CN102167300A - Preparation method of hexagonal columnar micro-powder hydroxyapatite material - Google Patents
Preparation method of hexagonal columnar micro-powder hydroxyapatite material Download PDFInfo
- Publication number
- CN102167300A CN102167300A CN201110056365.2A CN201110056365A CN102167300A CN 102167300 A CN102167300 A CN 102167300A CN 201110056365 A CN201110056365 A CN 201110056365A CN 102167300 A CN102167300 A CN 102167300A
- Authority
- CN
- China
- Prior art keywords
- hydroxyapatite
- preparation
- powder
- micro mist
- hexagonal column
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 58
- 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 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 title claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000003595 mist Substances 0.000 claims description 19
- 238000010298 pulverizing process Methods 0.000 claims description 10
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 28
- 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 abstract description 13
- 230000008569 process Effects 0.000 abstract description 11
- 238000001035 drying Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 7
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 4
- 238000001238 wet grinding Methods 0.000 abstract 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 2
- 235000019700 dicalcium phosphate Nutrition 0.000 abstract 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- 238000000498 ball milling Methods 0.000 abstract 1
- 230000033558 biomineral tissue development Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000008213 purified water Substances 0.000 abstract 1
- 239000002002 slurry Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 210000000988 bone and bone Anatomy 0.000 description 12
- 239000013078 crystal Substances 0.000 description 9
- 230000012010 growth Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 235000011010 calcium phosphates Nutrition 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012716 precipitator Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 206010006956 Calcium deficiency Diseases 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004068 calcium phosphate ceramic Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- MWKXCSMICWVRGW-UHFFFAOYSA-N calcium;phosphane Chemical compound P.[Ca] MWKXCSMICWVRGW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- HWJHWSBFPPPIPD-UHFFFAOYSA-N ethoxyethane;propan-2-one Chemical compound CC(C)=O.CCOCC HWJHWSBFPPPIPD-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002757 inflammatory effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a preparation method of hexagonal columnar micro-powder hydroxyapatite materials, which is characterized in that calcium carbonate and calcium hydrophosphate are used as initial reactants, a wet grinding method and a hydrothermal synthesis method are adopted, and hexagonal columnar micro-powder hydroxyapatite powder with the particle size of 1-3 mu m is synthesized according to a biomineralization principle. The synthesis process comprises mixing calcium hydrogen phosphate (CaHPO) with Ca/P mol ratio of 5/34·2H2O) and calcium carbonate (CaCO)3) And respectively adding purified water into an agate ball milling tank, adding a stirrer at the same time, and carrying out wet grinding at room temperature for 12-24 hours. And transferring the slurry obtained by wet grinding into a hydrothermal reaction kettle, adding a certain amount of citric acid into the reaction solution, and stirring and reacting the mixed solution at 160-220 ℃ for 5-10 hours under the environment of 5-10 atmospheric pressure. Washing, filtering and drying the obtained precipitate to obtain the required hexagonal columnar micro-powder hydroxyapatite product.
Description
Technical field
The present invention relates to a kind of preparation method of hexagonal column micro mist hydroxyapatite material.
Technical background
Hydroxyapatite [Ca
10(PO4)
6(OH)
2,-HAp]] be the essential mineral composition in the natural bone.HAp belongs to six side's product crystallographic systems, spacer p63/m, and its structure is the hexagonal cylinder, and square with the axis face is a hexagon, and the angle of a, b axle is 120 °, belongs to a kind of biological active materials in the calcium phosphate ceramic.
Its chemical constitution of the hydroxyapatite of synthetic and crystalline texture are similar to the phosphatic rock in the skeleton, and calcium phosphorus mol ratio is 1.67, and is approaching with nature bone, Ca
2+Can permutoid reaction take place with the amino acid that contains carboxyl, protein, organic acid etc., have good bone conduction performance and biological activity, can promote bone growth, phase is more stable, nontoxicity, inflammatory are widely used in the damaged reparation of consistency bone clinically and fill the bone material of shaping.
Mainly be distributed on the collagen stroma from the structure bone salts of bone with the form of needle-like hydroxyapatite (HAp) crystal and amorphous calcium phosphate, the crystallization direction of needle-like HAp distributes along the major axis of collegen filament, and crystalline central shaft (C axle) is parallel with the major axis of collegen filament.The skeleton construction that has overlapped bone salts between HAp xln and collagen layer and the layer, HAp crystal in the bone is in nano level, uniform distribution in ground substance of bone, therefore existing inorganic the enhancing mutually has the toughness reinforcing effect of organic phase again, and the directional profile of what is more important HAp needle has strengthened the mechanical property of bone greatly.
The approach of now synthetic HAp mainly contains 3 kinds: 1. react acquisition HAp under certain condition by calcium salt and phosphoric acid salt; 2. coral dermoskeleton and calcium phosphate salt react under hydrothermal condition and obtain HAp; 3. after the xenogenesis bone being boiled certain hour in deionized water, degreasing in acetone ether mixed solution again, calcining at last obtains the non-references 1 of HAp[].The method of at present synthetic HAp mainly contains microwave process for synthesizing such as drying process, the precipitator method, sol-gel method, hydrothermal method, microemulsion method and utilization ultrasonic wave, hertzian wave.
Drying process is solid-state calcium phosphate and the levigate uniform mixing of other compounds together, under the condition that has water vapour to exist, temperature of reaction is greater than 1000 ℃ (1000～1300 ℃), can obtain the hydroxyapatite of good crystallization, but the synthetic powder granularity is bigger, the sinterability of powder is poor, makes to use to be subjected to certain restriction.
The precipitator method are the most typical methods of preparation hydroxy apatite powder, this method adopts usually certain density ammonium hydrogen phosphate and nitrocalcite reaction or phosphoric acid and calcium hydroxide stirring reaction generation at a certain temperature precipitation, use ammoniacal liquor to regulate the pH value in the reaction process, thereby throw out high temperature satin burning is obtained nano level spherical powder.
Sol-gel method is the novel method that just grew up in the last few years.Finding so-gel system suitable, that can synthesize final hydroxyapatite is its synthetic key.Its principle is that alkoxide is dissolved in the selected organic solvent, and adding distil water generates colloidal sol after making alkoxide generation hydrolysis, polyreaction therein, again with Ca
2+Colloidal sol slowly is added drop-wise to (PO
4)
3-In the colloidal sol, add water and become gel, gel cryodrying under aging, washing, vacuum state obtains xerogel, again with the xerogel high-temperature calcination, will obtain the nano ultrafine powders body of hydroxyapatite.
Hydrothermal method is characterized in special enclosed autoclave reactor, the aqueous solution is reaction medium, in high temperature and high pressure environment, is not subjected to the restriction of boiling point, can make the temperature of medium rise to 200～400 ℃, make original indissoluble or insoluble substance dissolves also tie the method for product again.Can obtain high purity, the high degree of order, good crystallization hydroxyapatite crystal whisker by this method.
On precipitator method basis by utility appliance or process modification synthetic crystallization nanometer powder at a lower temperature.As Chinese patent CN1760121, mainly with the precipitator method and hydrothermal method combination, hydrothermal temperature carried out 8～12 hours at 80～160 ℃, can obtain nanocrystal HAp powder.
But above-mentioned method or patent do not have report to synthetic hexagonal column micro mist hydroxy apatite powder with certain mechanical property.
Crystallisation process is a complicated phase transition process, is subjected to the restriction of thermodynamics and dynamic conditions etc., with relevant [non-references 2] such as solubleness, temperature, degree of supersaturation, stirring, impurity.The generation of hydroxyapatite has been experienced by octocalcium phosphate → non-crystalline state calcium phosphate → calcium deficiency phosphatic rock → hydroxyapatite transformation process.Octocalcium phosphate, calcium phosphate and hydroxyapatite are water-soluble hardly under the normal temperature, add during reaction certain to make itself and Ca as organic acids such as citric acid or lactic acid in reaction soln
2+Form coordination, just can form very big degree of supersaturation, suppressed Ca in moment
2+Deposition, help obtaining the epitaxial crystal, nucleation process is based on homogeneous nucleation, under certain pH value condition, crystal is grown up by certain orientation, forms tiny hexagonal styloid at last simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who prepares hexagonal column micro mist hydroxyapatite material, this method is to be initial reactant with lime carbonate and secondary calcium phosphate, adopt case of wet attrition method and hydrothermal synthesis method, forming the synthetic particle diameter of mechanism according to hydroxyapatite is the hexagonal column micro mist hydroxy apatite powder of 1～2 μ m.
The present invention is realized that by following technology bill a kind of preparation method who prepares hexagonal column micro mist hydroxyapatite material comprises following process.
1.HAp the preparation of precursor
With Ca/P mol than being that 5/3 secondary calcium phosphate and lime carbonate and pure water add respectively in the agate system ball grinder, the weight of water is 1～10 times of powder weight, adding diameter simultaneously is the agate ball stirrer of 5～20mm, the weight of agate ball stirrer is 1～10 times of powder weight, room temperature wet pulverization 12～24 hours, machine speed are 40～70rmp;
2. the preparation of hexagonal column micro mist hydroxyapatite
With the resulting white emulsion of wet pulverization with pure water washing 2～3 times after, slip is transferred in the hydrothermal reaction kettle, in reaction soln, add the citric acid additive simultaneously, and make mixing solutions stir, react 5～10 hours in 5～10 atmospheric environment down at 160～220 ℃.
With the washing of gained throw out, suction filtration, be drying to obtain required hexagonal column micro mist hydroxyapatite product.
The hexagonal column micro mist hydroxy apatite powder that particle diameter is 1～2 μ m can be prepared by present method.
The preparation of HAp is carried out in acidic solution, has a large amount of H in the solution
+Ion makes that the HAp surface is positively charged.The process of the growth experience ionic absorption-transfer-reaction of plane of crystal is in process of growth, because electronegative negatively charged ion and the electrostatic interaction between positively charged surface are adsorbed and then participate in growth response easily; Because the anisotropy that surface field distributes causes negatively charged ion along some specific direction growth of crystalline; React and adsorb positively charged ion in the other direction, because the positively charged difficult deposition of positively charged ion, so finally obtain the non-references 3 of epitaxial HAp[].In the building-up process, certain make itself and Ca as organic acids such as citric acid or lactic acid owing in reaction soln, add
2+Form coordination, suppressed Ca
2+Deposition, help obtaining PO
4 3-(C axle) epitaxial HAp crystal forms tiny hexagonal styloid at last vertically.
[non-references 1] Murugan R, Ramakrishna S.[J] .Crystal Growth and Desgning, 2005,5 (1): 111-112.
[non-references 2] Liu Changsheng, Shen Wei, Cui Jinhua etc., Huadong Ligong Daxue (J.East China University of Science and Technology) 1996,10 (22), 530.
[non-references 3] Yao Lianzeng. Foundation of Crystal Growth [M]. Hefei: press of China Science ﹠ Technology University, 1994.377～408.
Description of drawings
Fig. 1 is the X-ray diffraction collection of illustrative plates of resulting hydroxyapatite particles in the specific embodiment of the invention 1.
This X-ray diffraction collection of illustrative plates explanation present embodiment synthetic hydroxyapatite powder degree of crystallinity is lower.
Fig. 2 is the X-ray diffraction collection of illustrative plates of resulting hydroxyapatite particles in the specific embodiment of the invention 2.
This X-ray diffraction collection of illustrative plates explanation present embodiment synthetic hydroxyapatite powder degree of crystallinity is higher.
Fig. 3 is the SEM Electronic Speculum figure of resulting hydroxyapatite particles in the specific embodiment of the invention 3.
Embodiment.
Embodiment 1
Step 1: the preparation of HAp precursor
With Ca/P mol than the secondary calcium phosphate (CaHPO that is 5/3
42H
2O) 0.06mol and lime carbonate (CaCO
3) 0.04mol is added in the 130ml pure water.Mixture is presented in the agate system ball grinder, and adding the 130g diameter simultaneously is the agate ball stirrer of 15mm, and room temperature wet pulverization 24 hours, machine speed are 60rmp.Mixing solutions is taken out a part placed 60 ℃ of loft drier dry 7 days, promptly obtain HAp precursor powder.Product hydroxyapatite precursor powder X-ray ray diffraction diagram spectrum is as shown in Figure 1 in the Figure of description, and its degree of crystallinity is lower.
Step 2: the preparation of hexagonal column micro mist hydroxyapatite
Slip with wet pulverization after good moves in the high-pressure hydrothermal reaction kettle, adds the citric acid of 0.3g simultaneously in reaction soln, and makes mixing solutions stir, react 5 hours in the 5 atmospheric environment down at 160 ℃.
With the washing of gained throw out, suction filtration, be drying to obtain required hexagonal column micro mist hydroxyapatite product.
Embodiment 2
Step 1: the preparation of HAp precursor
With Ca/P mol than the secondary calcium phosphate (CaHPO42H that is 5/3
2O) 0.075mol and lime carbonate (CaCO
3) 0.05mol is added in the 175ml pure water.Mixture is presented in the agate system ball grinder, and adding the 175g diameter simultaneously is the agate ball stirrer of 10mm, and room temperature wet pulverization 16 hours, machine speed are 50rmp.
Step 2: the preparation of hexagonal column micro mist hydroxyapatite
Slip with wet pulverization after good moves in the high-pressure hydrothermal reaction kettle, adds the citric acid of 0.8g simultaneously in reaction soln, and makes mixing solutions stir, react 7 hours in the 8 atmospheric environment down at 180 ℃.
With the washing of gained throw out, suction filtration, be drying to obtain required hexagonal column micro mist hydroxyapatite product.Shown in Figure 2 in product hydroxyapatite powder X-ray diffraction collection of illustrative plates such as the Figure of description, its degree of crystallinity is higher.
Embodiment 3
Step 1: the preparation of HAp precursor
With Ca/P mol than the secondary calcium phosphate (CaHPO42H that is 5/3
2O) 0.045mol and lime carbonate (CaCO
3) 0.03mol is added in the 100ml pure water.Mixture is presented in the agate system ball grinder, and adding the 100g diameter simultaneously is the agate ball stirrer of 5mm, and room temperature wet pulverization 20 hours, machine speed are 50rmp.
Step 2: the preparation of hexagonal column micro mist hydroxyapatite
Slip with wet pulverization after good is transferred in the high-pressure hydrothermal reaction kettle, adds the citric acid of 0.5g simultaneously in reaction soln, and makes mixing solutions stir, react 10 hours in the 10 atmospheric environment down at 220 ℃.
With the washing of gained throw out, suction filtration, be drying to obtain required hexagonal column micro mist hydroxyapatite product.
Shown in Figure 3 in the SEM Electronic Speculum figure of product hydroxyapatite particles such as the Figure of description, its pattern is the high-crystallinity HAp of hexagonal column.
Claims (3)
1. the preparation method of a hexagonal column micro mist hydroxyapatite material is characterized in that:
(1) preparation of hydroxyapatite precursor
With Ca/P mol than being that 5/3 secondary calcium phosphate and lime carbonate and pure water add respectively in the agate system ball grinder, the weight of water is 1～10 times of powder weight, adding diameter simultaneously is the agate ball stirrer of 5～20mm, the weight of agate ball stirrer is 1～10 times of powder weight, room temperature wet pulverization 12～24 hours, machine speed are 40～70rmp;
(2) preparation of hexagonal column micro mist hydroxyapatite
With the resulting white emulsion of wet pulverization with pure water washing 2～3 times after, slip is transferred in the hydrothermal reaction kettle, in reaction soln, add the citric acid additive simultaneously, and make mixing solutions stir, react 5～10 hours in 5～10 atmospheric environment down at 160～220 ℃.
2. the preparation method of the hexagonal column micro mist hydroxyapatite material of narrating according to claim 1 is characterized in that employed initial feed is secondary calcium phosphate and lime carbonate, and its chemical formula is respectively CaHPO
42H
2O and CaCO
3
3. the preparation method of the hexagonal column micro mist hydroxyapatite material of narrating according to claim 1 is characterized in that adding 1.5～7.5% citric acid as additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110056365.2A CN102167300A (en) | 2011-03-10 | 2011-03-10 | Preparation method of hexagonal columnar micro-powder hydroxyapatite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110056365.2A CN102167300A (en) | 2011-03-10 | 2011-03-10 | Preparation method of hexagonal columnar micro-powder hydroxyapatite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102167300A true CN102167300A (en) | 2011-08-31 |
Family
ID=44488656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110056365.2A Pending CN102167300A (en) | 2011-03-10 | 2011-03-10 | Preparation method of hexagonal columnar micro-powder hydroxyapatite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102167300A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103046112A (en) * | 2012-12-11 | 2013-04-17 | 昆明理工大学 | Monetite whisker and preparation method thereof |
| RU2505479C1 (en) * | 2012-06-28 | 2014-01-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Российский химико-технологический университет им. Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Method of obtaining hydroxyapatite |
| CN105293462A (en) * | 2015-12-02 | 2016-02-03 | 杭州电子科技大学 | Method of preparing hydroxyapatite by mechanochemical method |
| CN106082154A (en) * | 2016-06-12 | 2016-11-09 | 常州大学 | The method preparing mesoporous hydroxyapatite as phosphorus source hydro-thermal using water-soluble hexametaphosphates |
| CN107337188A (en) * | 2017-06-01 | 2017-11-10 | 苏州乔纳森新材料科技有限公司 | A kind of preparation method of hydroxyapatite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047627A (en) * | 1989-06-01 | 1990-12-12 | 河北轻化工学院 | Hydroox apatite artificial bone material preparation method |
| JPH0940408A (en) * | 1995-07-27 | 1997-02-10 | Taihei Kagaku Sangyo Kk | Production of hydroxyapatite platelike large-sized crystal |
-
2011
- 2011-03-10 CN CN201110056365.2A patent/CN102167300A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047627A (en) * | 1989-06-01 | 1990-12-12 | 河北轻化工学院 | Hydroox apatite artificial bone material preparation method |
| JPH0940408A (en) * | 1995-07-27 | 1997-02-10 | Taihei Kagaku Sangyo Kk | Production of hydroxyapatite platelike large-sized crystal |
Non-Patent Citations (2)
| Title |
|---|
| 《东南大学学报(自然科学版)》 20020531 郭大勇等 柠檬酸对溶胶凝胶法制备羟基磷灰石粉体的影响 第402-405页 1-3 第32卷, 第3期 * |
| 《功能材料》 20021231 廖其龙灯 纳米羟基磷灰石的水热合成 第338-340页 1-3 第33卷, 第3期 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2505479C1 (en) * | 2012-06-28 | 2014-01-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Российский химико-технологический университет им. Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Method of obtaining hydroxyapatite |
| CN103046112A (en) * | 2012-12-11 | 2013-04-17 | 昆明理工大学 | Monetite whisker and preparation method thereof |
| CN103046112B (en) * | 2012-12-11 | 2015-06-03 | 昆明理工大学 | Monetite whisker and preparation method thereof |
| CN105293462A (en) * | 2015-12-02 | 2016-02-03 | 杭州电子科技大学 | Method of preparing hydroxyapatite by mechanochemical method |
| CN106082154A (en) * | 2016-06-12 | 2016-11-09 | 常州大学 | The method preparing mesoporous hydroxyapatite as phosphorus source hydro-thermal using water-soluble hexametaphosphates |
| CN107337188A (en) * | 2017-06-01 | 2017-11-10 | 苏州乔纳森新材料科技有限公司 | A kind of preparation method of hydroxyapatite |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10525166B2 (en) | Selenium-doped hydroxyapatite and preparation method thereof | |
| CN102569749B (en) | Graphene/hydroxyapatite nano composite and preparation method thereof | |
| CN102616762B (en) | Method for hydro-thermal preparation of hydroxyapatite powder by calcium silicate precursor | |
| CN100584750C (en) | Method for preparing calcium phosphate composite powder | |
| CN102167300A (en) | Preparation method of hexagonal columnar micro-powder hydroxyapatite material | |
| CN101734635A (en) | Method for preparing nano hydroxyapatite powder | |
| Hao et al. | Controlled growth of hydroxyapatite fibers precipitated by propionamide through hydrothermal synthesis | |
| CN101920947A (en) | Preparation method of slice-shaped B type carbonate phosphorite | |
| CN112830464B (en) | Strontium-doped hydroxyapatite nanotube and preparation method thereof | |
| CN104961114A (en) | Calcium magnesium phosphate nanometer structure material and preparation method thereof | |
| CN103288066A (en) | Method for preparing hydroxyapatite and/or tricalcium phosphate by using gelatin production wastewater | |
| CN101716370B (en) | Method for preparing nano doped hydroxylapatite powder | |
| CN102897735A (en) | Microwave assisted preparation of hydroxyapatite hollow sphere | |
| CN103569991B (en) | Microwave-assisted synthesis method of nano fluorapatite powder | |
| JP5467432B2 (en) | Method for producing plate-like hydroxyapatite single crystal | |
| CN104944399B (en) | The preparation method of hydroxyapatite micro-sphere | |
| CN103832991A (en) | Preparation method of iron phosphate nano material | |
| CN103738932B (en) | A kind of nanometer hydroxyapatite and preparation method thereof | |
| CN103803519B (en) | There is the preparation method of the layered porous calcium phosphate powder of micro-nano multilevel hierarchy | |
| CN105948012A (en) | Method for preparing beta-tricalcium phosphate crystal material under low temperature condition | |
| CN100551820C (en) | The preparation method of crystallinity controllable nano hydroxyapatite powder | |
| CN100384720C (en) | Process for preparing modified hydroxy apatite powder | |
| CN101401951A (en) | Calcium phosphate biological active ceramic material containing silicon dioxide and preparation method thereof | |
| CN103935973B (en) | The preparation method of radial multilevel hierarchy nanometer hydroxyapatite under neutrallty condition | |
| Li et al. | Preparation of nanosized hydroxyapatite particles at low temperatures. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110831 |