CN102703977B - Hydroxyapatite mono-crystal nano-rod and preparation method thereof - Google Patents
Hydroxyapatite mono-crystal nano-rod and preparation method thereof Download PDFInfo
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- CN102703977B CN102703977B CN201210206824.5A CN201210206824A CN102703977B CN 102703977 B CN102703977 B CN 102703977B CN 201210206824 A CN201210206824 A CN 201210206824A CN 102703977 B CN102703977 B CN 102703977B
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 90
- 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 90
- 239000002073 nanorod Substances 0.000 title claims abstract description 84
- 239000013078 crystal Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 11
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 21
- 239000012498 ultrapure water Substances 0.000 claims description 21
- 229920000742 Cotton Polymers 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 229940093916 potassium phosphate Drugs 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000012456 homogeneous solution Substances 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- -1 polyoxyethylene Polymers 0.000 description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 4
- 235000011008 sodium phosphates Nutrition 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 230000001093 anti-cancer Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CGMRCMMOCQYHAD-UHFFFAOYSA-J dicalcium hydroxide phosphate Chemical compound [OH-].[Ca++].[Ca++].[O-]P([O-])([O-])=O CGMRCMMOCQYHAD-UHFFFAOYSA-J 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Materials For Medical Uses (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention discloses a hydroxyapatite mono-crystal nano-rod capable of forming a special microstructure of plants and a preparation method thereof. The preparation method comprises the following steps: taking soluble phosphate and calcium salt as raw materials; adding a plant template; synthesizing according to a hydrothermal method; ultrasonically washing and drying; placing into a muffle furnace for calcining at high temperature, thereby obtaining bar-shaped hydroxyapatite mono-crystal nano-grains; and stacking the grains, thereby forming the special microstructure of the plants. The mono-crystal nano-rod prepared according to the method provided by the invention has the advantages of 20nm-50nm diameter, 100nm-400nm length, excellent physical and chemical properties, and wide application prospect in the fields of environmental protection material, drug slow release, and the like. The raw materials adopted in the method provided by the invention are low-cost and easy to obtain. The preparation process for the material is simple and is pollution-free to environment.
Description
Technical field
The present invention relates to a kind of monodimension nanometer material and preparation method thereof, being specifically related to a kind of is that Template preparation can form Hydroxyapatite mono-crystal nano-rod of the special microtexture of plant and preparation method thereof with plant, belongs to technical field of material chemistry.
Background technology
Hydroxyapatite, also known as hydroxylapatite, molecular formula is Ca
10(PO
4)
6(OH)
2, be the widely used biological active ceramic material of a class.Because its composition is similar to the inorganic components of living organism bone, thus cause the extensive concern of people.Along with improving constantly of people's understanding, many results of study show, hydroxyapatite be a kind of nontoxic, without carcinogenic, have no side effect and there is the biological active materials of good biocompatibility, the growth of bootable new bone after implanting; People also find that hydroxyapatite has solid alkali performance and stronger ion-exchange capacity, therefore obtain use widely in catalytic carrier, ion-exchange field; Poisonous ion can also be adsorbed simultaneously and there is temperature sensitive, humidity effect.In addition, recent studies have found that, the growth of nanometer hydroxyapatite energy anticancer, is free from side effects to normal cell, for preparation new generation anti-cancer medicament provides new approach.
Hydroxyapatite has much excellent characteristic, except with self character mutually outside the Pass, also have close relationship with its preparation method and microtexture.
The synthetic method of hydroxyapatite is roughly divided into two classes: Dry synthesis and Moist chemical synthesis.Dry method comprises mechanochemical synthesis and microwave fixes synthesis method; Moist chemical synthesis comprises hydrothermal synthesis method, the precipitator method, microemulsion method and sol-gel method etc.The pattern of hydroxyapatite has needle-like, spherical, bar-shaped, sheet etc.
At present, hydroxyapatite monocrystalline is mainly prepared by hydrothermal method, Wang Youfa etc. (silicate circulate a notice of, 2001,2,30-34) with four water-calcium nitrate and DAP for needle-like hydroxyapatite monocrystalline prepared by raw material; Chinese invention (application number 201110116542.1) reports one and has fluorescently-labeled fluoridated hydroxyapatite nanometer monocrystalline shuttle and preparation method thereof, is prepared have fluorescently-labeled nanometer monocrystalline shuttle by doped with rare-earth elements europium and terbium in fluoridated hydroxyapatite preparation process; Chinese invention (application number 201110116552.5) reports the method preparing rare earth doped fluorine hydroxyapatite monocrystal nanowire by hydrothermal method; Liu Huijuan etc., to adopt mechanical attrition method, make ball-milling medium with ethanol, and successfully synthesis has the hydroxyapatite nano sheet of crystalline orientation; Yuxiu Sun etc. (
ceram. Int, 2006,32,951-954) and be that raw material has prepared Hydroxyapatite mono-crystal nano-rod by reverse microemulsion process with polyoxyethylene glycol, cetyl trimethylammonium bromide (CTAB), normal hexane, propyl carbinol, hexanaphthene, four water-calcium nitrate and DAP.
The deficiency that the hydroxyapatite monocrystalline utilizing above-mentioned technology to prepare exists is: hydroxyapatite single crystal particle irregular arrangement, cannot form specific pattern, and specific surface area is less.
Summary of the invention
The object of the present invention is to provide a kind of preparation method taking plant as Template preparation and can form the Hydroxyapatite mono-crystal nano-rod of the special microtexture of plant, with soluble phosphate and calcium salt for raw material, water heat transfer is adopted to go out the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of plant.It is simple that the method has reaction system, and raw material is easy to get, easy to operate, the advantages such as environmentally safe.
For achieving the above object, the technical solution used in the present invention step is as follows:
(1) soluble phosphate is dissolved in deionized water, stirring make it dissolve completely transparent and homogeneous solution, and add plant template wherein, wherein dissolve 0.01-0.5 mole of phosphoric acid salt in often liter of deionized water, in often liter of phosphate solution, add 0.5-15g plant template;
(2) calcium salt of certain mass is added dropwise in above-mentioned aqueous phosphatic while stirring, drip rear continuation and stir 0.1-1h, then ultrasonic 5-10 minute, wherein the mol ratio of Ca:P is 1.67, solution ph is 8-12(sodium hydroxide, potassium hydroxide or ammoniacal liquor adjust ph), the speed of stirring is 200-800rpm;
(3) solution of step (2) is proceeded in hydrothermal synthesis reaction still, at 85-200 DEG C after constant temperature process 10-24h, then naturally cool to room temperature;
(4) solution of filtration step (3) gained, collect filter residue, filter residue ultrapure water supersound washing 15 minutes, then in the baking oven of 65 DEG C dry 12 hours, finally dried sample is put into retort furnace to calcine, namely obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of plant.
Soluble phosphate described in the present invention be phosphoric acid normal salt or/and the acid salt of phosphoric acid, both mixing be arbitrary proportion mixing.
The normal salt of phosphoric acid described in the present invention be sodium phosphate or/and potassiumphosphate, both mixing be arbitrary proportion mixing; The acid salt of phosphoric acid be in disodium-hydrogen, potassium phosphate,monobasic, potassium primary phosphate, Secondary ammonium phosphate one or more arbitrarily than mixture.
The template of plant described in the present invention is the dried plant with macrofiber or dimension pipe.
The template of plant described in the present invention is a kind of in cotton, Herba Eichhorniae root, leaf, chalina, tealeaves.
Plant template can be for subsequent use after convection drying, also can be the salt acid soak 2-24 hour of 1%-8% with massfraction, and be washed till neutrality with ultrapure water, put into baking oven 60 DEG C of dry for standby.
Calcium salt described in the present invention is a kind of in calcium chloride, nitrocalcite, calcium carbonate.
The rate of addition of calcium salt described in the present invention is 1-10ml/min.
Calcining described in the present invention refers at 500-1000 DEG C of pyroprocessing 4-10h.
The Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of plant that the preparation method that another object of the present invention is to provide a kind of Hydroxyapatite mono-crystal nano-rod obtains.
The diameter of monocrystal nano rod described in the present invention is 20-50nm, and length is 100-400nm.
The advantage that the present invention has is as follows:
(1) the inventive method is a kind of simple to operate, reaction conditions is gentle, production cost is low hydrothermal synthesis method, synthesize the Hydroxyapatite mono-crystal nano-rod that can form the special microscopic appearance of plant, and hydroxyapatite nano monocrystalline is pure, therefore can be used for the inducible factor of bone or tooth, to tooth, there is good remineralization, desensitization and whitening function, and can fundamentally preventing dental caries is sick.
(2) water of environment for use friendly of the present invention makees solvent, and do not use any template (tensio-active agent) and organic solvent, so not only simplify reaction system, reduce costs but also can not introduce contaminating impurity environment and convenient for washing, the hydroxylapatite crystal degree that this kind of method obtains is better.
(3) diameter of Hydroxyapatite mono-crystal nano-rod that prepared by the present invention is 20-50nm, and length is 100-400nm, can be used for preparing biological ceramics.
(4) Hydroxyapatite mono-crystal nano-rod prepared by the inventive method has good degree of crystallinity and good dispersiveness, pattern rule, stable performance.
(5) hydroxy apatite powder with the special microtexture of plant be made up of Hydroxyapatite mono-crystal nano-rod provided by the invention is have mesoporous and material that is macropore concurrently, there is larger specific surface area, and by plant template difference regulation and control hydroxyapatite specific surface area.
(6) preparation method that energy composition provided by the invention has the Hydroxyapatite mono-crystal nano-rod of the special microtexture of plant can be applied to the preparation of other inorganics monocrystalline.
(7) Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of plant of the present invention can have wide application in medicament slow release, medical material, catalyzer, sorbent material, antiseptic-germicide etc.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum that can form the Hydroxyapatite mono-crystal nano-rod of the special microtexture of plant that in the present invention prepared by embodiment 1;
Fig. 2 is that in the present invention, embodiment 1 and embodiment 2 are the SEM figure that can form the Hydroxyapatite mono-crystal nano-rod of the special microtexture of plant of plant Template preparation respectively with cotton and chalina, wherein: (a) is cotton is template; B () is chalina is template;
Fig. 3 is the TEM figure that can form the Hydroxyapatite mono-crystal nano-rod of the special microtexture of plant that in the present invention prepared by embodiment 4;
Fig. 4 is the high resolution TEM photo schematic diagram that can form the Hydroxyapatite mono-crystal nano-rod of the special microtexture of plant that in the present invention prepared by embodiment 4;
Fig. 5 is the electron diffraction spectrogram that can form the Hydroxyapatite mono-crystal nano-rod of the special microtexture of plant that in the present invention prepared by embodiment 4.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail, but scope is not limited to described content.
embodiment 1:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) plant template cotton mass percent concentration is the salt acid soak 10 hours of 5%, and is washed till neutrality with ultrapure water, puts into baking oven 60 DEG C of dry for standby;
(2) Secondary ammonium phosphate is dissolved in deionized water, stir make it dissolve completely transparent and homogeneous solution, the concentration of phosphoric acid hydrogen radical ion is 0.01mol/L, adds dry cotton wherein as plant template in the ratio of 0.5g/L;
(3) calcium carbonate is added dropwise in above-mentioned aqueous phosphatic with the speed of 1ml/min while stirring, continues to stir 10min, ultrasonic 5 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 10(sodium hydroxide adjust pH), the speed of stirring is 200rpm;
(4) solution of step (3) is proceeded in hydrothermal synthesis reaction still, at 85 DEG C after constant temperature process 18h, then naturally cool to room temperature;
(5) solution of filtration step (4) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 4h at temperature is 600 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of cotton, see Fig. 2 (a).
Product conforms to standard card (PDF-74-0565) through X-ray diffraction qualification, and prove that product is pure hydroxyapatite, X-ray diffraction result as shown in Figure 1.
By the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of cotton that above-mentioned preparation method obtains, the diameter of its monocrystal nano rod is 20-35nm, and length is 100-200nm.
embodiment 2:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) the plant template chalina salt acid soak 20 hours of massfraction 2%, and be washed till neutrality with ultrapure water, put into baking oven 60 DEG C of dry for standby;
(2) sodium phosphate is dissolved in deionized water, stir make it dissolve completely transparent and homogeneous solution, the concentration of phosphate anion is 0.1mol/L, adds dry chalina wherein as plant template in the ratio of 5g/L;
(3) calcium carbonate is added dropwise in above-mentioned aqueous phosphatic with the speed of 5ml/min while stirring, continues to stir 30min, ultrasonic 8 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 8(potassium hydroxide adjust ph), the speed of stirring is 500rpm;
(4) solution of step (3) is proceeded in hydrothermal synthesis reaction still, at 100 DEG C after constant temperature process 12h, then naturally cool to room temperature;
(5) solution of filtration step (4) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 6h at temperature is 500 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of chalina, as Fig. 2 (b);
By the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of chalina that above-mentioned preparation method obtains, the diameter of its monocrystal nano rod is 20-40nm, and length is 100-250nm.
embodiment 3:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) the plant template leaf salt acid soak 16 hours of massfraction 8%, and be washed till neutrality with ultrapure water, put into baking oven 60 DEG C of dry for standby;
(2) potassiumphosphate is dissolved in deionized water, stir make it dissolve completely transparent and homogeneous solution, the concentration of phosphate anion is 0.05mol/L, adds dry leaf wherein as plant template in the ratio of 1g/L;
(3) calcium carbonate is added dropwise in above-mentioned aqueous phosphatic with the speed of 2ml/min while stirring, continues to stir 45min, ultrasonic 7 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 9(ammoniacal liquor adjust ph), the speed of stirring is 600rpm;
(4) solution of step (3) is proceeded in hydrothermal synthesis reaction still, at 150 DEG C after constant temperature process 10h, then naturally cool to room temperature;
(5) solution of filtration step (4) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 8h at temperature is 700 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of leaf.
By the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of leaf that above-mentioned preparation method obtains, the diameter of its monocrystal nano rod is 20-40nm, and length is 100-250nm.
embodiment 4:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) the plant template tealeaves salt acid soak 18 hours of massfraction 6%, and be washed till neutrality with ultrapure water, put into baking oven 60 DEG C of dry for standby;
(2) potassium primary phosphate is dissolved in deionized water, stir make it dissolve completely transparent and homogeneous solution, the concentration of dihydrogen phosphate ions is 0.2mol/L, adds dry tealeaves wherein as plant template in the ratio of 6g/L;
(3) calcium carbonate is added dropwise in above-mentioned aqueous phosphatic with the speed of 7ml/min while stirring, continues to stir 60min, ultrasonic 10 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 12(sodium hydroxide adjust ph), the speed of stirring is 300rpm;
(4) solution of step (3) is proceeded in hydrothermal synthesis reaction still, at 180 DEG C after constant temperature process 10h, then naturally cool to room temperature;
(5) solution of filtration step (4) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 6h at temperature is 600 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of tealeaves; Material morphology obtains dispersed nano rod maximum diameter by transmission electron microscope results (Fig. 3) and is distributed in as 20-50nm, and length is 100-400nm, is single crystal structure from known its of material high-resolution-ration transmission electric-lens figure (see figure 4); Be single crystal structure from material electronics diffraction spectrogram (Fig. 5) also provable nanometer rod.
By the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of tealeaves that above-mentioned preparation method obtains, the diameter of its monocrystal nano rod is 20-50nm, and length is 100-400nm.
embodiment 5:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) potassium phosphate,monobasic is dissolved in deionized water, stir make it dissolve completely transparent and homogeneous solution, the concentration of phosphoric acid one hydrogen radical ion is 0.25mol/L, adds dry Herba Eichhorniae root wherein as plant template in the ratio of 8g/L;
(2) calcium carbonate is added dropwise in above-mentioned aqueous phosphatic with the speed of 9ml/min while stirring, continues to stir 20min, ultrasonic 6 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 11(sodium hydroxide adjust ph), the speed of stirring is 800rpm;
(3) solution of step (2) is proceeded in hydrothermal synthesis reaction still, at 120 DEG C after constant temperature process 20h, then naturally cool to room temperature;
(4) solution of filtration step (3) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 10h at temperature is 800 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the different microtexture of Herba Eichhorniae Gent.
By the Hydroxyapatite mono-crystal nano-rod that can form the different microtexture of Herba Eichhorniae Gent that above-mentioned preparation method obtains, the diameter of its monocrystal nano rod is 20-40nm, and length is 100-250nm.
embodiment 6:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) disodium-hydrogen is dissolved in deionized water, stir make it dissolve completely transparent and homogeneous solution, the concentration of phosphoric acid one hydrogen radical ion is 0.5mol/L, adds dry cotton wherein as plant template in the ratio of 10g/L;
(2) calcium carbonate is added dropwise in above-mentioned aqueous phosphatic with the speed of 10ml/min while stirring, continues to stir 50min, ultrasonic 9 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 10.5(ammoniacal liquor adjust ph), the speed of stirring is 700rpm;
(3) solution of step (2) is proceeded in hydrothermal synthesis reaction still, at 200 DEG C after constant temperature process 24h, then naturally cool to room temperature;
(4) solution of filtration step (3) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 9h at temperature is 900 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of cotton.
By the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of cotton that above-mentioned preparation method obtains, the diameter of its monocrystal nano rod is 30-50nm, and length is 300-400nm.
embodiment 7:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) SODIUM PHOSPHATE, MONOBASIC is dissolved in deionized water, stir make it dissolve completely transparent and homogeneous solution, the concentration of dihydrogen phosphate ions is 0.05mol/L, adds dry chalina wherein as plant template in the ratio of 3g/L;
(2) nitrocalcite is added dropwise in above-mentioned aqueous phosphatic with the speed of 1ml/min while stirring, continues to stir 55min, ultrasonic 8 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 10.5(ammoniacal liquor adjust ph), the speed of stirring is 400rpm;
(3) solution of step (2) is proceeded in hydrothermal synthesis reaction still, at 200 DEG C after constant temperature process 24h, then naturally cool to room temperature;
(4) solution of filtration step (3) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 5h at temperature is 1000 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of chalina.
By the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of chalina that above-mentioned preparation method obtains, the diameter of its monocrystal nano rod is 30-45nm, and length is 100-250nm.
embodiment 8:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) SODIUM PHOSPHATE, MONOBASIC is dissolved in deionized water, stir make it dissolve completely transparent and homogeneous solution, the concentration of dihydrogen phosphate ions is 0.5mol/L, adds dry tealeaves wherein as plant template in the ratio of 9g/L;
(2) nitrocalcite is added dropwise in above-mentioned aqueous phosphatic with the speed of 3ml/min while stirring, continues to stir 25min, ultrasonic 6 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 10.5(ammoniacal liquor adjust ph), the speed of stirring is 550rpm;
(3) solution of step (2) is proceeded in hydrothermal synthesis reaction still, at 200 DEG C after constant temperature process 24h, then naturally cool to room temperature;
(4) solution of filtration step (3) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 7h at temperature is 650 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of tealeaves.
By the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of tealeaves that above-mentioned preparation method obtains, the diameter of its monocrystal nano rod is 20-40nm, and length is 100-250nm.
embodiment 9:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) sodium phosphate and disodium-hydrogen (1:1 mixing) are dissolved in deionized water, stirring make it dissolve completely transparent and homogeneous solution, in often liter of deionized water, phosphatic molar mass is 0.02 mole, adds dry tealeaves wherein as plant template in the ratio of 5g/L;
(2) calcium chloride is added dropwise in above-mentioned aqueous phosphatic with the speed of 5ml/min while stirring, continues to stir 30min, ultrasonic 5 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 9.5(ammoniacal liquor adjust ph), the speed of stirring is 300rpm;
(3) solution of step (2) is proceeded in hydrothermal synthesis reaction still, at 200 DEG C after constant temperature process 10h, then naturally cool to room temperature;
(4) solution of filtration step (3) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 6h at temperature is 750 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of tealeaves.
By the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of tealeaves that above-mentioned preparation method obtains, its monocrystalline is received
The diameter of rice rod is 25-40nm, and length is 150-300nm.
embodiment 10:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) SODIUM PHOSPHATE, MONOBASIC and potassium phosphate,monobasic (5:1 mixing) are dissolved in deionized water, stirring make it dissolve completely transparent and homogeneous solution, in often liter of deionized water, phosphatic molar mass is 0.05 mole, adds dry cotton wherein as plant template in the ratio of 1g/L;
(2) calcium chloride is added dropwise in above-mentioned aqueous phosphatic with the speed of 3ml/min while stirring, continues to stir 20min, ultrasonic 10 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 10(sodium hydroxide adjust ph), the speed of stirring is 350rpm;
(3) solution of step (2) is proceeded in hydrothermal synthesis reaction still, at 200 DEG C after constant temperature process 10h, then naturally cool to room temperature;
(4) solution of filtration step (3) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 6h at temperature is 900 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of cotton.
By the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of cotton that above-mentioned preparation method obtains, its monocrystalline is received
The diameter of rice rod is 30-50nm, and length is 250-400nm.
embodiment 11:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) primary ammonium phosphate and ammonium hydrogen phosphate (10:1 mixing) are dissolved in deionized water, stirring make it dissolve completely transparent and homogeneous solution, in often liter of deionized water, phosphatic molar mass is 0.04 mole, adds dry cotton wherein as plant template in the ratio of 4g/L;
(2) calcium chloride is added dropwise in above-mentioned aqueous phosphatic with the speed of 2ml/min while stirring, continues to stir 45min, ultrasonic 5 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 11(potassium hydroxide adjust ph), the speed of stirring is 600rpm;
(3) solution of step (2) is proceeded in hydrothermal synthesis reaction still, at 200 DEG C after constant temperature process 10h, then naturally cool to room temperature;
(4) solution of filtration step (3) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 10h at temperature is 800 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of cotton.
By the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of cotton that above-mentioned preparation method obtains, its monocrystalline is received
The diameter of rice rod is 25-50nm, and length is 250-400nm.
embodiment 12:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) sodium phosphate and primary ammonium phosphate (1:10 mixing) are dissolved in deionized water, stirring make it dissolve completely transparent and homogeneous solution, in often liter of deionized water, phosphatic molar mass is 0.02 mole, adds dry chalina wherein as plant template in the ratio of 6g/L;
(2) calcium chloride is added dropwise in above-mentioned aqueous phosphatic with the speed of 6ml/min while stirring, continues to stir 25min, ultrasonic 8 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 12(ammoniacal liquor adjust ph), the speed of stirring is 800rpm;
(3) solution of step (2) is proceeded in hydrothermal synthesis reaction still, at 200 DEG C after constant temperature process 10h, then naturally cool to room temperature;
(4) solution of filtration step (3) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 4h at temperature is 500 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of chalina.
By the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of chalina that above-mentioned preparation method obtains, the diameter of its monocrystal nano rod is 20-40nm, and length is 100-250nm.
embodiment 13:a preparation method for Hydroxyapatite mono-crystal nano-rod, concrete operations are as follows:
(1) potassium phosphate,monobasic sodium and SODIUM PHOSPHATE, MONOBASIC (1:20 mixing) are dissolved in deionized water, stirring make it dissolve completely transparent and homogeneous solution, in often liter of deionized water, phosphatic molar mass is 0.2 mole, adds dry Herba Eichhorniae root wherein as plant template in the ratio of 15g/L;
(2) calcium chloride is added dropwise in above-mentioned aqueous phosphatic with the speed of 1ml/min while stirring, continues to stir 15min, ultrasonic 7 minutes; Wherein the mol ratio of Ca:P is 1.67, and solution ph is 10.5(ammoniacal liquor adjust ph), the speed of stirring is 700rpm;
(3) solution of step (2) is proceeded in hydrothermal synthesis reaction still, at 200 DEG C after constant temperature process 10h, then naturally cool to room temperature;
(4) solution of filtration step (3) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, drying 12 hours in the baking oven of 65 DEG C; Finally dried sample is put into retort furnace and calcine 4h at temperature is 600 DEG C, obtain the Hydroxyapatite mono-crystal nano-rod that can form the different microtexture of Herba Eichhorniae Gent.
By the Hydroxyapatite mono-crystal nano-rod that can form the different microtexture of Herba Eichhorniae Gent that above-mentioned preparation method obtains, the diameter of its monocrystal nano rod is 20-40nm, and length is 150-400nm.
Claims (8)
1. a preparation method for Hydroxyapatite mono-crystal nano-rod, is characterized in that comprising the steps:
(1) soluble phosphate is dissolved in deionized water, stirs and make it dissolve completely, and add plant template wherein, wherein dissolve 0.01-0.5 mole of phosphoric acid salt in often liter of deionized water, in often liter of phosphate solution, add 0.5-15g plant template;
(2) be added dropwise to while stirring in aqueous phosphatic by calcium salt, drip rear continuation and stir 0.1-1h, then ultrasonic 5-10 minute, wherein stirring velocity is the mol ratio of 200-800rpm, Ca:P is 1.67, and solution ph is 8-12;
(3) solution of step (2) is proceeded in hydrothermal reaction kettle, at 85-200 DEG C after constant temperature process 10-24h, naturally cool to room temperature;
(4) solution of filtration step (3) gained, collects filter residue, filter residue ultrapure water supersound washing 15 minutes, then in the baking oven of 65 DEG C dry 12 hours; Finally dried sample is carried out high-temperature calcination, namely obtain the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of plant;
The rate of addition of described calcium salt is 1-10ml/min;
Described plant template is the dried plant with macrofiber or dimension pipe.
2. the preparation method of Hydroxyapatite mono-crystal nano-rod according to claim 1, is characterized in that: soluble phosphate is that phosphoric acid normal salt is or/and the acid salt of phosphoric acid.
3. the preparation method of Hydroxyapatite mono-crystal nano-rod according to claim 2, it is characterized in that: phosphoric acid normal salt be sodium phosphate or/and potassiumphosphate, the acid salt of phosphoric acid be in disodium-hydrogen, potassium phosphate,monobasic, potassium primary phosphate, Secondary ammonium phosphate one or more arbitrarily than mixture.
4. the preparation method of Hydroxyapatite mono-crystal nano-rod according to claim 1, it is characterized in that: plant template is a kind of in cotton, Herba Eichhorniae root, leaf, chalina, tealeaves, plant template massfraction is the salt acid soak 2-24 hour of 1-8%, and be washed till neutrality with ultrapure water, put into baking oven 60 DEG C of dry for standby.
5. the preparation method of Hydroxyapatite mono-crystal nano-rod according to claim 1, is characterized in that: calcium salt is a kind of in calcium chloride, nitrocalcite, calcium carbonate.
6. the preparation method of Hydroxyapatite mono-crystal nano-rod according to claim 1, is characterized in that: calcining refers at 500-1000 DEG C of pyroprocessing 4-10h.
7. the Hydroxyapatite mono-crystal nano-rod that can form the special microtexture of plant of preparation method's acquisition of Hydroxyapatite mono-crystal nano-rod described in claim 1.
8. Hydroxyapatite mono-crystal nano-rod according to claim 7, is characterized in that: the diameter of described monocrystal nano rod is 20-50nm, and length is 100-400nm.
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| CN109205581B (en) * | 2018-08-29 | 2022-04-22 | 湖北大学 | Preparation method of composite hydroxyapatite powder with photo-thermal synergistic antibacterial property |
| CN109110740B (en) * | 2018-10-26 | 2021-11-19 | 南昌航空大学 | Green method for preparing calcium hydroxy phosphate nano-rod |
| CN112645297A (en) * | 2020-12-14 | 2021-04-13 | 东南大学 | Method for preparing nano-hydroxyapatite with assistance of segmented pulse ultrasound |
| CN113213632B (en) * | 2021-06-15 | 2022-11-25 | 萍乡学院 | Nano-hydroxyapatite loofah sponge composite filler and preparation method and application thereof |
| CN113415792A (en) * | 2021-07-19 | 2021-09-21 | 陈基施展 | Preparation method of fluorescent terbium-doped hydroxyapatite nanorod water-based lyotropic liquid crystal |
| CN114797915A (en) * | 2022-04-15 | 2022-07-29 | 苏州大学 | Hydroxyapatite, preparation method thereof and application of hydroxyapatite in piezoelectric catalytic degradation of organic pollutants in water |
| CN115154657B (en) * | 2022-07-12 | 2023-12-26 | 山东大学齐鲁医院 | Hydroxyapatite nanorod and application thereof in bone defect repair field |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1821061A (en) * | 2006-02-22 | 2006-08-23 | 福建师范大学 | Method for prenaring spherical hydroxy-apatite nano crystal |
| CN102079514A (en) * | 2009-11-26 | 2011-06-01 | 宁波大学 | Preparation method of hydroxyapatite nanocrystal |
| CN102153059A (en) * | 2011-04-13 | 2011-08-17 | 上海师范大学 | Method for preparing monodisperse hydroxyapatite by taking blue algae as template |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1821061A (en) * | 2006-02-22 | 2006-08-23 | 福建师范大学 | Method for prenaring spherical hydroxy-apatite nano crystal |
| CN102079514A (en) * | 2009-11-26 | 2011-06-01 | 宁波大学 | Preparation method of hydroxyapatite nanocrystal |
| CN102153059A (en) * | 2011-04-13 | 2011-08-17 | 上海师范大学 | Method for preparing monodisperse hydroxyapatite by taking blue algae as template |
Non-Patent Citations (4)
| Title |
|---|
| Biomimetic Synthesis of hierarchical crystalline hydroxyapatite fibers in large-scale;Chaogang Xing et al;《Materials Research Bulletin》;20120222;第47卷(第6期);参见对比文件1第2.1小节"Synthesis"，图6-8 * |
| 微生物模板法制备纳米羟基磷灰石;李正茂;《山东轻工业学院学报》;20080915;第22卷(第3期);第5-6,37页 * |
| 水热条件下纳米羟基磷灰石的取向有序生长;陈景帝;《南京大学学报( 自然科学)》;20090330;第45卷(第2期);第230-233页 * |
| 生物模板法制备纳米羟基磷灰石及其结构研究;陈彰旭;《莆田学院学报》;20090425;第16卷(第2期);第83-86页 * |
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