CN1241879C - Method for forming osteolith class layer on surface of calcium phosphate ceramics - Google Patents
Method for forming osteolith class layer on surface of calcium phosphate ceramics Download PDFInfo
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- CN1241879C CN1241879C CN 200410033613 CN200410033613A CN1241879C CN 1241879 C CN1241879 C CN 1241879C CN 200410033613 CN200410033613 CN 200410033613 CN 200410033613 A CN200410033613 A CN 200410033613A CN 1241879 C CN1241879 C CN 1241879C
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- calcium phosphate
- phosphate ceramic
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- body fluid
- simulated body
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- 239000004068 calcium phosphate ceramic Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- 239000012890 simulated body fluid Substances 0.000 claims abstract description 32
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 21
- 229910052586 apatite Inorganic materials 0.000 claims abstract description 18
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 239000012153 distilled water Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 18
- 238000007654 immersion Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000002000 scavenging effect Effects 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 18
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 102000002260 Alkaline Phosphatase Human genes 0.000 description 6
- 108020004774 Alkaline Phosphatase Proteins 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 235000014653 Carica parviflora Nutrition 0.000 description 2
- 241000243321 Cnidaria Species 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000013096 assay test Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 210000004409 osteocyte Anatomy 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- -1 phosphate anions Chemical class 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 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
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The present invention relates to a method for forming a bone-like apatite layer on the surface of tricalcium phosphate ceramics, which belongs to the technical field of processing activity on the surface of the tricalcium phosphate ceramics. The method comprises the following steps: soaking the tricalcium phosphate ceramics with 1 to 12 mol sodium hydroxide solutions; soaking with simulated body fluid with different concentration; forming the bone-like apatite layer on the surface. The present invention has the advantages of low technology cost, good bioactivity on the surface of the tricalcium phosphate ceramics, and can be used as support materials of artificial bones and bone tissue engineering in clinical medicine.
Description
Technical field
The invention belongs to calcium phosphate ceramic surface-active-treatment technical field, particularly a kind of method that makes the calcium phosphate ceramic surface form bone like apatite layer.
Background technology
The inorganic components of the chemical constitution of calcium phosphate ceramic and human body bone is close, has excellent biological compatibility, is the very important bone impairment renovation material of a class.The preparation method of calcium phosphate ceramic mainly contains synthetic method, coral conversion method and nature bone calcination method etc., all to handle in the method for preparing process through the high temperature sintering about 1000 ℃, thereby the biological activity of calcium phosphate ceramic is reduced, implant as medical material, influenced cell and adhesion, propagation and the growth organized thereon.Activity is carried out on the calcium phosphate biological ceramic surface handle, make its surface form the bone like apatite layer close with inorganic components with the human body bone structure, the application in clinical medicine has important practical value for calcium phosphate ceramic.At present, at " biomedical engineering magazine " 2002 the 19th volumes the 2nd phase 186-190 page or leaf, Duan Yourong etc. have delivered exercise question and have been " the influence research that fine and close CaP ceramic surface pattern forms bone like apatite layer in dynamic simulation body fluid ", in this article, reported calcium phosphate ceramic has been soaked, formed the method for bone like apatite layer on the calcium phosphate ceramic surface with flow simulating body fluid.The device that this method is used is comparatively complicated, technology cost height; The speed that forms osteoid apatite on the calcium phosphate ceramic surface is slow, and quantity is few, and osteoid apatite is inhomogeneous in the calcium phosphate ceramic surface arrangement, has influenced the practical application of calcium phosphate ceramic in clinical medicine.
Summary of the invention
The objective of the invention is in order to overcome the deficiency that above-mentioned calcium phosphate ceramic surface forms the osteoid apatite layer method, provide a kind of calcium phosphate ceramic to form the method for osteoid apatite, before calcium phosphate ceramic is soaked with simulated body fluid, earlier with the aqueous sodium hydroxide solution of 1~12 mole of different concns to the calcium phosphate ceramic surface preparation, and then, make the calcium phosphate ceramic surface form bone like apatite layer through the simulated body fluid immersion treatment.
Technology of the present invention may further comprise the steps:
(1) calcium phosphate ceramic is cleaned up in deionized water or distilled water, in 80~100 ℃ of oven dry;
(2) use analytical pure sodium hydroxide reagent and deionized water or distilled water to prepare the aqueous sodium hydroxide solution of 1~12 volumetric molar concentration;
(3) in 1000 ml deionized water or distilled water, add sodium-chlor (NaCl) 8.00~24.00 grams, sodium bicarbonate (NaHCO
3) 0.35~1.01 gram, Repone K (KCl) 0.23~0.69 gram, dipotassium hydrogen phosphate (K
2HPO
43H
2O) 0.23~0.69 gram, magnesium chloride (MgCl
26H
2O) 0.31~0.93 gram, calcium chloride (CaCl
22H
2O) 0.28g~0.84 gram, sodium sulfate (Na
2SO
4) 0.07~0.21 gram, Tutofusin tris ((CH
2OH)
3CNH
2) 6.06~18.18 grams, prepare simulated body fluid, and the pH value of simulated body fluid is transferred to 7.2~7.4 with the hydrochloric acid soln of 1 volumetric molar concentration;
(4) the cleaned calcium phosphate ceramic of step (1) is placed Glass Containers, add the aqueous sodium hydroxide solution of 1~12 volumetric molar concentration of step (2) preparation, and calcium phosphate ceramic is fully immersed in the aqueous sodium hydroxide solution, normal temperature was placed 2~6 days down;
(5) with the calcium phosphate ceramic after step (4) immersion treatment, clean repeatedly, after the pH value of scavenging solution is 6.5~7.5, in 80~100 ℃ of oven dry with deionized water or distilled water;
(6) calcium phosphate ceramic after step (5) cleaning, the oven dry is placed Glass Containers, the simulated body fluid that adds step (3) preparation, and calcium phosphate ceramic is fully immersed in the simulated body fluid, 36~38 ℃ of temperature, under the condition of humidity 60~90%, immersion treatment 2~20 days, during every 24~48 hours, remove old liquid, change the fresh simulated body fluid of same concentrations;
(7) calcium phosphate ceramic after step (6) processing is taken out, clean up with deionized water or distilled water, in 80~100 ℃ of oven dry.
Characteristics of the present invention:
Treatment process is simple, and cost is low.
Adopt aqueous sodium hydroxide solution that calcium phosphate ceramic is soaked pre-treatment, and then use the simulated body fluid immersion treatment, because the calcium phosphate ceramic surface has great amount of hydroxy group, make calcium ion, phosphate anions etc. are adsorbed on the calcium phosphate ceramic surface easily, thereby make osteoid apatite fast in its surperficial sedimentation velocity, quantity is many, be evenly distributed, the surfactivity height of calcium phosphate ceramic implants this calcium phosphate ceramic, is convenient to osteocyte and new organization in the calcium phosphate ceramic surface adhesion, propagation and growth, also help calcium phosphate ceramic implant back and the combining of body osseous tissue, the growth of promotion new bone tissue and from the reconstruction of body bone.
Calcium phosphate ceramic after the present invention handles is mainly used in damaged reparation of bone and bone tissue engineering stent material, also can use as the tooth dental repair material.
Embodiment
Embodiment 1
(1) porous calcium phosphate ceramic with the preparation of synthetic method cleans up in deionized water or distilled water, in 80 ℃ of oven dry;
(2) prepare the aqueous sodium hydroxide solution of 12 volumetric molar concentrations with analytical pure sodium hydroxide reagent and deionized water or distilled water;
(3) in 1000 ml deionized water or distilled water, add sodium-chlor (NaCl) 24.00 grams, sodium bicarbonate (NaHCO
3) 1.01 grams, Repone K (KCl) 0.69 gram, dipotassium hydrogen phosphate (K
2HPO
43H
2O) 0.69 gram, magnesium chloride (MgCl
26H
2O) 0.93 gram, calcium chloride (CaCl
22H
2O) 0.84 gram, sodium sulfate (Na
2SO
4) 0.21 gram, Tutofusin tris ((CH
2OH)
3CNH
2) 18.18 grams, prepare simulated body fluid, and the pH value of simulated body fluid is transferred to 7.2~7.4, the preparation simulated body fluid with the hydrochloric acid soln of 1 volumetric molar concentration;
(4) the cleaned calcium phosphate ceramic of step (1) is placed Glass Containers, add the aqueous sodium hydroxide solution of 12 volumetric molar concentrations of step (2) preparation, and calcium phosphate ceramic is fully immersed in the aqueous sodium hydroxide solution, normal temperature was placed 6 days down;
(5) with the calcium phosphate ceramic after step (4) immersion treatment, clean repeatedly, after the pH value of scavenging solution is 6.5~7.5, in 80 ℃ of oven dry with deionized water or distilled water;
(6) calcium phosphate ceramic after step (5) cleaning, the oven dry is placed Glass Containers, the simulated body fluid that adds step (3) preparation, and calcium phosphate ceramic is fully immersed in the simulated body fluid, be placed on 36~37 ℃ of temperature, in the thermostat container of humidity 60~70%, immersion treatment 18 days, during every 48 hours, remove old liquid, change the fresh simulated body fluid of same concentrations;
(7) set by step after handle (6), calcium phosphate ceramic is taken out, clean up,,, show on the calcium phosphate ceramic surface to have formed bone like apatite layer by scanning electron microscopic observation and Infrared spectroscopy in 80 ℃ of oven dry with deionized water or distilled water.
Embodiment 2
(1) porous calcium phosphate ceramic with the preparation of coral conversion method cleans up in deionized water or distilled water, in 90 ℃ of oven dry;
(2) prepare the aqueous sodium hydroxide solution of 8 volumetric molar concentrations with analytical pure sodium hydroxide reagent and deionized water or distilled water;
(3) in 1000 ml deionized water or distilled water, add sodium-chlor (NaCl) 12.00 grams, sodium bicarbonate (NaHCO
3) 0.525 gram, Repone K (KCl) 0.345 gram, dipotassium hydrogen phosphate (K
2HPO
43H
2O) 0.345 gram, magnesium chloride (MgCl
26H
2O) 0.465 gram, calcium chloride (CaCl
22H
2O) 0.42 gram, sodium sulfate (Na
2SO
4) 0.105 gram, Tutofusin tris ((CH
2OH)
3CNH
2) 9.09 grams, prepare simulated body fluid, and the pH value of simulated body fluid is transferred to 7.2~7.4 with the hydrochloric acid soln of 1 volumetric molar concentration; The preparation simulated body fluid;
(4) the cleaned calcium phosphate ceramic of step (1) is placed Glass Containers, add the aqueous sodium hydroxide solution of 8 volumetric molar concentrations of step (2) preparation, and calcium phosphate ceramic is fully immersed in the aqueous sodium hydroxide solution, normal temperature was placed 4 days down;
(5) with the calcium phosphate ceramic after step (4) immersion treatment, clean repeatedly, after the pH value of scavenging solution is 6.5~7.5, in 90 ℃ of oven dry with deionized water or distilled water;
(6) with the calcium phosphate ceramic after step (5) cleaning, the oven dry, place Glass Containers, the simulated body fluid that adds step (3) preparation, and calcium phosphate ceramic is fully immersed in the simulated body fluid, be placed on 36~37 ℃ of temperature, in the thermostat container of humidity 70~80%, immersion treatment 10 days, every 36 hours, remove old liquid during this time, change the fresh simulated body fluid of same concentrations;
(7) set by step after handle (6), calcium phosphate ceramic is taken out, clean up,,, show on the calcium phosphate ceramic surface to have formed bone like apatite layer by scanning electron microscopic observation and Infrared spectroscopy in 90 ℃ of oven dry with deionized water or distilled water.
Embodiment 3
(1) porous calcium phosphate ceramic with the preparation of nature bone calcination method cleans up in deionized water or distilled water, in 100 ℃ of oven dry;
(2) prepare the aqueous sodium hydroxide solution of 1 volumetric molar concentration with analytical pure sodium hydroxide reagent and deionized water or distilled water;
(3) in 1000 ml deionized water or distilled water, add sodium-chlor (NaCl) 8.00 grams, sodium bicarbonate (NaHCO
3) 0.35 gram, Repone K (KCl) 0.23 gram, dipotassium hydrogen phosphate (K
2HPO
43H
2O) 0.23 gram, magnesium chloride (MgCl
26H
2O) 0.31 gram, calcium chloride (CaCl
22H
2O) 0.28g gram, sodium sulfate (Na
2SO
4) 0.07 gram, Tutofusin tris ((CH
2OH)
3CNH
2) 6.06 grams, prepare simulated body fluid, and the pH value of simulated body fluid is transferred to 7.2~7.4, the preparation simulated body fluid with the hydrochloric acid soln of 1 volumetric molar concentration;
(4) the cleaned calcium phosphate ceramic of step (1) is placed Glass Containers, add the aqueous sodium hydroxide solution of 1 volumetric molar concentration of step (2) preparation, and calcium phosphate ceramic is fully immersed in the aqueous sodium hydroxide solution, normal temperature was placed 2 days down;
(5) with the calcium phosphate ceramic after step (4) immersion treatment, clean repeatedly, after the pH value of scavenging solution is 6.5~7.5, in 100 ℃ of oven dry with deionized water or distilled water;
(6) the calcium phosphate ceramic material after step (5) cleaning, the oven dry is placed Glass Containers, the simulated body fluid that adds step (3) preparation, and calcium phosphate ceramic is fully immersed in the simulated body fluid, be placed on 36~37 ℃ of temperature, in the thermostat container of humidity 80~90%, immersion treatment 3 days, during every 24 hours, remove old liquid, change the fresh simulated body fluid of same concentrations;
(7) set by step after handle (6), calcium phosphate ceramic is taken out, clean up,,, show on the calcium phosphate ceramic surface to have formed bone like apatite layer by scanning electron microscopic observation and Infrared spectroscopy in 100 ℃ of oven dry with deionized water or distilled water.
Scleroblast is inoculated in the calcium phosphate ceramic of resulting surface generation bone like apatite layer among above-mentioned three embodiment, vitro culture 7 days, competence for added value with the mtt assay test cell, vitro culture 14 days, measure alkaline phosphatase activities (ALP), the result is as shown in table 1, this shows, the competence for added value of cell and alkaline phosphatase activities all than under the similarity condition without the present invention handle to calcium phosphate ceramic height in the same old way.
The MTT absorbance of the compound cultivation of table 1 calcium phosphate ceramic/scleroblast and ALP value
Embodiment 1 | Embodiment 2 | Embodiment 3 | To in the same old way | |
Mtt assay records absorbance | 1.245 | 0.823 | 2.014 | 0.508 |
Alkaline phosphatase (ALP) (U/L) | 16.451 | 15.523 | 18.264 | 10.825 |
Claims (1)
1, a kind of method of calcium phosphate ceramic surface formation bone like apatite layer, technology may further comprise the steps:
(1) calcium phosphate ceramic is cleaned up in deionized water or distilled water, in 80~100 ℃ of oven dry;
(2) use analytical pure sodium hydroxide reagent and deionized water or distilled water to prepare the aqueous sodium hydroxide solution of 1~12 volumetric molar concentration;
(3) in 1000 ml deionized water or distilled water, add 8.00~24.00 gram NaCl, 0.35~1.01 gram NaHCO
3, 0.23~0.69 gram KCl, 0.23~0.69 gram K
2HPO
43H
2O, 0.31~0.93 gram MgCl
26H
2O, 0.28g~0.84 gram CaCl
22H
2O, 0.07~0.21 gram Na
2SO
4, 6.06~18.18 gram (CH
2OH)
3CNH
2, prepare simulated body fluid, and the pH value of simulated body fluid be transferred to 7.2~7.4 with the hydrochloric acid soln of 1 volumetric molar concentration;
(4) the cleaned calcium phosphate ceramic of step (1) is placed Glass Containers, add the aqueous sodium hydroxide solution of 1~12 volumetric molar concentration of step (2) preparation, and calcium phosphate ceramic is fully immersed in the aqueous sodium hydroxide solution, normal temperature was placed 2~6 days down;
(5) with the calcium phosphate ceramic after step (4) immersion treatment, clean repeatedly, after the pH value of scavenging solution is 6.5~7.5, in 80~100 ℃ of oven dry with deionized water or distilled water;
(6) calcium phosphate ceramic after step (5) cleaning, the oven dry is placed Glass Containers, the simulated body fluid that adds step (3) preparation, and calcium phosphate ceramic is fully immersed in the simulated body fluid, 36~38 ℃ of temperature, under the condition of humidity 60~90%, immersion treatment 2~20 days, during every 24~48 hours, remove old liquid, change the fresh simulated body fluid of same concentrations;
(7) calcium phosphate ceramic after step (6) processing is taken out, clean up with deionized water or distillation, in 80~100 ℃ of oven dry.
Priority Applications (1)
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CN 200410033613 CN1241879C (en) | 2004-04-13 | 2004-04-13 | Method for forming osteolith class layer on surface of calcium phosphate ceramics |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 200410033613 CN1241879C (en) | 2004-04-13 | 2004-04-13 | Method for forming osteolith class layer on surface of calcium phosphate ceramics |
Publications (2)
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CN1562894A CN1562894A (en) | 2005-01-12 |
CN1241879C true CN1241879C (en) | 2006-02-15 |
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CN 200410033613 Expired - Fee Related CN1241879C (en) | 2004-04-13 | 2004-04-13 | Method for forming osteolith class layer on surface of calcium phosphate ceramics |
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Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PT2445543E (en) * | 2009-06-23 | 2013-04-03 | Geistlich Pharma Ag | Bone substitute material |
CN103341206B (en) * | 2013-06-09 | 2014-11-19 | 四川大学 | Calcium phosphate/collagen/bone-like apatite three-level bionic bone tissue engineering scaffold and preparation method thereof |
CN107050508B (en) * | 2017-01-19 | 2020-12-18 | 深圳清华大学研究院 | Injectable bone repair material and preparation method thereof |
CN107141022B (en) * | 2017-04-14 | 2020-08-18 | 华南理工大学 | Whitlockite coating constructed on surface of calcium phosphate biological ceramic matrix and preparation method thereof |
CN107397977B (en) * | 2017-08-03 | 2021-01-26 | 广东工业大学 | 3D printing metal matrix surface modification method, 3D printing metal matrix biological ceramic support and preparation method thereof |
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