CN101857372B - Nanometer metallic in-situ grown and enhanced porous calcium-phosphorus glass ceramic and preparation method thereof - Google Patents
Nanometer metallic in-situ grown and enhanced porous calcium-phosphorus glass ceramic and preparation method thereof Download PDFInfo
- Publication number
- CN101857372B CN101857372B CN201010200945XA CN201010200945A CN101857372B CN 101857372 B CN101857372 B CN 101857372B CN 201010200945X A CN201010200945X A CN 201010200945XA CN 201010200945 A CN201010200945 A CN 201010200945A CN 101857372 B CN101857372 B CN 101857372B
- Authority
- CN
- China
- Prior art keywords
- preparation
- powder
- cao
- porous calcium
- porous
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Glass Compositions (AREA)
Abstract
The invention relates to a nanometer metallic in-situ grown and enhanced porous calcium-phosphorus glass ceramic and a preparation method thereof. The method taking CaO-P2O5-Na2O as a matrix belongs to the technical field of biological ceramics preparation, and is characterized by comprising the following steps: taking a CaO-P2O5-Na2O (CPN) system as the matrix, wherein the mass percent of CaO to P2O5 to Na2O is 50:45:5; mixing glass-ceramic matrix power and a metallic oxide of trace elements containing bone, and adding polyacrylic acid dispersing agent to obtain slurry; and under the protective atmosphere, reducing the metallic oxide by C generated through the splitting of polyurethane foams by a porous foam infusion method so as to obtain the nanometer metallic in-situ grown and enhanced porous calcium-phosphorus glass ceramic. The invention has the advantages that the nanometer metallic in-situ grown and enhanced porous calcium-phosphorus glass ceramic prepared by the method has porosity of 60-83% and compression strength of 10-18MPa, excellent degradation property and can be used for bone tissue defect treating, repairing and the like.
Description
Technical field
The present invention relates to a kind of nanometer metallic in-situ grown and enhanced porous calcium-phosphorus glass pottery and preparation method thereof, belong to the biological ceramics preparing technical field.
Background technology
Calcium phosphorus bio-vitric is a kind of surface active material, has excellent biological compatibility, has no side effect and workability, can form physiology with human body bone or soft tissue under the certain condition and combine.But void content is high low with intensity, and the high contradiction with the biological activity difference of intensity restricts this Development of Materials and application always.
Influencing CaO-P
2O
5-Na
2In bioactive each factor of O system material, some factor can directly influence the biological activity of material, as the microtexture of the kind of interpolation, the crystallization phase of the original composition of material, trace element and content, timbering material etc.In addition, bone tissue engineer also requires support to have the macroporous structure that is interconnected.Pore structure can promote absorption, the propagation of cell, can also provide passage for the liquid-flow in the organism.Yet the raising of void content can be accelerated degraded on the one hand, but also causes the reduction of ultimate compression strength simultaneously.And ultimate compression strength and void content almost exponentially form fall sharply, and therefore how to guarantee that material has under the prerequisite of suitable aperture size and porosity, and the mechanical property of high as far as possible raising material becomes such timbering material key in application problem that limits.Carried out the mechanical strength that a large amount of correlative studys are intended to keep improve on the basis of better degradation property material in recent years, found that the existence of nanophase can significantly improve the intensity of porous material.
The method for preparing the porous glass ceramics material mainly comprises: add pore-forming material method, extrinsion pressing, particle packing method, foam impregnation method, foaming, sol-gel method etc.; Wherein, the foam impregnation method is to prepare one of most widely used method of porous ceramics at present.The unique distinction of this method is the three-dimensional netted skeleton structure of its perforate by the organic foam body, and the pore texture of gained porous ceramics product is intimate identical with used organic foam body, and aperture size also depends primarily on the aperture size of organic foam body.The patent of relevant porous bioglass ceramic preparation is more, as CN20040087429, and gram B2407812 etc.US2004087429 has introduced by adding bioactivity glass and has prepared CaO-SiO as sintering aid
2The method of base calcium phosphate glass-ceramic, average grain size is 10～20nm, has improved the physical strength of material.Japanese Patent JP2005008440 has introduced a kind of C reduction that utilizes in the air, and calcium phosphate glass fibre enhanced method has improved the thermal insulation of material, friction resistant performance etc.JP9087124, JP61072638 and JP19840193477 have introduced by surface treatment and have improved bioactive method, and wherein latter Ca/P atomic ratio is between 0.35～1.7.DE4131212 has introduced metallic substance and the compound method of improving mechanical property of calcium phosphate, and two kinds of materials connect by the crystal boundary glassy phase, have mechanical property and biological activity preferably.The porous calcium phosphate glass that patent DE19744809 introduces is with Ca2KNa (PO
4)
2, Ca
5Na
2(PO
4)
2Or Ca
6Na
3(PO
4)
5Be principal crystalline phase, void content is 33～80%, and dissolution rate is exceedingly fast, and reaches 300～4000 mg/litre/skies.It is 20～90% that United States Patent (USP) 20020035402 report bones are induced the biomaterial total porosity, and mesoporous particle diameter is 0.1～1.5mm.Relevant bibliographical information is also more, as people such as TeixeiraS
[1]Adopted the foam impregnation method under 1300 ℃ of thermal treatment temps, to prepare porous HA support, the macroporous structure that the prepared porous HA support of this method has stable homogeneous, its pore diameter range is at 100～400 μ m, and has microvoid structure on the hole wall, micropore size remains on 1～10 μ m, guaranteed the connectivity between the macropore, timbering material all is made up of HA crystal grain, does not contain other crystallization phase and glassy phase.People such as RamayHR
[2]The gel injection molding combined with the foam impregnation method prepared porous HA support, this is than adopting the microtexture that single method more can the control bracket material, the porous support materials of preparing has homogeneous, the good macroporous structure of connectivity, and pore diameter range remains on 200～400 μ m; At solid load is 50% o'clock, and the support void content reaches 71%, and its ultimate compression strength can reach 5MPa.Up to the present, published thesis and patent all just utilize the template of foams as vesicular structure.
In addition, the bone trace element is promoting aspect the new bone growth irreplaceable effect is arranged.The Zn element can promote sticking of cell significantly and grow, and can promote timbering material at the intravital mineralization rate of machine; Sr can promote osteoblastic formation, suppresses the absorption of osteoclast; MG can change the porosity and the specific surface area of bio-vitric, improves the mechanical property of material.As patent JP19960120556, P19860148177, US4626514 and JP4325442 etc. have introduced mechanical property and the bioactive method that improves bio-vitric by doped with trace elements; US4681633 has introduced by doping bone trace elements zn and has improved intensity and toughness method; US5236495 has introduced the method that the micro-Sr of a kind of usefulness replaces Ca, and the prepared glass shape that is translucent has mechanical property and chemical resistant properties preferably, can be used for the tooth equivalent material.
Above-mentioned porous support is lower because of mechanical strength, only can be difficult to satisfy the mechanical property of load bone, and degradation property be difficult to also be complementary with new bone growth speed as the packing material of bone reparation.Therefore explore a kind of have higher mechanical property and the suitable biological degradability and the preparation method of bioactive biologic bracket material, will help the damaged treatment of bone.
Summary of the invention
And unique distinction of the present invention is with CaO-P
2O
5-Na
2The O system is a matrix, control its microtexture, its key and be that the bone trace element finally is present in the glassy phase with the form of metallics, plays the effect of growth in situ nano metal particles enhanced by adding one or both metal oxides that contain the bone trace element.
Technical scheme of the present invention is as follows:
Nano metal particles growth in situ enhanced porous calcium phosphate glass pottery, it consists of: P
2O
5-CaO-Na
2O-AO-BO, wherein A, B are Zn, Sr or Mg; A, B exist or single existence simultaneously, and A, B are different elements when existing simultaneously.The glass-ceramic void content is 60～83%, and ultimate compression strength is 10～18MPa.
Nano metal particles growth in situ enhanced porous calcium phosphate glass ceramic preparation of the present invention, step is as follows:
1. select P
2O
5-CaO-Na
2The mass percent of O matrix is 50: 45: 5;
2.P
2O
5The preparation of precursor solution: with P
20
5Join in the small molecules organic solvent, be made into concentration for being 0.08～0.21g/ml; Because P
2O
5Emitting big calorimetric during dissolving, thus should slowly add, and temperature is controlled at below 40 ℃, to prevent P
2O
5Volatilization; Mix the back and stir the stable clear solution of formation;
3. the preparation of colloidal sol: calcium salt and sodium salt are splashed into P
2O
5Precursor solution in, fully stir, and regulate between pH value to 7～8 with ammoniacal liquor, ultra-sonic dispersion 10～15 minutes obtains uniform mixed sols;
4. the preparation of gel: with the sealing of the mixed sols of step 3), leave standstill under the room temperature fully react gel; Dry in 60～120 ℃ of baking ovens again, obtain white dry gel powder; This dry gel powder is carried out pre-burning discharge ethanol, obtain pale powder; Sieve, make its grain diameter less than 200 μ m;
5. the preparation of porous support: the metal oxide that in the powder of step 4), adds massfraction (metal oxide is with respect to the massfraction of matrix) respectively or simultaneously and be 1～3%, 2.5～4.0% or 1.5～3.5% bone trace elements zn, Sr or Mg, in mixed powder, add polyacrylic acid dispersant PVA (if massfraction is 5% PVA, the mass ratio of itself and CPN is 1: 2), and regulate pH to 9～10 with ammoniacal liquor, mechanical stirring made slurry in 15～30 minutes; Use immersion process for preparing porous support base substrate then, and at air drying; N
2Handle the porous calcium phosphate glass pottery that obtained the nano metal particles growth in situ in 1～3 hour for 500～750 ℃ in the protective atmosphere.
Described calcium salt is Ca (NO
3)
24H
2O.Sodium salt is CH
3ONa.The metal oxide of Sr is SrO.The metal oxide of Mg is MgO.The metal oxide of Zn is ZnO.
With immersion process for preparing porous support base substrate, used organic foam body structure as shown in Figure 1, and at air drying.N
2Handle that to obtain void content in 1～3 hour be 60～83% for 500～750 ℃ in the protective atmosphere, ultimate compression strength is the porous calcium phosphate glass pottery of the nano metal particles growth in situ of 10～18MPa.
The present invention contains the metal oxide of bone trace element by doping, utilizes the carbon reduction metal oxide that the foam cracking produces under the protective atmosphere, thereby reaches the purpose of nano metal particles reinforcing glass ceramics strength.Porous glass ceramics with the preparation of this method has high compression strength and good degradation property, can be used for that osseous tissue is damaged, reparation etc.
Description of drawings
Fig. 1 is the microstructure of used organic foam body;
Fig. 2 is the stereoscan photograph of porous support;
Fig. 3 mostly is the microstructure of hole support;
Fig. 4 is the XRD figure spectrum after the example 5 sample thermal treatments;
Fig. 5 is not for adding the cell adhesion figure on the micro-porous support;
Fig. 6 cultivates the cell adhesion figure that does not add after 7 days on the micro-porous support;
Fig. 7 is the cell adhesion figure that adds on the micro-porous support;
Fig. 8 cultivates the cell adhesion figure that adds after 7 days on the micro-porous support.
Embodiment
Embodiment 1:CaO-P
2O
5-Na
2O-ZnO system (ZnO%=1～3%)
With P
2O
5, Ca (NO
3)
24H
2O, CH
3ONa, Zn (NO
3)
26H
2O is a raw material, presses the P in the raw material
2O
5-CaO-Na
2The O mass percent is 50: 45: 5, accurately takes by weighing 19.162 gram P
2O
5, 35.423 gram Ca (NO
3)
24H
2O, 2.702 gram CH
3ONa.Prepare P earlier
2O
5Ethanolic soln: with the P that takes by weighing
2O
5Slowly add (because P in the 100ml ethanol
2O
5Emitting big calorimetric during dissolving, thus should slowly add, and temperature is controlled at below 40 ℃, to prevent P
2O
5Volatilization), obtain stable clear solution A.Refabrication Ca (NO
3)
24H
2O, CH
3The ethanolic soln of ONa: the calcium salt and the sodium salt that take by weighing are dissolved in the 90ml ethanol, and stirring obtains solution B.B is slowly added among the A, stir, and regulate pH to 7～8, can obtain transparent even colloidal sol in ultrasonic 10～15 minutes behind the thorough mixing.With prepared mixed sols sealing, at room temperature leave standstill and obtain the form homogeneous gel; Again it is inserted drying in 60～120 ℃ of baking ovens, obtain white dry gel powder.This dry gel powder is carried out pre-burning, obtain pale powder CPN; Sieve, make its grain diameter less than 200 μ m.Taking by weighing 0.810～2.430 gram ZnO by massfraction ZnO%=1～3%, is 5% polyacrylic acid dispersant PVA (mass ratio of PVA and mixed powder is 1: 2) with adding massfraction after the CPN powder mixes.Regulate pH to 9～10 with ammoniacal liquor again, mechanical stirring made mobile suitable slurry in 15～30 minutes; Use immersion process for preparing porous support base substrate (used organic foam body structure is as shown in Figure 1) then, and at air drying.Made base substrate is placed N respectively
2(sealing) 550～750 ℃ heat-treated under the protective atmosphere, and can obtain porosity is 60～64%, and intensity is 11.5～14.0MPa, and average intensity is the porous calcium phosphate glass pottery of 12.5MPa.
Embodiment 2:CaO-P
2O
5-Na
2O-ZnO-SrO system (ZnO%=2%, SrO%=2.5～4.0%)
With P
2O
5, Ca (NO
3)
24H
2O, CH
3ONa, Zn (NO
3)
26H
2O, Sr (NO
3)
2Be raw material, press the P in the raw material
2O
5-CaO-Na
2The O mass percent is 50: 45: 5, accurately takes by weighing 19.162 gram P
2O
5, 35.423 gram Ca (NO
3)
24H
2O, 2.702 gram CH
3ONa.Prepare P earlier
2O
5Ethanolic soln: with the P that takes by weighing
2O
5Slowly add (because P in the 100ml ethanol
2O
5Emitting big calorimetric during dissolving, thus should slowly add, and temperature is controlled at below 40 ℃, to prevent P
2O
5Volatilization), obtain stable clear solution A.Refabrication Ca (NO
3)
24H
2O, CH
3The ethanolic soln of ONa: the calcium salt and the sodium salt that take by weighing are dissolved in the 90ml ethanol, and stirring obtains solution B.B is slowly added among the A, stir, and regulate pH to 7～8, can obtain transparent even colloidal sol in ultrasonic 10～15 minutes behind the thorough mixing.With prepared mixed sols sealing, at room temperature leave standstill and obtain the form homogeneous gel; Again it is inserted drying in 60～120 ℃ of baking ovens, obtain white dry gel powder.This dry gel powder is carried out pre-burning, obtain pale powder CPN, sieve; Make its grain diameter less than 200 μ m.Press massfraction ZnO%=2%, SrO%=2.5～4.0% takes by weighing 1.620 gram ZnO and 2.591～4.145 gram SrO respectively, is 5% polyacrylic acid dispersant PVA (mass ratio of PVA and mixed powder is 1: 2) with adding massfraction after the CPN powder mixes.Regulate pH to 9～10 with ammoniacal liquor again, mechanical stirring made mobile suitable slurry in 15～30 minutes; Use immersion process for preparing porous support base substrate (used organic foam body structure is as shown in Figure 1) then, and at air drying.Made base substrate is placed N respectively
2(sealing) 500～750 ℃ heat-treated under the protective atmosphere, and can obtain void content is 61～79%, and intensity is 10～13MPa, and average intensity is the porous calcium phosphate glass pottery of 12MPa.
Embodiment 3:CaO-P
2O
5-Na
2The O-ZnO-SrO system (ZnO%=2%, SrO%=3%)
With P
2O
5, Ca (NO
3)
24H
2O, CH
3ONa, Zn (NO
3)
26H
2O, Sr (NO
3)
2Be raw material, press the P in the raw material
2O
5-CaO-Na
2The O mass percent is 50: 45: 5, accurately takes by weighing 19.162 gram P
2O
5, 35.423 gram Ca (NO
3)
24H
2O, 2.702 gram CH
3ONa.Prepare P earlier
2O
5Ethanolic soln: with the P that takes by weighing
2O
5Slowly add (because P in the 100ml ethanol
2O
5Emitting big calorimetric during dissolving, thus should slowly add, and temperature is controlled at below 40 ℃, to prevent P
2O
5Volatilization), obtain stable clear solution A.Refabrication Ca (NO
3)
24H
2O, CH
3The ethanolic soln of ONa: the calcium salt and the sodium salt that take by weighing are dissolved in the 90ml ethanol, and stirring obtains solution B.B is slowly added among the A, stir, and regulate pH to 7～8, can obtain transparent even colloidal sol in ultrasonic 10～15 minutes behind the thorough mixing.With prepared mixed sols sealing, at room temperature leave standstill and obtain the form homogeneous gel; Again it is inserted drying in 60～120 ℃ of baking ovens, obtain white dry gel powder.This dry gel powder is carried out pre-burning, obtain pale powder CPN; Sieve, make its grain diameter less than 200 μ m.Press massfraction ZnO%=2%, SrO%=3% takes by weighing 1.620 gram ZnO and 3.109 gram SrO respectively, is 5% polyacrylic acid dispersant PVA (mass ratio of PVA and mixed powder is 1: 2) with adding massfraction after the CPN powder mixes.Regulate pH to 9～10 with ammoniacal liquor again, mechanical stirring made mobile suitable slurry in 15～30 minutes; Use immersion process for preparing porous support base substrate (used organic foam body structure is as shown in Figure 1) then, and at air drying.Made base substrate is placed N respectively
2(sealing) 750 ℃ heat-treated under the protective atmosphere, and can obtain intensity is 13MPa, and porosity is 70% porous calcium phosphate glass pottery.
Embodiment 4:CaO-P
2O
5-Na
2O-SrO-MgO system (SrO%=3%, MgO%=1.5～3.5%)
With P
2O
5, Ca (NO
3)
24H
2O, CH
3ONa, Sr (NO
3)
2, Mg (NO
3)
2Be raw material, press the P in the raw material
2O
5-CaO-Na
2The O mass percent is 50: 45: 5, accurately takes by weighing 19.162 gram P
2O
5, 35.423 gram Ca (NO
3)
24H
2O, 2.702 gram CH
3ONa.Prepare P earlier
2O
5Ethanolic soln: with the P that takes by weighing
2O
5Slowly add (because P in the 100ml ethanol
2O
5Emitting big calorimetric during dissolving, thus should slowly add, and temperature is controlled at below 40 ℃, to prevent P
2O
5Volatilization), obtain stable clear solution A.Refabrication Ca (NO
3)
24H
2O, CH
3The ethanolic soln of ONa: the calcium salt and the sodium salt that take by weighing are dissolved in the 90ml ethanol, and stirring obtains solution B.B is slowly added among the A, stir, and regulate pH to 7～8, can obtain transparent even colloidal sol in ultrasonic 10～15 minutes behind the thorough mixing.With prepared mixed sols sealing, at room temperature leave standstill and obtain the form homogeneous gel; Again it is inserted drying in 60～120 ℃ of baking ovens, obtain white dry gel powder.This dry gel powder is carried out pre-burning, obtain pale powder CPN; Sieve, make its grain diameter less than 200 μ m.Press massfraction SrO%=3%, MgO%=1.5～3.5% takes by weighing 3.109 gram SrO and 0.600～1.400 gram MgO respectively, is 5% polyacrylic acid dispersant PVA (mass ratio of PVA and mixed powder is 1: 2) with adding massfraction after the CPN powder mixes.Regulate pH to 9～10 with ammoniacal liquor again, mechanical stirring made mobile suitable slurry in 15～30 minutes; Use immersion process for preparing porous support base substrate (used organic foam body structure is as shown in Figure 1) then, and at air drying.Made base substrate is placed N respectively
2(sealing) 550～700 ℃ heat-treated under the protective atmosphere, and can obtain porosity is 68～83%, and intensity is 12～18MPa, and average intensity is the porous calcium phosphate glass pottery of 16MPa.
Embodiment 5:CaO-P
2O
5-Na
2The O-SrO-MgO system (SrO%=3%, MgO%=2%)
With P
2O
5, Ca (NO
3)
24H
2O, CH
3ONa, Sr (NO
3)
2, Mg (NO
3)
2Be raw material, press the P in the raw material
2O
5-CaO-Na
2The O mass percent is 50: 45: 5, accurately takes by weighing 19.162 gram P
2O
5, 35.423 gram Ca (NO
3)
24H
2O, 2.702 gram CH
3ONa.Prepare P earlier
2O
5Ethanolic soln: with the P that takes by weighing
2O
5Slowly add (because P in the 100ml ethanol
2O
5Emitting big calorimetric during dissolving, thus should slowly add, and temperature is controlled at below 40 ℃, to prevent P
2O
5Volatilization), obtain stable clear solution A.Refabrication Ca (NO
3)
24H
2O, CH
3The ethanolic soln of ONa: the calcium salt and the sodium salt that take by weighing are dissolved in the 90ml ethanol, and stirring obtains solution B.B is slowly added among the A, stir, and regulate pH to 7～8, can obtain transparent even colloidal sol in ultrasonic 10～15 minutes behind the thorough mixing.With prepared mixed sols sealing, at room temperature leave standstill and obtain the form homogeneous gel; Again it is inserted drying in 60～120 ℃ of baking ovens, obtain white dry gel powder.This dry gel powder is carried out pre-burning, obtain pale powder CPN; Sieve, make its grain diameter less than 200 μ m.Press massfraction SrO%=3%, MgO%=2% takes by weighing 3.109 gram SrO and 0.8 gram MgO respectively, is 5% polyacrylic acid dispersant PVA (mass ratio of PVA and mixed powder is 1: 2) with adding massfraction after the CPN powder mixes.Regulate pH to 9～10 with ammoniacal liquor again, mechanical stirring made mobile suitable slurry in 15～30 minutes; Use immersion process for preparing porous support base substrate (used organic foam body structure is as shown in Figure 1) then, and at air drying.Made base substrate is placed N respectively
2(sealing) 700 ℃ heat-treated under the protective atmosphere, and can obtain intensity is 18MPa, and porosity is 78% porous calcium phosphate glass pottery.The stereoscan photograph of porous support as shown in Figure 2, porous body after heat treatment can obtain to have a large amount of communicating apertures as seen from Figure 2, and has the structure of a large amount of micropores on the hole wall.This makes material when being in physiological environment, for the formation of the dissolving of material intermediate ion and hydroxyapatite provides bigger reaction interface and more nucleation site.This is highly beneficial for the biological activity and the degradation property that improve glass-ceramic.The porous support micro-structure diagram as shown in Figure 3, from figure as can be seen, the hole muscle of material be fine and close glassy phase, and hole wall surface is made of crystallization phase and glassy phase, the embedding of nanocrystal can significantly improve the mechanical property of material in the glass.XRD figure after the sample thermal treatment is composed as shown in Figure 4, and from figure as can be seen, the sample principal crystalline phase is Ca
4P
6O
19Ca
4P
6O
19(its Ca/P ratio is between β-Ca
2P
2O
7And CaP
2O
6Between), also have β-Ca in addition
2P
2O
7And Ca
7Mg
2P
6O
24Existence.
Embodiment 6: Bioexperiment
Embodiment 5 prepared porous ceramicss are carried out cell adhesion, growth and propagation test; Concrete grammar is: the porous support to embodiment 5 carries out high temperature, autoclave sterilization, places the nutrient solution of mice embryonic scleroblast (MC3T3-E1) to carry out cell culture experiments, and incubation time is 7 days.Per 3 days of MC3T3-E1 cell culture fluid is changed once, takes out the porous support sample after 7 days, and with phosphorus base damping fluid (PBS) flushing, observes the mineralising of MC3T3-E1 cell sticking on porous support materials, distribution and phosphatic rock under SEM.Fig. 5 is not for adding the cell adhesion figure on the micro-porous support; Fig. 6 cultivates the cell adhesion figure that does not add after 7 days on the micro-porous support; Can observe some white fine particles from 6, these white fine particles are the support hydroapatite particles that mineralising produces in cell culture fluid.Fig. 7 is the cell adhesion figure that adds on the micro-porous support; Fig. 8 cultivates the cell adhesion figure that adds after 7 days on the micro-porous support.Compare with Fig. 7, can find out obviously that formed apatite particle is no matter on number, tangible increase is still all arranged on particle diameter, and this shows that the glass-ceramic support pair cell ability of sticking behind the interpolation trace element improves, and the mineralization rate of phosphatic rock is obviously strengthened.The shape appearance figure (Fig. 6) of the glass-ceramic support of trace element is not added in contrast, can also obviously observe multi-layer cellular attached on the rack surface, and more firm with adhering to of timbering material, the obvious increase of cell adhesion degree shows that adding trace element can improve sticking of glass-ceramic support pair cell to a great extent.
The partial reference document:
[1]Teixeira?S，Rodriguez?MA，PenaP，etal.Physicalcharacterization?of?hydroxyapatite?porousscaffolds?for?tissue?engineering.Materials?Science?andEngineeringC，2009，29，1510-1514.
[2]Ramay?HR，Zhang?MQ.Preparation?of?porous?hydroxyapatite?scaffolds?by?combination?ofthe?gel-casting?and?polymersponge?me．ods.Biomaterials，2003，24，3293-3302.
Claims (6)
1. nano metal particles growth in situ enhanced porous calcium phosphate glass ceramic preparation, step is as follows:
1) selects P
2O
5-CaO-Na
2The mass percent of O matrix is 50: 45: 5;
2) preparation of precursor solution: with P
2O
5Join in the small molecules organic solvent, being made into concentration is 0.08～0.21g/ml solution; Temperature is controlled at below 40 ℃, mixes the back and stirs the stable clear solution of formation;
3) preparation of colloidal sol: calcium salt and sodium salt are splashed into P
2O
5Precursor solution in, fully stir, and regulate between pH value to 7～8 with ammoniacal liquor, ultra-sonic dispersion 10～15 minutes obtains uniform mixed sols;
4) preparation of gel: with the sealing of the mixed sols of step 3), leave standstill under the room temperature fully react gel; Dry in 60～120 ℃ of baking ovens again, obtain white dry gel powder; This dry gel powder is carried out pre-burning discharge the small molecules organic solvent, obtain pale powder; Sieve, make its grain diameter less than 200 μ m;
5) preparation of porous support: the metal oxide that in the powder of step 4), adds mass percent with respect to matrix respectively or simultaneously and be 1～3%, 2.5～4.0% or 1.5～3.5% bone trace elements zn, Sr or Mg, in mixed powder, add polyacrylic acid dispersant, 5% the polyacrylic acid dispersant and the mass ratio of pale powder are 1: 2, and regulate pH to 9～10 with ammoniacal liquor, mechanical stirring made slurry in 15～30 minutes; Use immersion process for preparing porous support base substrate then, and at air drying; N
2Handle the porous calcium phosphate glass pottery that obtained the nano metal particles growth in situ in 1～3 hour for 500～750 ℃ in the protective atmosphere;
Glass-ceramic consists of: P
2O
5-CaO-Na
2O-AO-BO, wherein A, B are Zn, Sr or Mg; A, B exist or single existence simultaneously, and A, B are different elements when existing simultaneously; The glass-ceramic void content is 60～83%, and ultimate compression strength is 10～18MPa.
2. the method for claim 1 is characterized in that described calcium salt is Ca (NO
3)
24H
2O.
3. the method for claim 1 is characterized in that described sodium salt is CH
3ONa or NaNO
3
4. the method for claim 1, the metal oxide that it is characterized in that described Sr is SrO.
5. the method for claim 1, the metal oxide that it is characterized in that described Mg is MgO.
6. the method for claim 1, the metal oxide that it is characterized in that described Zn is ZnO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010200945XA CN101857372B (en) | 2010-06-17 | 2010-06-17 | Nanometer metallic in-situ grown and enhanced porous calcium-phosphorus glass ceramic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010200945XA CN101857372B (en) | 2010-06-17 | 2010-06-17 | Nanometer metallic in-situ grown and enhanced porous calcium-phosphorus glass ceramic and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101857372A CN101857372A (en) | 2010-10-13 |
| CN101857372B true CN101857372B (en) | 2011-11-30 |
Family
ID=42943568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010200945XA Expired - Fee Related CN101857372B (en) | 2010-06-17 | 2010-06-17 | Nanometer metallic in-situ grown and enhanced porous calcium-phosphorus glass ceramic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101857372B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886073A (en) * | 2012-10-09 | 2013-01-23 | 天津大学 | Biological glass coat for medical magnesium alloy surface and preparation method of biological glass coat |
| CN107185033B (en) * | 2017-06-27 | 2020-09-11 | 广东工业大学 | Anti-infection bioceramic artificial bone and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4871384A (en) * | 1987-04-28 | 1989-10-03 | Hoya Corporation | Process for surface modification of inorganic biomaterial |
| CN1830907A (en) * | 2006-03-20 | 2006-09-13 | 天津大学 | Method for preparing CaO-P2O5-MgO glass reinforced porous beta-tricalcium phosphate bioceramics |
| CN101143718A (en) * | 2007-08-30 | 2008-03-19 | 天津大学 | Method for preparing crystallinity controllable nano hydroxyapatite powder |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63285153A (en) * | 1987-05-15 | 1988-11-22 | Lion Corp | Production of ceramic sintered material |
-
2010
- 2010-06-17 CN CN201010200945XA patent/CN101857372B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4871384A (en) * | 1987-04-28 | 1989-10-03 | Hoya Corporation | Process for surface modification of inorganic biomaterial |
| CN1830907A (en) * | 2006-03-20 | 2006-09-13 | 天津大学 | Method for preparing CaO-P2O5-MgO glass reinforced porous beta-tricalcium phosphate bioceramics |
| CN101143718A (en) * | 2007-08-30 | 2008-03-19 | 天津大学 | Method for preparing crystallinity controllable nano hydroxyapatite powder |
Non-Patent Citations (2)
| Title |
|---|
| JP昭63-285153A 1988.11.22 |
| 姜伟,等.CaO-P205-SrO-MgO-Na20 玻璃陶瓷的析晶控制和微观结构的研究.《稀有金属材料与工程》.2009,第38卷(第增刊2期),814-820. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101857372A (en) | 2010-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103585677B (en) | A kind of HA micro-nano whisker reinforcement calcium phosphate ceramic material and its preparation method and application | |
| CN106310381B (en) | A kind of calcium sulfate porous compound bio bracket of the degradable calcium phosphate-containing magnesium | |
| CN105194728B (en) | A kind of degradable biological porous ceramic film material, preparation method and applications | |
| CN108404203B (en) | Preparation method of reduced graphene oxide/biological glass nanofiber scaffold | |
| CN103585672B (en) | Preparation method of bioglass fiber reinforced hydroxyapatite porous composite material | |
| CN104710188A (en) | Porous calc silicate bioceramic material, preparation method and application | |
| CN114452439B (en) | Hydroxyapatite/whitlockite bioactive ceramic scaffold consisting of bionic natural bone minerals and preparation method thereof | |
| CN107185033A (en) | A kind of anti-infection bio ceramic artificial bone and its application | |
| CN1830907A (en) | Method for preparing CaO-P2O5-MgO glass reinforced porous beta-tricalcium phosphate bioceramics | |
| Valerio et al. | Primary osteoblast cell response to sol-gel derived bioactive glass foams | |
| CN102604146A (en) | Inorganic bioactive material and method for preparing polymer porous composite material | |
| CN102764450B (en) | Cuttlebone transformation series porous composite bio-ceramic, its preparation method and application | |
| KR20090017470A (en) | Osteoinductive calcium phosphates | |
| FU et al. | Zirconia incorporation in 3D printed β-Ca2SiO4 scaffolds on their physicochemical and biological property | |
| CN100591365C (en) | Inorganic resorbable bone substitute material | |
| EP1501771B1 (en) | Method of preparing porous calcium phosphate granules | |
| CN1762897A (en) | Preparation process of degradable foam-like strontium-doped calcium phosphate ceramic bone holder material | |
| CN101857372B (en) | Nanometer metallic in-situ grown and enhanced porous calcium-phosphorus glass ceramic and preparation method thereof | |
| CN108144113A (en) | A kind of porous bone repair material of bioactivity glass and preparation method thereof | |
| Dobriţa et al. | Porous bioceramic scaffolds based on akermanite obtained by 3D printing for bone tissue engineering | |
| CN101050053A (en) | Method for preparing engineering material of bone tissue and application | |
| CN103830774B (en) | A kind of bone cement and preparation method thereof | |
| CN1232472C (en) | Process for preparing self-growing calcium phosphate crystal whisker strengthened porous bioceramic materials | |
| Hesaraki et al. | Investigation of an effervescent additive as porogenic agent for bone cement macroporosity | |
| CN1200043C (en) | Inorganic/organic nano-composite bioactivity porous material and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111130 Termination date: 20120617 |