CN100509695C - Method for preparing porous hydroxyapatite and calcium carbonate nano ceramic - Google Patents
Method for preparing porous hydroxyapatite and calcium carbonate nano ceramic Download PDFInfo
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- CN100509695C CN100509695C CNB2006100203209A CN200610020320A CN100509695C CN 100509695 C CN100509695 C CN 100509695C CN B2006100203209 A CNB2006100203209 A CN B2006100203209A CN 200610020320 A CN200610020320 A CN 200610020320A CN 100509695 C CN100509695 C CN 100509695C
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Abstract
The invention discloses a manufacturing method for porous hydroxyapatite and calcium phosphate nanometer ceramic. It uses alcohol dissolving phosphorus-containing compound and alcohol dissolving calcium-containing compounds as raw material to make porous hydroxyapatite and calcium phosphate nanometer ceramic. The method does not have the power making process that makes the cost sharply decreased. The porosity could reach over 90%. It is especially suitable for supporting material and bone repairing material.
Description
Technical field
The present invention relates to the porous functional ceramic material and make the timbering material and the preparation thereof of field, especially bone renovating material and bone tissue engineer.
Background technology
Hydroxyapatite and calcium phosphate are the main inorganic compositions that constitutes human body hard tissue, it has excellent biological compatibility and biological activity, promptly tissue and cell nontoxicity, NIP and rejection and material surface are suited sticking of cell and growing, after implanting, it can form good bone bonding with osseous tissue on every side, therefore, porous hydroxyapatite and calcium phosphate ceramic are own makes timbering material and bone renovating material through being widely used in bone tissue engineer.Its technical process of present method comprises preparation, foaming and three main technique steps of sintering of powder.The preparation of powder, foaming and agglomerating technological process are relatively independent.There is significant disadvantages in this preparation method: promptly the quality of porous ceramic articles depends on that the preparation of dry powder body is the quality of powder, and the quality control of powder is very complicated process, for example when wet method and hydrothermal Synthesis of Hydroxy Apatite and calcium phosphate powder, need the long pH value that wears out and need regulation system, this will cause the increase of production cycle and production cost.In addition, its connectivity of porous ceramics and the homogeneity for preparing with aforesaid method is relatively poor.
In view of the above shortcoming of prior art, the purpose of this invention is to provide the method that a kind of preparation has the hydroxyapatite and the calcium phosphate ceramic of high connectivity and high uniformity, it is low relatively to make it have a production cost, the advantage that technical process is easy.
The objective of the invention is to realize by following means.
Summary of the invention
The preparation method of porous hydroxyapatite-calcium phosphate complex phase ceramic is raw material makes high connectivity and high uniformity through foaming and sintering porous hydroxyapatite and a calcium carbonate nano ceramic with molten P contained compound of alcohol and pure molten calcium containing compound.Synthetic and the foaming of hydroxyapatite and calcium phosphate is carried out under the condition that reactive blowing agent participates in synchronously, that is: at first distinguish pure molten P contained compound and calcium containing compound, treat solution to be poured in the same container after the fully dissolving mixed, stirring is placed on evaporating solvent in the water-bath again; After most of solvent evaporates, the container that fills colloid is placed the baking oven foaming of heating; After this further oven dry directly obtains porous hydroxyapatite and calcium phosphate base substrate; Described base substrate places Ma Fulu slowly to rise to more than 1000 ℃ and insulation is handled; To be cooled to the room temperature porous ceramics; Behind oversintering, obtain high connectivity and high uniformity porous hydroxyapatite and calcium phosphate biological ceramic product; The hole of described product is the three-dimensional sponge form that connects, and the cross section of hole wall is triangular in shape; Porosity is between 70%～96%.
Present method can provide the mixing on molecular level of calcium and phosphorus, thereby has improved the homogeneity of final product on structure and phase composition greatly, and this provides condition for the porous bio-ceramic for preparing high regularity and high uniformity.In addition, in the transition process of gel, because the viscosity of system increases sharply, thereby stablized the bubble that produces in earlier stage at colloidal sol, therefore this method can obtain high porosity and three-dimensionally connect good porous ceramics.
Description of drawings:
Fig. 1 is preparation technology's schema of the present invention.
Fig. 2 is the pattern photo of the scanning electronic microscope of embodiment 1 porous hydroxyapatite pottery.
Fig. 3 is the pattern of the scanning electronic microscope of porous hydroxyapatite pottery hole wall.
Fig. 4 is the X-ray diffraction spectrum of porous hydroxyapatite pottery.
Embodiment
Below in conjunction with accompanying drawing technology of the present invention is described in further detail.
Preparation technology's flow process of the present invention is at first distinguished pure molten P contained compound and calcium containing compound as shown in Figure 1, solution is poured in the same container after treating fully to dissolve to mix again, and stirring is placed on evaporating solvent in the water-bath; After most of solvent evaporates, the container that fills colloid is placed the baking oven foaming of heating; After this further oven dry directly obtains porous hydroxyapatite and calcium phosphate base substrate, obtains porous hydroxyapatite and calcium phosphate ceramic again behind sintering.In preparation, the material ratio of molten P contained compound of raw alcohol and pure molten calcium containing compound is expressed as calcium/phosphorus atom than decision by the atomic ratio of calcium and phosphorus.This ratio has determined the phase composition of the finished product: coordinating at 1.50 o'clock products is divided into tricalcium phosphate; Coordinate at 1.50～1.67 o'clock products and to be divided into hydroxyapatite and tricalcium phosphate mixture; Coordinate at 1.67 o'clock products and to be divided into hydroxyapatite.
Example 1, at first respectively with calcium/phosphorus atom than being pack into container and use anhydrous alcohol solution of 1.67 Vanadium Pentoxide in FLAKES and nitrocalcite, pour into then in the identical container, through stirring the mixed evaporating solvent in 75 ℃ of water-baths that is placed on, after most of solvent evaporates, the mixing solutions agglutination of this moment also is mixed with a large amount of bubble generations.The container that will fill colloid then places baking oven 80 ℃ of foaming down, after this 100 ℃ of oven dry down.With the porigelinite high alumina ceramic crucible of packing into of oven dry, place Ma Fulu slowly to rise to 1150 ℃ and be incubated 2 hours then.To be cooled to room temperature, take out burner hearth, so obtain porous ceramics shown in Figure 2.Figure 3 shows that the pattern of the scanning electronic microscope of porous ceramics hole wall, visible ceramic crystalline grain and micropore are nano level.X-ray diffraction spectrum shows that the composition of the product of gained is a hydroxyapatite, as shown in Figure 4.
Example 2, at first respectively with calcium/phosphorus atom than being pack into container and use anhydrous alcohol solution of 1.50 Vanadium Pentoxide in FLAKES and nitrocalcite, pour into then in the identical container, be placed on evaporating solvent in 75 ℃ of water-baths through stirring to mix.All the other processes are handled with embodiment 1, obtain tricalcium phosphate porous ceramic.
Example 3, at first respectively with calcium/phosphorus atom than being pack into container and use anhydrous alcohol solution of 1.63 Vanadium Pentoxide in FLAKES and nitrocalcite, pour into then in the identical container, through stirring the mixed evaporating solvent in 75 ℃ of water-baths that is placed on, all the other processes are handled and are obtained containing 70% hydroxyapatite and 30% tricalcium phosphate two-phase porous ceramics with embodiment 1.
Example 4 is poured calcium/phosphorus atom in the identical container into the nitrocalcite dehydrated alcohol than the tricresyl phosphate second fat that is 1.67 at first respectively, and through stirring the mixed evaporating solvent in 75 ℃ of water-baths that is placed on, all the other processes are handled and obtained the hydroxyapatite porous ceramics with embodiment 1.
Example 5 is poured calcium/phosphorus atom in the identical container into the nitrocalcite dehydrated alcohol than the tbp that is 1.67 at first respectively, and through stirring the mixed evaporating solvent in 75 ℃ of water-baths that is placed on, all the other processes are handled and obtained the hydroxyapatite porous ceramics with embodiment 1.
Example 6 is poured calcium/phosphorus atom in the identical container into the nitrocalcite dehydrated alcohol than the tricresyl phosphate second fat that is 1.50 at first respectively, and through stirring the mixed evaporating solvent in 75 ℃ of water-baths that is placed on, all the other processes are handled with 1 and obtained tricalcium phosphate porous ceramic.
Example 7, at first respectively calcium/phosphorus atom is poured in the identical container with the Vanadium Pentoxide in FLAKES dehydrated alcohol than the diethoxy calcium that is 1.67, through stirring the mixed evaporating solvent in 75 ℃ of water-baths that is placed on, all the other processes are handled and are obtained the hydroxyapatite porous ceramics with embodiment 1.
Example eight, at first respectively calcium/phosphorus atom is poured in the identical container with the Vanadium Pentoxide in FLAKES dehydrated alcohol than the diethoxy calcium that is 1.50, through stirring the mixed evaporating solvent in 75 ℃ of water-baths that is placed on, all the other processes are handled and are obtained tricalcium phosphate porous ceramic with embodiment 1.
In implementation process of the present invention, grain-size is by foaming sintering temperature and sintering time control, and high relatively sintering temperature obtains big relatively average grain size with relative long sintering time.Sintering temperature is at 1000 ℃～1200 ℃.Porous hydroxyapatite and tricalcium phosphate pottery mean pore size can be controlled in 100 μ m between the 2000 μ m, but average grain size 200nm is between the 1 μ m.Suitably regulate the material of foaming process in addition, the powder that for example before the foaming beginning, in the raw material system, adds the two-phase of hydroxyapatite powder, tricalcium phosphate powder or hydroxyapatite and tricalcium phosphate, also will produce regulating effect to the porosity of product, this can obtain porous hydroxyapatite and the calcium phosphate biological ceramic of porosity below 70%.When reality was implemented, some auxiliary processing condition can have suitable variation range, and generally speaking, baking oven is heated and is controlled at 75 ℃-90 ℃ foaming down; Porous body places Ma Fulu slowly to rise to and slowly rises to 1000 ℃ of-1200 ℃ of temperature ranges and through in good time insulation, can both obtain porous hydroxyapatite and calcium carbonate nano ceramic.
Make the common intellectual matter in field in view of the molten P contained compound of alcohol and pure molten calcium containing compound at porous hydroxyapatite and calcium carbonate nano ceramic, the molten P contained compound of described alcohol can be a kind of following material at least: Vanadium Pentoxide in FLAKES, trimethyl phosphate, tricresyl phosphate second fat, tricresyl phosphate third fat, tbp and di(2-ethylhexyl)phosphate (ethylhexyl) fat; The molten calcium containing compound of described alcohol can be a kind of following material at least: diethoxy calcium and nitrocalcite.
Beneficial effect compared with prior art is; The present invention's innovation has been to save the preparation process of powder, The process of gel-forming is finished foaming, and mole atomic ratio control by calcium and phosphorus obtains different proportion Hydroxyapatite and calcium phosphate, therefore, the present invention is porous hydroxyapatite and calcium phosphate biological ceramic undoubtedly Preparation and the preparation of associated materials provide easy method and production cost are reduced greatly, this just this Bright purpose. The porous hydroxyapatite and the calcium phosphate biological ceramic pore size distribution that obtain by this method evenly are three Foam-like and porosity that dimension connects can reach more than 90%, and it will become the support of good bone tissue engineer Material and bone renovating material.
Claims (2)
1, the preparation method of a kind of porous hydroxyapatite-calcium phosphate complex phase ceramic, with molten P contained compound of alcohol and pure molten calcium containing compound is raw material makes high connectivity and high uniformity through foaming and sintering porous hydroxyapatite and calcium carbonate nano ceramic, it is characterized in that: the synthetic and foaming of hydroxyapatite and calcium phosphate is carried out under the condition that reactive blowing agent participates in synchronously, that is: at first distinguish pure molten P contained compound and calcium containing compound, treat solution to be poured in the same container after the fully dissolving mixed, stirring is placed on evaporating solvent in the water-bath again; After most of solvent evaporates, the container that fills colloid is placed the baking oven foaming of heating; After this further oven dry directly obtains porous hydroxyapatite and calcium phosphate base substrate; Described base substrate places Ma Fulu slowly to rise to more than 1000 ℃ and insulation is handled; To be cooled to the room temperature porous ceramics; Behind oversintering, obtain high connectivity and high uniformity porous hydroxyapatite and calcium phosphate biological ceramic product; The hole of described product is the three-dimensional sponge form that connects, and the cross section of hole wall is triangular in shape; Porosity is between 70%-96%; The molten P contained compound of described alcohol can be a kind of following material at least: Vanadium Pentoxide in FLAKES, trimethyl phosphate, tricresyl phosphate second fat, tricresyl phosphate third fat, tbp and di(2-ethylhexyl)phosphate (ethylhexyl) fat; The molten calcium containing compound of described alcohol can be a kind of following material at least: diethoxy calcium and nitrocalcite; Evaporating solvent in 75 ℃ of water-baths; Baking oven is heated to foaming down at 75 ℃-90 ℃; Porous body places Ma Fulu slowly to rise to slowly to rise to 1000 ℃-1200 ℃ and after insulation is handled, and obtains porous hydroxyapatite and calcium carbonate nano ceramic.
According to the preparation method of the described a kind of porous hydroxyapatite-calcium phosphate complex phase ceramic of claim 1, it is characterized in that 2, calcium/phosphorus atom is than the phase composition that has determined the finished product: coordinating at 1.50 o'clock products is divided into tricalcium phosphate; Coordinate at 1.50～1.67 o'clock products and to be divided into hydroxyapatite and tricalcium phosphate mixture; Coordinate at 1.67 o'clock products and to be divided into hydroxyapatite; The material ratio of molten P contained compound of raw alcohol and pure molten calcium containing compound is by calcium/phosphorus atom ratio decision.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8052787B2 (en) * | 2007-09-28 | 2011-11-08 | National Taiwan University | Bio-material and method of preparation thereof |
| MY162982A (en) * | 2008-09-23 | 2017-07-31 | Laboratory Skin Care Inc | Active agent loaded uniform, rigid, spherical, nanoporous calcium phosphate particles and methods of making and using the same |
| WO2011081874A1 (en) | 2009-12-29 | 2011-07-07 | W. R. Grace & Co.-Conn. | Composite inorganic particles and methods of making and using the same |
| CN102557716B (en) * | 2012-02-14 | 2013-07-03 | 西南交通大学 | Direct interface method for preparing porous calcium phosphate nano ceramics with three-dimensional hierarchical surface morphologies |
| CN103183507A (en) * | 2013-03-19 | 2013-07-03 | 徐州工业职业技术学院 | Preparation method of biphase calcium phosphate ceramic containing beta-calcium pyrophosphate |
| CN106674830B (en) * | 2015-11-11 | 2021-01-26 | 重庆润泽医药有限公司 | Porous non-metallic material |
| CN106565229A (en) * | 2016-10-09 | 2017-04-19 | 洛阳鼎威材料科技有限公司 | Preparation method of compact hydroxyapatite material used for bone substitute |
| CN107176832B (en) * | 2017-03-30 | 2020-02-07 | 苏州鼎安科技有限公司 | Preparation method of biphase calcium phosphate composite powder synthesized by high-temperature solid-phase reaction |
| CN109133022A (en) * | 2018-09-12 | 2019-01-04 | 河南大学 | A kind of hydroxyapatite nano-structure of morphology controllable, preparation method and application |
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Non-Patent Citations (4)
| Title |
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| 快速熔胶-凝胶法制备纳米级羟基磷灰石. 王峰等.生物骨科材料与临床研究，第1卷第4期. 2004 |
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