CN105152151A - Method for preparing beta-tricalcium phosphate based on multidimensional oscillating nanometer ball milling - Google Patents
Method for preparing beta-tricalcium phosphate based on multidimensional oscillating nanometer ball milling Download PDFInfo
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- CN105152151A CN105152151A CN201510472440.1A CN201510472440A CN105152151A CN 105152151 A CN105152151 A CN 105152151A CN 201510472440 A CN201510472440 A CN 201510472440A CN 105152151 A CN105152151 A CN 105152151A
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- tricalcium phosphate
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Abstract
The invention belongs to the technical field of a biological medical material, and discloses a method for preparing beta-tricalcium phosphate based on multidimensional oscillating nanometer ball milling. The method comprises the following steps: performing ball milling of phosphorus-containing and calcium-containing raw materials, respectively, by adopting a multidimensional oscillating nanometer ball mill; adding the processed raw materials into a volatilizable dispersant according to a ratio; performing uniform mixing and dispersion under an ultrasonic and stirring condition to obtain a thick liquid; drying the thick liquid to remove the dispersant; performing high-temperature calcination for a solid-phase reaction to obtain powder; dispersing the powder into deionized water; and performing suction filtration and drying to obtain beta-tricalcium phosphate. The process technology of multidimensional oscillating nanometer ball milling is stable and simple, and is suitable for mass production. The obtained beta-tricalcium phosphate is high in purity, and the method has a bright application prospect.
Description
Technical field
The invention belongs to biology medical material technical field, be specifically related to a kind of method preparing bata-tricalcium phosphate based on multi-D swing nano ball grinding.
Background technology
Bata-tricalcium phosphate not only has good biocompatibility, and there is excellent biological activity and biodegradability, after implanting, material self is converted into a part for host freshman bone tissue by body fluid solution absorption, finally make the position of defect completely replace by the osseous tissue of new life, be a kind of Biodegradable material of excellent property, play huge effect in bone tissue engineer field.
In general the preparation method of bata-tricalcium phosphate mainly contains wet processing, hydrothermal method technique and dry process etc.Namely wet processing is synthesized by solution reaction, can obtain small grains or amorphous powder.Wet processing mainly contains three kinds of methods such as chemical precipitation method, acid-base neutralisation reaction method, alkylol cpd method.The reactant concn of wet processing can not be too large, and rate of addition can not be too fast, and wherein chemical precipitation method also needs constantly to regulate pH value with ammoniacal liquor, and technique is comparatively complicated.
Hydrothermal method technique is in special closed reaction vessel, adopt the aqueous solution as reaction medium, to reaction vessel create a high temperature, high pressure reaction environment to prepare a kind of method of material.Hydrothermal method technique requires higher to reaction conditions, applies less and is unsuitable for producing in enormous quantities.
Dry process is by raw material solid phase Reactive Synthesis, can obtain the good powder of crystallization.In dry process, comparative maturity mainly contains solid-phase synthesis, traditional solid-phase synthesis adopts planetary ball mill ball milling mixing raw material, after ball milling, the particle diameter of raw material is larger, simultaneously in mechanical milling process, often to make in raw material calcium phosphorus atom than unbalance because raw material glues tank or slimeball, thus cause having impurity phase to exist in the bata-tricalcium phosphate obtained.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, the object of the present invention is to provide a kind of method preparing bata-tricalcium phosphate based on multi-D swing nano ball grinding.
The object of the invention is achieved through the following technical solutions:
Prepare a method for bata-tricalcium phosphate based on multi-D swing nano ball grinding, comprise following preparation process:
Adopt multi-D swing nanon ball-mill by phosphorous raw material and the ball milling processing respectively of calcic raw material, then the raw material after processing is prepared burden in proportion and added volatile dispersion agent, ultrasonic even with blending dispersion under agitation condition, obtain slip; By slip drying removing dispersion agent, then solid state reaction is carried out in high-temperature calcination, obtains powder; Powder is scattered in deionized water, suction filtration, after drying, obtains bata-tricalcium phosphate.
Preferably, described phosphorous raw material refers to one or both the mixing in secondary calcium phosphate and Calcium Pyrophosphate; Described calcic raw material refers to one or both the mixing in calcium carbonate and calcium hydroxide.
Preferably, described ball milling processing refers to ball milling 6 ~ 12h under rotating speed is 300 ~ 500r/min condition.
Preferably, described batching in proportion refers to by the mol ratio of Ca/P is 1.50 ~ 1.64 to prepare burden.
Preferably, described volatile dispersion agent refers to dehydrated alcohol or deionized water.
Preferably, the described time that is ultrasonic and that stir is 2 ~ 4h; The speed stirred is 100 ~ 300r/min.
Preferably, described high-temperature calcination refers to calcining 2 ~ 3h under temperature is 850 ~ 1100 DEG C of conditions.
The fundamental diagram of multi-D swing nanon ball-mill of the present invention as shown in Figure 1 (in figure, α represents pendulum angle).This ball grinding technique, by tank body multi-D swing motion at a high speed, makes the irregular movement of grinding medium in tank more violent, produces the collision impact of the many intensity of multi-frequency, make powder stock be obtained refinement more by ball milling; Reduce simultaneously and clash into blind spot, improve grinding efficiency.
Preparation method's tool of the present invention has the following advantages and beneficial effect:
(1) preparation technology of the present invention is simple, less demanding to preparation condition, is conducive to mass production;
(2) preparation technology of the present invention is more stable, and it adopts multi-D swing nano ball grinding processing technology, makes the particle diameter after raw material ball milling less, disperses more stable in dispersion agent, thus make solid state reaction more abundant;
(3) preparation method of the present invention is by first for raw material ball milling processing, and the method for then preparing burden in proportion avoids calcium phosphorus atom that in mechanical milling process, sticky wall or slimeball cause than unbalance, improves the purity of last obtained bata-tricalcium phosphate powder.
Accompanying drawing explanation
Fig. 1 is the fundamental diagram of multi-D swing nanon ball-mill of the present invention;
Fig. 2 is the median size that embodiment 1 adopts the secondary calcium phosphate after multi-D swing nanon ball-mill ball milling and calcium carbonate, with the comparison diagram of the median size after common planetary ball mill ball milling;
Fig. 3 is the XRD spectra of embodiment 1 ~ 3 gained bata-tricalcium phosphate powder and the comparison diagram of standard spectrogram;
Fig. 4 is the IR spectrogram of embodiment 1 ~ 3 gained bata-tricalcium phosphate powder.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Adopting multi-D swing nanon ball-mill with the rotating speed of 300r/min, by secondary calcium phosphate and calcium carbonate ball milling 6h respectively, is 1.50 take the secondary calcium phosphate (CaHPO after ball milling according to Ca/P mol ratio subsequently
42H
2o) 37.86g and calcium carbonate (CaCO
3) 11.81g, then add 70mL dehydrated alcohol; By above-mentioned mixed solution at ultrasonic lower electric stirring 3h, make its abundant blending dispersion even, obtain slip; Slip is put in baking oven dry, is then placed in retort furnace and calcines 3h at 900 DEG C, obtain powder; Finally the powder after calcining is scattered in also suction filtration drying in deionized water, obtains bata-tricalcium phosphate powder.
The present embodiment adopts the median size of the secondary calcium phosphate after multi-D swing nanon ball-mill ball milling and calcium carbonate, contrast with the median size after common planetary ball mill ball milling, (in figure, 1# is the secondary calcium phosphate median size after common planetary ball mill ball milling to result as shown in Figure 2,2# is the median size of the calcium carbonate after common planetary ball mill ball milling, 3# is the median size of the secondary calcium phosphate after the present embodiment multi-D swing nanon ball-mill ball milling, and 4# is the median size of the calcium carbonate after the present embodiment multi-D swing nanon ball-mill ball milling).As seen from Figure 2, the median size of raw material after the processing of multi-D swing nano ball grinding is significantly less than the processing of common planetary ball milling, and the particle diameter of raw material is less, its blending dispersion more even in dispersion agent, solid state reaction will be more abundant, and the purity of the powder obtained also can be higher.
Embodiment 2
Adopting multi-D swing nanon ball-mill with the rotating speed of 500r/min, by Calcium Pyrophosphate and calcium carbonate ball milling 12h respectively, is 1.50 take the Calcium Pyrophosphate (Ca after ball milling according to Ca/P mol ratio subsequently
2p
2o
7) 45.91g and calcium carbonate (CaCO
3) 18.09g, then add 100mL deionized water; By above-mentioned mixed solution at ultrasonic lower electric stirring 4h, make its abundant blending dispersion even, obtain slip; Slip is put in baking oven dry, is then placed in retort furnace and calcines 2h at 1000 DEG C, obtain powder; Finally powder after calcining is scattered in also suction filtration drying in deionized water, obtains bata-tricalcium phosphate powder.
Embodiment 3
Adopting multi-D swing nanon ball-mill with the rotating speed of 400r/min, by Calcium Pyrophosphate and calcium hydroxide ball milling 9h respectively, is 1.50 take the Calcium Pyrophosphate (Ca after ball milling according to Ca/P mol ratio subsequently
2p
2o
7) 45.91g and calcium hydroxide (Ca (OH)
2) 13.39g, then add 90mL dehydrated alcohol; By above-mentioned mixed solution at ultrasonic lower electric stirring 4h, make its abundant blending dispersion even, obtain slip; Slip is put in baking oven dry, is then placed in retort furnace and calcines 3h at 850 DEG C, obtain powder; Finally powder after calcining is scattered in also suction filtration drying in deionized water, obtains bata-tricalcium phosphate powder.
The XRD spectra of embodiment 1 ~ 3 gained bata-tricalcium phosphate powder and the comparison diagram of standard spectrogram are as shown in Figure 3; Its IR spectrogram as shown in Figure 4.As can be seen from Fig. 3 and Fig. 4, the bata-tricalcium phosphate inclusion-free phase component that the present invention obtains, purity is higher.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. prepare a method for bata-tricalcium phosphate based on multi-D swing nano ball grinding, it is characterized in that comprising following preparation process:
Adopt multi-D swing nanon ball-mill by phosphorous raw material and the ball milling processing respectively of calcic raw material, then the raw material after processing is prepared burden in proportion and added volatile dispersion agent, ultrasonic even with blending dispersion under agitation condition, obtain slip; By slip drying removing dispersion agent, then solid state reaction is carried out in high-temperature calcination, obtains powder; Powder is scattered in deionized water, suction filtration, after drying, obtains bata-tricalcium phosphate.
2. a kind of method preparing bata-tricalcium phosphate based on multi-D swing nano ball grinding according to claim 1, is characterized in that: described phosphorous raw material refers to one or both the mixing in secondary calcium phosphate and Calcium Pyrophosphate; Described calcic raw material refers to one or both the mixing in calcium carbonate and calcium hydroxide.
3. a kind of method preparing bata-tricalcium phosphate based on multi-D swing nano ball grinding according to claim 1, is characterized in that: described ball milling processing refers to ball milling 6 ~ 12h under rotating speed is 300 ~ 500r/min condition.
4. a kind of method preparing bata-tricalcium phosphate based on multi-D swing nano ball grinding according to claim 1, is characterized in that: it is 1.50 ~ 1.64 to prepare burden that described batching in proportion refers to by the mol ratio of Ca/P.
5. a kind of method preparing bata-tricalcium phosphate based on multi-D swing nano ball grinding according to claim 1, is characterized in that: described volatile dispersion agent refers to dehydrated alcohol or deionized water.
6. a kind of method preparing bata-tricalcium phosphate based on multi-D swing nano ball grinding according to claim 1, is characterized in that: the described time that is ultrasonic and that stir is 2 ~ 4h; The speed stirred is 100 ~ 300r/min.
7. a kind of method preparing bata-tricalcium phosphate based on multi-D swing nano ball grinding according to claim 1, is characterized in that: described high-temperature calcination refers to calcining 2 ~ 3h under temperature is 850 ~ 1100 DEG C of conditions.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106276835A (en) * | 2016-07-28 | 2017-01-04 | 复旦大学附属中山医院 | A kind of nano beta tricalcium phosphate and preparation method thereof |
| CN106892414A (en) * | 2017-03-30 | 2017-06-27 | 华南理工大学 | It is a kind of to add the method that surfactant auxiliary ball mill prepares β tricalcium phosphate powders |
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| CN2437403Y (en) * | 2000-08-08 | 2001-07-04 | 吕庆 | Multi-D swing ball mill |
| CN104108693A (en) * | 2013-04-22 | 2014-10-22 | 赵柏松 | Preparation method of special-morphology lamellar crystal calcium phosphate powder |
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2015
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN2437403Y (en) * | 2000-08-08 | 2001-07-04 | 吕庆 | Multi-D swing ball mill |
| CN104108693A (en) * | 2013-04-22 | 2014-10-22 | 赵柏松 | Preparation method of special-morphology lamellar crystal calcium phosphate powder |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106276835A (en) * | 2016-07-28 | 2017-01-04 | 复旦大学附属中山医院 | A kind of nano beta tricalcium phosphate and preparation method thereof |
| CN106892414A (en) * | 2017-03-30 | 2017-06-27 | 华南理工大学 | It is a kind of to add the method that surfactant auxiliary ball mill prepares β tricalcium phosphate powders |
| CN106892414B (en) * | 2017-03-30 | 2019-05-17 | 华南理工大学 | A method of addition surfactant auxiliary ball mill prepares bata-tricalcium phosphate powder |
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