシウムを溶解させ、その溶液中にリン酸を滴下し、pHを5~9に調整することにより沈殿(種結晶)を生じさせる。この共沈法により調整した種結晶を、チョクラルスキー法により種結晶成長させる。CaCl2-Ca2ClPO4系相図において、Ca2ClPO4濃度が15mol%のものを1200℃まで加熱し、高温溶液となった中に種結晶を浸し、1200℃から1050℃まで徐冷しながら結晶を引き上げることにより、塩素アパタイト単結晶を得た。
はじめに、蒸留水に硝酸カルシウムを溶解させ、更にリン酸エトキシドを添加して(カルシウムとリンの合計モル濃度;0.05モル/リットル)撹拌した後、濃塩酸(カルシウム1モルに対して塩素は1モル)を加えた。この溶液を60℃で2時間乾燥して蒸留水を除去し、種結晶を得た。このゾル-ゲル法により調整した種結晶を、チョクラルスキー法により種結晶成長させる。CaCl2-Ca2ClPO4系相図において、Ca2ClPO4濃度が15mol%のものを1200℃まで加熱し、高温溶液となった中に種結晶を浸し、1200℃から1050℃まで徐冷しながら結晶を引き上げることにより、塩素アパタイト単結晶を得た。
はじめに、蒸留水にカルシウムエトキシドを溶解させ、更にリン酸を添加して(カルシウムとリンの合計モル濃度;0.05モル/リットル)撹拌した後、濃塩酸を加えた。この溶液を60℃で2時間乾燥して蒸留水を除去し、種結晶を得た。このゾル-ゲル法により調整した種結晶を、チョクラルスキー法により種結晶成長させる。CaCl2-Ca2ClPO4系相図において、Ca2ClPO4濃度が15mol%のものを1200℃まで加熱し、高温溶液となった中に種結晶を浸し、1200℃から1050℃まで徐冷しながら結晶を引き上げることにより、塩素アパタイト単結晶を得た。
(実施例8:共沈法)
0.3mol/Lの水酸化カルシウム懸濁液に、0.5mol/Lのリン酸水溶液を滴下し、単結晶が生成するよう留意してpHを5~9に調整することにより、単結晶沈殿物(種結晶)を得た。この共沈法により調整した種結晶を、チョクラルスキー法により種結晶成長させる。水酸化カルシウムを1650℃まで加熱し、高温溶液となった中に種結晶を浸し、1650℃から1000℃まで徐冷しながら結晶を引き上げることにより、針状の水酸アパタイト単結晶を得た。
はじめに、水1リットルに乳酸63.37gを溶解し、次に水酸化カルシウム22.11gを加え、更にリン酸6.92gを混合溶解させる。こうして調製したスラリーをオートクレーブに充填し、165℃で5時間、水熱処理を施す。そして、処理後のスラリーを濾過乾燥し、水酸アパタイト単結晶を得た。
カルシウムジエトキシド1.0×10-2モル分を6.5mlのエチレングリコールに溶解させる。次に、亜リン酸トリエチルを、水酸アパタイトの組成比がCa/P=5/3となるように、6.0×10-3モル採取し、所定量のエタノールに溶かして使用する。その後、カルシウムジエトキシドのエチレングリコール溶液と亜リン酸トリエチルとの混合溶液を2時間撹拌し、沈殿物を生じさせる。それを200℃で2時間加熱し、種結晶を得た。このゾル-ゲル法により調整した種結晶を、チョクラルスキー法により種結晶成長させる。水酸化カルシウムを1650℃まで加熱し、高温溶液となった中に種結晶を浸し、1650℃から1000℃まで徐冷しながら結晶を引き上げることにより、針状の水酸アパタイト単結晶を得た。
(実施例11)
塩素アパタイト単結晶(20mg)を6.25(mol/L)の水酸化カリウム(KOH)水溶液(40μl)とともに、白金カプセル(2.6mmφ、長さ3.3mm)中に入れ溶封する。水熱処理は、テストチューブ型オートクレーブで圧力媒体として水を用い、100MPaの条件下で行う。昇温速度は毎分20℃とし、処理温度は400℃で行い、処理時間は48時間一定とする。これにより水酸アパタイト単結晶を得た。
塩素アパタイト単結晶(20mg)を1300℃に加熱し、炉内に水蒸気を通じて2週間かけて反応させて、水酸アパタイト単結晶に変換する。
次に、実施例の方法で作成した塩素アパタイト結晶の組成について検討した。図1は、実施例の方法で作成された結晶のX線回折パターンの一例である。図1に示すように、結晶は、塩素アパタイト結晶Ca5(PO4)3Clの単一層であった。
次に、塩素アパタイトチューブ単結晶の元素分析を行った。その結果、この結晶は、Ca=39.10mass%、P=18.00mass%、Cl=5.30mass%であった。
次に、塩素アパタイトチューブ単結晶の形状を走査型電子顕微鏡(SEM)にて観察した。図2は、SEMで観察した塩素アパタイトチューブ単結晶の一例を示す写真である。図2に示すように、本実施の形態に係るアパタイト単結晶は、チューブ状であり、外形が六角柱である。また、六角柱の上面または下面に形成されている穴の開口部の形状が六角形である。そのため、チューブの外壁の厚みがほぼ一様になっている。
次に、アパタイトのチューブ状単結晶の用途について説明する。
チューブ状のアパタイト単結晶は、内部に他の物質を収容できるため、新たな用途への適用が可能となる。例えば、
(1)Mg-Ni合金をアパタイト単結晶の内部に充填することにより、水素吸蔵材料として燃料電池に利用することが可能となる。
(2)ガス分子吸着材をアパタイト単結晶の内部に閉じ込めることにより、ナノ細孔材料として利用することが可能となる。
(3)アミノ酸をアパタイト単結晶の内部に充填することにより、細胞からDNAを分離精製するバイオカラムとして利用することが可能となる。
(4)触媒や酵素をアパタイト単結晶の内部に充填することにより、ガス、溶剤の分解カラム、バイオリアクタの反応場として利用することが可能となる。
(5)カーボンナノチューブや有機材料をアパタイト単結晶の内部に挿入し、挿入物の配列を揃えるカラムとして利用することが可能となる。
チューブ状のアパタイト単結晶は、その形状や大きさによって、以下の用途への適用が可能となる。
(6)チューブ状のアパタイト単結晶の内部に薬を充填することにより、ドラッグデリバリーシステムとしての利用が可能となる。
(7)チューブ状のアパタイト単結晶が高アスペクト比であるため、複合材での強化材(補強材)としての利用が可能となる。
(8)チューブ状のアパタイト単結晶の形状を利用した雰囲気培養場としての利用が可能となる。
(9)テラヘルツ発光デバイスとしての利用が可能となる。
(10)チューブ内部での体積膨張・収縮を利用した用途への適用が可能となる。
蛍光体、電子放出材料、光触媒アパタイト、人工骨の補強材などへの利用が可能となる。また、透明である光学特性を利用した応用も可能である。
Claims (6)
- 一般式がM2 5(PO4)3X(M2は2価のアルカリ土類金属及びEuからなる群より選ばれる少なくとも1種の元素、Xはハロゲン元素及びOHからなる群より選ばれる少なくとも一種の元素または分子を示す。)で表される単結晶であって、
前記単結晶がチューブ状であるアパタイト結晶。 - 外形が六角柱であり、六角柱の上面または下面に形成されている穴の開口部の形状が六角形であることを特徴とする請求項1に記載のアパタイト結晶。
- 前記穴の内径が10nm~60μmであることを特徴とする請求項2に記載のアパタイト結晶。
- 直径が20nm~100μmであることを特徴とする請求項1乃至3のいずれか1項に記載のアパタイト結晶。
- 長手方向の長さが50nm~4mmであることを特徴とする請求項1乃至4のいずれか1項に記載のアパタイト結晶。
- 可視光に対して透過率が65%以上であることを特徴とする請求項1乃至5のいずれか1項に記載のアパタイト結晶。
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JPWO2014045534A1 (ja) * | 2012-09-18 | 2016-08-18 | 株式会社小糸製作所 | 吸着方法、吸着分離方法およびドラッグデリバリー用担持体 |
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