CN100371290C - Preparation method of ceramic nanometer granule with bioactivity - Google Patents
Preparation method of ceramic nanometer granule with bioactivity Download PDFInfo
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- CN100371290C CN100371290C CNB2005100171044A CN200510017104A CN100371290C CN 100371290 C CN100371290 C CN 100371290C CN B2005100171044 A CNB2005100171044 A CN B2005100171044A CN 200510017104 A CN200510017104 A CN 200510017104A CN 100371290 C CN100371290 C CN 100371290C
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Abstract
The present invention relates to a preparation method for a bioactive ceramic nanometer particle, which comprises the preparation for bioactive ceramic nanometer particles with a three-element systems of SiO2-CaO-P2O5 and a two-element system of SiO2-CaO. Under the condition of intense stirring, adding the ethanol solution of ethyl silicate into the water solution of calcium nitrate; making a hydrolytic reaction with acid as catalyst; dripping the reaction solution slowly to the alkaline solution stirred intensely for polycondensation deposition after clarifying the reaction solution; separating the reaction solution in a centrifugal mode; freezing and drying reaction solution; calcinating the reaction solution at the high temperature; finally, obtaining the white bioactive ceramic nanometer particle. The present invention increases the specific surface area of the ceramic particle. The large interface and the strong bonding strength can be provided when the ceramic particle is compounded with polymer, so a support material with good integrative performance for bone tissue engineering is obtained. The bioactive ceramic nanometer particle of the present invention has the advantage of high useful value in the biomedicine and the hylology. Particularly, the bioactive ceramic nanometer particle which is used as the support material for the bone tissue engineering can be widely used for clinical operation.
Description
Technical field
The invention belongs to a kind of preparing technical field of biological ceramics nano particle.
Background technology
Bioactive ceramics is a kind of ceramic material, and its essentially consist is SiO
2And CaO, can add some other composition in addition as P
2O
5, Na
2O and MgO etc. are by changing the ratio between each component and adding the biological active ceramic material that some components with specific function can obtain many different purposes and function.The peculiar active surface of bioactive ceramics need not just can directly be connected with the live body osseous tissue by the transition of any soft tissue layer.The most frequently used bioactive ceramics is the Bioglass by people such as Hench exploitation at present
-45S5, it is by 45%SiO
2, 24.5%Na
2O, 24.5%CaO, and 6%P
2O
5Form.Bioglass
-45S5 orthopaedics and dentistry obtained clinically widely use.Under alkaline condition, when contacting with receptor tissue, bioactive ceramics can form a kind of colloid layer that is rich in calcium ion, phosphate anion and activated silica on its surface.The appearance of this colloid layer can stimulate the formation of bone.According to another reported in literature, people have attempted bioactive ceramics is made the research of having carried out osteogenesis mechanism behind the external coating (EC) of implant, and this method has obtained application in the reparation of femur at present, has tentatively obtained gratifying result.Recent studies show that, being of a size of the 90-300mm bioactive ceramics fully can be as the repair materials of dog rib.People such as the Price of Univ Maryland-Coll Park USA study the reactive behavior of bioactive ceramics scleroblast MG63, and result of study shows that this kind material can promote the propagation and the functionalization of cell.According to another studies show that, implanting the intravital bioactive ceramics of animal can be sponged by scleroblast step by step.The people such as Wheeler of the upright university in Colorado show the result of study that the bone inducibility of bioactive ceramics and HAP carries out: as tissue engineering material, the osteanagenesis ability of bioactive ceramics pottery obviously is better than hydroxyapatite material.At present, bioactive ceramics is with its good osteoinductive, and osteoconductive, is generally believed it is the biological active materials of " A " level, and HAP then is considered to the biological active materials of " B " level.
After people such as Hench develop bioactive ceramics first, substitute and repair materials as the bone of a kind of tool clinical value and high biological activity, many siliceous potteries dissimilar, different components have obtained a large amount of research.The making method of bioactive ceramics mainly contains two kinds, and a kind of is scorification, and another kind is that collosol and gel is sent out (Sol-gel) method.Wherein scorification is that people such as Hench at first use, and they utilize scorification to prepare the most representative Bioglass
-45S5, the proportioning that changes again afterwards between each component has been developed a series of biological active ceramic materials with difference in functionality, has wherein much realized commercialization.Yet, easily sneak into other impurity with the pottery of scorification preparation, so that it is formed is very complicated, there are some that the deleterious material of animal body is sneaked into unavoidably, finally cause bad influence, cause the failure for the treatment of.Thereby people constantly explore new now, have more the preparation method of the biological active ceramic material of clinical value, as: coprecipitation method, sol-gel method etc.As everyone knows, the stupalith of utilization Sol-gel method preparation because its reaction conditions gentleness, product are purer, does not almost have other impurity, and component also is very easy to control, so people utilize the Sol-gel method to prepare the biological active ceramic material of various different componentss.Studies show that afterwards, the biological active ceramic material of Sol-gel method preparation has very high biological activity, in simulated body fluid, utilizes the Sol-gel legal system to be equipped with SiO
2-CaO-P
2O
5Series ternary bioactive ceramics and SiO
2Even-CaO series binary bioactive ceramics is simple SiO
2Material also can both generate one deck phosphorite crystal on its surface very soon.People's such as the Pilar Sepulveda of London Imperial College result of study shows that also the biological activity of Sol-gel method bioactive ceramics is higher than the activity with the bioactive ceramics of scorification preparation far away.Morphological structure is to influence the bioactive most critical factor of biological active ceramic material, and by the biological active ceramic material smooth surface of scorification preparation, and corner angle are clearly demarcated, and porosity is very low, and density is bigger, and specific surface area only is 0.15-2.7m
2/ g, and the bioactive ceramics surface irregularity that utilizes the Sol-gel method to prepare, porosity is very high, and specific surface area is 126.5-164.7m
2/ g is so can adsorb more protein and cell behind the implant into body.At present, at biomedical sector, the bioactive ceramics of Sol-gel method preparation substitutes traditional scorification biological active ceramic material just gradually.
Because the bioactive ceramics particle diameter that is used on the bone tissue engineering stent material at present is bigger, so increase along with filler content in the matrix material, the porosity of material reduces gradually, and the porosity of material can be reduced to 5.7cm by 9.5 of pure PLA when filler content reaches 40wt% in the system
3/ g, this regeneration to tissue is very unfavorable.So how to reduce biological ceramics particle grain size size is the hot issue that present stage various countries' stupalith researchist is paid close attention to.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of bioactive ceramics nano particle.
The present invention is hydrolyzed into colloidal sol with nitrocalcite with tetraethoxy under acidic conditions, gel particle is made in polycondensation under alkaline condition then, obtains very uniform spherical bioactive ceramics particle of white size distribution at last through ageing, centrifugation, lyophilize and high-temperature calcination again.
Realize that technical scheme of the present invention is as follows: the concrete SiO that comprises
2-CaO-P
2O
5Be ternary bioactive ceramics nano particle and SiO
2-CaO is the preparation method of binary bioactive ceramics nano particle.
I, SiO
2-CaO-P
2O
5It is the preparation of bioactive ceramics nano particle
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material;
(2) in the reactor of magnetic agitation, respectively tetraethoxy and nitrocalcite are made into tetraethoxy-ethanolic soln of 2-50% (volume) and nitrocalcite-aqueous solution of 1-10% (quality) by feed ratio, then two kinds of solution are mixed under intense stirring condition, add acid simultaneously and regulate the potential of hydrogen of mixing solutions to PH ≈ 1-3, vigorous stirring 3-24h under 25-55 ℃ of condition obtains transparent solution at last;
(3) in the reactor of magnetic agitation, Secondary ammonium phosphate is made into the aqueous solution of 0.01-1% by feed ratio, add the polyoxyethylene glycol dissolving again by feed ratio, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 9-12, after temperature risen to 25-55 ℃ the clear solution that obtains in (2) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 12-48h, reduce to the room temperature ageing then at 25-55 ℃ of constant temperature;
(4) the reaction solution centrifugation of Huaing, precipitation is carried out lyophilize, and 500-1100 ℃ of temperature lower calcination 2-10h in retort furnace obtains white biological ceramic powder at last;
II, SiO
2-CaO is the preparation of bioactive ceramics nano particle
(1)) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material;
(2) condition is with (2) among the I;
(3) clear solution that above-mentioned (2) are obtained slowly is added drop-wise in the weak ammonia of PH ≈ 9-12, and solution keeps vigorous stirring in the dropping process.Dropwise the back and stirred 12-48 hour, reduce to the room temperature ageing at 25-55 ℃ of constant temperature;
(4)) condition is with (4) among the I;
Aforesaid method, step I (2) can add catalyzer, and described catalyzer is citric acid, nitric acid or hydrochloric acid;
Aforesaid preparation method, step I (3) can add tensio-active agent, and described tensio-active agent is a polyoxyethylene glycol;
Aforesaid preparation method, preparation SiO
2During-CaO binary biological ceramics, (3) polycondensation process of Step II is carried out in the following manner: the clear solution that (2) among the II are obtained slowly is added drop-wise to 1-5 doubly in the weak ammonia of the PH ≈ 9-12 under the vigorous stirring of (volume ratio), and solution keeps vigorous stirring in the dropping process.Dropwise the back and stirred 12-48 hour, reduce to the room temperature ageing at 25-55 ℃ of constant temperature.
The present invention utilizes the So1-gel method to prepare spheric SiO
2-CaO-P
2O
5Be ternary bioactive ceramics and SiO
2-CaO is a binary bioactive ceramics particle.Main purpose is to obtain the nano grade biological ceramic particle, improves the specific surface area of ceramic powder, when providing bigger interface and cohesive strength with the polymkeric substance compound tense, thereby obtains the bone tissue engineering stent material of high comprehensive performance.Therefore, the prepared bioactive ceramics nano particle of the present invention will have very high use value on biomedicine and materialogy, particularly have boundless application prospect clinically as a kind of bone tissue engineering stent material.
Embodiment:
Embodiment 1
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 2g tetraethoxy is dissolved in the 40ml ethanol, joins 20ml then and be dissolved with in the aqueous solution of 0.5g nitrocalcite and mix, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 24h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, 0.1g Secondary ammonium phosphate and 5g polyoxyethylene glycol are dissolved in the 100ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 9, after temperature risen to 25 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise after stirring 12h under 25 ℃ of temperature and reduce to the room temperature ageing.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 60nm.
Embodiment 2
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 10g tetraethoxy is dissolved in the 100ml ethanol, joins 250ml then and be dissolved with in the aqueous solution of 5g nitrocalcite and mix, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 24h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, 1g Secondary ammonium phosphate and 5g polyoxyethylene glycol are dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 9, after temperature risen to 25 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise after stirring 12h under 25 ℃ of temperature and reduce to the room temperature ageing.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 60nm.
Embodiment 3
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 5.1ml ethanol, joining 23.6ml then is dissolved with in the aqueous solution of 2.36g nitrocalcite and mixes, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 24h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, 0.33g Secondary ammonium phosphate and 5g polyoxyethylene glycol are dissolved in the 100ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 9, after temperature risen to 25 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise after stirring 12h under 25 ℃ of temperature and reduce to the room temperature ageing.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 60nm.
Embodiment 4
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 120ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 6h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, 0.33g Secondary ammonium phosphate and 5g polyoxyethylene glycol are dissolved in the 500ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 12, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise after stirring 24h under 40 ℃ of temperature and reduce to the room temperature ageing.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 5h under 700 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 45nm.
Embodiment 5
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 12h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, 0.33g Secondary ammonium phosphate and 5g polyoxyethylene glycol are dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and under 40 ℃ of temperature, stir 24h, reduce to the room temperature ageing then.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 500 ℃, 700 ℃, 900 ℃ and 1100 ℃ of conditions at last in retort furnace, obtains a series of biological ceramic powder, and test result sees Table 1.
Table 1
| Calcining temperature (℃) | Mean diameter (nm) | Color |
| 500 700 900 1100 | 40 45 60 200 | Black Dark grey white white |
Embodiment 6
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 120ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add citric acid and be adjusted to PH ≈ 3, vigorous stirring 24h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, 0.33g Secondary ammonium phosphate and 5g polyoxyethylene glycol are dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 12, after temperature risen to 55 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Stir 24h after dropwising at a certain temperature, reduce to the room temperature ageing then.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 45nm.
Embodiment 7
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 255ml ethanol, joins 120ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 6h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 0.33g Secondary ammonium phosphate is dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 60nm.
Embodiment 8
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 120ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add citric acid and be adjusted to PH ≈ 2, vigorous stirring 12h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, 0.33g Secondary ammonium phosphate and 5g polyoxyethylene glycol are dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 2h, 4h, 6h, 8h and 10h under 700 ℃ of conditions at last in retort furnace, obtains a series of biological ceramic powder, and test result sees Table 2.
Table 2
| Calcination time (h) | Color | Mean diameter (nm) |
| 2 4 6 8 10 | The light grey white white of black Dark grey | 35 45 45 50 50 |
Embodiment 9
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: l-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add hydrochloric acid and be adjusted to PH ≈ 1, vigorous stirring 6h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, 0.33g Secondary ammonium phosphate and 5g polyoxyethylene glycol are dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 45nm.
Embodiment 10
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add nitric acid and be adjusted to PH ≈ 1, vigorous stirring 12h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, molten and the 5g polyoxyethylene glycol of 0.33g Secondary ammonium phosphate is separated in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 60nm.
Embodiment 11
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 240ml ethanol, joins 60ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add nitric acid and be adjusted to PH ≈ 1, vigorous stirring 12h obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, 0.33g Secondary ammonium phosphate and 5g polyoxyethylene glycol are dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is 55nm, and mean length is the white bar-shaped biological ceramic powder of 150nm.
Embodiment 12
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 6h under 40 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, 0.33g Secondary ammonium phosphate and 5g polyoxyethylene glycol are dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 50nm.
Embodiment 13
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add nitric acid and be adjusted to PH ≈ 1, vigorous stirring 6h under 55 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, 0.33g Secondary ammonium phosphate and 5g polyoxyethylene glycol are dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 55nm.Embodiment 14
(1) be tetraethoxy by feed ratio: nitrocalcite: Secondary ammonium phosphate: polyoxyethylene glycol=2-4: 1: 0.1-0.2: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add nitric acid and be adjusted to PH ≈ 1, vigorous stirring 6h under 55 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, 0.33g Secondary ammonium phosphate and 1g polyoxyethylene glycol are dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 55nm.
Embodiment 15
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 2g tetraethoxy is dissolved in the 40ml ethanol, joins 20ml then and be dissolved with in the aqueous solution of 0.5g nitrocalcite and mix, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 24h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 5g polyoxyethylene glycol is dissolved in the 100ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 9, after temperature risen to 25 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise after stirring 12h under 25 ℃ of temperature and reduce to the room temperature ageing.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 60nm.
Embodiment 16
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 10g tetraethoxy is dissolved in the 100ml ethanol, joins 250ml then and be dissolved with in the aqueous solution of 5g nitrocalcite and mix, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 24h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 5g polyoxyethylene glycol is dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 9, after temperature risen to 25 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise after stirring 12h under 25 ℃ of temperature and reduce to the room temperature ageing.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 60nm.
Embodiment 17
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 5.1ml ethanol, joining 23.6ml then is dissolved with in the aqueous solution of 2.36g nitrocalcite and stirs, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 24h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 5g polyoxyethylene glycol is dissolved in the 100ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 9, after temperature risen to 25 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 25 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 180nm.
Embodiment 18
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 120ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 6h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 5g polyoxyethylene glycol is dissolved in the 500ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 12, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 5h under 700 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 180nm.
Embodiment 19
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 12h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 5g polyoxyethylene glycol is dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 500 ℃, 700 ℃, 900 ℃ and 1100 ℃ of conditions at last in retort furnace, obtains a series of biological ceramic powder, and test result sees Table 3.
Table 3
| Calcining temperature (℃) | Mean diameter (nm) | Color |
| 500 700 900 1100 | 140 150 160 400 | Black Dark grey white white |
Embodiment 20
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 120ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add citric acid and be adjusted to PH ≈ 3, vigorous stirring 24h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 5g polyoxyethylene glycol is dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 12, after temperature risen to 55 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 55 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 150nm.
Embodiment 21
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 255ml ethanol, joins 120ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add citric acid and be adjusted to PH ≈ 1, vigorous stirring 6h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the potential of hydrogen of regulating the 1000ml deionized water with ammoniacal liquor is to PH ≈ 11 then, the clear solution that obtains in (1) slowly splashed in this solution solution maintenance vigorous stirring in the dropping process after temperature is risen to 40 ℃.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 200 nm.
Embodiment 22
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 120ml ethanol, adds 236ml then and in the aqueous solution that is dissolved with 2.36g nitrocalcite, stir, add citric acid and be adjusted to PH ≈ 2, vigorous stirring 12h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 5g polyoxyethylene glycol is dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 2h, 4h, 8h and 10h under 700 ℃ of conditions at last in retort furnace, obtains a series of biological ceramic powder, and test result sees Table 4.
Table 4
| Calcination time (h) | Color | Mean diameter (nm) |
| 2 4 8 10 | Black Dark grey white white | 170 170 180 180 |
Embodiment 23
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins then to be dissolved with in the 2.36g nitrocalcite 236ml aqueous solution and stir, add hydrochloric acid and be adjusted to PH ≈ 1, vigorous stirring 6h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 5g polyoxyethylene glycol is dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 155nm.
Embodiment 24
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add nitric acid and be adjusted to PH ≈ 1, vigorous stirring 12h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 5g polyoxyethylene glycol is dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 185nm.
Embodiment 25
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add nitric acid and be adjusted to PH ≈ 1, vigorous stirring 12h under 40 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 5g polyoxyethylene glycol is dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 165nm.
Embodiment 26
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add nitric acid and be adjusted to PH ≈ 1, vigorous stirring 6h under 55 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 5g polyoxyethylene glycol is dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 180nm.
Embodiment 27
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol=2-4: 1: 1-10 (mass ratio) takes by weighing various starting material.
(2) in the reaction flask of magnetic agitation is housed, at first the 5.1g tetraethoxy is dissolved in the 60ml ethanol, joins 236ml then and be dissolved with in the aqueous solution of 2.36g nitrocalcite and stir, add nitric acid and be adjusted to PH ≈ 1, vigorous stirring 12h under 25 ℃ of conditions obtains transparent solution at last.
(3) in the reaction flask of magnetic agitation is housed, the 1g polyoxyethylene glycol is dissolved in the 1000ml deionized water, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 11, after temperature risen to 40 ℃ the clear solution that obtains in (1) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process.Dropwise the back and stir 24h, reduce to the room temperature ageing then at 40 ℃ of constant temperature.
(4) with the reaction solution centrifugation, precipitation is carried out lyophilize, calcines 3h under 900 ℃ of conditions at last in retort furnace, and obtaining mean diameter is the white biological ceramic powder of 200nm.
Claims (5)
1. the preparation method of a bioactive ceramics nano particle, described for the bioactive ceramics nano particle be SiO
2-CaO-P
2O
5Three component system is characterized in that, its step and condition are:
(1) be tetraethoxy by feed ratio: nitrocalcite: polyoxyethylene glycol: Secondary ammonium phosphate=2-4: 1: 1-10: 0.1-0.2 (mass ratio) takes by weighing various starting material;
(2) in the reactor of magnetic agitation is housed, respectively tetraethoxy and nitrocalcite are made into tetraethoxy-ethanolic soln of 2-50% (volume) and nitrocalcite-aqueous solution of 1-10% (quality) by feed ratio, then two kinds of solution are mixed under intense stirring condition, add acid simultaneously and regulate the potential of hydrogen of mixing solutions to PH ≈ 1-3, vigorous stirring 3-24h under 25-55 ℃ of condition obtains transparent solution at last;
(3) in the reactor of magnetic agitation is housed, Secondary ammonium phosphate is made into the aqueous solution of 0.01-1% by feed ratio, add the polyoxyethylene glycol dissolving again by feed ratio, the potential of hydrogen of using the ammoniacal liquor regulator solution then is to PH ≈ 9-12, after temperature risen to 25-55 ℃ the clear solution that obtains in (2) is slowly splashed in this solution, solution keeps vigorous stirring in the dropping process, dropwises the back and stirs 12-48h at 25-55 ℃ of constant temperature, reduces to the room temperature ageing then;
(4) will be through aged reaction solution centrifugation, precipitation is carried out lyophilize, and 500-1100 ℃ of temperature lower calcination 2-10h in retort furnace obtains white bioactive ceramics nano particle at last.
2. the preparation method of a kind of bioactive ceramics nano particle as claimed in claim 1, step (2) adds catalyzer, and this catalyzer is citric acid, nitric acid or hydrochloric acid.
3. as the preparation method of the described a kind of bioactive ceramics nano particle of 1 or 2 any one claim, it is characterized in that step (3) adds tensio-active agent, this tensio-active agent is an ethylene glycol.
4. the preparation method of a bioactive ceramics nano particle, described for the bioactive ceramics nano particle be SiO
2-CaO two component system is characterized in that, its step and condition are:
(1) by tetraethoxy: nitrocalcite: the feed ratio of polyoxyethylene glycol (mass ratio)=2-4: 1: 1-10 takes by weighing various starting material;
(2) in the reactor of magnetic agitation is housed, respectively tetraethoxy and nitrocalcite are made into tetraethoxy-ethanolic soln of 2-50% (volume) and nitrocalcite-aqueous solution of 1-10% (quality) by feed ratio, then two kinds of solution are mixed under intense stirring condition, add acid simultaneously and regulate the potential of hydrogen of mixing solutions to PH ≈ 1-3, vigorous stirring 3-24h under 25-55 ℃ of condition obtains transparent solution at last;
(3) be that the clear solution that above-mentioned (2) obtain slowly is added drop-wise in the weak ammonia of PH ≈ 9-12, solution keeps vigorous stirring in the dropping process, dropwises the back and stirs 12-48 hour at 25-55 ℃ of constant temperature, reduces to the room temperature ageing;
(4) will be through aged reaction solution centrifugation, precipitation is carried out lyophilize, and 500-1100 ℃ of temperature lower calcination 2-10h in retort furnace obtains white bioactive ceramics nano particle at last.
5. the preparation method of a kind of bioactive ceramics nano particle as claimed in claim 4 is characterized in that, step (3) polycondensation process is carried out in the following manner: the clear solution that (2) are obtained slowly is added drop-wise in the described weak ammonia of 1-5 times (volume ratio).
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| CN1623952A (en) * | 2004-10-28 | 2005-06-08 | 中国科学院上海硅酸盐研究所 | Bredigites biological ceramic and preparation method and application thereof |
| CN1636936A (en) * | 2004-12-03 | 2005-07-13 | 中国科学院长春应用化学研究所 | Prepn process of spinel type nanometer composite ferrite material |
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| CN1623952A (en) * | 2004-10-28 | 2005-06-08 | 中国科学院上海硅酸盐研究所 | Bredigites biological ceramic and preparation method and application thereof |
| CN1636936A (en) * | 2004-12-03 | 2005-07-13 | 中国科学院长春应用化学研究所 | Prepn process of spinel type nanometer composite ferrite material |
Non-Patent Citations (3)
| Title |
|---|
| CaO-SiO2-P2O5-H2O系统中CBC材料的溶胶-凝胶过程研究. 冯秀平.硅酸盐学报，第25卷第4期. 1997 * |
| 溶胶-凝胶法制备羟基磷灰石粉末的研究. 刘晶冰.功能材料，第34卷第1期. 2003 * |
| 纳米羟基磷灰石的溶胶-凝胶制备及其特性研究. 朱晓丽.硅酸盐通报，第2期. 2003 * |
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