CN103011115A - Hydroxyapatite whisker and preparation method thereof - Google Patents
Hydroxyapatite whisker and preparation method thereof Download PDFInfo
- Publication number
- CN103011115A CN103011115A CN2012105287456A CN201210528745A CN103011115A CN 103011115 A CN103011115 A CN 103011115A CN 2012105287456 A CN2012105287456 A CN 2012105287456A CN 201210528745 A CN201210528745 A CN 201210528745A CN 103011115 A CN103011115 A CN 103011115A
- Authority
- CN
- China
- Prior art keywords
- whisker
- crystal whisker
- hydroxyapatite crystal
- hydroxyapatite
- ammonium phosphate
- 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 45
- 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 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 11
- 210000000988 bone and bone Anatomy 0.000 abstract description 5
- 239000005548 dental material Substances 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000278 osteoconductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Landscapes
- Materials For Medical Uses (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a preparation method of hydroxyapatite whisker. According to the method, urea and HA whisker seed crystal are adopted as additives, and the temperature, pH value and reaction time of a reaction system are controlled, so as to prepare the hydroxyapatite whisker with stable yield. The method has the advantages that the process is simple, the operation is convenient, the yield is stable, and the obtained product is excellent in performance and can be used in the field of bio-engineering materials such as bone tissue engineering scaffold materials and dental materials.
Description
Technical field
The present invention relates to a kind of novel hydroxyapatite whisker and preparation method thereof, belong to chemistry and biological engineering material field.
Background technology
Hydroxyapatite (Ca
10(PO
4)
6(OH)
2), be called for short HA or HAP, to the organism osseous tissue similar chemical composition and structure is arranged, have good bio-compatibility and biological activity, behind the implant into body to organizing the toxic side effect such as non-stimulated and repulsion, and have good osteoconductive, can on being organized in the interface, form very strong chemical key and be combined, so hydroxyapatite is widely used in the biological and medicinal implant material field.But HAP compares with skeleton that fragility is large, intensity is low, and its relatively poor mechanical property has limited its use at human body loading position greatly, only can be applied to nonbearing small-sized planting body, and is damaged etc. such as artificial dentary, otica, filling bone.
There are some researches show, whisker is compared with non-whisker, the HAP of crystal whisker-shaped has high specific strength, high ratio modulus, better creep resistance and high-temperature behavior, rely on bridge joint, the crack deflection of whisker and extract effect and absorb energy, eliminate the stress that crack tip is concentrated, make stress in whisker by load transmission, thus the suffered stress of body material around reducing, reach the purpose of the toughness that strengthens biomaterial, thereby can effectively improve the mechanical mechanics property of material.Based on above advantage, the HAP whisker is doped in the material usually for the preparation of the damaged repair materials of trunk bone.
The preparation method of HA whisker mainly contains solid reaction process, sol-gel method, hydrothermal method and homogeneous precipitation method.Yoshimura prepares whisker with solid reaction process, although the whisker integrity of solid reaction process preparation is better, process is complicated, long reaction time, and condition is wayward.The sol-gel method temperature of reaction is low, and preparation technology is simple, but the HAP whisker degree of crystallinity of preparation is relatively poor, the Ca/P mol ratio is on the low side, easily reunites, and whisker chemical stability when pyroprocessing is bad, the cost of material of reaction use is higher in addition, productive rate is low, and organic solvent also has certain toxicity.Hydrothermal method is at first proposed by Kinoshita, and the HA whisker of preparation is crystalline state directly, need not the sintering crystallization, and is few without reuniting or reuniting, epigranular, and the form comparison rule, but higher to the requirement of instrument, restricted industrial production.The usefulness homogeneous precipitation methods such as Zhang H Q are prepared long and the larger HA whisker of length-to-diameter ratio in weakly acidic solution, but the homogeneous precipitation method speed of response is slower, synthetic HA contains calcium defect more, is difficult to synthetic HA crystal with standard chemical metering, and output is also unstable.Therefore, study a kind of method of production high quality HA whisker of efficient stable, attracting investigator's sight always.
Summary of the invention
The object of the invention is to provide a kind of preparation method of hydroxyapatite crystal whisker, the method guides the growth of hydroxyapatite crystal whisker with the hydroxyapatite crystal whisker seed crystal, adopt a step method of temperature-control by, and be aided with the hydroxyapatite crystal whisker that auxiliary agent prepares stable yield, preparation method's technique is simple, with low cost, products obtained therefrom excellent property purity is high, quality product and stable yield, and have excellent biocompatibility and good mechanical property, for further developing with application of hydroxyapatite crystal whisker provides the foundation.
The present invention realizes the object of the invention by following concrete scheme:
(1) in being housed, the reactor of distilled water adds successively four water-calcium nitrate, Secondary ammonium phosphate, after the mixing, add urea, speed with 2000～3500r/min stirred 8～15 minutes, add concentrated nitric acid and regulate the pH value at 2.5～4, continue to stir 25～40 minutes, add the hydroxyapatite crystal whisker seed crystal, continue to stir 25～45 minutes, wherein the mass ratio of four water-calcium nitrate and Secondary ammonium phosphate is 2.5～3.0:1, the mass ratio of urea and Secondary ammonium phosphate is 3.0～5.5:1, and the mass ratio of whisker seed crystal and Secondary ammonium phosphate is 0.01～0.06:1, and the mass ratio of distilled water and Secondary ammonium phosphate is 75～78:1;
(2) solution behind the mixing is placed 92 ℃～95 ℃ water-bath isothermal reaction 12～36 hours, reaction naturally cools to room temperature after finishing, ageing 0.5～12 hour, take out the reaction product of precipitation, clean 5 times with distilled water, obtain the whisker filter cake behind the suction filtration, lower dry at 45～80 ℃ at last, 10～20 hours, namely obtain hydroxyapatite crystal whisker.
The hydroxyapatite crystal whisker seed crystal is template among the present invention, and guiding hydroxyapatite crystal whisker crystallization nucleation is also grown up, and behind the adding seed crystal, the purity of hydroxyapatite crystal whisker and output increase.
The hydroxyapatite crystal whisker seed crystal is to prepare with reference to disclosed method in " the hydro-thermal preparation of the auxiliary lower hydroxyapatite crystal whisker of sorbyl alcohol " among the present invention.
Another purpose of the present invention provides a kind of hydroxyapatite crystal whisker, and its whisker aspect ratio distribution scope is 8～120.
The present invention has the following advantages:
1, the inventive method is carried out under normal pressure, and technique is simple, and operational safety is simple, settles at one go;
2, the product performance that prepare by present method are good, and the purity of HA whisker is high, and impurity is few, stable yield;
3, the biocompatibility of HA whisker and active good can be used for the biological engineering material fields such as bone tissue engineering stent material and dental material.
Description of drawings
Fig. 1 is the XRD figure spectrum that does not add the whisker that the hydroxyapatite crystal whisker seed crystal makes;
Fig. 2 is the XRD figure spectrum of hydroxyapatite crystal whisker embodiment 2 of the present invention;
Fig. 3 is the SEM photo of hydroxyapatite crystal whisker embodiment 2 of the present invention;
Fig. 4 is the length-to-diameter ratio statistical Butut of hydroxyapatite crystal whisker embodiment 2 of the present invention.
Embodiment
Below by embodiment the present invention is described in further detail, but protection domain of the present invention is not limited to described content.
Embodiment 1: the preparation method of hydroxyapatite crystal whisker, and concrete operations are as follows:
(1) in the reactor that 400ml distilled water is housed, adds successively 15.8472g four water-calcium nitrate, 5.2824g Secondary ammonium phosphate, after the mixing, add 29.0532g urea, speed with 3500r/min stirred 15 minutes, add concentrated nitric acid and regulate pH value to 2.51, continue to stir 40 minutes, add 0.3169g hydroxyapatite crystal whisker seed crystal, continue to stir 45 minutes;
(2) solution behind the mixing is placed 95 ℃ water-bath isothermal reaction 12 hours, reaction naturally cools to room temperature after finishing, the reaction product that precipitates is taken out in ageing 12 hours, cleans 5 times with distilled water, obtain the whisker filter cake behind the suction filtration, descended dry 10 hours at 80 ℃ at last, namely obtain hydroxyapatite crystal whisker, output is 5.6883g, the aspect ratio distribution scope is 8～120, and average aspect ratio is 32.53.Wherein, the preparation of hydroxyapatite crystal whisker seed crystal is to prepare with reference to the auxiliary method for preparing hydroxyapatite crystal whisker of sorbyl alcohol.
Embodiment 2: the preparation method of hydroxyapatite crystal whisker, and concrete operations are as follows:
(1) in the reactor that 410ml distilled water is housed, adds successively 15.7748g four water-calcium nitrate, 5.2824g Secondary ammonium phosphate, after the mixing, add 24.002g urea, speed with 3000r/min stirred 10 minutes, add concentrated nitric acid and regulate pH value to 3.03, continue to stir 30 minutes, add 0.1015g hydroxyapatite crystal whisker seed crystal, continue to stir 30 minutes
(2) solution behind the mixing is placed 94 ℃ water-bath isothermal reaction 24 hours, reaction naturally cools to room temperature after finishing, and the reaction product that precipitates is taken out in ageing 6 hours, clean 5 times with distilled water, obtain the whisker filter cake behind the suction filtration, descended dry 15 hours at 70 ℃ at last, namely obtain hydroxyapatite crystal whisker, output is 5.6862g, the aspect ratio distribution scope is 8～120, and average aspect ratio is that 32.78(sees Fig. 2-4), the output that does not add the hydroxyapatite crystal whisker seed crystal is that 5.1395g(sees Fig. 1).Fine from the pattern of scheming hydroxyapatite crystal whisker as can be known, the spectrum peak is corresponding with standard spectrum fine, add seed crystal after, the output increase of hydroxyapatite crystal whisker, purity increases.
Embodiment 3: the preparation method of hydroxyapatite crystal whisker, and concrete operations are as follows:
(1) in the reactor that 400ml distilled water is housed, adds successively 13.2065g four water-calcium nitrate, 5.2824g Secondary ammonium phosphate, after the mixing, add 15.8472g urea, speed with 2000r/min stirred 8 minutes, add concentrated nitric acid and regulate pH value to 3.95, continue to stir 25 minutes, add 0.0529g hydroxyapatite crystal whisker seed crystal, continue to stir 25 minutes
(2) solution behind the mixing is placed 92 ℃ water-bath isothermal reaction 36 hours, reaction naturally cools to room temperature after finishing, the reaction product that precipitates is taken out in ageing 0.5 hour, cleans 5 times with distilled water, obtain the whisker filter cake behind the suction filtration, descended dry 20 hours at 45 ℃ at last, namely obtain hydroxyapatite crystal whisker, output is 5.6595g, the aspect ratio distribution scope is 8～120, and average aspect ratio is 32.55.
Claims (2)
1. the preparation method of a hydroxyapatite crystal whisker is characterized in that carrying out as follows:
(1) in being housed, the reactor of distilled water adds successively four water-calcium nitrate, Secondary ammonium phosphate, after the mixing, add urea, speed with 2000～3500r/min stirred 8～15 minutes, add concentrated nitric acid and regulate the pH value at 2.5～4, continue to stir 25～40 minutes, add the hydroxyapatite crystal whisker seed crystal, continue to stir 25～45 minutes, wherein the mass ratio of four water-calcium nitrate and Secondary ammonium phosphate is 2.5～3.0:1, the mass ratio of urea and Secondary ammonium phosphate is 3.0～5.5:1, and the mass ratio of hydroxyapatite crystal whisker seed crystal and Secondary ammonium phosphate is 0.01～0.06:1, and the mass ratio of distilled water and Secondary ammonium phosphate is 75～78:1;
(2) solution behind the mixing is placed 92 ℃～95 ℃ water-bath isothermal reaction 12～36 hours, reaction naturally cools to room temperature after finishing, ageing 0.5～12 hour, take out the reaction product of precipitation, clean 5 times with distilled water, obtain the whisker filter cake behind the suction filtration, lower dry at 45～80 ℃ at last, 10～20 hours, namely obtain hydroxyapatite crystal whisker.
2. the hydroxyapatite crystal whisker that makes of the preparation method of hydroxyapatite crystal whisker claimed in claim 1, it is characterized in that: the aspect ratio distribution scope of hydroxyapatite crystal whisker is 8～120.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105287456A CN103011115A (en) | 2012-12-11 | 2012-12-11 | Hydroxyapatite whisker and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105287456A CN103011115A (en) | 2012-12-11 | 2012-12-11 | Hydroxyapatite whisker and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103011115A true CN103011115A (en) | 2013-04-03 |
Family
ID=47960299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105287456A Pending CN103011115A (en) | 2012-12-11 | 2012-12-11 | Hydroxyapatite whisker and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103011115A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103541006A (en) * | 2013-10-29 | 2014-01-29 | 昆明理工大学 | Preparation method of hydroxyapatite whisker |
| CN103541005A (en) * | 2013-10-31 | 2014-01-29 | 昆明理工大学 | Preparation method of magnetic hydroxylapatite crystal whisker ball |
| CN103585677A (en) * | 2013-10-30 | 2014-02-19 | 四川大学 | HA (hydroxylapatite) micro-nano whisker reinforced calcium phosphate ceramic material and preparation method and application thereof |
| CN106729949A (en) * | 2016-12-16 | 2017-05-31 | 昆明理工大学 | Compound operation suture thread of a kind of absorbable macromolecule/hydroxyapatite crystal whisker and preparation method thereof |
| CN108946690A (en) * | 2018-07-02 | 2018-12-07 | 昆明理工大学 | A kind of preparation method of antibacterial modified hydroxyapatite material |
| CN109809809A (en) * | 2019-03-07 | 2019-05-28 | 华南理工大学 | A kind of construction method of the hexagonal prisms microarray of hydroxyapatite scaffold apparent height orientation |
| CN110885071A (en) * | 2019-12-17 | 2020-03-17 | 衢州学院 | Micron-sized ultra-long calcium-based wormlike micelle template and hydroxy calcium apatite whisker |
| JP2020111484A (en) * | 2019-01-11 | 2020-07-27 | 国立研究開発法人物質・材料研究機構 | Acicular hydroxyapatite particle and method for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102556993A (en) * | 2012-01-06 | 2012-07-11 | 青岛科技大学 | Method of preparing hydroxyapatite with three-dimensional nanoflower structure |
-
2012
- 2012-12-11 CN CN2012105287456A patent/CN103011115A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102556993A (en) * | 2012-01-06 | 2012-07-11 | 青岛科技大学 | Method of preparing hydroxyapatite with three-dimensional nanoflower structure |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103541006A (en) * | 2013-10-29 | 2014-01-29 | 昆明理工大学 | Preparation method of hydroxyapatite whisker |
| CN103541006B (en) * | 2013-10-29 | 2016-06-08 | 昆明理工大学 | A kind of preparation method of hydroxyapatite crystal whisker |
| CN103585677A (en) * | 2013-10-30 | 2014-02-19 | 四川大学 | HA (hydroxylapatite) micro-nano whisker reinforced calcium phosphate ceramic material and preparation method and application thereof |
| CN103585677B (en) * | 2013-10-30 | 2015-09-09 | 四川大学 | A kind of HA micro-nano whisker reinforcement calcium phosphate ceramic material and its preparation method and application |
| CN103541005A (en) * | 2013-10-31 | 2014-01-29 | 昆明理工大学 | Preparation method of magnetic hydroxylapatite crystal whisker ball |
| CN103541005B (en) * | 2013-10-31 | 2016-06-22 | 昆明理工大学 | A kind of preparation method of magnetic hydroxylapatite crystal whisker ball |
| CN106729949A (en) * | 2016-12-16 | 2017-05-31 | 昆明理工大学 | Compound operation suture thread of a kind of absorbable macromolecule/hydroxyapatite crystal whisker and preparation method thereof |
| CN108946690A (en) * | 2018-07-02 | 2018-12-07 | 昆明理工大学 | A kind of preparation method of antibacterial modified hydroxyapatite material |
| JP2020111484A (en) * | 2019-01-11 | 2020-07-27 | 国立研究開発法人物質・材料研究機構 | Acicular hydroxyapatite particle and method for producing the same |
| JP7217937B2 (en) | 2019-01-11 | 2023-02-06 | 国立研究開発法人物質・材料研究機構 | Needle-shaped hydroxyapatite particles and method for producing the same |
| CN109809809A (en) * | 2019-03-07 | 2019-05-28 | 华南理工大学 | A kind of construction method of the hexagonal prisms microarray of hydroxyapatite scaffold apparent height orientation |
| CN110885071A (en) * | 2019-12-17 | 2020-03-17 | 衢州学院 | Micron-sized ultra-long calcium-based wormlike micelle template and hydroxy calcium apatite whisker |
| CN110885071B (en) * | 2019-12-17 | 2021-07-09 | 衢州学院 | Micron-sized ultra-long calcium-based wormlike micelle template and hydroxy calcium apatite whisker |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103011115A (en) | Hydroxyapatite whisker and preparation method thereof | |
| CN103014832A (en) | Strontium-doped hydroxyapatite crystal whisker and preparation method thereof | |
| CN103541006B (en) | A kind of preparation method of hydroxyapatite crystal whisker | |
| CN103585672B (en) | Preparation method of bioglass fiber reinforced hydroxyapatite porous composite material | |
| CN103272269B (en) | Hydroxyapatite/chitosan composite coating and preparation method thereof | |
| CN103086337B (en) | Preparation method of nanometer strontium hydroxyapatite and application thereof | |
| CN102250615B (en) | Fluorine-containing hydroxylapatite single crystal nano shuttle with fluorescence labeling and preparation method thereof | |
| CN102008752B (en) | Porous biphasic calcium phosphate biological scaffold with nano hydroxyapatite coating and preparation method thereof | |
| CN114452439B (en) | Hydroxyapatite/whitlockite bioactive ceramic scaffold consisting of bionic natural bone minerals and preparation method thereof | |
| CN102390823A (en) | Preparation method of nanometer strontium-doped hydroxyapatite powder | |
| CN104117098A (en) | Magnetic hydroxyl apatite/polymer tridimensional porous stent material with oriented magnetic field and preparation method thereof | |
| CN103690996A (en) | Biological compound material based on fish skin collagen and preparation method of biological compound material | |
| CN103342555A (en) | Strontium magnesium-doped nano-hydroxyapatite and preparation method thereof | |
| CN103656756B (en) | Nano-hydroxyapatite/silk fibroin composite membrane material and preparation method thereof | |
| CN107188148A (en) | A kind of method that low temperature calcination prepares α tricalcium phosphates | |
| CN111138186B (en) | Alpha-tricalcium phosphate biological ceramic material and preparation method thereof | |
| CN101716370A (en) | Method for preparing nano doped hydroxylapatite powder | |
| CN101928136A (en) | Method for preparing fluoridated hydroxyapatite and application thereof | |
| CN103073279A (en) | Preparation method for sodium-carbon-silicon composite doped HA biological ceramics | |
| CN106966375B (en) | A kind of hydroxyapatite and preparation method thereof of nano bar-shape structure | |
| CN104909345A (en) | Preparation method for carbonate-doped rod hydroxyapatite powder | |
| CN103803519B (en) | There is the preparation method of the layered porous calcium phosphate powder of micro-nano multilevel hierarchy | |
| CN106747566A (en) | A kind of preparation method of new mg-doped bioceramic porous material | |
| CN104557015A (en) | Preparation method of silicon-doped alpha-tricalcium phosphate ceramic | |
| CN104071764B (en) | A kind of preparation method mixing fluorine, potassium hydroxyapatite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130403 |