CN101293112B - Method for preparing biological activity glass nano-fibre cluster - Google Patents
Method for preparing biological activity glass nano-fibre cluster Download PDFInfo
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- CN101293112B CN101293112B CN2008100289887A CN200810028988A CN101293112B CN 101293112 B CN101293112 B CN 101293112B CN 2008100289887 A CN2008100289887 A CN 2008100289887A CN 200810028988 A CN200810028988 A CN 200810028988A CN 101293112 B CN101293112 B CN 101293112B
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Abstract
The invention relates to a preparation method of a bioactive glass nanofiber cluster, which is characterized in that A solution which is composed of tetraethyl orthosilicate and triethyl phosphate and B solution which is composed of calcium nitrate tetrahydrate, deionized water, a template agent and a catalyst are firstly prepared, the B solution is slowly dropped into the A solution to form a sol, the sol forms a gel by aging for 4 to 7 days, the gel is dried for 2 to 3 days at the temperature of 80 to 140 DEG C, and finally the nanofiber cluster material is obtained by heat treatment and solidification process at 400 to 700 DEG C and grinding. The weight percentage of the components of the nanofiber cluster is that: 60 to 80 percent of SiO2, 36 to 16 percent of CaO and 4 percent of P2O5. The bioactive glass nanofiber cluster prepared by the invention is composed of nano-fibers that are regularly arranged, thus showing good biological mineralization characteristics in simulated physiological solution and being used in the fields such as bone tissue repair and bone tissue engineering.
Description
Technical field
The present invention relates to a kind of method that is used to prepare the inorganic particle of biomedical materials field, be specifically related to a kind of method for preparing biological activity glass nano-fibre cluster.
Background technology
Bioactivity glass is a kind of important biological material, but is mostly micron level through the bioactive glass particle of conventional high-temperature fusion method preparation, and in the preparation process, introduces impurity easily.And have a chemical uniformity of special nanometer microstructure, high specific surface area, regulatable composition and structure and molecular level through the bioactivity glass of sol-gel process preparation.This material has good biomineralization performance in simulated body fluid.Cytology and zoopery show that also it has good bone repair ability.And the template self-assembly process is a kind of Technology for preparing extraordinary nano material.The inorganic matter component that natural bone tissue comprises is the acicular nanometer apatite with given shape, and from the angle of nano bionic, people hope that the nano material for preparing has some specific microscopic patterns simultaneously, to investigate its biology performance.Can prepare in conjunction with sol-gel and template self-assembly process and to have extraordinary nano-bioactive glass material.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency that prior art exists; A kind of method for preparing of biological activity glass nano-fibre cluster is provided; The biological activity glass nano-fibre cluster that the present invention makes is formed by nanofiber is regularly arranged; In simulated body fluid, show good biomineralization characteristic, can be used on bone tissue restoration and bone tissue engineer field.The present invention realizes through following technical scheme.
A kind of method for preparing of biological activity glass nano-fibre cluster comprises the steps:
(1) with tetraethoxysilance and tricresyl phosphate second fat wiring solution-forming A; With four water-calcium nitrate, catalyst, deionized water and template wiring solution-forming B; B solution is slowly added in the A solution, stir the colloidal sol that the back obtains transparent stable homogeneous; The molar percentage that said tetraethoxysilance, tricresyl phosphate second fat and four water-calcium nitrate account for these three kinds of material total amounts is respectively 60～80%, 4% and 16～36%; The mol ratio of deionized water and ethyl orthosilicate is 8～12: 1, and said catalyst is acidic catalyst or base catalyst;
The at room temperature static ageing of colloidal sol that (2) will in step (1), obtain 4～7 days is fully carried out hydrolysis-condensation reaction, forms wet gel;
(3) wet gel that obtains in the step (2) is placed 80～140 ℃ of drying baker 2～3 days, obtain xerogel after the solvent evaporation;
(4) xerogel that obtains in the step (3) is placed cabinet-type electric furnace; Obtain the micron particles that the bioactive sol-gel glass nano-fibre cluster is reunited and formed through 400～700 ℃ of heat treatment for solidification technologies, after grinding, obtain final biological activity glass nano-fibre cluster.
In the said method, catalyst is an acidic catalyst described in the step (1), and the pH value of solution B is 1～3.
In the said method, catalyst is a base catalyst described in the step (1), and the pH value of solution B is 10～14;
In the said method, said acidic catalyst is hydrochloric acid or Fluohydric acid. etc.
In the said method, said base catalyst is an ammonia etc.
In the said method, said template is the tween series non-ionic surfactants, and concentration is 0.5～3 * 10
-2Mol/L.
Preparation principle of the present invention be with the immiscible tetraethoxysilance of water, tricresyl phosphate second fat under the effect of catalyst hydrochloric acid or ammonia; Fully hydrolysis in water; And four water-calcium nitrate dissolving fully in water, these raw materials react on molecular level, mix evenly; Process in hydrolysis forms countless micelles, and micelle is regularly arranged under the effect of template; Along with the carrying out of polycondensation reaction forms Si-O-Si and P-O network structure in wet gel, calcium ion and solvent are as network intermediate uniform distribution wherein; Through super-dry and heat treatment process, solvent evaporation, and template is burnt, and finally forms product, said nano-fibre cluster constituent mass percentage ratio is SiO260～80%, CaO36～16%, P2O54%.
With respect to prior art, the present invention has following advantage and remarkable result: the present invention combines sol-gel process and template self-assembly process, and the biological activity glass nano-fibre cluster of preparation is made up of regularly arranged nanofiber.The bioactivity glass material of preparation is not only nano material, and has the microscopic appearance of specific linearity, will more help in the bone tissue restoration application in engineering.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Fig. 1 is the typical microscopic appearance figure of product in the embodiment of the invention.
The specific embodiment
Can see that from Fig. 1 nano-cluster is made up of regularly arranged nano wire.
Embodiment 1
(1) earlier with a certain amount of tetraethoxysilance, tricresyl phosphate second fat wiring solution-forming A; With a certain amount of four water-calcium nitrate, hydrochloric acid, deionized water, tween template, wiring solution-forming B, using the hydrochloric acid conditioning solution pH value is 1, template concentration is 0.5 * 10
-2Mol/L; B solution is slowly added in the A solution, stir the colloidal sol that the back obtains transparent stable homogeneous; Wherein, the molar percentage that tetraethoxysilance, tricresyl phosphate second fat and four water-calcium nitrate account for these three kinds of material total amounts is respectively 60%, 4% and 36%, and the mol ratio of deionized water and ethyl orthosilicate is 12: 1;
The at room temperature static ageing of colloidal sol that (4) will in step (3), obtain 4 days is fully carried out hydrolysis-condensation reaction, forms wet gel;
(5) wet gel that obtains in the step (4) is placed 140 ℃ of drying baker 2 days, obtain xerogel after the solvent evaporation;
(6) xerogel that obtains in the step (5) is placed cabinet-type electric furnace; Obtain the micron particles that the bioactive sol-gel glass nano-fibre is reunited and formed through 500 ℃ of heat treatment for solidification technologies, after grinding, obtain final biological activity glass nano-fibre cluster.
Embodiment 2
(1) earlier with a certain amount of tetraethoxysilance, tricresyl phosphate second fat wiring solution-forming A; With a certain amount of four water-calcium nitrate, Fluohydric acid., deionized water, tween template, wiring solution-forming B, using Fluohydric acid. regulator solution pH value is 3, template concentration is 1.5 * 10
-2Mol/L; B solution is slowly added in the A solution, stir the colloidal sol that the back obtains transparent stable homogeneous; Wherein, the molar percentage that tetraethoxysilance, tricresyl phosphate second fat and four water-calcium nitrate account for these three kinds of material total amounts is respectively 70%, 4% and 26%, and the mol ratio of deionized water and ethyl orthosilicate is 11: 1;
The at room temperature static ageing of colloidal sol that (4) will in step (3), obtain 5 days is fully carried out hydrolysis-condensation reaction, forms wet gel;
(5) wet gel that obtains in the step (4) is placed 80 ℃ of drying baker 3 days, obtain xerogel after the solvent evaporation;
(6) xerogel that obtains in the step (5) is placed cabinet-type electric furnace; Obtain the micron particles that the bioactive sol-gel glass nano-fibre is reunited and formed through 700 ℃ of heat treatment for solidification technologies, after grinding, obtain final biological activity glass nano-fibre cluster.
Embodiment 3
(1) earlier with a certain amount of tetraethoxysilance, tricresyl phosphate second fat wiring solution-forming A; With a certain amount of four water-calcium nitrate, ammonia, deionized water, tween template, wiring solution-forming B, using base catalyst regulator solution pH value is 10, template concentration is 3 * 10
-2Mol/L; B solution is slowly added in the A solution, stir the colloidal sol that the back obtains transparent stable homogeneous; Wherein, the molar percentage that tetraethoxysilance, tricresyl phosphate second fat and four water-calcium nitrate account for these three kinds of material total amounts is respectively 80%, 4% and 16%, and the mol ratio of deionized water and ethyl orthosilicate is 8: 1;
The at room temperature static ageing of colloidal sol that (4) will in step (3), obtain 7 days is fully carried out hydrolysis-condensation reaction, forms wet gel;
(5) wet gel that obtains in the step (4) is placed 100 ℃ of drying baker 2 days, obtain xerogel after the solvent evaporation;
(6) xerogel that obtains in the step (5) is placed cabinet-type electric furnace; Obtain the micron particles that the bioactive sol-gel glass nano-fibre is reunited and formed through 400 ℃ of heat treatment for solidification technologies, after grinding, obtain final biological activity glass nano-fibre cluster.
Embodiment 4
(1) earlier with a certain amount of tetraethoxysilance, tricresyl phosphate second fat wiring solution-forming A; With a certain amount of four water-calcium nitrate, sodium hydroxide, deionized water, tween template, wiring solution-forming B, using base catalyst regulator solution pH value is 14, template concentration is 2 * 10
-2Mol/L; B solution is slowly added in the A solution, stir the colloidal sol that the back obtains transparent stable homogeneous; Wherein, the molar percentage that tetraethoxysilance, tricresyl phosphate second fat and four water-calcium nitrate account for these three kinds of material total amounts is respectively 65%, 4% and 31%, and the mol ratio of deionized water and ethyl orthosilicate is 9: 1;
The at room temperature static ageing of colloidal sol that (4) will in step (3), obtain 6 days is fully carried out hydrolysis-condensation reaction, forms wet gel;
(5) wet gel that obtains in the step (4) is placed 120 ℃ of drying baker 2.5 days, obtain xerogel after the solvent evaporation;
(6) xerogel that obtains in the step (5) is placed electric furnace, obtain the micron particles that the bioactive sol-gel glass nano-fibre is reunited and formed, after grinding, obtain final biological activity glass nano-fibre cluster through 600 ℃ of heat treatment for solidification technologies.
Embodiment 5
(1) earlier with a certain amount of tetraethoxysilance, tricresyl phosphate second fat wiring solution-forming A; With a certain amount of four water-calcium nitrate, nitric acid, deionized water, tween template, wiring solution-forming B, using base catalyst regulator solution pH value is 2, template concentration is 2.5 * 10
-2Mol/L; B solution is slowly added in the A solution, stir the back obtain transparent all-stable sols; Wherein, the molar percentage that tetraethoxysilance, tricresyl phosphate second fat and four water-calcium nitrate account for these three kinds of material total amounts is respectively 75%, 4% and 21%, and the mol ratio of deionized water and ethyl orthosilicate is 10: 1;
The at room temperature static ageing of colloidal sol that (4) will in step (3), obtain 4.5 days is fully carried out hydrolysis-condensation reaction, forms wet gel;
(5) wet gel that obtains in the step (4) is placed 100 ℃ of drying baker 2.5 days, obtain xerogel after the solvent evaporation;
(6) xerogel that obtains in the step (5) is placed electric furnace, obtain the micron particles that the bioactive sol-gel glass nano-fibre is reunited and formed, after grinding, obtain final biological activity glass nano-fibre cluster through 650 ℃ of heat treatment for solidification technologies.
Embodiment 6
(1) earlier with a certain amount of tetraethoxysilance, tricresyl phosphate second fat wiring solution-forming A; With a certain amount of four water-calcium nitrate, ammonia, deionized water, tween template, wiring solution-forming B, using base catalyst regulator solution pH value is 12, template concentration is 2.5 * 10
-2Mol/L; B solution is slowly added in the A solution, stir the colloidal sol that the back obtains transparent stable homogeneous; Wherein, the molar percentage that tetraethoxysilance, tricresyl phosphate second fat and four water-calcium nitrate account for these three kinds of material total amounts is respectively 65%, 4% and 31%, and the mol ratio of deionized water and ethyl orthosilicate is 8.5: 1;
The at room temperature static ageing of colloidal sol that (4) will in step (3), obtain 5.5 days is fully carried out hydrolysis-condensation reaction, forms wet gel;
(5) wet gel that obtains in the step (4) is placed 95 ℃ of drying baker 2.5 days, obtain xerogel after the solvent evaporation;
(6) xerogel that obtains in the step (5) is placed electric furnace, obtain the micron particles that the bioactive sol-gel glass nano-fibre is reunited and formed, after grinding, obtain final biological activity glass nano-fibre cluster through 550 ℃ of heat treatment for solidification technologies.
Claims (1)
1. the method for preparing of a biological activity glass nano-fibre cluster is characterized in that comprising the steps:
(1) with ethyl orthosilicate and triethyl phosphate wiring solution-forming A; With four water-calcium nitrate, catalyst, deionized water and template wiring solution-forming B; B solution is slowly added in the A solution, and the back that stirs obtains the colloidal sol of transparent stable homogeneous; The molar percentage that said ethyl orthosilicate, triethyl phosphate and four water-calcium nitrate account for these three kinds of material total amounts is respectively 60～80%, 4% and 16～36%; The mol ratio of deionized water and ethyl orthosilicate is 8～12: 1, and said catalyst is acidic catalyst or base catalyst; When said catalyst was acidic catalyst, the pH value of solution B was 1～3; When said catalyst was base catalyst, the pH value of solution B was 10～14; Said acidic catalyst is hydrochloric acid or Fluohydric acid.; Said base catalyst is an ammonia; Said template is the tween series non-ionic surfactants, and concentration is (0.5～3) * 10
-2Mol/L;
The at room temperature static ageing of colloidal sol that (2) will in step (1), obtain 4～7 days is fully carried out hydrolysis-condensation reaction, forms wet gel;
(3) wet gel that obtains in the step (2) is placed 80～140 ℃ of drying baker 2～3 days, obtain xerogel after the solvent evaporation;
(4) xerogel that obtains in the step (3) is placed cabinet-type electric furnace; Obtain the micron particles that the bioactive sol-gel glass nano-fibre cluster is reunited and formed through 400～700 ℃ of heat treatment for solidification technologies, after grinding, obtain final biological activity glass nano-fibre cluster.
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| CN101921061B (en) * | 2010-08-06 | 2012-01-11 | 中国科学院化学研究所 | Method for preparing phosphosilicate based glass |
| CN102923957B (en) * | 2012-11-30 | 2014-12-31 | 浙江理工大学 | Method for producing ordered mesoporous bioactive microcrystal glass |
| CN104225660B (en) * | 2014-09-12 | 2016-10-05 | 华南理工大学 | Bioactive glass fiber-polycaprolactone composite membrane and preparation method and application |
| CN104288830B (en) * | 2014-09-12 | 2017-10-20 | 华南理工大学 | A kind of micro-nano bar-shaped bioactivity glass and preparation method and application |
| CN105130202B (en) * | 2015-07-24 | 2018-08-24 | 苏州荣昌复合材料有限公司 | A kind of bioactive glass fiber and preparation method thereof |
| CN107162388B (en) * | 2017-06-30 | 2020-03-13 | 西安交通大学 | Method for preparing macroporous bioactive glass nanocluster by using dendritic polyethyleneimine as template agent and catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5874101A (en) * | 1997-04-14 | 1999-02-23 | Usbiomaterials Corp. | Bioactive-gel compositions and methods |
| CN1554607A (en) * | 2003-12-22 | 2004-12-15 | 复旦大学 | Nano mesoporous and mesoporous-macroporous composite biological glass and its preparing method |
| CN1974448A (en) * | 2006-12-01 | 2007-06-06 | 华南理工大学 | Prepn process of bioactive sol-gel glass fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5874101A (en) * | 1997-04-14 | 1999-02-23 | Usbiomaterials Corp. | Bioactive-gel compositions and methods |
| CN1554607A (en) * | 2003-12-22 | 2004-12-15 | 复旦大学 | Nano mesoporous and mesoporous-macroporous composite biological glass and its preparing method |
| CN1974448A (en) * | 2006-12-01 | 2007-06-06 | 华南理工大学 | Prepn process of bioactive sol-gel glass fiber |
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