CN100480177C - Method for synthesizing nano hydroxy-apatite micro powder containing carbonate radical - Google Patents
Method for synthesizing nano hydroxy-apatite micro powder containing carbonate radical Download PDFInfo
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- CN100480177C CN100480177C CNB2004100532086A CN200410053208A CN100480177C CN 100480177 C CN100480177 C CN 100480177C CN B2004100532086 A CNB2004100532086 A CN B2004100532086A CN 200410053208 A CN200410053208 A CN 200410053208A CN 100480177 C CN100480177 C CN 100480177C
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Abstract
The synthesizing process of nanometer hydroxyapatite powder containing carbonate radical disease the following steps: dissolving calcium salt and P2O5 in mixed sol of anhydrous alcohol to form molar Ca/P ratio of 1.67-1.75, stirring to form stable sol, reacting to form gel, drying the gel to obtain dry gel, and final calcining the dry gel at 600-800 deg.c inside muffle for 0.5-2 hr to obtain the nanometer hydroxyapatite containing carbonate radical. Synthesizing nanometer hydroxyapatite powder in the said process has low cost, simple technological process, short reaction period, low synthesizing temperature and precisely controlled Ca/P ratio.
Description
Technical field
The present invention relates to biomedical materials field, be specifically related to contain the synthetic method of carbonate nanometer hydroxyapatite micro mist.
Background technology
The preparation method of hydroxyapatite mainly contains solid reaction process, hydrothermal synthesis method, liquid-phase precipitation method, sol-gel processing etc.
Solid reaction process also claims dry method, mechanochemical reaction, is through levigate, by the mixed back of suitable proportion (more than 1000 ℃) solid state reaction under hot conditions with calcium salt and phosphate compounds raw material.Solid reaction process is owing to be solid state reaction, so speed of response is slow, reaction time is long, and it is big to generate the product particle diameter, and raw material powder needs long-time mix grinding, the easy pickup of process, the poor activity of product.
Hydrothermal synthesis method is meant in an airtight pressurized vessel, makes reaction medium with the aqueous solution, by to reaction vessel heating, makes indissoluble or insoluble substance dissolves and recrystallization under usual conditions.Hydrothermal synthesis method can obtain big and complete HA monocrystalline, remedies lattice imperfection, but equipment requirements intensity height, the cost height.
Liquid-phase precipitation method is to stir the aqueous solution of certain calcium salt of concentration and microcosmic salt is mixed, and the pH value by control solution makes it to take place chemical reaction, produces colloid HAP throw out, obtains the HAP crystal powder through calcining.The temperature of reaction of liquid-phase precipitation method is not high, and synthetic powder purity height, particle are thin, but needs pH value and other processing condition of strict control solution, otherwise very easily generates the calcium-deficient apatite that Ca/P is lower than HAP theoretical value (1.67).
Sol-gel method is to be presoma with metal alkoxide or inorganic salt, precursor is dissolved in and forms uniform solution in the solvent, and solute and solvent produce hydrolysis or alcoholysis reaction, and resultant of reaction is through assembling gelation, gel drying, roasting obtain hydroxyapatite powder at last.The feed composition of sol-gel method can be on molecular level uniform mixing, be reflected on atom, the molecular level and carry out, be fit to preparation high-purity tiny, uniform hydroxylapatite powder, and thermal treatment temp is low.People such as Wu Hongyan are with four water-calcium nitrate Ca (NO
3) 24H
2The O aqueous solution and trimethyl phosphate PO (CH
3O)
3Alcoholic solution is a presoma, adopting sol-gel method to synthesize particle diameter is 60nm～1 μ m particulate hydroxyapatite, and studied pH value, sintering temperature and constant temperature time influence (Wu Hongyan for the synthetic product particle diameter, Zhu Minggang, Kong Lingyi, Deng. the novel preparation method .[J of nano-grade hydroxy apatite biological ceramic powder] Hebei Normal University's journal, 1997,21 (3): 266-269.).People such as Yuan Yuan also adopt four water-calcium nitrate Ca (NO3) 24H
2The O aqueous solution and trimethyl phosphate PO (CH
3O)
3Alcoholic solution is a presoma, place 80 ℃ of stirred in water bath to form stable sols two kinds of presomas, the colloidal sol that forms is moved in the baking oven, in the constant temp drying, treat that moisture dries the formation xerogel fully, grind back 600 ℃ of roasting 3h in retort furnace, obtain particle diameter 50nm, equally distributed nano-HAP powder, and studied pH value and ethylene glycol add-on influence (Yuan Yuan to product, Liu Changsheng. sol-gel processing prepares nanometer hydroxyapatite .[J] Chinese Academy of Medical Sciences's journal, 2002,24 (2): 129-133.).People such as Layrolle are with ethylene glycol calcium Ca (OEt)
2With phosphoric acid H
3PO
4For adopting sol-gel method, presoma synthesized hydroxyapatite (Layrolle P., Lebugle A.Characterization and reactivity of nanosized calcium phosphates prepared in anhydrousethanol[J] .Chem.Mater, 1994, (6): 1996-2004.).But these methods all exist cost higher, the shortcoming that reaction time is long.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method that contains carbonate nanometer hydroxyapatite micro mist.
For achieving the above object, the present invention is achieved in that a kind of synthetic method that contains carbonate nanometer hydroxyapatite micro mist, may further comprise the steps: with calcium salt and P
2O
5Be dissolved in dehydrated alcohol preparation mixed sols, the mol ratio of Ca and P is 1.67-1.75 in the described mixed sols, described mixed sols is stirred, form stable sols, afterwards described formation stable sols reaction is formed gel, with described gel drying, obtain xerogel then, at last described xerogel is put into retort furnace and calcined 0.5-2 hours down, obtain containing the nanometer hydroxyapatite of carbonate at 600 ℃-800 ℃.
Preferable, described mixed sols stirs in this step, and churning time is 0.5-2 hours.
Preferable, forming the stable sols reaction and form in this step of gel, temperature of reaction is 55 ℃-70 ℃.
Preferable, in this step of described gel drying, drying temperature is 90 ℃-0150 ℃, be 12-72 hours time of drying.
Preferable, described calcium salt is four water-calcium nitrate or calcium acetate.
The invention has the beneficial effects as follows: utilize the inventive method synthesizing hydroxylapatite micro mist to have that cost is low, technology is simple, reaction time is short, can carry out the synthetic advantage at low temperatures, can be under the condition of accurate control ratio of calcium and phosphorus high-purity tiny, the uniform nano hydroxyapatite powder of preparation.And prepared hydroxyapatite micro mist be in similar people's bone the nanometer needle contain the carbonate nanometer hydroxyapatite.
Description of drawings
Fig. 1 is 600 ℃ of X ray diffracting spectrums of calcining the nanometer hydroxyapatite micro mist that obtains after 2 hours
Fig. 2 is 600 ℃ of infared spectrums of calcining the nanometer hydroxyapatite micro mist that obtains after 2 hours
Fig. 3 is 600 ℃ of transmission electron microscope photos of calcining the nanometer hydroxyapatite micro mist that obtains after 2 hours
Fig. 4 is 600 ℃ of laser particle size analysis results that calcine the nanometer hydroxyapatite micro mist that obtains after 2 hours
Fig. 5 is 800 ℃ of X ray diffracting spectrums of calcining the nanometer hydroxyapatite micro mist that obtains after 30 minutes
Embodiment
The present invention will be further described below in conjunction with drawings and Examples.
Example 1:
Take by weighing 47.2 gram four water-calcium nitrates and be dissolved in dehydrated alcohol, stirring and dissolving is made into the ethanol solution of the 2mol/l four water-calcium nitrate of 100ml, and it is standby to measure the ethanol solution of the above-mentioned four water-calcium nitrate of 25ml; Take by weighing 2.15 gram Vanadium Pentoxide in FLAKESs and be dissolved in the 15ml dehydrated alcohol, stirring and dissolving dropwise is added drop-wise to it in ethanol solution of above-mentioned 25ml four water-calcium nitrate then to forming stable clarification water white transparency colloidal sol, stirs 1 hour to forming stable sols; Place 55 ℃ of baking ovens to react this colloidal sol, to forming gel.After forming gel, with gel in 90 ℃ dry 24 hours down, put into retort furnace then in 600 ℃ of calcinings 2 hours down, furnace cooling then finally obtains the nanometer hydroxyapatite micro mist of white.As shown in Figure 1, its main crystalline phase is a hydroxyapatite; As shown in Figure 2, the synthetic hydroxyapatite contains carbonate; The hydroxy apatite powder particle diameter is 30-50nm as shown in Figure 3; As shown in Figure 4, through the laser particle size analyzer analysis, the quadratic average particle diameter of micro mist is 95nm.
Example 2:
Take by weighing 47.2 gram four water-calcium nitrates and be dissolved in dehydrated alcohol, stirring and dissolving is made into the ethanol solution of the 2mol/l four water-calcium nitrate of 100ml, and it is standby to measure the ethanol solution of the above-mentioned four water-calcium nitrate of 25ml; Take by weighing 2.15 gram Vanadium Pentoxide in FLAKESs and be dissolved in the 15ml dehydrated alcohol, stirring and dissolving dropwise is added drop-wise to it in ethanol solution of above-mentioned 25ml four water-calcium nitrate then to forming stable clarification water white transparency colloidal sol, stirs 1 hour to forming stable sols; Place 55 ℃ of baking ovens to react this colloidal sol, to forming gel.After forming gel, with gel in 90 ℃ dry 24 hours down, put into retort furnace then in 800 ℃ of calcinings 30 minutes down, furnace cooling then finally obtains the nanometer hydroxyapatite micro mist of white.As shown in Figure 5, its main crystalline phase is a hydroxyapatite, and through the laser particle size analyzer analysis, the quadratic average particle diameter of micro mist is 102nm.
Example 3:
Take by weighing 47.2 gram four water-calcium nitrates and be dissolved in dehydrated alcohol, stirring and dissolving is made into the ethanol solution of the 2mol/l four water-calcium nitrate of 100ml, and it is standby to measure the ethanol solution of the above-mentioned four water-calcium nitrate of 25ml; Take by weighing 2.15 gram Vanadium Pentoxide in FLAKESs and be dissolved in the 15ml dehydrated alcohol, stirring and dissolving dropwise is added drop-wise to it in ethanol solution of above-mentioned 25ml four water-calcium nitrate then to forming stable clarification water white transparency colloidal sol, stirs l hour to forming stable sols; Place 70 ℃ of baking ovens to react this colloidal sol, to forming gel.After forming gel, with gel in 90 ℃ dry 24 hours down, put into retort furnace then in 600 ℃ of calcinings 2 hours down, furnace cooling then finally obtains the nanometer hydroxyapatite micro mist of white.According to XRD and FTIR result, its main crystalline phase is a hydroxyapatite; Through the laser particle size analyzer analysis, the quadratic average particle diameter of micro mist is 99nm.
Example 4:
Take by weighing 47.2 gram four water-calcium nitrates and be dissolved in dehydrated alcohol, stirring and dissolving is made into the ethanol solution of the 2mol/l four water-calcium nitrate of 100ml, and it is standby to measure the ethanol solution of the above-mentioned four water-calcium nitrate of 25ml; Take by weighing 2.15 gram Vanadium Pentoxide in FLAKESs and be dissolved in the 15ml dehydrated alcohol, stirring and dissolving dropwise is added drop-wise to it in ethanol solution of above-mentioned 25ml four water-calcium nitrate then to forming stable clarification water white transparency colloidal sol, stirs 1 hour to forming stable sols; Place 70 ℃ of baking ovens to react this colloidal sol, to forming gel.After forming gel, with gel in 90 ℃ dry 24 hours down, put into retort furnace then in 800 ℃ of calcinings 30 minutes down, furnace cooling then finally obtains the nanometer hydroxyapatite micro mist of white.According to XRD and FTIR result, its main crystalline phase is a hydroxyapatite; Through the laser particle size analyzer analysis, the quadratic average particle diameter of micro mist is 97nm.
Example 5:
Take by weighing 47.2 gram four water-calcium nitrates and be dissolved in dehydrated alcohol, stirring and dissolving is made into the ethanol solution of the 2mol/1 four water-calcium nitrate of 100ml, and it is standby to measure the ethanol solution of the above-mentioned four water-calcium nitrate of 21ml; Take by weighing 1.704 gram Vanadium Pentoxide in FLAKESs and be dissolved in the 12ml dehydrated alcohol, stirring and dissolving dropwise is added drop-wise to it in ethanol solution of above-mentioned 21ml four water-calcium nitrate then to forming stable clarification water white transparency colloidal sol, stirs 1 hour to forming stable sols; Place 55 ℃ of baking ovens to react this colloidal sol, to forming gel.After forming gel, with gel in 90 ℃ dry 24 hours down, put into retort furnace then in 600 ℃ of calcinings down, furnace cooling then finally obtains the nanometer hydroxyapatite micro mist of white.According to XRD and FTIR result, its main crystalline phase is a hydroxyapatite; Through the laser particle size analyzer analysis, the quadratic average particle diameter of micro mist is 106nm.
Example 6:
Take by weighing 35.2 gram calcium acetate ((CH
3COOH)
2Ca.H
2O) be dissolved in dehydrated alcohol, stirring and dissolving is made into the ethanol solution of the 2mol/l calcium acetate of 100ml, and it is standby to measure the ethanol solution of the above-mentioned calcium acetate of 25ml; Take by weighing 2.15 gram Vanadium Pentoxide in FLAKESs and be dissolved in the 15ml dehydrated alcohol, stirring and dissolving dropwise is added drop-wise to it in ethanol solution of above-mentioned 25ml calcium acetate then to forming stable clarification water white transparency colloidal sol, stirs 2 hours to forming stable sols; Place 60 ℃ of baking ovens to react this colloidal sol, to forming gel.After forming gel, with gel in 90 ℃ dry 24 hours down, put into retort furnace then in 700 ℃ of calcinings 1 hour down, furnace cooling then finally obtains the nanometer hydroxyapatite micro mist of white.According to XRD and FTIR result, its main crystalline phase is a hydroxyapatite; Through the laser particle size analyzer analysis, the quadratic average particle diameter of micro mist is 104nm.
Claims (4)
1. a synthetic method that contains carbonate nanometer hydroxyapatite micro mist is characterized in that may further comprise the steps: with calcium acetate and P
2O
5Be dissolved in dehydrated alcohol preparation mixed sols, the mol ratio of Ca and P is 1.67-1.75 in the described mixed sols, described mixed sols is stirred, form stable sols, afterwards described formation stable sols reaction is formed gel, with described gel drying, obtain xerogel then, at last described xerogel is put into retort furnace and calcined 0.5-2 hours down, obtain containing the nanometer hydroxyapatite of carbonate at 600 ℃-800 ℃.
2. the synthetic method that contains carbonate nanometer hydroxyapatite micro mist according to claim 1 is characterized in that: in this step of described gel drying, drying temperature is 90 ℃-150 ℃, and be 12-72 hours time of drying.
3. the synthetic method that contains carbonate nanometer hydroxyapatite micro mist according to claim 1 is characterized in that: described formation stable sols reaction is being formed in this step of gel, and temperature of reaction is 55 ℃-70 ℃.
4. the synthetic method that contains carbonate nanometer hydroxyapatite micro mist according to claim 1 is characterized in that: described mixed sols is being stirred in this step, and churning time is 0.5-2 hours.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371290C (en) * | 2005-09-02 | 2008-02-27 | 中国科学院长春应用化学研究所 | Preparation method of ceramic nanometer granule with bioactivity |
| CN100390051C (en) * | 2005-11-15 | 2008-05-28 | 清华大学 | Preparation method of non-agglomeration nano-grade hydroxy apatite |
| CN101486453B (en) * | 2009-02-16 | 2011-09-28 | 重庆大学 | Preparation of carbonate-containing hydroxylapatite powder |
| CN106747425A (en) * | 2016-12-01 | 2017-05-31 | 东莞市联洲知识产权运营管理有限公司 | A kind of hydroxyl apatite coating do not split high density nano gadolinium zirconate ceramics |
| CN107232229A (en) * | 2017-06-07 | 2017-10-10 | 常州诺澜复合材料有限公司 | A kind of preparation method of nano silver antimicrobials |
| CN107353016B (en) * | 2017-06-16 | 2020-11-03 | 浙江大学 | Preparation method of hydroxyapatite and application of hydroxyapatite in 3D printing and forming |
| CN108355401B (en) * | 2018-02-09 | 2021-01-08 | 纳琦环保科技有限公司 | Preparation method of inorganic porous purification filter element |
| CN108807002B (en) * | 2018-08-02 | 2020-10-30 | 宝应县光华陶瓷有限公司 | Preparation method of biological ceramic composite porous electrode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107584A (en) * | 1985-09-23 | 1987-07-15 | 东亚燃料工业株式会社 | Calcium phosphate type hydroxyapatite and production method thereof with the what chromatographic separation |
| CN1386700A (en) * | 2002-06-28 | 2002-12-25 | 武汉理工大学 | Process for synthesizing superfine hydroxyapatite powder by self combustion method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107584A (en) * | 1985-09-23 | 1987-07-15 | 东亚燃料工业株式会社 | Calcium phosphate type hydroxyapatite and production method thereof with the what chromatographic separation |
| CN1386700A (en) * | 2002-06-28 | 2002-12-25 | 武汉理工大学 | Process for synthesizing superfine hydroxyapatite powder by self combustion method |
Non-Patent Citations (2)
| Title |
|---|
| 溶胶凝胶法羟基磷灰石纳米粉体的制备. 李霞.山东轻工业学院学报，第17卷第2期. 2003 * |
| 高品质羟基磷灰石纳米粉体的制备及物理化学过程研究. 宋云京，温树林，李木森，宿庆财，姜庆辉.无机材料学报，第17卷第5期. 2002 * |
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