CN1151086C - Nanometer level bioactive glass powder material and its prepn - Google Patents

Nanometer level bioactive glass powder material and its prepn Download PDF

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Publication number
CN1151086C
CN1151086C CNB021105863A CN02110586A CN1151086C CN 1151086 C CN1151086 C CN 1151086C CN B021105863 A CNB021105863 A CN B021105863A CN 02110586 A CN02110586 A CN 02110586A CN 1151086 C CN1151086 C CN 1151086C
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China
Prior art keywords
bioactive glass
solution
glass powder
powder material
preparation
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Expired - Fee Related
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CNB021105863A
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Chinese (zh)
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CN1361076A (en
Inventor
钟吉品
常江
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Priority to CNB021105863A priority Critical patent/CN1151086C/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0007—Compositions for glass with special properties for biologically-compatible glass

Abstract

The present invention relates to a nanometer bioactive glass powder material and a preparation method thereof, more specifically to bioactive glass powder in the size range of 20 nanometers to 500 nanometers and a preparation method thereof. The nanometer bioactive glass powder material is characterized in that the powder comprises components (wt): 42% to 90% of SiO2, 5% to 30% of CaO, 1% to 15% of P2O5 and 0 to 25% of Na2O. In the preparation method, Ca <2+> or Ca<2+> and Na<+> are introduced into deionized water in a solution or an inorganic salt form, NH3OH or NaOH is used for regulating the pH value of the solution; then, a mixture of TEOS and TEP is added to the solution, and is mixed with the solution so that the mixture is hydrolyzed and polymerized; when a SiO2 network is formed, the ion genes of Ca<2+> and PO4<3-> and Na<+> ions enter the SiO2 network to form colloidal particles of bioactive glass; and the nanometer bioactive glass powder material is manufactured through deposition, filtration and drying in an alkaline solution. The preparation method has the characteristics of simple technology, high collection rate, easy control of nanometer dimension, etc.

Description

Nanometer level bioactive glass powder material and preparation method
Technical field
The present invention relates to a kind of nano-bioactive glass powder material and preparation method, relate to 20-500 nano-scale range bioactive glass powder and preparation method or rather, belong to the bioglass material field.
Background technology
Since Hench report bioactivity glass in 1971 can become bond to close with osseous tissue, the history in existing more than 30 year of the research of bioactivity glass.Use more than ten years clinically as the bone defect repair.Successful clinical application derives from it not only bone guided, and the biological activity that promotes the osseous tissue growth is arranged.Much studies show that recently, the degraded product of bioactivity glass can promote somatomedin generation, promote cell procreation, activate osteoblastic genetic expression.Moreover, bioactivity glass is uniquely can become bond to close with osseous tissue at present, also artificial bio-membrane's material that can be connected with soft tissue.The characteristic that these are unique makes bioactivity glass use clinically as medicine equipment and has huge potential value, causes the bigger concern of academia and industrial community.
Although excellent biological compatibility and biological activity are arranged, yet bioactivity glass has only a kind of granular form at present as the clinical application product.As the bone defect repair, often need block timbering material to fill reparation clinically.Now very pay close attention in the world, develop faster organizational engineering and also suddenly treat active timbering material.Also often need bone water conservancy biomaterial syringeability and solidifiable to come to plant with a definite target in view clinically to be placed on damaged wound to carry out repairing and treating, the biomaterial of syringeability also can be used as pharmaceutical carrier medicine is delivered to treatment place.High-intensity planting body such as joint prosthesis planting body, tooth implant common metal alloy, stainless steel and structural ceramics etc., these materials do not connect with biological tissue usually and merge, and often cause planting the loosening of body.For a long time, bioactive coating is considered to improve the optimal path of planting body and biological tissue connection and fusion.The medical device of some long-term implant into body such as conduit etc. are often needed the surface bioactive modification.
Nanotechnology will be brought great variety to Materials science, and nano particle is meant the particulate of 1-100nm scope usually.People expect that quantum size effect, surface effects and the macro quanta tunnel effect of nanometer can cause the appearance of super performance materials.On biomaterial was used, existing nano hydroxyl phosphorite crystal may have inhibiting report to growth of cancer cells.But up to the present the nano-bioactive glass material does not appear in the newspapers.The nano-bioactive glass powder prepares timbering material might be reduced preparation temperature, reduce or avoid crystallization phases, improve mechanical strength, keep biological activity.The nano-bioactive glass material can be used for bone cement and improves biological activity and do not reduce mechanical property.The superfluidity of nano material liquid will strengthen syringeability (Injectable) greatly, be used for the biomaterial of syringeability.The premium properties of nano material all helps top coat, the coating of nano-bioactive glass material may break through existing coating technology can cause evenly, fine and close, stablize, bioactive coating that bonding strength is high.And develop the difficulty that above-described new generation product exists some to be difficult to break through with the general bioactive glass powder of present development and use.
Goal of the invention
The objective of the invention is to develop a kind of new nanometer level bioactive glass material and preparation method, to satisfy the needs of biomaterial development of new generation.The objective of the invention is to implement by following manner:
With the solution form with Ca 2+Ion and Na +Ion is introduced in the deionized water, and uses NH 3The PH degree of OH or NaOH regulator solution.Then with tetraethoxy TEOS and triethyl phosphate TEP (OP (OC 2H 5) 3) mixed solution joins in the above-mentioned solution, keeps mixing, and makes its hydrolysis and polymerization, at SiO 2When network forms, Ca 2+Ion, PO 4 3-Ionic group, Na +Ion enters SiO 2Network forms the colloidal solid of bioactivity glass.Wherein, CaO can be with Ca (NO 3) 24H 2The form of O adds.In basic solution, precipitation will occur.Prepare the nano-bioactive powder with drying after filtration.By regulating and control pH or some ion such as Na +Ionic concn and R recently change polyreaction, thereby regulate particle size.The nanometer level bioactive glass powder of preparation is of a size of the 20-500 nanometer, more precisely the 60-200 nanometer.
Can in mixed solution, add an amount of ethanol for reducing hydrolysis and polymerization rate with control particle growth and sedimentation speed,, reach changing down rate purpose to increase TEOS and TEP and water molecules at the solution middle distance.
The ultimate principle of preparation is in acidic sol, SiO 2Micelle is about 2 nanometers.Along with increasing of pH, polymerization (Polycondensition) reaction is quickened, and micelle increases.In high alkalinity colloidal sol, micelle will precipitate the generation granularity in solution be that the hundreds of nanometer arrives several microns superfine powder.Bioactivity glass is prepared by sol-gel method.In preparation with SiO 2For matrix colloidal sol is introduced Ca 2+Ion and P group ion and Na +Ion is prepared into gelinite at last, makes general granular powder after the pulverizing.
In different alkaline environments, prepare SiO 2, Ca 2+Ion and P group ion and Na +Solion (Sol).Along with the carrying out of hydrolysis (Hydrolysis) and polymerization (Polycondensition) reaction, precipitation will take place in the different time with alkaline degree.By regulating pH is alkaline degree, some ionic concn such as Na +The mole ratio of ion and water and tetraethoxy (TEOS) (R ratio) obtains the nanometer level bioactive glass powder of 20-500 nanometer.
Nanometer level bioactive glass powder and preparation thereof that the present invention proposes have two key points: the one, regulate and control pH or some ion such as Na +Ionic concn and R are than being the key of obtaining the nano particle powder.The 2nd, Si, Ca 2+Ion, P group from introducing form and order also will be the important factor that influences granular size.Explore by technology, search out the ideal condition in the present invention, finally prepare the bioactive glass powder of 20 to 50 nanometer range.Its compositing range is (weight ratio): SiO 2: 42%-90%; CaO:5%-30%; P 2O 5: 1%-15%; Na 2O:0%-25%.
With bioactive glass powder drying provided by the invention and after 700 ℃ of thermal treatment, carry out external solution biological activity test.Used solution is anthropomorphic liquid solution SBF (Simulated Body Fluid).Anthropomorphic liquid solution SBF contains ion identical with human plasma and ionic group concentration.SBF consists of:
NaCl： 7.996g/l
NaHCO 3： 0.350g/l
KCl： 0.224g/l
K 2HPO 4·3H 2O：?0.228g/l
MgCl 2·6H 2O： 0.305g/l
1N?HCl： 43ml/l
CaCl 2： 0.278g/l
Na 2SO 4： 0.071g/l
NH 2C(CH 2OH) 3： 6.057g/l
Powder is in SBF, and reaction conditions is that 0.05g powder, 200ml SBF, temperature of reaction are that 37 ℃, shaking speed are 175RPM.After 24 hours, 72 hours, powder and solution are separated by filtering respectively, powder is tested with fourier infrared inversion spectrum (FTIR) instrument.In 24 hours, the powder that preparation method of the present invention provides all can generate hydroxyapatite at spatial induction, thereby shows these material biologically actives.
This shows that the present invention adopts sol-gel process, by pH value and Na +, P + 5Or Ca ++Concentration control and introducing form and order and secondary collect to control preparation process, and it is simple to have technology, collection rate height, nano-scale characteristics easy to control.
Description of drawings
Fig. 1 is the SEM photo of the nanometer level bioactive glass powder for preparing of the present invention.
Embodiment
Below by embodiment, with further elaboration substantive distinguishing features of the present invention and marked improvement, but the present invention only limits to embodiment by no means.
Embodiment 1 high-alkali preparation powder
Mixture I:NH 3OH (14.8M): 2.29ml
H 2O： 2.00ml
Ca(NO 3) 2·4H 2O： 1g
Ethanol： 23.80ml
Mixed 10 minutes earlier;
Mixtures II: Ethanol:20.00ml
TEOS： 1.77ml
TEP： 0.2ml
Mixed 10 minutes;
Mixtures II gradually to going among the mixture I, is kept mixing.After 5 minutes, it is muddy that mixing solutions becomes, and precipitation occurs.After 20 minutes, collect powder through vacuum filtration or centrifugation.Solution after the separation will be muddy once more, precipitation occur.Collect powder, improve the powder production rate greatly for twice.Powder microstructure test shows particle size range is that 150 nanometers are to 400 nanometers.
Embodiment 2 Sol-Gel are low, and alkali prepares powder
Mixture I:NH 3OH (14.8M): 1.15ml
H 2O： 2.00ml
Ca(NO 3) 2·4H 2O：1g
Ethanol： 23.80ml
Mixed 10 minutes;
Mixtures II: Ethanol:20.00ml
TEOS： 1.77ml
TEP： 0.2ml
Mixed 10 minutes;
Mixtures II gradually to going among the mixture I, is kept mixing.After 10 minutes, it is muddy that mixing solutions becomes, and precipitation occurs.After 20 minutes, collect powder through vacuum filtration or centrifugation.Solution after the separation will be muddy once more, precipitation occur.Collect powder, improve the powder production rate greatly for twice.Powder microstructure test shows particle size range is that 50 nanometers are to 150 nanometers.
Embodiment 3 Na, P, Ca add preparation Sol-Gel powder simultaneously
Mixture I:NH 3OH (14.8M): 2.29ml
H 2O： 2.00ml
Ca(NO 3) 2·4H 2O：1g
NaCl： 0.5g
Ethanol： 23.80ml
Mixed 10 minutes;
Mixtures II: Ethanol:20.00ml
TEOS： 1.77ml
TEP： 0.2ml
Mixed 10 minutes;
Mixtures II gradually to going among the mixture I, is kept mixing.After 2 minutes, it is muddy that mixing solutions becomes, and precipitation occurs.But precipitate slower.After 20 minutes, collect powder through vacuum filtration or centrifugation.Solution after the separation will be muddy once more, precipitation occur.Collect powder twice, improve the powder production rate.Powder microstructure test shows particle size range is that 150 nanometers are to 400 nanometers.

Claims (4)

1. one kind is of a size of the 50-500nm bioactive glass powder material, it is characterized in that, it forms (wt%) by following component:
SiO 2 42-90 CaO 5-30
P 2O 5?1-15 Na 2O 0-25
2. by the described preparation method who is of a size of the 50-500nm bioactive glass powder material of claim 1, adopt sol-gel technology, it is characterized in that, with the form of solution with Ca 2+Or/and Na +Introduce in the deionized water, and use NH 3OH or NaOH regulator solution pH value join tetraethoxy and triethyl phosphate mixture in the above-mentioned solution then and mix, and make its hydrolysis and polymerization, at SiO 2When network forms, Ca 2+, PO 4 3-Ionic group, Na +Ion enters SiO 2Network forms the colloidal solid of biological glass; In basic solution, precipitation, after filtration, dry and prepare the nano-bioactive powder.
3. by the described preparation method who is of a size of the 50-500nm bioactive glass powder material of claim 2, it is characterized in that hydrolysis and polymerization rate are by adding ethanol control in mixed solution.
4. by the described preparation method who is of a size of the 50-500nm bioactive glass powder material of claim 2, it is characterized in that CaO is with Ca (NO 3) 24H 2O forms adding.
CNB021105863A 2002-01-18 2002-01-18 Nanometer level bioactive glass powder material and its prepn Expired - Fee Related CN1151086C (en)

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Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004026433A1 (en) * 2004-05-29 2005-12-22 Schott Ag Nanoglass powder and its use
CN1300026C (en) * 2004-10-12 2007-02-14 西北有色金属研究院 Method for synthesizing high pure superfine biological glass powder
CN1843994B (en) * 2006-04-21 2010-09-01 华南理工大学 Bioactive glass nano powder and its biomimetic synthesis method
CN101200348B (en) * 2007-12-21 2010-08-11 天津大学 CaO-B2O3-SiO2 glass powder and preparation method
CN101215153B (en) * 2008-01-04 2010-06-02 华南理工大学 Method for preparing amorphous biological activity superfine powder
CN102531385A (en) * 2012-01-17 2012-07-04 上海中山医疗科技发展公司 Bioactive glass and preparation method thereof
CN102826752B (en) * 2012-08-23 2015-07-15 北京大清生物技术有限公司 Bioactive mineral powder containing quasi-nanometer particles, preparation method and application thereof in dental treatment
CN103848566A (en) * 2012-12-04 2014-06-11 董毅翔 Method for preparing micron-sized biological activity glass and application thereof in departments of orthopedics and dentistry
CN106673426A (en) * 2017-01-13 2017-05-17 上海师范大学 Porous-microsphere nanoscale bioglass material doped with rare earth element as well as preparation method and application of porous-microsphere nanoscale bioglass material
WO2018167724A1 (en) * 2017-03-16 2018-09-20 Lakhkar Nilay Jayant Manufacture of porous glass and glass-ceramic particulate structures by gel casting
CN109771692B (en) * 2018-01-12 2022-02-11 北京幸福益生再生医学科技有限公司 Formula and preparation method of POSS (polyhedral oligomeric silsesquioxane) -based regenerative medical material
CN110859767B (en) * 2019-11-21 2021-07-16 李向军 Bioactive glass composition, and preparation method and application thereof

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